WO2026010972A1 - Non-equilibrium electrochemical plasma catalysis (ne-epc) systems for green ammonia synthesis - Google Patents

Non-equilibrium electrochemical plasma catalysis (ne-epc) systems for green ammonia synthesis

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Publication number
WO2026010972A1
WO2026010972A1 PCT/US2025/036110 US2025036110W WO2026010972A1 WO 2026010972 A1 WO2026010972 A1 WO 2026010972A1 US 2025036110 W US2025036110 W US 2025036110W WO 2026010972 A1 WO2026010972 A1 WO 2026010972A1
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WIPO (PCT)
Prior art keywords
tmo
plasma
membrane
certain embodiments
catalyst
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PCT/US2025/036110
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French (fr)
Inventor
Huixin He
Yiguang Ju
Zhiyuan Zhang
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Rutgers State University of New Jersey
Princeton University
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Rutgers State University of New Jersey
Princeton University
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Publication of WO2026010972A1 publication Critical patent/WO2026010972A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/145—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing embedded catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/148—Organic/inorganic mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B01D71/0212—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0221—Group 4 or 5 metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by diffusion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/42—Catalysts within the flow path
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material

Definitions

  • FIG.1 shows scanning electron microscope (SEM) images of microwave enabled fast and direct growth of WO 3 on porous carbon support with different image areas. Scale bars: 5.00 ⁇ m (top left), 1.00 ⁇ m (top right), 500 nm (bottom left), 500 nm (bottom right). Samples were prepared with precursor and (NH 4 ) 2 SO 4 as the capping agent to control the shape of the nanostructures of the formed WO3.
  • FIG.2 shows another example of microwave enabled fast and direct growth of WO3 on porous carbon support of different imaging area.
  • FIG.3 shows an image of compositions comprising WO3 on porous carbon support produced by a method that enables one step, one pot direct growth of WO 3 nanostructures with Ru doping to further enhance catalytic performance.
  • Image (5.00 ⁇ m scale bar).
  • FIG.4 shows an image of compositions comprising WO 3 on porous carbon support produced by a method that enables one step, one pot direct growth of WO3 nanostructures with Ru doping to further enhance catalytic performance.
  • FIG.5 shows tungsten (W) imaging of compositions comprising WO3 on porous carbon support produced by a method that enables one step, one pot direct growth of WO 3 nanostructures with Ru to further enhance catalytic performance. Scale bar: 1 ⁇ m.
  • FIG.6 shows tungsten (O) imaging of compositions comprising WO 3 on porous carbon support produced by a method that enables one step, one pot direct growth of WO3 nanostructures with Ru to further enhance catalytic performance. Scale bar: 1 ⁇ m.
  • FIG.7 shows tungsten (Ru) imaging of compositions comprising WO3 on porous carbon support produced by a method that enables one step, one pot direct growth of WO 3 nanostructures with Ru to further enhance catalytic performance.
  • Scale bar 1 ⁇ m.
  • FIG.8 shows elemental analysis of a non-limiting, exemplary transition metal oxide (TMO) or catalytic substrate composition comprising W, O, and Ru. Note the C and Al is from carbon paper support and Al is from SEM sample holder.
  • TMO transition metal oxide
  • FIG.9 provides a schematic depicting an exemplary NE-EPC system of the disclosure (i.e., the non-equilibrium electrochemical plasma catalysis system), wherein the system is used to efficiently produce ammonia (NH 3 ) from water (H 2 O) and nitrogen (N 2 ) under ambient conditions.
  • a hydrogen selective membrane including metal based and transition metal oxide (TMO) based - 2 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) hydrogen atom transportation membrane, is used to electrochemically split water to generate protons (H + ).
  • the generated protons are then intercalated to the TMO based membrane and converted to hydrogen atoms, selectively and efficiently transported to the other side of the membrane.
  • plasma creates active atomic nitrogen and vibrationally excited nitrogen, and induces in situ surface nitridation of the membrane.
  • the nitrided surface acts as a plasma catalyst facilitating ammonia production through a plasma assisted Mars-Van Krevelen (PA-MvK) mechanism, or a layer of plasma catalysts are coated on the membrane surface facilitates ammonia production.
  • PA-MvK plasma assisted Mars-Van Krevelen
  • FIGs.10A-10B provide schematics depicting an exemplary NE-EPC system of the disclosure, wherein the system is used to efficiently produce ammonia (NH 3 ) from gaseous water (i.e., steam) and nitrogen (N2).
  • a high temperature proton selective membrane is used to electrochemically split water steam to generate protons (H + ), which are then selectively transported to the other side of the membrane (FIG.10A).
  • plasma creates active atomic nitrogen and vibrationally excited nitrogen and induces in situ surface nitridation of the membrane (FIG.10B).
  • the nitrided surface acts as plasma catalysts facilitating ammonia production through a plasma assisted Mars-Van Krevelen (PA-MvK) mechanism, or a layer of plasma catalysts is coated on the membrane surface facilitates ammonia production through a plasma assisted Mars-Van Krevelen (PA-MvK) mechanism.
  • PA-MvK plasma assisted Mars-Van Krevelen
  • FIGs.11A-11B show (FIG.11A) a schematic illustration depicting how the designed WO x N y /WO 3 electrocatalyst with a heterogenous interfacial complex (HIC) structure enables in-situ generation of H * via proton intercalation to promote the hydrogenation of lattice nitrogen (N) in WO x N y , leading to the formation of nitrogen vacancies (Nv) and the creation of new catalytic centers for enhanced eNRR, in accordance with various embodiments.
  • FIG.11B is a schematic representation of the orbital interaction between N2 and the catalytic center, which is highly active and selective for N2 absorption and activation, in accordance with various embodiments.
  • FIGs.12A-12B are a schematic illustrations of a two-step process for preparing largely vertically aligned WO x N y /WO 3 with the designed HIC architecture on a piece of carbon cloth with a hydrophobic MPL.
  • FIG.12A microwave-assisted hydrothermal growth of WO 3 nanosheet array on the MPL of carbon cloth
  • FIG.12B surface selective nitridation of the WO3 nanosheets via non-equilibrium plasma to form WOxNy/WO3, while leaving the WO 3 crystal structure and the underneath hydrophobic MPL intact, therefore the as-prepared WOxNy/WO3 hybrid catalyst electrodes were directly employed as gas diffusion electrodes - 3 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) for eNRR.
  • FIGs.13A-13D show (FIG.13A and FIG.13B) SEM images of the h-WO 3 nanosheets at different magnifications, which directly grow on a piece carbon cloth with a hydrophobic microporous layer.
  • FIG.13C shows PXRD patterns of h-WO 3 before and after plasma-assisted nitridation.
  • FIG.13D shows surface reconstruction of h-WO3 after plasma treatment.
  • Atomic resolution HAADF-STEM imaging reveals the presence of surface reconstruction and defects in h-WO3.
  • FIGs.14A-14B show high-resolution XPS spectra of h-WO 3 before and after plasma nitridation under different conditions: (FIG.14A) N 1s, (FIG.14B) W 4f.
  • FIGs.15A-15C show (FIG.15A) a comparison of the eNRR performance of WO 3 with different plasma treatments under identical conditions (at -0.15 V vs RHE) in the first half hour.
  • FIG.15B shows a comparison of eNRR performance of TMN and TMO x N y based catalysts.
  • FIG.15C shows 1 H nuclear magnetic resonance (NMR) spectra of the electrolyte after eNRR electrolysis on WO 3 -H 2 /N 2 -2h under 15 N 2 purging.
  • NMR nuclear magnetic resonance
  • FIG.16 shows specific yield rate and faradaic efficiency of WO3-H2/N2-2h at -0.15V in a three hour cycle, demonstrating that the initial NH3 yield rate is ⁇ 200 times higher NH3 yield than that of the Ni/Ni3N membrane. However, its eNRR activity drops over time.
  • FIG.19A-19B show surface nitridation of WO 3 after plasma treatment using EELS.
  • FIG.19A N-rich regions of WO3 are evident by the presence of severe surface reconstruction.
  • FIG.19B minimal N-signal is observed when bulk WO 3 EELS signals dominate the spectra.
  • FIGs.20A-20F show (FIGs.20A-20C) typical SEM images of h-WO 3 at different magnifications, in accordance with various embodiments.
  • FIGs.20D-20F show typical SEM images of WO x N y /WO 3 -H 2 /N 2 -2h with the same magnifications as in FIGs.20A-20C for comparison, in accordance with various embodiments.
  • FIGs.21A-21B show schematic illustrating the (FIG.21A) set-up for the eNRR electrolysis.
  • FIG.21B NOx control set-up: any NOx breakthrough from the oxidizing trap (filled with 0.1 M KMnO 4 in aqueous 0.1 M KOH) is captured by an alkaline trap (filled with aqueous 0.1 M KOH). All NH3 breakthrough and alkaline solution will be captured by the - 4 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) acid trap (filled with concentrated H2SO4).
  • FIGs.22A-22B show (FIG.22A) UV–vis spectra of the electrolytes collected from the various control experiments following the indophenol blue spectrophotometric method.
  • FIG.22B comparison of NH 3 yield rate with/without NO x removal from the N 2 feed.
  • FIGs.23A-23B shows (FIG.23A) UV-VIS spectra of various N 2 H 4 concentrations after incubated for 15 min at room temperature.
  • FIG.23B Calibration curve used for calculation of N 2 H 4 concentrations.
  • FIG.24 is a schematic drawing showing a set-up for the 15 N2 isotope eNRR electrolysis, in accordance with various embodiments. DETAILED DESCRIPTION
  • a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range.
  • the statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise.
  • the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.
  • NH3 has traditionally been used as a fertilizer and a key chemical in chemical industries. More recently, NH3 has emerged as a promising hydrogen (H2) carrier for green power storage and generation, due to its higher energy density, lower storage and transport costs, and lower flammability compared to H2.
  • H-B the Haber-Bosch
  • H2O water
  • Plasma catalysis offers non-equilibrium reaction pathways for NH 3 synthesis by utilizing active atomic nitrogen (N) and vibrationally excited nitrogen (N2( ⁇ )), as well as catalyst surface nitridation.
  • N active atomic nitrogen
  • N2( ⁇ ) vibrationally excited nitrogen
  • the energy efficiency of plasma-assisted NH 3 synthesis remains significantly lower (8.7 g-NH3/kWh) than that of the H-B process (500 g-NH3/kWh).
  • H 2 O is used as a hydrogen source in plasma, undesired byproducts such as NOx and H2O2 can be generated.
  • Electrocatalytic nitrogen reduction reaction eNRR allows green production of NH 3 from N 2 and H 2 O under ambient conditions without the undesired pollutants and other harmful byproducts.
  • eNRR electrochemical nitrogen reduction reaction
  • FE Faradaic efficiencies
  • the low NH 3 yield intrinsically stems from the inertness and nonpolar structure of N 2 molecules for effective reductive hydrogenation under mild conditions.
  • the low aqueous solubility of N 2 further slows down the reaction kinetics.
  • the low FE/low selectivity of eNRR is due to the overwhelming hydrogen evolution reaction (HER) competition during eNRR. Even though the thermodynamic potentials for HER and eNRR are close, the complete conversion of N2 into NH3 involves a difficult N2 activation process and 6 electrons and protons coupled electron transfer (PCET) reactions.
  • HER is a 2-electron proton PCET reaction, which is kinetically preferred, it is worthy to emphasize that HER not only directly causes the low FE but also results in low eNRR activity of the catalysts, especially at higher electrochemical overpotentials, where higher eNRR rate should be expected based on normal electrochemistry reaction principles. This is because not only is HER the kinetically preferred process, but, most importantly, the active sites on the catalysts for eNRR are predominately occupied by protons (H + ), adsorbed H atoms (H*), and/or the generated H 2 nanobubbles. Consequently, these active sites are severely blocked for N2 to access.
  • Transition metal nitrides TMSs
  • TMOxNy Transition metal nitrides
  • MvK Mars-van Krevelen
  • PCET direct proton-coupled electron transfer
  • This process significantly reduces the energy barrier for NH 3 production as it avoids the need for direct activation and cleavage of the N ⁇ N triple bond in N2.
  • Desorption of these NH3 molecules generate nitrogen vacancies (Nv) on the catalyst surface, which subsequently act as the catalytic sites, adsorbing and activating the dissolved N2 from the electrolyte and completing the catalytic cycles.
  • Nv nitrogen vacancies
  • the subsequent steps still require the cleavage of the N ⁇ N triple bond, it is noteworthy that the nitrogen vacancies not only provide unsaturated coordination sites that facilitate N2 adsorption but also efficiently activate the adsorbed N 2 molecules by accommodating the lone pair of electrons from N2 due to the electron-deficient nature of the vacancies.
  • the electron-deficient nature of nitrogen vacancies selectively favors the adsorption and activation of N2 over H + , thereby minimizing competition from hydrogen evolution reaction (HER).
  • HER hydrogen evolution reaction
  • the concurrent high activity and selectivity for eNRR stands in stark contrast to oxygen vacancies (Ov) on transition metal oxides (TMO).
  • the NH3 yield gradually declines over time, which is primarily attributed to nitrogen loss from the TMNs or TMOxNy catalysts. This depletion occurs due to the inertness of molecular N2, which cannot efficiently and promptly replenish the lost nitrogen during NH3 synthesis.
  • active species generated from non-equilibrium N 2 plasma could timely and effectively restore the lost nitrogen from the TMNs or TMOxNy catalysts.
  • the NE-EPC systems and the TMO membranes of the disclosure combine the strengths of plasma-based activation of nitrogen gas (N 2 ), which facilitates ex situ or in situ surface oxynitride and/or nitride (TMOxNy and/or TMNs) formation, and their in-situ regeneration on the hydrogen atom transportation membrane surface with electrochemical activation of water to produce and deliver H atoms.
  • N 2 nitrogen gas
  • TMOxNy and/or TMNs ex situ surface oxynitride and/or nitride
  • the compositions and/or the NE-EPC systems of the present disclosure represent a significant leap forward in green synthesis technology and catalysis.
  • a surprising and unexpected breakthrough lies in the development of hybrid ferroelectric plasma, which can controllably and selectively generate highly active N atoms and vibrational N2( ⁇ ) with a drastic improvement in plasma generation, afterglow discharge, and energy efficiency.
  • Another key breakthrough is the development of multifunctional transition metal oxide (TMO)-based hydrogen atom transport membranes.
  • TMO transition metal oxide
  • NE-EPC systems of the disclosure herein may comprise metal based or transition metal oxides (TMO) based hydrogen atom membranes, or proton selective membranes, that may be doped with additional elements to further improve their performance.
  • TMO transition metal oxides
  • the NE-EPC systems of the disclosure can generate ammonia and related compositions under mild conditions including ambient temperature and pressure.
  • the NE-EPC systems of the disclosure herein may comprise proton selective membranes, wherein the system is used to efficiently produce ammonia (NH3) from water steam and nitrogen (N2).
  • NH3 ammonia
  • N2 nitrogen
  • the net reaction is as follows: 2 N2 + 6 H2O ⁇ 4 NH3 + 3 O2 where water or water steam is electrochemically split to O 2 and protons (H + ) on the anode of the electrochemical cell of the NE-EPC systems.
  • the generated protons are then diffused to the cathode side, intercalated into the TMO based membranes, and converted to H atoms during transporting inside of the membrane.
  • the systems of the disclosure permit direct use of H 2 O or water steam, instead of H2 as the hydrogen source.
  • the systems of the disclosure permit production of ammonia in one step, and the issues related to generation of toxic byproducts, such as NO x , H 2 O 2 , are naturally avoided.
  • the systems of the disclosure drastically improve energy efficiency due to the hybrid ferroelectric plasma, which is highly energy efficient in controllably and selectively generating highly active species of N atoms and vibrational N2( ⁇ ).
  • the membranes and/or systems, and methods of use thereof, provided herein represent a viable alternative or complementary approach to the energy ⁇ and capital ⁇ intensive Haber ⁇ Bosch process.
  • the term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range.
  • active species refers to an excited state of an atom or molecule. In some aspects, an active species is readily converted into a desirable chemical product.
  • alkali earth metal refers to the six chemical elements that comprise Group IIa of the periodic table.
  • the elements include Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra).
  • alkaline refers to a molecular or atomic substance that is basic in nature, i.e. the substance is capable of forming a complex with one or more protons.
  • ambient conditions or “standard temperature and pressure” as used herein refers to about 20 °C and about 101 kPa.
  • carbon cloth as used herein refers to a type of porous, conductive fabric made from interwoven carbon fibers and/or filaments. In certain embodiments, the interwoven carbon fibers and/or filaments have a diameter of about 5-10 ⁇ m.
  • the material is used to support growth of transition metal oxides.
  • the term “carbon paper” as used herein refers to a sheet comprising carbon fibers stably adhered thereto while non-woven which forms a gas permeable paper-like structure having sufficient strength to function as a support plate for an electrode.
  • the fibrous sheet comprises one or more waxy mediums, including but not limited to paraffin, carnauba, oleic resin, and rosin.
  • the paper includes fibers such as rag, wood, manila, and jute.
  • alyst refers to an atom, molecule, or composition which promotes a chemical reaction, and further encompasses a combination of a catalyst with one or more non-catalytic materials, such as supports or stabilizers (e.g., substrates), and the like.
  • composite refers to an amalgam of one or more materials that are bonded or stabilized as a single entity.
  • a composite comprises one or more polymers, one or more TMOs, one or more nanomaterials, one or more dopants, and/or one or more support material such as a porous carbon support, a dielectric, and the like.
  • dielectric material refers to a material which is an electrical insulator or a very poor conductor of electric current.
  • discharge refers to release or transmission of electricity in a system.
  • electrochemical cell or “electrolyte cell” as used herein refers to an assembly, device, or system that converts chemical energy into electrical energy or electrical energy into chemical energy. Electrochemical cells comprise at least two electrodes (i.e., anode and a cathode) and an electrolyte, wherein electrode reactions occurring at the electrode surfaces result in charge transfer processes. In certain embodiments, the electrochemical cells described herein comprise a cathode comprising the hydrogen atom transportation membrane of the disclosure.
  • the hydrogen atom transport membrane comprises a transition metal oxide (TMO) membrane of the disclosure.
  • TMO transition metal oxide
  • the hydrogen ion transport membrane is directly attached to the anode in one side, and the other side is directly attached to the cathode, which have the plasma catalysts being exposed to the plasma as shown in FIG.10.
  • electroactive polyte refers to an ion-conducting liquid or solid material which facilitates ionic conductivity.
  • the term “electrode” refers to an electrical conductor used to make - 11 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) contact with a nonmetallic part of a circuit (e.g., a semiconductor, an electrolyte, or a vacuum). In certain embodiments, the term “electrode” may also refer to either an anode or a cathode.
  • the term “embedded” as used herein means at least partially enclosed within a supporting substrate or material. In certain embodiments, an object which is “embedded” in a substrate is at least partially exposed to at least one surface of the substrate.
  • FE Fluorescence efficiency
  • Faradaic yield refers to the fraction or percentage of the electrons applied to the cell that participate in the desired electrochemical reaction (e.g., fraction of applied electrons which participate in conversion of N 2 to NH 3 ).
  • the term “hydrogen” as used herein refers to the chemical element having an atomic number of 1. In certain embodiments, “hydrogen” refers to a proton or cation species (i.e., H + or H3O + or any hydrate of H + /H3O + ). In certain embodiments, “hydrogen” refers to molecular hydrogen gas (H 2 ). In certain embodiments, “hydrogen” refers to a radical species of hydrogen (H•).
  • X 1 , X 2 , and X 3 are independently selected from noble gases” would include the scenario where, for example, X 1 , X 2 , and X 3 are all the same, where X 1 , X 2 , and X 3 are all different, where X 1 and X 2 are the same but X 3 is different, and other analogous permutations.
  • intercalatable refers to a reversible inclusion or insertion of a molecule or ion into a solid substance or material.
  • membrane refers to a barrier material that is fashioned into a sheet or layer of material. In some aspects, the membrane is capable of permitting selective transport of hydrogen atoms (H*) or hydrogen ions (protons, H + ) under various conditions.
  • nanomaterial refers to a material which has at least one dimension in the nanometer-size range.
  • carbon nanomaterial includes, but is not limited to, carbon nanotubes (including multi-wall carbon nanotubes and single-wall carbon nanotubes), carbon nanoparticles, carbon nanofibers, carbon nanoropes, carbon nanoribbons, carbon nanofibrils, carbon nanoneedles, carbon nanosheets, carbon nanorods, carbon nanohorns, carbon nanocones, carbon nanoscrolls, graphite nanoplatelets, graphite nanoparticles, nanodots, other fullerene materials, or a combination thereof.
  • multi- wall is meant to include double-wall nanotubes (DWNTs) and few-wall nanotubes - 12 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) (FWNTs).
  • nanostructure refers to a structure that has at least one dimension of approximately nanometer range. Examples of nanostructures include nanoparticles, quantum dots, nanorods, nanowires, nanofilms, as well as other nanomaterials.
  • ferrroelectric as used herein refers to a material or substance that exhibits a permanent electrical polarization which varies in strength with the applied electrical field.
  • piezoelectric refers to a material or substance that undergoes electrical polarization from the application of mechanical stress.
  • pyroelectric refers to a material that has the property of becoming electrically charged when it is heated.
  • plasma refers to a (partially) ionized gas-like mass comprising a mixture of ions, electrons, and neutral species.
  • plasma catalyst refers to a material (e.g., transition metal oxide (TMO) substrate), or a surface thereof, which facilitates a chemical reaction under plasma irradiation.
  • the “plasma catalyst” may react with, or is modified by reaction with, a nitrogen (N) atom and/or vibrational N2 species formed in the plasma phase to form a reactive intermediate.
  • the reactive species comprises a reactive transition metal nitride (TMN), transition metal oxynitride (TMON), or N-doped TMO species.
  • TBN reactive transition metal nitride
  • TMON transition metal oxynitride
  • N-doped TMO species N-doped TMO species.
  • the term “porous” as used herein refers a material or substance having small regions, spaces, or holes through which liquid or gas may pass through.
  • reduction as used herein, as applied to a particular substance, means a chemical reaction whereby a chemical species receives an electron or an electron paired with a proton (i.e., hydrogen atom, H*).
  • exemplary reduction reactions include the transfer of hydrogen atoms to N 2 to form ammonia (NH 3 ).
  • room temperature refers to a temperature of about 15 °C to about 28 °C.
  • solvent refers to a liquid that can dissolve a solid, liquid, or gas. Non-limiting examples of solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.
  • substantially refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.
  • substantially free of can mean having none or having a trivial amount of, such that the amount of material present - 13 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) does not affect the material properties of the composition including the material, such that the composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0s001 wt% or less.
  • substantially free of can mean having a trivial amount of, such that a composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%.
  • substrate refers to a material comprising one or more layers of one or more materials that can be rigid or flexible and can include, but are not limited to, carbon nanomaterials, one or more polymers, glass, metal, ceramic materials, or combinations thereof.
  • surface modification refers to the chemical and/or physical alteration of a surface by an additive or subtractive process to change one or more chemical and/or physical properties of a substrate surface or a selected site or region of a substrate surface.
  • transition metal refers to any of the metallic elements within Groups 3 to 12 in the Periodic Table that have an incomplete inner electron shell and that serve as transitional links between the most and the least electropositive in a series of elements.
  • a transition metal element can be any of scandium (Sc), titanium (Ti), vanadium (Va), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mb), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), rutherfordium (Rf), dubnium (Db), seaborgium (Sb), bohrium (Bh), hassium (Hs), and meitnerium (Mt).
  • Sc scan
  • the disclosure provides a hydrogen atom transportation membrane comprising a porous support and a transition metal oxide (TMO) or a composite thereof.
  • hydrogen atom transportation membrane comprises a standalone TMO composite membrane.
  • the term "standalone” refers to membrane that is not supported by another solid surface, such as a porous support.
  • the TMO or TMO composite is deposited on the surface of the porous support.
  • the TMO or TMO composite is embedded in the porous support.
  • TMO or TMO composite is deposited on the surface thereof.
  • the TMO composite comprises a TMO, a carbon nanomaterial, and a polymer. In certain embodiments, the TMO composite comprises a TMO and a metal nanoparticle, In certain embodiments, the TMO composite comprises a TMO and a carbon nanomaterial. In certain embodiments, the TMO composite comprises a TMO, a metal nanoparticle, and a polymer. In certain embodiments, the TMO composite comprises a TMO, a carbon nanomaterial, and a polymer. In certain embodiments, the TMO composite comprises a TMO, a carbon nanomaterial, a metal nanoparticle, and a polymer. In certain embodiments, the TMO and the TMO composite comprises a plasma catalyst layer.
  • the plasma catalyst layer comprises a transition metal nitride (TMN).
  • TBN transition metal nitride
  • the TMN is doped with at least one metal element.
  • This metal element can be selected from a wide range of elements across the periodic table. Examples include, but are not limited to, Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm.
  • This metal element can be selected from a wide range of elements across the periodic table. Examples can be consisting of Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm.
  • the plasma catalyst layer comprises a transition metal oxynitride (TMOxNy).
  • the transition metal oxynitride is doped with at least one metal element.
  • This metal element can be selected from a broad range of elements across the periodic table, including, but not limited to, Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm.
  • the porous support is conductive metal and conductive metal oxide-based membranes, including, but not limited to, nickel foam, copper foam, titanium foil, stainless steel mesh, and conductive oxide-coated glass.
  • the porous support comprises nonconductive ceramic based membranes., including but not limited to, porous alumina (Al 2 O 3 ), porous titania (TiO 2 ), zirconia (ZrO 2 ), silicon carbide (SiC), and perovskite-type oxides.
  • the porous support can be polymer-based membranes. , including but not limited to, . porous polycarbonate, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethersulfone (PES), nylon, and polypropylene (PP).
  • the porous support can be carbon based membranes.
  • the porous carbon support comprises carbon paper.
  • the carbon paper is surface modified.
  • the porous carbon support comprises carbon cloth.
  • the porous carbon support comprises a carbon nanotube film.
  • the porous carbon support comprises a composite of carbon nanotube and graphene film.
  • the porous carbon support comprises a composite of other carbon nanomaterials.
  • the porous support is surface modified.
  • the surface modification comprises a modification which increases hydrophobicity.
  • the surface modification comprises a modification which increases hydrophilicity.
  • the transition metal oxide (TMO) is a proton intercalatable TMO.
  • the proton intercalatable TMO comprises WO3. In certain embodiments, the proton intercalatable TMO comprises MoO 3 . In certain embodiments, the proton intercalatable TMO comprises TiO2. In certain embodiments, the proton intercalatable TMO comprises VO 2 . In certain embodiments, the proton intercalatable TMO comprises Nb2O5. In certain embodiments, the proton intercalatable TMO comprises MnO2. In certain embodiments, the proton intercalatable TMO comprises HfO 2 . In certain embodiments, the proton intercalatable TMO comprises at least one hybrid TMO.
  • the proton intercalatable TMO comprises at least one hybrid TMO selected from the group consisting of (WO3)m-(WO2)n, (Nb2O5)m-(WO3)n, (MoO3)m - (VO2)n, (Nb2O5)m-(TiO2)n, (Nb2O5)m-(NbO2)n, (Nb2O5)m-(WO2)n, MomVOn, and WmNbOn, and wherein m and n are each 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10
  • TMO is doped with P.
  • TMO is doped with S.
  • TMO is doped with N.
  • TMO is doped with B.
  • TMO is doped with Se. In certain embodiments, TMO is doped with Ru. In certain embodiments, TMO is doped with Mo. In certain embodiments, TMO is doped with Nb. In certain embodiments, TMO is doped with Ti. In certain embodiments, TMO is doped with V. In certain embodiments, TMO is doped with Fe. In certain embodiments, TMO is doped with Co. In certain embodiments, TMO is doped with Ni. In certain embodiments, TMO is doped with Sb. In certain embodiments, TMO is doped with Mn. In certain embodiments, TMO is doped with Rh. In certain embodiments, TMO is doped with Re. In certain embodiments, TMO is doped with Cu.
  • TMO is doped with Pt. In certain embodiments, TMO is doped with Ir. In certain embodiments, TMO is doped with Au. In certain embodiments, TMO is doped with Ag. In certain embodiments, TMO is doped with Ge. In certain embodiments, TMO is doped with Pd. In certain embodiments, TMO is doped with Zr. In certain embodiments, TMO is doped with Y. In certain embodiments, TMO is doped with La. In certain embodiments, TMO is doped with Ce. In certain embodiments, TMO is doped with Ta. In certain embodiments, TMO is doped with Zn.
  • the carbon nanomaterial comprises carbon black. In certain embodiments, the carbon nanomaterial comprises carbon nanotubes. In certain embodiments, the carbon nanomaterial comprises graphene. In certain embodiments, the polymer comprises sulfonated tetrafluoroethylene (NafionTM). In certain embodiments, the polymer comprises polyaniline. In certain embodiments, the polymer comprises poly(pyrrole). In certain embodiments, the polymer comprises polyacrylate. In certain embodiments, the hydrogen atom transportation membrane further comprises at least one additional catalyst embedded in the TMO. In certain embodiments, the hydrogen atom transportation membrane further comprises at least one additional catalyst deposited on the surface thereof.
  • the additional metal catalyst is a transition metal nitride (TMN).
  • the TMN comprises at least one metal selected from the group consisting of W, Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm.
  • the additional catalyst is a transition metal oxynitride (TMON).
  • the TMON comprises at least one metal selected from the group consisting of W, Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm.
  • the at least one additional metal catalyst is a nitrogen (N) doped transition metal oxide (TMO).
  • the N-doped TMO comprises at least one metal selected from the group consisting of W, Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm.
  • Example TMO/TMON Catalyst In various embodiments, provided herein are WOxNy/WO3 hybrid electrochemical catalysts featuring a heterogeneous interfacial complexion (HIC) structure (FIG.11A). Without being bound by theory, this HIC structure is believed to enable in-situ generation of H * via proton intercalation, thereby promoting eNRR performance with a HIC enhanced Mars–van Krevelen (MvK) mechanism.
  • HIC interfacial complexion
  • WOxNy was selected for its potential to enhance eNRR activity via a Mars-van Krevelen (MvK) mechanism and superior stability against chemical decomposition, outperforming tungsten nitride (WN) due to its elevated N2p orbital positioned closer to the Fermi level (E F ).
  • MvK Mars-van Krevelen
  • WN tungsten nitride
  • E F Fermi level
  • WO3 offers an exceptional ability to undergo in-situ bulk proton (H + ) intercalation ( WO 3 + xH + + xe- ⁇ H x WO 3 ), generating mobile, active, and relatively long- lived H atoms (in the form of weakly bound hydrogen, denoted as W-H * ) in acidic electrolyte.
  • the WO x N y /WO 3 catalysts were designed with a HIC structure, as illustrated in FIGs.13A-13B.
  • This structural - 17 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) architecture ensures that WO3 retains its proton intercalation capability along the electron/proton transport pathway.
  • the abundance of H + ions in the acidic electrolyte facilitates the protonation and subsequent desorption of the produced NH3 from the WOxNy catalyst surface, facilitating generation of nitrogen vacancies (Nv).
  • these nitrogen vacancies (Nv) combined with the continuously supplied H * at neighboring W centers, form new catalytic sites, as illustrated in FIG.11B.
  • the newly formed catalytic sites at the WO x N y /WO 3 interface facilitate bidirectional electron transfer, a critical requirement for efficient N2 activation, thereby significantly enhancing activation capability.
  • the Nv preferentially adsorbs electron donor like N2 over H + due to their electron-deficient nature.
  • Non-Equilibrium Electrochemical Plasma Catalysis (NE-EPC) Systems provides a non-equilibrium electrochemical plasma catalysis (NE-EPC) system.
  • the system comprises an electrochemical cell.
  • the system comprises a plasma catalytic reaction chamber.
  • the system comprises a hydrogen atom transportation membrane comprising a porous carbon support, a transition metal oxide (TMO) layer, and a plasma catalyst layer.
  • the electrochemical cell and plasma catalytic reaction chamber are connected through, and separated by, the hydrogen atom transportation membrane.
  • the system comprises a water streaming chamber.
  • the electrochemical cell comprises an anode and a cathode.
  • the cathode comprises a water streaming oxidation anode.
  • the cathode comprises a transition metal nitride (TMN). In certain embodiments, the cathode is in contact with the plasma catalytic reaction chamber.
  • the hydrogen atom transportation membrane further comprises a transition metal-based hydrogen atom transportation membrane comprising Pd. In certain embodiments, the hydrogen atom transportation membrane further comprises a transition metal-based hydrogen atom transportation membrane comprising Ni. In certain embodiments, the hydrogen atom transportation membrane further comprises a transition metal-based hydrogen atom transportation membrane comprising V. In certain embodiments, the hydrogen atom transportation membrane further comprises a transition metal-based hydrogen atom transportation membrane comprising Nb.
  • the hydrogen atom transportation membrane comprises the hydrogen atom transportation membrane of the disclosure.
  • TMO layer further comprises one or more substantially vertically aligned nanostructures.
  • the nanostructures comprise nanosheets.
  • the nanostructures comprise nanorods.
  • the nanostructures comprise nanospikes.
  • the system further comprises a plasma source.
  • the plasma source comprises one or more electrodes and one or more reactants.
  • the reactant is nitrogen (N 2 ).
  • the reactant is hydrogen (H2).
  • the reactant is methane (CH4).
  • the reactant is carbon dioxide (CO 2 ).
  • the TMO layer further comprises a heteroatom-doped transition metal oxide (TMO).
  • TMO transition metal oxide
  • the TMO comprises WO 3 .
  • the hydrogen transportation membrane has a thickness selected from the group consisting of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or about 25 ⁇ m.
  • the plasma catalyst layer comprises at least one transition metal nitride (TMN) catalyst.
  • the TMN is additionally doped with Ru.
  • the TMN is additionally doped with Rh.
  • the TMN is additionally doped with Co. In certain embodiments, the TMN comprises Mo. In certain embodiments, the TMN is additionally doped with Nb. In certain embodiments, the TMN is additionally doped with V. In certain embodiments, the TMN comprises Ni. In certain embodiments, the TMN is additionally doped with La. In certain embodiments, the - 19 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) TMN is additionally doped with Ce. In certain embodiments, the TMN is additionally doped with Sm.
  • the amount of the Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, or Sm dopant in the TMN can be from about 0.0001 to 5% w/w relative to the weight of the TMN, or about 0.0001, 0.0002, 0.0003, 0.004, 0.0005, 0.0006, 0.0007, 0.0008, 0.0009, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6,
  • the plasma catalyst layer comprises at least one transition metal oxynitride (TMON) catalyst.
  • the TMON is additionally doped with Ru.
  • the TMON is additionally doped with Rh.
  • the TMON is additionally doped with Co.
  • the TMON is additionally doped with Mo.
  • the TMON is additionally doped with Nb.
  • the TMON is additionally doped with V.
  • the TMON is additionally doped with Ni.
  • the TMON is additionally doped with La.
  • the TMON is additionally doped with Ce.
  • the TMON is additionally doped with Sm.
  • the amount of the Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, or Sm dopant in the TMON can be from about 0.0001 to 5% w/w relative to the weight of the TMON, or about 0.0001, 0.0002, 0.0003, 0.004, 0.0005, 0.0006, 0.0007, 0.0008, 0.0009, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7
  • the plasma catalyst is formed in situ or ex situ by contact with N2 plasma.
  • the plasma catalyst is formed by deposition of a pre- synthesized layer of TMN and/or TMON nanostructures.
  • the lifetime of plasma catalysts of the disclosure are greatly extended.
  • the plasma catalysts of the disclosure last over 120 minutes of operation.
  • the element for the doped TMO comprises at least one selected from the group consisting of Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, and Sm.
  • the Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, and Sm comprise about 0.5% of the TMO by weight.
  • the element for the doped TMO comprises about 0.5% Ru by weight.
  • the TMO comprises about 0.5% Rh by weight.
  • the TMO comprises about 0.5% Co by weight.
  • the TMO comprises about 0.5% Mo by weight.
  • the TMO comprises about 0.5% Nb by weight.
  • the TMO comprises about 0.5% V by weight.
  • the TMO comprises about 0.5% Ni by weight.
  • the TMO comprises about 0.5% La by weight. In certain embodiments, the TMO comprises about 0.5% Ce by weight. In certain embodiments, the TMO comprises about 0.5% Sm by weight.
  • the plasma catalytic reaction chamber further comprises a plasma control unit or plasma control chamber. In certain embodiments, an electrical current is used to generate the source of plasma. In certain embodiments, the source of plasma comprises one or more electrodes and one or more reactants.
  • the current is selected from the group consisting of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or about 1000 mA.
  • water is a proton donor of the electrochemical cell.
  • the hydrogen atom transportation membrane is a cathode in the electrochemical cell.
  • the electrochemical cell comprises a metal anode.
  • the electrochemical cell comprises a liquid electrolyte that has a pH less than 5, such as a pH of about 4.5, 4, 3.5, 3, 2.5, 2, 1.5, or about 1.
  • the liquid electrolyte comprises one or more inorganic acids, alkaline, or alkaline earth metal salts. In certain embodiments, the liquid electrolyte comprises sulfuric acid. In certain embodiments, the liquid electrolyte comprises an aqueous solution.
  • a predominantly vertically aligned WO3 nanosheet array is first grown - 21 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) on highly conductive carbon cloth with a hydrophobic microporous layer (MPL) using a facile microwave-assisted hydrothermal method. This is followed by a plasma-assisted surface-selective nitridation process to convert part of the outer layer of WO3 into WOxNy while preserving the bulk WO 3 structure.
  • MPL microporous layer
  • a catalyst which includes: a first layer containing WO3; a second layer containing WO x N y ; wherein x is about 1.2 to about 2.8; wherein y is about 0.2 to about 1.8; and wherein the sum of x and y is about 3.
  • x is equal to y.
  • x is about 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, or about 2.8.
  • y is about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, or about 1.8.
  • the first layer has substantially the same crystal structure as pure WO 3 .
  • the first layer has the same crystal structure as pure WO3.
  • the WO3 in the first layer is hexagonal WO3 (h-WO3).
  • the second layer includes an amorphous layer of WO x N y .
  • the catalyst has a Faradaic efficiency of at least about 25%. In various embodiments, the catalyst has a Faradaic efficiency of at least about 25, 30, 35, 36, 37, 38, 39, 40, or 41%, or more. In various embodiments, the catalyst has a Faradaic efficiency of at least about 25, 30, 35, 36, 37, 38, 39, 40, or 41%, or more in a process that uses the catalyst to produce NH3. In various embodiments, the catalyst exhibits a powder x-ray diffraction (PXRD) peak at 63.6° 2 ⁇ as measured using Co K ⁇ radiation with a wavelength ( ⁇ ) of 1.789 ⁇ .
  • PXRD powder x-ray diffraction
  • the second layer has a thickness of about 0.01 to about 10 nm. In various embodiments, the second layer has a thickness of about 0.01, 0.05, 0.10, 0.15, - 22 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4
  • the first layer is adjacent to and in contact with the second layer.
  • MPL microporous layer
  • FIG.13A shows the nanosheet-like morphology of the as-prepared WO3, with the nanosheets predominantly aligned vertically but exhibiting random orientations.
  • Each individual nanostructure appears as a thin, platelet-like crystal measuring a few tens to hundreds of nanometers in thickness and extending laterally on the order of hundreds of nanometers to a few micrometers.
  • FIG.13B further reveals that each nanosheet is composed of an assembly of nanocrystals, suggesting a high surface area, which is highly beneficial for catalytic applications.
  • the crystal structure of the WO 3 was characterized with powder X-ray diffraction (PXRD).
  • the diffraction peaks of the as- prepared WO 3 align well with hexagonal WO 3 (h-WO 3 , JCPDS No.33-1387).
  • h-WO 3 hexagonal WO 3
  • JCPDS No.33-1387 a room-temperature, non-equilibrium plasma-assisted surface nitridation approach was developed.
  • This method utilizes a hydrogen/nitrogen mixture plasma, enabling the direct fabrication of the hybrid WOxNy/WO3 catalyst electrode with the designed HIC architecture at room temperature. This approach ensures precise control over nitridation while maintaining the structural integrity and electronic properties essential for efficient proton and electron transport.
  • the synthesized WO 3 nanosheets on carbon cloth described above were used as the precursor, directly located in a H2/N2 dielectric barrier discharge (DBD) plasma chamber for the surface selective nitridation.
  • DBD dielectric barrier discharge
  • Various plasma treatment conditions including N2 plasma for 1 hour, first H2 plasma for half hour, followed by N2 plasma for 1 - 23 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) hour, H2/N2 (1:4) plasma for 1 hour, and H2/N2 plasma for 2 hours, were tested to optimize the surface nitridation.
  • the resulting hybrid WO x N y /WO 3 catalyst electrode was accordingly named as WO3-N2-1h, WO3-H2-0.5h-N2-1h, WO3-H2/N2-1h, and WO3-H2/N2-2h, respectively.
  • SEM and PXRD were also used to study their morphology and crystal structural change after plasma treatment.
  • FIGs.19A-19C SEM as-prepared WO 3
  • FIGs.19D-19F SEM post-nitridation
  • HAADF-STEM high-angle annular dark-field scanning transmission electron microscopy
  • the h-WO 3 crystal structure represents an intermediate phase within the WO 3 family. At elevated temperatures, around 400 °C, h-WO3 transitions into monoclinic WO3 (m-WO3), the most thermodynamically stable form of WO 3 .
  • X-ray photoelectron spectroscopy a surface-sensitive technique
  • XPS X-ray photoelectron spectroscopy
  • the nitridated surface likely consists of WO x N y rather than WN.
  • the surface composition was further quantified based on the integrated peak areas in their respected XPS spectrum.
  • the WO 3 -H 2 /N 2 -2h sample exhibits the highest nitrogen content of 14.3 at%, which remains significantly lower than that of any known tungsten oxynitride phases.
  • the amorphous HIC layer observed in FIG.13D is not composed solely of a uniform WOxNy phase. Instead, it likely consists of a heterogeneous mixture of WO3 and WOxNy domains, as schematically illustrated in FIGs.13A-13B.
  • the intensity of the W-N peak in the WO3-H2/N2-1h sample is significantly lower than in the WO3-H2/N2-2h sample, indicating that longer treatment times facilitate more N-W bond formation.
  • all the samples show high peak densities corresponding to N-O bonds and N-W-O/Nv- related bonds.
  • the peak associated with N-W-O/Nv-related bonds in the WO 3 - H2/N2-1h sample is even higher than in the WO3-H2/N2-2h sample.
  • the coexistence of WO3 domains and the unique HIC architecture of the catalyst is expected to sustain proton intercalation, ensuring the continuous generation and delivery of active H * species to the WOxNy regions for the formation of W-H * FIG.11A).
  • significantly enhanced eNRR activity is anticipated.
  • the eNRR performance of the WOxNy/WO3 hybrid catalyst electrodes was evaluated and the correlation between their structural characteristics and catalytic activity was investigated.
  • the WOxNy/WO3 hybrid catalysts were directly employed as gas diffusion electrodes (GDEs) to address the low solubility of N 2 in water (0.71 mg/L).
  • GDEs gas diffusion electrodes
  • the electrolyte in the working electrode (WE) side of the cell was collected for quantification of ammonium (NH4 + ) and possible hydrazine (N 2 H 4 ) byproduct using the indophenol blue UV-Vis spectroscopy method, the Watt-Chrisp method, and NMR spectroscopy as detailed in herein.
  • the NH3 yield rate and Faradic efficiency (FE) for the nitrogen-ammonia conversion were calculated as detailed in herein.
  • FIG.15A presents the NH 3 yield rate and Faradaic efficiency (FE) of WO x N y /WO 3 catalysts fabricated under various plasma treatment conditions at -0.15 V vs. RHE during the first half hour of electrolysis.
  • the NH 3 yield rate and FE of WO x N y /WO 3 -H 2 /N 2 -1h are lower than those of WO3-H2/N2-2h, which can be attributed to its reduced W-N content and the - 26 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) absence of W 5+ species, as confirmed by the N 1s and W 4f XPS spectra.
  • WO3-H2/N2-2h demonstrates the highest NH3 yield rate of 3.2 ⁇ 10 -10 mol ⁇ cm -2 ⁇ s -1 , accompanied by a FE of 40.1%. This enhanced performance correlates with the fact that WO3-H2/N2-2h contains the highest number of W-N species and exhibits the highest electron density at the W centers, both of which facilitate the formation of W-H * species, as discussed previously.
  • the feed N2 gas was passed three purification traps to effectively eliminate any NOx impurities in the gas feed: (1) a KMnO 4 oxidation trap to oxidize any NO x present in the N 2 gas into soluble NO3-, (2) a KOH trap to remove the possibly formed NO3-, and (3) a 0.1 M H2SO4 solution to trap any residual NH 3 in the N 2 gas.
  • a KMnO 4 oxidation trap to oxidize any NO x present in the N 2 gas into soluble NO3-
  • a KOH trap to remove the possibly formed NO3-
  • a 0.1 M H2SO4 solution to trap any residual NH 3 in the N 2 gas.
  • the NH 3 yield obtained after NO x purification was approximately 8% lower than the yield achieved using only the NH3 trap - 27 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) without NOx purification.
  • the 1 H NMR spectrum of the electrolyte after eNRR electrolysis using the WO x N y /WO 3 -H 2 /N 2 -2h catalyst with 15 N 2 as the gas feed (top curve) displays five peaks.
  • This spectrum closely matches a standard sample containing both 15 NH4 + and 14 NH 4 + .
  • the peak height for 15 NH 4 + peaks is much higher than those of 14 NH 4 + suggested that most of the detected NH4 + comes from electrocatalytic reduction of the 15 N2 feed.
  • the simultaneous detection of 15 NH4 + and a small amount of 14 NH4 + in 15 N isotope labeling experiments has been used as an indication of MvK mechanism as both lattice nitrogen on the catalyst surface and the N2 feed contribute to nitrogen turnover during eNRR. This is because the initial NH 3 generation originates from the hydrogenation of lattice nitrogen on TMN and TMOxNy-based electrocatalysts.
  • NH3 can be produced at the start of electrolysis without the need for an external N 2 feed, distinguishing this process from direct proton-coupled electron transfer (PCET) of adsorbate nitrogen.
  • PCET direct proton-coupled electron transfer
  • TMN and TMO x N y -based electrocatalysts can also generate NH3 without an external N2 feed through electrochemically driven decomposition, rather than by hydrogenation of surface lattice nitrogen under acidic conditions. It has been reported that electrochemical-driven decomposition of TMN has led to false positives in discovering new electrocatalysts for eNRR. Therefore, the detection of 14 NH 4 + in the NMR does not yet confirm that the eNRR is proceeding via the MvK mechanism.
  • HIC-enhanced MvK mechanism owing to the unique structure and properties of the heterogeneous interfacial complexion (HIC) in the catalyst.
  • HIC heterogeneous interfacial complexion
  • the disclosure provides a method of generating a chemical species, comprising contacting a plasma with the NE-EPC systems of the disclosure.
  • the chemical species is ammonia (NH 3 ).
  • the chemical species is hydrogen (H2).
  • the chemical species is carbon monoxide (CO).
  • the chemical species is methanol (CH3OH).
  • the method of generating a chemical species comprises a reduction reaction.
  • the chemical species is a reduced chemical species.
  • the reduced chemical species is NH 3 .
  • the chemical species is generated under ambient conditions.
  • the reduction reaction has a specific yield of at least 1 x 10 -10 mol•cm -2 s -1 (hydrogen atom transportation membrane).
  • the plasma is derived from nitrogen (N 2 ).
  • the plasma has a frequency ranging from about 0 GHz to about 10 GHz.
  • the plasma has a gas temperature ranging from about 300 K to about 1,000 K.
  • the plasma has an electron temperature ranging from about 1 eV to about 100 eV. In certain embodiments, the plasma has a pressure ranging from about 20 Torr to about 760 Torr. In certain embodiments, the plasma is enhanced by contacting one or more electrodes with at least one dielectric material. In certain embodiments, the dielectric material is a piezoelectric material. In certain embodiments, the dielectric material is a ferroelectric material. In certain embodiments, the dielectric material is a pyroelectric material. In certain embodiments, the dielectric material is flat. In certain embodiments, the dielectric material is porous. In certain embodiments, the dielectric material is microstructured. In certain embodiments, the dielectric material is nanostructured.
  • the plasma is generated by a discharge.
  • the discharge is a direct current (DC) discharge.
  • the discharge is a alternating current (AC) discharge.
  • the discharge is a radio frequency (RF) discharge.
  • the discharge is a microwave (MW) frequency discharge.
  • the discharge with a duration in the range of about 1 nanosecond to about 1 microsecond.
  • the faradic efficiency of the NE-EPC system is at least about 5%.
  • the methods of the disclosure e.g., use of the NE-EPC system of the disclosure permits ammonia production of at least 30 nmol/s ⁇ cm 2 .
  • the methods of the disclosure permits ammonia production of at least 100 nmol/s ⁇ cm 2 In certain embodiments, the methods of the disclosure permits ammonia production of at least 1,000 nmol/s ⁇ cm 2 .
  • EXAMPLES Various embodiments of the present application can be better understood by reference to the following Examples which are offered by way of illustration. The scope of the present application is not limited to the Examples given herein.
  • Example 1 Non-equilibrium electrochemical plasma electrocatalysis (NE-EPC) system design
  • the disclosure relates to the development of a strategy to overcome the - 30 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) fundamental challenges impeding practical green ammonia production.
  • the approach described herein leverages the efficient N 2 activation by plasma and the facile activation of water by electrochemistry. These two initially incompatible systems are integrated by constructing a non-equilibrium electrochemical plasma electrocatalysis (NE-EPC) system, enabling efficient green synthesis of NH3 at ambient pressures and room temperature, as well as higher temperatures.
  • NE-EPC non-equilibrium electrochemical plasma electrocatalysis
  • the two major competing reactions i.e. water activation and N2 activation
  • a hydrogen atom selective membrane i.e., hydrogen atom transportation membrane
  • metal based- and the multifunctional transition metal oxide (TMO)-based hydrogen-selective membrane plays a crucial role in constructing the non-equilibrium electrochemical plasma catalysis (NE-EPC) system of the disclosure.
  • TMO transition metal oxide
  • the features of the electrochemical system of the disclosure are described herein. Spatial/Temporal Separation avoids competition of the active sites In one aspect, spatial and/or temporal separation of the coupled reactions (i.e., water activation and N2 activation) avoids active site competition.
  • the positions of the active sites responsible for electrochemically generating active hydrogen are distinct from the sites dedicated to N2 activation, hydrogenation, and NH3 generation.
  • This separation eliminates the competition for catalytic sites on the surfaces for H 2 activation in previous reported plasma- enhanced NH3 synthesis where H2 was used as the hydrogen resource, or for water and proton activation, which would lead to overwhelming hydrogen evolution reaction (HER) in electrochemical cells.
  • This separation ensures unimpeded access for N2 to the catalytic sites for eNRR. Simultaneously, it guarantees an ample supply of hydrogen resources for eNRR, thanks to the mixed electron-hydrogen transportation property of the hydrogen atom selective membranes. It is worth noting that TMO based hydrogen atom selective membranes also compare favorably with metal-based hydrogen atom membranes.
  • the spatial/temporal separation allows independently optimization of the environments for the reactions at each side of the membrane for efficient green NH3 production.
  • spatial and/or temporal separation of the coupled reactions permits independent optimization for efficient NH3 production.
  • Spatial and/or temporal separation enables plasma-enhanced N 2 activation and hydrogenation of the activated N2 to the NH3 product in an electrolyte-free and hydrogen gas- - 31 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) free environment.
  • inert N2 can be effectively activated by N2 plasma under optimized conditions, transforming into highly reactive vibrational nitrogen (N 2 ( ⁇ )) and atomic N as the reactants for NH 3 generation.
  • water molecules are electrochemically activated into protons or active H atoms, which are transported through the membrane, and become available for the hydrogenation of the activated N2 ( ⁇ ) and atomic N.
  • the system(s) e.g., membranes and/or NE-EPC
  • the methods of the present disclosure facilitate the one-step, highly selective synthesis of NH3 with remarkable yield and Faradaic efficiency, while minimizing the production of undesirable byproducts such as NOx and H2O2.
  • Product Protection Mechanism In another aspect, the vertically aligned and densely packed TMO nanostructures on the surface of the membranes of the disclosure not only offer large surface area for efficient NH 3 production, but also provide safeguarding of the NH 3 products, protecting them from plasma-induced decomposition.
  • Transition metal nitrides (TMNs) and Transition metal oxynitrides (TMO x N y ) are a class of catalysts for electrochemical N2 fixation. Unlike other catalysts, where Proton- Coupled Electron Transfer (PCET) pathway is widely accepted as the catalytic reaction mechanism for eNRR, TMN catalysts, in contrast, proceeds via a Mars-van Krevelen (MvK) catalytic reaction pathway. Specifically, the lattice N atoms on the surface of TMNs are first hydrogenated to produce NH 3 , leaving N vacancies behind. These N vacancies are subsequently refilled by the dissolved N2 from the electrolyte.
  • PCET Proton- Coupled Electron Transfer
  • MvK Mars-van Krevelen
  • Example 2 Exemplary membrane compositions and electrochemical cells of the disclosure and methods of use thereof
  • the hydrogen atom transportation membranes of the disclosure, and NE-EPC systems comprising the same are prepared by microwave enabled growth of WO3 on a porous carbon support (FIGs.1-2).
  • the membranes are prepared by microwave irradiation of precursors with (NH 4 ) 2 SO 4 (FIG.1) or Na2SO4 (FIG.2) as the capping agent.
  • the microwave irradiation method enables one step, one pot direct growth of WO 3 structures in combination with additional heteroatom doping elements (e.g., Ru) to further enhance catalytic performance of the membranes of the disclosure in NE-EPC systems of the disclosure (FIGs.3-8).
  • additional heteroatom doping elements e.g., Ru
  • Selected preliminary results include evaluation of ex situ N2 plasma treatment to generate tungsten oxynitride layer as the catalytic layer on the tungsten oxide (WO 3 ) membrane surface in a single chamber (i.e., eNRR).
  • eNRR of a plasma treated catalytic substrate of the disclosure comprising WOxNy demonstrated a NH3 yield about 200 times greater than that which was observed using a Ni 3 N membrane (FIG.15A).
  • N2 plasma treatment of a WO3 surface generates catalytic centers for NH 3 synthesis and shows that eNRR activity of the WO x N y -WO 3 decreases over time (FIG.15A) due to the slow refilling of the nitrogen vacancies by the inert N2, which is depicted in FIG.11.
  • Example 3 Fast fabrication of WO 3 nanosheet array on carbon cloth with the microporous layer (MPL) via a microwave hydrothermal method A microwave hydrothermal method was applied to fabricate the WO 3 nanosheet array directly on a carbon cloth support with the microporous layer (MPL). The recipe for the fabrication was slightly modified from the work by Gao et al., "High-performance energy- storage devices based on WO3 nanowire arrays/carbon cloth integrated electrodes," Journal of Materials Chemistry A 2013, 1 (24), 7167-7173.
  • the as-prepared 4 mL H 2 WO 4 precursor was transferred into a microwave tube, and then 0.1 g of Na 2 SO 4 was added to the solution to control the structure.
  • Example 4 Plasma assisted surface nitridation of the WO 3 nanosheet array
  • the as-fabricated WO3 nanosheet arrays on carbon cloth support were treated with 16-torr N2 and N2/H2 plasma for different durations, as specified in the sample names.
  • the plasma was generated in a home-made DBD cell, powered by a 20-kHz, 13-kV AC power supply.
  • the composition, oxidation states, and morphology of the samples were analyzed by a range of surface characterization techniques, including X-ray photoelectron spectroscope (XPS), scanning electron microscope (SEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM).
  • XPS X-ray photoelectron spectroscope
  • SEM scanning electron microscope
  • HAADF-STEM high-angle annular dark-field scanning transmission electron microscopy
  • Example 5 Characterization of the Electrocatalysts
  • FE-SEM field emission scanning electron microscope
  • XRD X ray diffraction
  • High-angle annular dark-field scanning transmission electron microscopy (HAADF- STEM) was acquired on an aberration-corrected JEOL NEOARM operating at 200 kV using a convergence semi-angle of 28 mrad.
  • Any electron energy loss spectroscopy (EELS) data was acquired on an aberration corrected FEI Titan microscope operating at 300 kV using a convergence semi-angle of 19.3 mrad.
  • a 0.1 eV/channel dispersion was used during dual EELS data acquisition, wherein the low loss contains the zero-loss peak and the high loss contains both the O K-edge and N K-edge simultaneously.
  • a full-width half maximum of the zero-loss peak registers an energy resolution of 1.0 eV.
  • STEM samples were prepared using a solution-casting technique. The initial sample powders were dispersed in isopropyl alcohol and sonicated. Thereafter, the solution was applied to conventional lacey carbon TEM foil grids.
  • Example 6 Assessment of eNRR performance of the WOxNy/WO3 hybrid catalyst electrodes All the electrochemical measurements were performed using a CHI 760 C Potentiostat (CH Instruments, USA). Ag/AgCl (sat.
  • KCl KCl
  • Pt wire Pt wire
  • RE reference
  • CE counter electrodes
  • RHE EAg/AgCl + 0.197 V + 0.059 ⁇ pH (eq1)
  • Example 7 eNRR setup The eNRR performance of the WOxNy/WO3 hybrid catalyst electrodes was evaluated using a CH Instruments 760E Potentiostat with a homemade designed N 2 flow electrolysis cell as shown in FIG.19A.
  • This cell consists of a proton exchange membrane (Nafion 117, Dupont), a piece of Pt plate, Ag/AgCl (saturated KCl) electrode, which act as the counter electrode (CE), and reference electrode, respectively.
  • the working electrode (WE) is the as- prepared WOxNy/WO3 hybrid catalyst electrodes with a size of 0.7 ⁇ 0.7 cm, which were directly used as a catalytic gas-diffusion electrode (GDE) for eNRR to alleviate the low solubility issue of N2 in water-based electrolytes (0.71 mg/mL).
  • GDE catalytic gas-diffusion electrode
  • pressurized N2 (flow rate: 2.5 mL/min) from the gas tank was passed through three traps arranged in series before being introduced to the backside of the GDE (the side without catalyst coating) for eNRR (FIG.19B).
  • the three purification traps included: (1) A KMnO4 oxidation trap to oxidize any NO 3 present in the N2 gas into soluble NO3 ⁇ . (2) A KOH trap to remove the possibly formed NO3 ⁇ . (3) A 0.1 M H2SO4 solution to trap any residual NH3 in the N2 gas.
  • the N2 gas was purged onto the backside of the GDE to initiate eNRR and the excess gas was purged back to the electrolyte to avoid the loss of the produced NH 3 carried over by the N 2 flow during the eNRR.
  • the WE side and the CE side were separated by a Nafion 117 membrane (Fuel cell store).
  • the electrolyte in the WE side of the cell was collected for ammonium (NH 3 ) and hydrazine (N 2 H 4 ) detection using the indophenol blue UV-Vis spectroscopy method and NMR spectroscopy as detailed herein.
  • Example 8 Determination of NH 4 + via the indophenol blue method The concentration of the produced NH4 + was spectrophotometrically determined by the indophenol blue method. Typically, 1 mL of electrolyzed electrolyte was transferred from the electrochemical cell to a clean vial. Then 1 mL of solution containing 1M NaOH with 5 wt% salicylic acid and 5 wt% sodium citrate was added to the vial.
  • the color reagent was obtained by mixing concentrated HCl (30 mL), C 2 H 5 OH (300 mL) and C 9 H 11 NO (5.99 g). And 5 mL electrolyte was taken from the cathodic chamber and added into 5 mL above as-prepared color reagent. After standing for 15 minutes, the absorption spectrum of the solution was collected in the wavelength range of 420-500 nm, and the peak appears at 455 nm. The calibration curve was measured using the absorbance of N 2 H 4 solution with different concentrations.
  • Example 10 15 N 2 isotope label experiment and NMR Analysis: Before starting the nitrogen reduction reaction (NRR) experiment using 15N-labeled nitrogen, the system was purged with argon gas three times over a total of 30 minutes to remove any residual air. After purging, the argon supply was turned off, and the balloon was evacuated by pump before being filled with 15N2 gas. The electrolysis was then conducted at - 0.15 V vs RHE for 30 minutes.
  • the electrolyte was collected for further analysis of the 15N-labeled products.
  • the pH of the electrolyte was adjusted to 4.5, maleic acid was added as an internal standard, and DMSO-d6 was used to lock the sample.
  • NH 4 + detection via NMR was performed using the excitation sculpting water suppression (zgesgp pulse sequence) on a Bruker 500 MHz Avance III HD spectrometer.
  • the following parameters were optimized: frequency offset (O1P), size of the free induction decay (FID) (TD), pre-scan delay (D1), and the number of scans (NS).
  • TD was set to 16,378, D1 to 1 s, and NS to 16,378.
  • the system was purged with argon gas three times over a total of 30 minutes to remove residual air. Afterward, the argon supply was shut off, and the balloon was evacuated by pump and subsequently filled with 15 N2 gas. The electrolysis was then carried out at -0.15V vs RHE for 30 minutes. Finally, the electrolyte was collected for further analysis of the 15 N-labeled products.
  • NMR samples were prepared in the particular way: after electrolysis pH was adjusted to 4.5, maleic acid was added as internal standard, and DMSO-d6 to lock.
  • NH 4 + detection via NMR was performed using the excitation sculpting water suppression (zgesgp pulse sequence) on Bruker 500 MHz Avance III HD spectrometer.
  • O1P frequency offset
  • TD size of FID
  • D1 pre-scan delay
  • NS number of scans
  • Example 11 Calculation of NH 3 yield rate and Faradic efficiency for ammonia production
  • the NH3 yield rate was calculated by Eq.2: - 37 - 55799713.4
  • Attorney Docket No.370602-7078WO1 (00278) ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ (Eq.2) where C[NH 4 + ] in the WE side, V is the volume of the electrolyte, Scat is the catalyst electrode area, t is the electrolysis duration.
  • the Faradic efficiency for the nitrogen-ammonia conversion was calculated by Eq. (Eq.3): ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ (Eq.3) where Q is the constant (96485 C mol -1 ).
  • Embodiment 1 provides a hydrogen atom transportation membrane comprising: i) a transition metal oxide (TMO) standalone membrane, or ii) a porous support and a TMO membrane, wherein the TMO membrane is embedded in the porous support or deposited on a surface of the porous support.
  • Embodiment 2 provides the hydrogen atom transportation membrane of embodiment 1, wherein the TMO comprises a plasma catalyst layer.
  • TMO transition metal oxide
  • Embodiment 3 provides the hydrogen atom transportation membrane of any one of embodiments 1-2, wherein the porous support comprises at least one selected from the group consisting of a conductive metal- or metal-oxide-based membrane, a nonconductive ceramics-based membrane, a polymer-based membrane, and a carbon-based membrane, or combinations thereof.
  • Embodiment 4 provides the hydrogen atom transportation membrane of any one of embodiments 1-3, wherein the porous support is surface modified, optionally wherein surface modification improves hydrophobicity or hydrophilicity.
  • Embodiment 5 provides the hydrogen atom transportation membrane of any one of embodiments 1-4, wherein the TMO comprises a proton intercalatable TMO or a polymer composite thereof, a metal nanoparticle composite, a carbon nanomaterial composite, a metal nanoparticle polymer composite, a carbon nanomaterial composite, or a metal nanoparticle and carbon nanomaterial polymer thereof.
  • the TMO comprises at least one selected from the group consisting of WO3, MoO3, TiO2, VO2, Nb2O5, ZrO2, HfO2, and MnO2.
  • Embodiment 7 provides the hydrogen atom transportation membrane of any one of embodiments 1-6, wherein the proton intercalatable TMO comprises at least one hybrid TMO selected from the group consisting of, but not limited to, (WO 3 ) m -(WO 2 ) n , (Nb 2 O 5 ) m -(WO 3 ) n , (MoO3)m -(VO2)n, (Nb2O5)m-(TiO2)n, (Nb2O5)m-(NbO2)n, (Nb2O5)m-(WO2)n, MomVOn, and W m NbO n , and wherein m and n are each independently an integer selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.
  • Embodiment 8 provides the hydrogen atom transportation membrane of any one of embodiments 5-7, wherein the polymer composite comprises at least one polymer comprising at least one of sulfonated tetrafluoroethylene, polyaniline, polypyrrole, and polyacrylate.
  • Embodiment 9 provides the hydrogen atom transportation membrane of any one of embodiments 5-7, wherein the composite comprises at least one metal nanostructure comprising at least one of Pd, Ni, Pt, and Ru.
  • Embodiment 10 provides the hydrogen atom transportation membrane of any one of embodiments 1-9, wherein the TMO is doped with at least one element selected from the group consisting of P, S, N, B, Se, Ru, Mo, Nb, Ti, V, Fe, Co, Ni, Sb, Mn, Rh, Re, Cu, Pt, Ir, Au, Ag, Ge, Pt, Zr, and Zn.
  • the TMO is doped with at least one element selected from the group consisting of P, S, N, B, Se, Ru, Mo, Nb, Ti, V, Fe, Co, Ni, Sb, Mn, Rh, Re, Cu, Pt, Ir, Au, Ag, Ge, Pt, Zr, and Zn.
  • Embodiment 11 provides the hydrogen atom transportation membrane of any one of embodiments 1-10, wherein the hydrogen atom transportation membrane further comprises at least one additional metal catalyst embedded in the TMO, or deposited on the surface thereof, optionally wherein the at least one additional metal catalyst is selected from the group consisting of a transition metal nitride (TMN), a transition metal oxynitride (TMON), and a nitrogen (N) doped TMO.
  • Embodiment 12 provides the hydrogen atom transportation membrane of any one of embodiments 1-11, wherein the TMN, TMON, or (N)-doped TMO comprises at least one metal selected from the group consisting of Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, and Sm.
  • Embodiment 13 provides a non-equilibrium electrochemical plasma catalysis (NE- EPC) system comprising: (a) an electrochemical cell; (b) a plasma catalytic reaction chamber; and (c) a hydrogen atom transportation membrane comprising a porous carbon support, a transition metal oxide (TMO) layer, and a plasma catalyst layer, - 39 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) wherein the electrochemical cell and plasma catalytic reaction chamber are connected through, and separated by, the hydrogen atom transportation membrane.
  • Embodiment 14 provides the system of any one of embodiments 13, wherein the system further comprises a water streaming chamber.
  • Embodiment 15 provides the system of any one of embodiments 13 or 14, wherein the electrochemical cell comprises an anode and a cathode and at least one of the following applies: (a) the anode comprises a water streaming oxidation anode; (b) the cathode comprises a transition metal nitride (TMN); and (c) the cathode is in contact with the plasma catalytic reaction chamber.
  • Embodiment 16 provides the system of any one of embodiments 13-15, wherein the hydrogen atom transportation membrane further comprises a transition metal-based hydrogen atom transportation membrane comprising at least one of Pd, Ni, V, and Nb.
  • Embodiment 17 provides the system of any one of embodiments 13-16, wherein the hydrogen atom transportation membrane comprises the membrane of any one of embodiments 1-13.
  • Embodiment 18 provides the system of any one of embodiments 13-17, wherein the TMO layer further comprises one or more substantially vertically aligned nanostructures, optionally wherein the nanostructures are selected from the group consisting of nanosheets, nanorods, and nanospikes.
  • Embodiment 19 provides the system of any one of embodiments 13-18, further comprising a plasma source comprising one or more electrodes and one or more reactants, optionally wherein the reactant is at least one selected from the group consisting of nitrogen (N 2 ), hydrogen (H 2 ), methane (CH 4 ), and carbon dioxide (CO 2 ).
  • Embodiment 20 provides the system of any one of embodiments 13-19, wherein the TMO layer further comprises a heteroatom-doped transition metal oxide (TMO).
  • Embodiment 21 provides the system of any one of embodiments 13-20, wherein the TMO comprises WO 3 .
  • Embodiment 22 provides the system of any one of embodiments 13-21, wherein the hydrogen transportation membrane has a thickness ranging from about 100 nm to about 25 ⁇ m.
  • Embodiment 23 provides the system of any one of embodiments 13-22, wherein the plasma catalyst layer comprises at least one transition metal nitride (TMN) or transition metal - 40 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) oxynitride (TMON) catalyst, wherein the TMN or TMON comprises at least one metal selected from the group consisting of Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, and Sm.
  • TNN transition metal nitride
  • TMON oxynitride
  • Embodiment 24 provides the system of any one of embodiments 13-23, wherein the TMO doped with about 0.5% Ru, P, S, N, B, Se, Mo, Nb, Ti, V, Fe, Co, Ni, Sb, Mn, Rh, Re, Cu, Pt, Ir, Au, Ag, Ge, Pt, Zr, or Zn by weight.
  • Embodiment 25 provides the system of any one of embodiments 13-24, wherein the plasma catalytic reaction chamber further comprises a plasma control unit or plasma control chamber.
  • Embodiment 26 provides the system of any one of embodiments 13-25, wherein an electrical current is used to generate the source of plasma.
  • Embodiment 27 provides the system of any one of embodiments 26, wherein the current ranges from about 100 ⁇ A to about 1000 mA, optionally wherein the current ranges from about 1 mA to about 1000 mA.
  • Embodiment 28 provides the system of any one of embodiments 13-27, wherein water is a proton donor of the electrochemical cell.
  • Embodiment 29 provides the system of any one of embodiments 13-28, wherein the hydrogen atom transportation membrane is a cathode in the electrochemical cell, optionally wherein the electrochemical cell comprises a metal anode.
  • Embodiment 30 provides the system of any one of embodiments 13-29, wherein the electrochemical cell comprises a liquid electrolyte that has a pH less than 5.
  • Embodiment 31 provides the system of any one of embodiments 30, wherein the liquid electrolyte comprises one or more inorganic acids, alkaline, or alkaline earth metal salts, optionally wherein the liquid electrolyte comprises sulfuric acid.
  • Embodiment 32 provides the system of any one of embodiments 30 or 31, wherein the liquid electrolyte comprises an aqueous solution.
  • Embodiment 33 provides a method of generating a chemical species, comprising contacting a plasma with the system of any one of embodiments 13-32 to form the chemical species.
  • Embodiment 34 provides the method of embodiment 33, wherein the plasma is derived from nitrogen (N2).
  • Embodiment 35 provides the method of embodiments 33 or 34, wherein the chemical species is selected from the group consisting of ammonia (NH3), hydrogen (H2), carbon monoxide (CO), and methanol (CH 3 OH).
  • the chemical species is selected from the group consisting of ammonia (NH3), hydrogen (H2), carbon monoxide (CO), and methanol (CH 3 OH).
  • NH3 ammonia
  • H2 hydrogen
  • CO carbon monoxide
  • CH 3 OH methanol
  • Embodiment 36 provides the method of any one of embodiments 33-35, wherein at least one of the following applies: (a) the plasma has a frequency ranging from about 0 GHz to about 10 GHz; (b) the plasma has a gas temperature ranging from about 300 K to about 1,000 K; (c) the plasma has an electron temperature ranging from about 1 eV to about 100 eV; and (d) the plasma has a pressure ranging from about 20 Torr to about 760 Torr.
  • Embodiment 37 provides the method of any one of embodiments 33-36, wherein the plasma is enhanced by contact with an electrode comprising at least one dielectric material selected from the group consisting of a piezoelectric material, a ferroelectric material, and a pyroelectric material, optionally wherein the electrode or dielectric material is flat or porous, and optionally wherein the electrode or dielectric material is microstructured or nanostructured.
  • Embodiment 38 provides the method of any one of embodiments 33-37, wherein the chemical species is generated under ambient conditions.
  • Embodiment 39 provides the method of any one of embodiments 33-38, wherein the plasma is generated by a discharge selected from the group consisting of direct current (DC) discharge, alternating current (AC) discharge, radio frequency (RF) discharge, and microwave (MW) frequency discharge, or a combination of thereof, optionally wherein the discharge occurs with a duration in the range of about 1 nanosecond to about 1 microsecond.
  • Embodiment 40 provides the method of any one of embodiments 33-39, wherein the system has a Faradaic efficiency of at least about 5%.
  • Embodiment 41 provides a catalyst comprising: a first layer comprising WO3; a second layer comprising WO x N y ; wherein x is about 1.2 to about 2.8; wherein y is about 0.2 to about 1.8; and wherein the sum of x and y is about 3.
  • Embodiment 42 provides the catalyst of embodiment 41, wherein the first layer has substantially the same crystal structure as pure WO3.
  • Embodiment 43 provides the catalyst of any one of embodiments 41-42, wherein the WO3 in the first layer is hexagonal WO3 (h-WO3).
  • Embodiment 44 provides the catalyst of any one of embodiments 41-43, wherein the WO3 in the first layer is h'-hexagonal WO3 (h'-WO3). - 42 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278)
  • Embodiment 45 provides the catalyst of any one of embodiments 41-44, wherein the second layer comprises an amorphous layer of WOxNy.
  • Embodiment 46 provides the catalyst of any one of embodiments 41-45, wherein the catalyst has a Faradaic efficiency of at least 25%.
  • Embodiment 47 provides the catalyst of any one of embodiments 41-46, wherein the catalyst exhibits a powder x-ray diffraction (PXRD) peak at 63.6° 2 ⁇ as measured using Co K ⁇ radiation with a wavelength ( ⁇ ) of 1.789 ⁇ .
  • Embodiment 48 provides the catalyst of any one of embodiments 41-47, wherein the second layer has a thickness of about 0.01 to about 10 nm.
  • Embodiment 49 provides the catalyst of any one of embodiments 41-48, wherein the first layer is adjacent to and in contact with the second layer.

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Abstract

In one aspect, the disclosure relates to membrane compositions, non-equilibrium plasma catalysis (NE-EPC) systems comprising the same, and methods of use thereof for performing electrified synthesis of certain chemical species. In certain embodiments, NH3 is 5 synthesized from N2 and H2O using the NE-EPC systems.

Description

Attorney Docket No.370602-7078WO1 (00278) TITLE Non-Equilibrium Electrochemical Plasma Catalysis (NE-EPC) Systems for Green Ammonia Synthesis CROSS-REFERENCE TO RELATED APPLICATION This application claims priority to U.S. Provisional Patent Application No. 63/666,511 entitled "NON-EQUILIBRIUM ELECTROCHEMICAL PLASMA CATALYSIS (NE-EPC) SYSTEMS FOR GREEN AMMONIA SYNTHESIS," filed July 1, 2024, the disclosure of which is incorporated herein by reference in its entirety. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH This invention was made with government support under grant numbers 2428523, 1742807, and 2025064 awarded by the National Science Foundation and grant numbers DE- SC0025371 and DEAC0209CH11466 awarded by the Department of Energy. The government has certain rights in the invention. BACKGROUND Ammonia (NH3) is a critical chemical compound with significant industrial and agricultural applications (e.g., fertilizer production) and is a hydrogen carrier for power and electricity generation. The Haber-Bosch process, developed in the early 20th century, has been the primary industrial method for synthesizing NH3 from abundant N2 and H2 feedstocks. While the Haber-Bosch process has enabled large-scale production of NH3, the process is both energy- and capital-intensive, and generates a significant amount of greenhouse gases (~420 Mt CO2 annually). There is thus a need in the art for compositions, systems, and/or methods suitable for efficient reduction of nitrogen gas for green ammonia synthesis. The present disclosure addresses this unmet need. BRIEF DESCRIPTION OF THE FIGURES The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments of the present application. The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee. - 1 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) FIG.1 shows scanning electron microscope (SEM) images of microwave enabled fast and direct growth of WO3 on porous carbon support with different image areas. Scale bars: 5.00 µm (top left), 1.00 µm (top right), 500 nm (bottom left), 500 nm (bottom right). Samples were prepared with precursor and (NH4)2SO4 as the capping agent to control the shape of the nanostructures of the formed WO3. FIG.2 shows another example of microwave enabled fast and direct growth of WO3 on porous carbon support of different imaging area. Scale bars: 10.0 µm (top left), 5.00 µm (top right), 1.00 µm (bottom left), and 500 nm (bottom right). Samples were prepared with precursor and Na2SO4 as the capping agent to control the shape of the nanostructures of the formed WO3. FIG.3 shows an image of compositions comprising WO3 on porous carbon support produced by a method that enables one step, one pot direct growth of WO3 nanostructures with Ru doping to further enhance catalytic performance. Image: (5.00 µm scale bar). FIG.4 shows an image of compositions comprising WO3 on porous carbon support produced by a method that enables one step, one pot direct growth of WO3 nanostructures with Ru doping to further enhance catalytic performance. Image: 500 nm scale. FIG.5 shows tungsten (W) imaging of compositions comprising WO3 on porous carbon support produced by a method that enables one step, one pot direct growth of WO3 nanostructures with Ru to further enhance catalytic performance. Scale bar: 1 µm. FIG.6 shows tungsten (O) imaging of compositions comprising WO3 on porous carbon support produced by a method that enables one step, one pot direct growth of WO3 nanostructures with Ru to further enhance catalytic performance. Scale bar: 1 µm. FIG.7 shows tungsten (Ru) imaging of compositions comprising WO3 on porous carbon support produced by a method that enables one step, one pot direct growth of WO3 nanostructures with Ru to further enhance catalytic performance. Scale bar: 1 µm. FIG.8 shows elemental analysis of a non-limiting, exemplary transition metal oxide (TMO) or catalytic substrate composition comprising W, O, and Ru. Note the C and Al is from carbon paper support and Al is from SEM sample holder. FIG.9 provides a schematic depicting an exemplary NE-EPC system of the disclosure (i.e., the non-equilibrium electrochemical plasma catalysis system), wherein the system is used to efficiently produce ammonia (NH3) from water (H2O) and nitrogen (N2) under ambient conditions. In some embodiments of the NE-EPC system of the disclosure, a hydrogen selective membrane, including metal based and transition metal oxide (TMO) based - 2 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) hydrogen atom transportation membrane, is used to electrochemically split water to generate protons (H+). The generated protons are then intercalated to the TMO based membrane and converted to hydrogen atoms, selectively and efficiently transported to the other side of the membrane. There, plasma creates active atomic nitrogen and vibrationally excited nitrogen, and induces in situ surface nitridation of the membrane. Without wishing to be bound by theory, the nitrided surface acts as a plasma catalyst facilitating ammonia production through a plasma assisted Mars-Van Krevelen (PA-MvK) mechanism, or a layer of plasma catalysts are coated on the membrane surface facilitates ammonia production. FIGs.10A-10B provide schematics depicting an exemplary NE-EPC system of the disclosure, wherein the system is used to efficiently produce ammonia (NH3) from gaseous water (i.e., steam) and nitrogen (N2). In this non-limiting embodiment, a high temperature proton selective membrane is used to electrochemically split water steam to generate protons (H+), which are then selectively transported to the other side of the membrane (FIG.10A). There, plasma creates active atomic nitrogen and vibrationally excited nitrogen and induces in situ surface nitridation of the membrane (FIG.10B). Without being bound by theory, the nitrided surface acts as plasma catalysts facilitating ammonia production through a plasma assisted Mars-Van Krevelen (PA-MvK) mechanism, or a layer of plasma catalysts is coated on the membrane surface facilitates ammonia production through a plasma assisted Mars-Van Krevelen (PA-MvK) mechanism. FIGs.11A-11B (Scheme 1 Manu) show (FIG.11A) a schematic illustration depicting how the designed WOxNy/WO3 electrocatalyst with a heterogenous interfacial complex (HIC) structure enables in-situ generation of H* via proton intercalation to promote the hydrogenation of lattice nitrogen (N) in WOxNy, leading to the formation of nitrogen vacancies (Nv) and the creation of new catalytic centers for enhanced eNRR, in accordance with various embodiments. FIG.11B is a schematic representation of the orbital interaction between N2 and the catalytic center, which is highly active and selective for N2 absorption and activation, in accordance with various embodiments. FIGs.12A-12B are a schematic illustrations of a two-step process for preparing largely vertically aligned WOxNy/WO3 with the designed HIC architecture on a piece of carbon cloth with a hydrophobic MPL. (FIG.12A) microwave-assisted hydrothermal growth of WO3 nanosheet array on the MPL of carbon cloth; (FIG.12B) surface selective nitridation of the WO₃ nanosheets via non-equilibrium plasma to form WOxNy/WO3, while leaving the WO3 crystal structure and the underneath hydrophobic MPL intact, therefore the as-prepared WOxNy/WO3 hybrid catalyst electrodes were directly employed as gas diffusion electrodes - 3 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) for eNRR. FIGs.13A-13D show (FIG.13A and FIG.13B) SEM images of the h-WO3 nanosheets at different magnifications, which directly grow on a piece carbon cloth with a hydrophobic microporous layer. FIG.13C shows PXRD patterns of h-WO3 before and after plasma-assisted nitridation. FIG.13D shows surface reconstruction of h-WO3 after plasma treatment. Atomic resolution HAADF-STEM imaging reveals the presence of surface reconstruction and defects in h-WO3. FIGs.14A-14B show high-resolution XPS spectra of h-WO3 before and after plasma nitridation under different conditions: (FIG.14A) N 1s, (FIG.14B) W 4f. FIGs.15A-15C show (FIG.15A) a comparison of the eNRR performance of WO3 with different plasma treatments under identical conditions (at -0.15 V vs RHE) in the first half hour. FIG.15B shows a comparison of eNRR performance of TMN and TMOxNy based catalysts. FIG.15C shows 1H nuclear magnetic resonance (NMR) spectra of the electrolyte after eNRR electrolysis on WO3-H2/N2-2h under 15N2 purging. FIG.16 shows specific yield rate and faradaic efficiency of WO3-H2/N2-2h at -0.15V in a three hour cycle, demonstrating that the initial NH3 yield rate is ~200 times higher NH3 yield than that of the Ni/Ni3N membrane. However, its eNRR activity drops over time. FIG.17 shows the full scan of XPS spectra of WO3/WOxNy before and after eNRR electrolysis for 3 hours in 5 mM H2SO4 electrolyte (pH=2) under N2. FIGs.18A-18D show high-resolution XPS spectra of WOxNy/WO3 catalyst before (FIG.18A, FIG.18C) and after (FIG.18B, FIG.18D) eNRR electrolysis for 3 hours in 5 mM H2SO4 electrolyte (pH=2) under N2. FIG.19A-19B show surface nitridation of WO3 after plasma treatment using EELS. (FIG.19A) N-rich regions of WO3 are evident by the presence of severe surface reconstruction. By comparison, (FIG.19B), minimal N-signal is observed when bulk WO3 EELS signals dominate the spectra. FIGs.20A-20F show (FIGs.20A-20C) typical SEM images of h-WO3 at different magnifications, in accordance with various embodiments. FIGs.20D-20F show typical SEM images of WOxNy/WO3-H2/N2-2h with the same magnifications as in FIGs.20A-20C for comparison, in accordance with various embodiments. FIGs.21A-21B show schematic illustrating the (FIG.21A) set-up for the eNRR electrolysis. (FIG.21B) NOx control set-up: any NOx breakthrough from the oxidizing trap (filled with 0.1 M KMnO4 in aqueous 0.1 M KOH) is captured by an alkaline trap (filled with aqueous 0.1 M KOH). All NH3 breakthrough and alkaline solution will be captured by the - 4 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) acid trap (filled with concentrated H2SO4). FIGs.22A-22B show (FIG.22A) UV–vis spectra of the electrolytes collected from the various control experiments following the indophenol blue spectrophotometric method. (FIG.22B) comparison of NH3 yield rate with/without NOx removal from the N2 feed. FIGs.23A-23B shows (FIG.23A) UV-VIS spectra of various N2H4 concentrations after incubated for 15 min at room temperature. (FIG.23B) Calibration curve used for calculation of N2H4 concentrations. FIG.24 is a schematic drawing showing a set-up for the 15N2 isotope eNRR electrolysis, in accordance with various embodiments. DETAILED DESCRIPTION Reference will now be made in detail to certain embodiments of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter. Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise. In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” or “at least one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information - 5 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) that is relevant to a section heading may occur within or outside of that particular section. All publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls. In the methods described herein, the acts can be carried out in any order, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process. Description Ammonia (NH3) has traditionally been used as a fertilizer and a key chemical in chemical industries. More recently, NH3 has emerged as a promising hydrogen (H2) carrier for green power storage and generation, due to its higher energy density, lower storage and transport costs, and lower flammability compared to H2. However, the current production method, the Haber-Bosch (H-B) process operates under high temperatures (~500 °C) and pressures (~250 atm) and relies on H2 produced from fossil fuels. This makes it not only energy- and CO2-intensive, but also highly centralized, limiting its integration with intermittent and location specific renewable electricity. To address these challenges, it is essential to develop efficient, distributed, and electrified methods to produce green NH3 directly from water (H2O) using renewable electricity. To overcome the challenges of the H-B process and enable electrified synthesis of NH3, plasma-catalytic NH3 synthesis from N2 and water (H2O) or H2 has been pursued. Plasma catalysis offers non-equilibrium reaction pathways for NH3 synthesis by utilizing active atomic nitrogen (N) and vibrationally excited nitrogen (N₂(ν)), as well as catalyst surface nitridation. However, the energy efficiency of plasma-assisted NH3 synthesis remains significantly lower (8.7 g-NH3/kWh) than that of the H-B process (500 g-NH3/kWh). Additionally, when H2O is used as a hydrogen source in plasma, undesired byproducts such as NOx and H2O2 can be generated. Electrocatalytic nitrogen reduction reaction (eNRR) allows green production of NH3 from N2 and H2O under ambient conditions without the undesired pollutants and other harmful byproducts. However, the practical implementation of - 6 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) eNRR for NH3 production is impeded by the extremely low NH3 yield and low Faradaic efficiency (FE) due to the high activation energy of inert N2 molecules, and the overwhelming HER competition reaction. In one aspect, the disclosure relates to the development of compositions, systems or hybrid electrochemical plasma cells, and methods for the reduction of N2 to produce NH3. The practical application of electrochemical nitrogen reduction reaction (eNRR) to produce NH3 is hindered by the extremely low NH3 yields and Faradaic efficiencies (FE) observed with such processes, which are far from appropriate for practical applications, especially when performed in water-based solutions. The low NH3 yield intrinsically stems from the inertness and nonpolar structure of N2 molecules for effective reductive hydrogenation under mild conditions. The low aqueous solubility of N2 further slows down the reaction kinetics. The low FE/low selectivity of eNRR is due to the overwhelming hydrogen evolution reaction (HER) competition during eNRR. Even though the thermodynamic potentials for HER and eNRR are close, the complete conversion of N2 into NH3 involves a difficult N2 activation process and 6 electrons and protons coupled electron transfer (PCET) reactions. While HER is a 2-electron proton PCET reaction, which is kinetically preferred, it is worthy to emphasize that HER not only directly causes the low FE but also results in low eNRR activity of the catalysts, especially at higher electrochemical overpotentials, where higher eNRR rate should be expected based on normal electrochemistry reaction principles. This is because not only is HER the kinetically preferred process, but, most importantly, the active sites on the catalysts for eNRR are predominately occupied by protons (H+), adsorbed H atoms (H*), and/or the generated H2 nanobubbles. Consequently, these active sites are severely blocked for N2 to access. Efforts have therefore been devoted to developing catalysts which can efficiently suppress HER with an aim to improve NH3 production rate and faradaic efficiency (FE). However, simply eliminating HER or pushing HER reaction to very negative potentials by removing /minimizing H+ resource cannot improve the NRR activity either, simply because hydrogen (H+ / H*) is also required for the hydrogenation of N2 to the product NH3. It is fundamentally challenging to concurrently, selectively promote eNRR and suppress HER due to the scaling relationships of N and H intermediates during eNRR. Transition metal nitrides (TMNs) and oxynitrides (TMOxNy) have emerged as promising catalysts for eNRR due to their distinctive structural properties, which enable nitrogen reduction through the Mars-van Krevelen (MvK) catalytic pathway with much lower - 7 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) energy barrier compared to N adsorbate reduction via direct proton-coupled electron transfer (PCET). In MvK pathway, ammonia (NH3) is initially produced by hydrogenating lattice nitrogen (N) atoms on the surface of TMNs or TMOxNy. This process significantly reduces the energy barrier for NH3 production as it avoids the need for direct activation and cleavage of the N≡N triple bond in N2. Desorption of these NH3 molecules generate nitrogen vacancies (Nv) on the catalyst surface, which subsequently act as the catalytic sites, adsorbing and activating the dissolved N2 from the electrolyte and completing the catalytic cycles. Although the subsequent steps still require the cleavage of the N≡N triple bond, it is noteworthy that the nitrogen vacancies not only provide unsaturated coordination sites that facilitate N2 adsorption but also efficiently activate the adsorbed N2 molecules by accommodating the lone pair of electrons from N2 due to the electron-deficient nature of the vacancies. Importantly, the electron-deficient nature of nitrogen vacancies selectively favors the adsorption and activation of N2 over H⁺, thereby minimizing competition from hydrogen evolution reaction (HER). The concurrent high activity and selectivity for eNRR stands in stark contrast to oxygen vacancies (Ov) on transition metal oxides (TMO). However, the NH₃ yield gradually declines over time, which is primarily attributed to nitrogen loss from the TMNs or TMOxNy catalysts. This depletion occurs due to the inertness of molecular N₂, which cannot efficiently and promptly replenish the lost nitrogen during NH₃ synthesis. We hypothesize that active species generated from non-equilibrium N2 plasma could timely and effectively restore the lost nitrogen from the TMNs or TMOxNy catalysts. This in-situ regeneration of the catalyst surface helps sustain efficient and continuous ammonia production. In one aspect, the NE-EPC systems and the TMO membranes of the disclosure combine the strengths of plasma-based activation of nitrogen gas (N2), which facilitates ex situ or in situ surface oxynitride and/or nitride (TMOxNy and/or TMNs) formation, and their in-situ regeneration on the hydrogen atom transportation membrane surface with electrochemical activation of water to produce and deliver H atoms. Thus, in one aspect, the compositions and/or the NE-EPC systems of the present disclosure represent a significant leap forward in green synthesis technology and catalysis. In one aspect, a surprising and unexpected breakthrough lies in the development of hybrid ferroelectric plasma, which can controllably and selectively generate highly active N atoms and vibrational N2(^) with a drastic improvement in plasma generation, afterglow discharge, and energy efficiency. Another key breakthrough is the development of multifunctional transition metal oxide (TMO)-based hydrogen atom transport membranes. - 8 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) These membranes not only enable the electrochemical splitting of water into protons (H⁺), which are subsequently converted into highly active hydrogen atoms (TM–H*) via the TMO, but also facilitate the in-situ conversion of any molecular hydrogen (H2) byproduct into metal-bound hydrogen atoms (M–H*) through room-temperature hydrogen spillover on embedded metal nanostructures. The resulting H* species are then transported across the TMO membrane to the opposite side, where they participate in efficient NH3 synthesis. This novel multifunctional membrane ensures that hydrogen derived from water electrolysis is fully utilized for ammonia production, significantly enhancing the overall Faradaic efficiency. Another innovation is the use of non‐equilibrium plasma to generate active nitrogen atoms (N) and vibrationally excited nitrogen (N2 (^)) and create surface nitride and/or oxynitride on the hydrogen selective TMO membranes to lower the activation energy for NH3 synthesis. Therefore, in one aspect, the invention of the disclosure facilitates the seamless integration of an electrochemical system with plasma discharge. This integration not only enhances the respective advantages of each system but also effectively mitigates their inherent limitations. The NE-EPC systems of the disclosure herein may comprise metal based or transition metal oxides (TMO) based hydrogen atom membranes, or proton selective membranes, that may be doped with additional elements to further improve their performance. The NE-EPC systems of the disclosure can generate ammonia and related compositions under mild conditions including ambient temperature and pressure. In some embodiments, the NE-EPC systems of the disclosure herein may comprise proton selective membranes, wherein the system is used to efficiently produce ammonia (NH3) from water steam and nitrogen (N2). In some embodiments, the net reaction is as follows: 2 N2 + 6 H2O ^ 4 NH3 + 3 O2 where water or water steam is electrochemically split to O2 and protons (H+) on the anode of the electrochemical cell of the NE-EPC systems. The generated protons are then diffused to the cathode side, intercalated into the TMO based membranes, and converted to H atoms during transporting inside of the membrane. Eventually these H atoms are delivered to the other side of the membrane, and being exposed to the active N atoms and vibrational N2 produced via N2 plasma to efficiently generate NH3 at ambient conditions. Further advantages of the NE-EPC system are the avoidance of generating carbon dioxide as a byproduct of ammonia synthesis compared to the Haber‐Bosch (H-B) processes, alleviating climate - 9 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) change. Compared to the eNRR processes, systems of the disclosure can drastically improve the ammonia yield and FE. Compared to most of the previously reported plasma catalysis systems for ammonia synthesis, the systems of the disclosure permit direct use of H2O or water steam, instead of H2 as the hydrogen source. Compared to the previous reported plasma catalysis systems using H2O as the hydrogen resources, the systems of the disclosure permit production of ammonia in one step, and the issues related to generation of toxic byproducts, such as NOx, H2O2, are naturally avoided. Compared to previously reported electrochemical plasma catalysis systems using water steam as the hydrogen resources, the systems of the disclosure drastically improve energy efficiency due to the hybrid ferroelectric plasma, which is highly energy efficient in controllably and selectively generating highly active species of N atoms and vibrational N2(^). Thus, the membranes and/or systems, and methods of use thereof, provided herein represent a viable alternative or complementary approach to the energy‐ and capital‐intensive Haber‐Bosch process. Definitions The term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range. The term “active species” as used herein refers to an excited state of an atom or molecule. In some aspects, an active species is readily converted into a desirable chemical product. The term “alkali earth metal” refers to the six chemical elements that comprise Group IIa of the periodic table. The elements include Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). The term “alkaline” refers to a molecular or atomic substance that is basic in nature, i.e. the substance is capable of forming a complex with one or more protons. The terms “ambient conditions” or “standard temperature and pressure” as used herein refers to about 20 °C and about 101 kPa. The term “carbon cloth” as used herein refers to a type of porous, conductive fabric made from interwoven carbon fibers and/or filaments. In certain embodiments, the interwoven carbon fibers and/or filaments have a diameter of about 5-10 µm. In certain - 10 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) embodiments, the material is used to support growth of transition metal oxides. The term “carbon paper” as used herein refers to a sheet comprising carbon fibers stably adhered thereto while non-woven which forms a gas permeable paper-like structure having sufficient strength to function as a support plate for an electrode. In certain embodiments, the fibrous sheet comprises one or more waxy mediums, including but not limited to paraffin, carnauba, oleic resin, and rosin. The paper includes fibers such as rag, wood, manila, and jute. The term “catalyst” as used herein refers to an atom, molecule, or composition which promotes a chemical reaction, and further encompasses a combination of a catalyst with one or more non-catalytic materials, such as supports or stabilizers (e.g., substrates), and the like. The term “composite” as used herein refers to an amalgam of one or more materials that are bonded or stabilized as a single entity. In some embodiments of the disclosure, a composite comprises one or more polymers, one or more TMOs, one or more nanomaterials, one or more dopants, and/or one or more support material such as a porous carbon support, a dielectric, and the like. The term “dielectric material” as used herein refers to a material which is an electrical insulator or a very poor conductor of electric current. The term “discharge” as used herein refers to release or transmission of electricity in a system. The term “electrochemical cell” or “electrolyte cell” as used herein refers to an assembly, device, or system that converts chemical energy into electrical energy or electrical energy into chemical energy. Electrochemical cells comprise at least two electrodes (i.e., anode and a cathode) and an electrolyte, wherein electrode reactions occurring at the electrode surfaces result in charge transfer processes. In certain embodiments, the electrochemical cells described herein comprise a cathode comprising the hydrogen atom transportation membrane of the disclosure. A non-limiting, exemplary system of the disclosure is depicted in FIG.9. In certain embodiments, the hydrogen atom transport membrane comprises a transition metal oxide (TMO) membrane of the disclosure. In certain embodiments, the hydrogen ion transport membrane is directly attached to the anode in one side, and the other side is directly attached to the cathode, which have the plasma catalysts being exposed to the plasma as shown in FIG.10. The term “electrolyte” as used herein refers to an ion-conducting liquid or solid material which facilitates ionic conductivity. As used herein, the term “electrode” refers to an electrical conductor used to make - 11 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) contact with a nonmetallic part of a circuit (e.g., a semiconductor, an electrolyte, or a vacuum). In certain embodiments, the term “electrode” may also refer to either an anode or a cathode. The term “embedded” as used herein means at least partially enclosed within a supporting substrate or material. In certain embodiments, an object which is “embedded” in a substrate is at least partially exposed to at least one surface of the substrate. The term “Faradaic efficiency” (FE) or “Faradaic yield” as used here refers to the fraction or percentage of the electrons applied to the cell that participate in the desired electrochemical reaction (e.g., fraction of applied electrons which participate in conversion of N2 to NH3). The term “hydrogen” as used herein refers to the chemical element having an atomic number of 1. In certain embodiments, “hydrogen” refers to a proton or cation species (i.e., H+ or H3O+ or any hydrate of H+/H3O+). In certain embodiments, “hydrogen” refers to molecular hydrogen gas (H2). In certain embodiments, “hydrogen” refers to a radical species of hydrogen (H•). The term “independently selected from” as used herein refers to referenced groups being the same, different, or a mixture thereof, unless the context clearly indicates otherwise. Thus, under this definition, the phrase “X1, X2, and X3 are independently selected from noble gases” would include the scenario where, for example, X1, X2, and X3 are all the same, where X1, X2, and X3 are all different, where X1 and X2 are the same but X3 is different, and other analogous permutations. The term “intercalatable” as used herein refers to a reversible inclusion or insertion of a molecule or ion into a solid substance or material. The term “membrane” as used herein refers to a barrier material that is fashioned into a sheet or layer of material. In some aspects, the membrane is capable of permitting selective transport of hydrogen atoms (H*) or hydrogen ions (protons, H+) under various conditions. The term “nanomaterial” as used herein refers to a material which has at least one dimension in the nanometer-size range. The term “carbon nanomaterial” includes, but is not limited to, carbon nanotubes (including multi-wall carbon nanotubes and single-wall carbon nanotubes), carbon nanoparticles, carbon nanofibers, carbon nanoropes, carbon nanoribbons, carbon nanofibrils, carbon nanoneedles, carbon nanosheets, carbon nanorods, carbon nanohorns, carbon nanocones, carbon nanoscrolls, graphite nanoplatelets, graphite nanoparticles, nanodots, other fullerene materials, or a combination thereof. The term, “multi- wall,” is meant to include double-wall nanotubes (DWNTs) and few-wall nanotubes - 12 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) (FWNTs). The term “nanostructure” as used herein refers to a structure that has at least one dimension of approximately nanometer range. Examples of nanostructures include nanoparticles, quantum dots, nanorods, nanowires, nanofilms, as well as other nanomaterials. The term “ferroelectric” as used herein refers to a material or substance that exhibits a permanent electrical polarization which varies in strength with the applied electrical field. The term “piezoelectric” as used herein refers to a material or substance that undergoes electrical polarization from the application of mechanical stress. The term “pyroelectric” as used herein refers to a material that has the property of becoming electrically charged when it is heated. The term “plasma” as used herein refers to a (partially) ionized gas-like mass comprising a mixture of ions, electrons, and neutral species. The term “plasma catalyst” as used herein refers to a material (e.g., transition metal oxide (TMO) substrate), or a surface thereof, which facilitates a chemical reaction under plasma irradiation. In certain embodiments, the “plasma catalyst” may react with, or is modified by reaction with, a nitrogen (N) atom and/or vibrational N2 species formed in the plasma phase to form a reactive intermediate. In certain non-limiting embodiments, the reactive species comprises a reactive transition metal nitride (TMN), transition metal oxynitride (TMON), or N-doped TMO species. The term “porous” as used herein refers a material or substance having small regions, spaces, or holes through which liquid or gas may pass through. The term “reduction” as used herein, as applied to a particular substance, means a chemical reaction whereby a chemical species receives an electron or an electron paired with a proton (i.e., hydrogen atom, H*). In certain non-limiting embodiments, exemplary reduction reactions include the transfer of hydrogen atoms to N2 to form ammonia (NH3). The term “room temperature” as used herein refers to a temperature of about 15 °C to about 28 °C. The term “solvent” as used herein refers to a liquid that can dissolve a solid, liquid, or gas. Non-limiting examples of solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids. The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. The term “substantially free of” as used herein can mean having none or having a trivial amount of, such that the amount of material present - 13 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) does not affect the material properties of the composition including the material, such that the composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0s001 wt% or less. The term “substantially free of” can mean having a trivial amount of, such that a composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%. The term “substrate” as used herein refers to a material comprising one or more layers of one or more materials that can be rigid or flexible and can include, but are not limited to, carbon nanomaterials, one or more polymers, glass, metal, ceramic materials, or combinations thereof. The term “surface modification” as used herein refers to the chemical and/or physical alteration of a surface by an additive or subtractive process to change one or more chemical and/or physical properties of a substrate surface or a selected site or region of a substrate surface. The term “transition metal” as used herein refers to any of the metallic elements within Groups 3 to 12 in the Periodic Table that have an incomplete inner electron shell and that serve as transitional links between the most and the least electropositive in a series of elements. A transition metal element can be any of scandium (Sc), titanium (Ti), vanadium (Va), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mb), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), rutherfordium (Rf), dubnium (Db), seaborgium (Sb), bohrium (Bh), hassium (Hs), and meitnerium (Mt). Hydrogen Atom Transportation Membranes In one aspect, the disclosure provides a hydrogen atom transportation membrane comprising a porous support and a transition metal oxide (TMO) or a composite thereof. In certain embodiments, hydrogen atom transportation membrane comprises a standalone TMO composite membrane. As used herein, the term "standalone" refers to membrane that is not supported by another solid surface, such as a porous support. In certain embodiments, the TMO or TMO composite is deposited on the surface of the porous support. In certain - 14 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) embodiments, the TMO or TMO composite is embedded in the porous support. In certain embodiments, TMO or TMO composite is deposited on the surface thereof. In certain embodiments, the TMO composite comprises a TMO, a carbon nanomaterial, and a polymer. In certain embodiments, the TMO composite comprises a TMO and a metal nanoparticle, In certain embodiments, the TMO composite comprises a TMO and a carbon nanomaterial. In certain embodiments, the TMO composite comprises a TMO, a metal nanoparticle, and a polymer. In certain embodiments, the TMO composite comprises a TMO, a carbon nanomaterial, and a polymer. In certain embodiments, the TMO composite comprises a TMO, a carbon nanomaterial, a metal nanoparticle, and a polymer. In certain embodiments, the TMO and the TMO composite comprises a plasma catalyst layer. In certain embodiments, the plasma catalyst layer comprises a transition metal nitride (TMN). In certain embodiments, the TMN is doped with at least one metal element. This metal element can be selected from a wide range of elements across the periodic table. Examples include, but are not limited to, Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm. This metal element can be selected from a wide range of elements across the periodic table. Examples can be consisting of Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm. In certain embodiments, the plasma catalyst layer comprises a transition metal oxynitride (TMOxNy). In certain embodiments, the transition metal oxynitride is doped with at least one metal element. This metal element can be selected from a broad range of elements across the periodic table, including, but not limited to, Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm. In certain embodiments, the porous support is conductive metal and conductive metal oxide-based membranes, including, but not limited to, nickel foam, copper foam, titanium foil, stainless steel mesh, and conductive oxide-coated glass. In certain embodiments, the porous support comprises nonconductive ceramic based membranes., including but not limited to, porous alumina (Al2O3), porous titania (TiO2), zirconia (ZrO2), silicon carbide (SiC), and perovskite-type oxides. In certain embodiments, the porous support can be polymer-based membranes. , including but not limited to, . porous polycarbonate, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethersulfone (PES), nylon, and polypropylene (PP). In certain embodiments, the porous support can be carbon based membranes. In certain embodiments, the porous carbon support comprises carbon paper. In certain embodiments, the carbon paper is surface modified. In certain embodiments, the porous carbon support comprises carbon cloth. In certain embodiments, the porous carbon support comprises a carbon nanotube film. In certain embodiments, the porous carbon support comprises a composite of carbon nanotube and graphene film. In certain - 15 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) embodiments, the porous carbon support comprises a composite of other carbon nanomaterials. In certain embodiments, the porous support is surface modified. In certain embodiments, the surface modification comprises a modification which increases hydrophobicity. In certain embodiments, the surface modification comprises a modification which increases hydrophilicity. In certain embodiments, the transition metal oxide (TMO) is a proton intercalatable TMO. In certain embodiments, the proton intercalatable TMO comprises WO3. In certain embodiments, the proton intercalatable TMO comprises MoO3. In certain embodiments, the proton intercalatable TMO comprises TiO2. In certain embodiments, the proton intercalatable TMO comprises VO2. In certain embodiments, the proton intercalatable TMO comprises Nb2O5. In certain embodiments, the proton intercalatable TMO comprises MnO2. In certain embodiments, the proton intercalatable TMO comprises HfO2. In certain embodiments, the proton intercalatable TMO comprises at least one hybrid TMO. In certain embodiments, the proton intercalatable TMO comprises at least one hybrid TMO selected from the group consisting of (WO3)m-(WO2)n, (Nb2O5)m-(WO3)n, (MoO3)m - (VO2)n, (Nb2O5)m-(TiO2)n, (Nb2O5)m-(NbO2)n, (Nb2O5)m-(WO2)n, MomVOn, and WmNbOn, and wherein m and n are each 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 In certain embodiments, TMO is doped with P. In certain embodiments, TMO is doped with S. In certain embodiments, TMO is doped with N. In certain embodiments, TMO is doped with B. In certain embodiments, TMO is doped with Se. In certain embodiments, TMO is doped with Ru. In certain embodiments, TMO is doped with Mo. In certain embodiments, TMO is doped with Nb. In certain embodiments, TMO is doped with Ti. In certain embodiments, TMO is doped with V. In certain embodiments, TMO is doped with Fe. In certain embodiments, TMO is doped with Co. In certain embodiments, TMO is doped with Ni. In certain embodiments, TMO is doped with Sb. In certain embodiments, TMO is doped with Mn. In certain embodiments, TMO is doped with Rh. In certain embodiments, TMO is doped with Re. In certain embodiments, TMO is doped with Cu. In certain embodiments, TMO is doped with Pt. In certain embodiments, TMO is doped with Ir. In certain embodiments, TMO is doped with Au. In certain embodiments, TMO is doped with Ag. In certain embodiments, TMO is doped with Ge. In certain embodiments, TMO is doped with Pd. In certain embodiments, TMO is doped with Zr. In certain embodiments, TMO is doped with Y. In certain embodiments, TMO is doped with La. In certain embodiments, TMO is doped with Ce. In certain embodiments, TMO is doped with Ta. In certain embodiments, TMO is doped with Zn. - 16 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) In certain embodiments, the carbon nanomaterial comprises carbon black. In certain embodiments, the carbon nanomaterial comprises carbon nanotubes. In certain embodiments, the carbon nanomaterial comprises graphene. In certain embodiments, the polymer comprises sulfonated tetrafluoroethylene (Nafion™). In certain embodiments, the polymer comprises polyaniline. In certain embodiments, the polymer comprises poly(pyrrole). In certain embodiments, the polymer comprises polyacrylate. In certain embodiments, the hydrogen atom transportation membrane further comprises at least one additional catalyst embedded in the TMO. In certain embodiments, the hydrogen atom transportation membrane further comprises at least one additional catalyst deposited on the surface thereof. In certain embodiments, the additional metal catalyst is a transition metal nitride (TMN). In certain embodiments, the TMN comprises at least one metal selected from the group consisting of W, Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm. In certain embodiments, the additional catalyst is a transition metal oxynitride (TMON). In certain embodiments, the TMON comprises at least one metal selected from the group consisting of W, Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm. In certain embodiments, the at least one additional metal catalyst is a nitrogen (N) doped transition metal oxide (TMO). In certain embodiments, the N-doped TMO comprises at least one metal selected from the group consisting of W, Ru, Rh, Co, Mo, Nb, V, Ni, Cu, Pd, La, Ce, and Sm. Example TMO/TMON Catalyst In various embodiments, provided herein are WOxNy/WO3 hybrid electrochemical catalysts featuring a heterogeneous interfacial complexion (HIC) structure (FIG.11A). Without being bound by theory, this HIC structure is believed to enable in-situ generation of H* via proton intercalation, thereby promoting eNRR performance with a HIC enhanced Mars–van Krevelen (MvK) mechanism. In this design, WOxNy was selected for its potential to enhance eNRR activity via a Mars-van Krevelen (MvK) mechanism and superior stability against chemical decomposition, outperforming tungsten nitride (WN) due to its elevated N2p orbital positioned closer to the Fermi level (EF). Meanwhile, WO3 offers an exceptional ability to undergo in-situ bulk proton (H⁺) intercalation ( WO3+ xH⁺ + xe- ⇌ HxWO3), generating mobile, active, and relatively long- lived H atoms (in the form of weakly bound hydrogen, denoted as W-H*) in acidic electrolyte. To fully harness this property, in various embodiments, the WOxNy/WO3 catalysts were designed with a HIC structure, as illustrated in FIGs.13A-13B. This structural - 17 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) architecture ensures that WO3 retains its proton intercalation capability along the electron/proton transport pathway. Without being bound by theory, it is believed that the generation of highly active W-H* at the WOxNy/WO3 interface, or the migration of H* from WO3 domains to this interface, enables the efficient hydrogenation of lattice nitrogen in WOxNy to form NH3. The abundance of H⁺ ions in the acidic electrolyte facilitates the protonation and subsequent desorption of the produced NH3 from the WOxNy catalyst surface, facilitating generation of nitrogen vacancies (Nv). In the subsequent steps, these nitrogen vacancies (Nv), combined with the continuously supplied H* at neighboring W centers, form new catalytic sites, as illustrated in FIG.11B. The newly formed catalytic sites at the WOxNy/WO3 interface facilitate bidirectional electron transfer, a critical requirement for efficient N₂ activation, thereby significantly enhancing activation capability. Specifically, the Nv preferentially adsorbs electron donor like N2 over H⁺ due to their electron-deficient nature. This deficiency also enables Nv to effectively accept the lone pair electrons from adsorbed N2, facilitating strong σ-donation. Simultaneously, H* on adjacent W sites donate electrons into the antibonding ^ orbitals ( ^*) of the adsorbed N2, weakening the N≡N triple bond and significantly enhancing its activation. This cooperative interaction leads to a substantial increase in selective ammonia synthesis while effectively suppressing the competing hydrogen evolution reaction (HER). Non-Equilibrium Electrochemical Plasma Catalysis (NE-EPC) Systems In another aspect, the disclosure provides a non-equilibrium electrochemical plasma catalysis (NE-EPC) system. In certain embodiments, the system comprises an electrochemical cell. In certain embodiments, the system comprises a plasma catalytic reaction chamber. In certain embodiments, the system comprises a hydrogen atom transportation membrane comprising a porous carbon support, a transition metal oxide (TMO) layer, and a plasma catalyst layer. In certain embodiments, the electrochemical cell and plasma catalytic reaction chamber are connected through, and separated by, the hydrogen atom transportation membrane. In certain embodiments, the system comprises a water streaming chamber. In certain embodiments, the electrochemical cell comprises an anode and a cathode. In certain embodiments, the cathode comprises a water streaming oxidation anode. In certain - 18 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) embodiments, the cathode comprises a transition metal nitride (TMN). In certain embodiments, the cathode is in contact with the plasma catalytic reaction chamber. In certain embodiments, the hydrogen atom transportation membrane further comprises a transition metal-based hydrogen atom transportation membrane comprising Pd. In certain embodiments, the hydrogen atom transportation membrane further comprises a transition metal-based hydrogen atom transportation membrane comprising Ni. In certain embodiments, the hydrogen atom transportation membrane further comprises a transition metal-based hydrogen atom transportation membrane comprising V. In certain embodiments, the hydrogen atom transportation membrane further comprises a transition metal-based hydrogen atom transportation membrane comprising Nb. In certain embodiments, the hydrogen atom transportation membrane comprises the hydrogen atom transportation membrane of the disclosure. In certain embodiments, TMO layer further comprises one or more substantially vertically aligned nanostructures. In certain embodiments, the nanostructures comprise nanosheets. In certain embodiments, the nanostructures comprise nanorods. In certain embodiments, the nanostructures comprise nanospikes. In certain embodiments, the system further comprises a plasma source. In certain embodiments, the plasma source comprises one or more electrodes and one or more reactants. In certain embodiments, the reactant is nitrogen (N2). In certain embodiments, the reactant is hydrogen (H2). In certain embodiments, the reactant is methane (CH4). In certain embodiments, the reactant is carbon dioxide (CO2). In certain embodiments, the TMO layer further comprises a heteroatom-doped transition metal oxide (TMO). In certain embodiments, the TMO comprises WO3. In certain embodiments, the hydrogen transportation membrane has a thickness selected from the group consisting of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or about 25 µm. In certain embodiments, the plasma catalyst layer comprises at least one transition metal nitride (TMN) catalyst. In certain embodiments, the TMN is additionally doped with Ru. In certain embodiments, the TMN is additionally doped with Rh. In certain embodiments, the TMN is additionally doped with Co. In certain embodiments, the TMN comprises Mo. In certain embodiments, the TMN is additionally doped with Nb. In certain embodiments, the TMN is additionally doped with V. In certain embodiments, the TMN comprises Ni. In certain embodiments, the TMN is additionally doped with La. In certain embodiments, the - 19 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) TMN is additionally doped with Ce. In certain embodiments, the TMN is additionally doped with Sm. In various embodiments, the amount of the Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, or Sm dopant in the TMN can be from about 0.0001 to 5% w/w relative to the weight of the TMN, or about 0.0001, 0.0002, 0.0003, 0.004, 0.0005, 0.0006, 0.0007, 0.0008, 0.0009, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or about 5% w/w relative to the weight of the TMN. In certain embodiments, the plasma catalyst layer comprises at least one transition metal oxynitride (TMON) catalyst. In certain embodiments, the TMON is additionally doped with Ru. In certain embodiments, the TMON is additionally doped with Rh. In certain embodiments, the TMON is additionally doped with Co. In certain embodiments, the TMON is additionally doped with Mo. In certain embodiments, the TMON is additionally doped with Nb. In certain embodiments, the TMON is additionally doped with V. In certain embodiments, the TMON is additionally doped with Ni. In certain embodiments, the TMON is additionally doped with La. In certain embodiments, the TMON is additionally doped with Ce. In certain embodiments, the TMON is additionally doped with Sm. In various embodiments, the amount of the Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, or Sm dopant in the TMON can be from about 0.0001 to 5% w/w relative to the weight of the TMON, or about 0.0001, 0.0002, 0.0003, 0.004, 0.0005, 0.0006, 0.0007, 0.0008, 0.0009, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or about 5% w/w relative to the weight of the TMON. In certain embodiments, the plasma catalyst is formed in situ or ex situ by contact with N2 plasma. In certain embodiments, the plasma catalyst is formed by deposition of a pre- synthesized layer of TMN and/or TMON nanostructures. Without being bound by theory, at least in part due to milder conditions of ammonia formation of the NE-EPC system of the disclosure, the lifetime of plasma catalysts of the disclosure are greatly extended. In certain embodiments, the plasma catalysts of the disclosure last over 120 minutes of operation. In certain embodiments, the element for the doped TMO comprises at least one selected from the group consisting of Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, and Sm. In certain - 20 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) embodiments, the Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, and Sm comprise about 0.5% of the TMO by weight. In certain embodiments, the element for the doped TMO comprises about 0.5% Ru by weight. In certain embodiments, the TMO comprises about 0.5% Rh by weight. In certain embodiments, the TMO comprises about 0.5% Co by weight. In certain embodiments, the TMO comprises about 0.5% Mo by weight. In certain embodiments, the TMO comprises about 0.5% Nb by weight. In certain embodiments, the TMO comprises about 0.5% V by weight. In certain embodiments, the TMO comprises about 0.5% Ni by weight. In certain embodiments, the TMO comprises about 0.5% La by weight. In certain embodiments, the TMO comprises about 0.5% Ce by weight. In certain embodiments, the TMO comprises about 0.5% Sm by weight. In certain embodiments, the plasma catalytic reaction chamber further comprises a plasma control unit or plasma control chamber. In certain embodiments, an electrical current is used to generate the source of plasma. In certain embodiments, the source of plasma comprises one or more electrodes and one or more reactants. In certain embodiments, the current is selected from the group consisting of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or about 1000 mA. In certain embodiments, water is a proton donor of the electrochemical cell. In certain embodiments, the hydrogen atom transportation membrane is a cathode in the electrochemical cell. In certain embodiments, the electrochemical cell comprises a metal anode. In certain embodiments, the electrochemical cell comprises a liquid electrolyte that has a pH less than 5, such as a pH of about 4.5, 4, 3.5, 3, 2.5, 2, 1.5, or about 1. In certain embodiments, the liquid electrolyte comprises one or more inorganic acids, alkaline, or alkaline earth metal salts. In certain embodiments, the liquid electrolyte comprises sulfuric acid. In certain embodiments, the liquid electrolyte comprises an aqueous solution. Methods of Making Electrocatalysts with HIC Structure(s) To fabricate the WOxNy/WO3 hybrid catalysts with the proposed HIC architecture, a two-step process was developed. This process involves the facile microwave-assisted hydrothermal growth of a WO3 nanosheet array, followed by a selective surface nitridation process achieved through non-equilibrium hydrogen/nitrogen plasma-assisted nitridation. As illustrated in FIG.12, a predominantly vertically aligned WO3 nanosheet array is first grown - 21 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) on highly conductive carbon cloth with a hydrophobic microporous layer (MPL) using a facile microwave-assisted hydrothermal method. This is followed by a plasma-assisted surface-selective nitridation process to convert part of the outer layer of WO3 into WOxNy while preserving the bulk WO3 structure. Upon optimization, the developed WOxNy/WO3 catalyst electrode achieved an impressive NH3 yield rate of 3.2 × 10-10 mol^cm-2^s-1 at -0.15 V vs. RHE in an acidic H2SO4 electrolyte (pH = 2). This yield is approximately eight times higher than that of a single-layer 2D W2N3 catalyst, which theoretically possesses significantly more catalytic centers due to its single-layer structure. Remarkably, this high yield is accompanied by an unprecedented Faradaic efficiency (FE) of 40.1%, the highest reported for any transition metal nitride (TMN) or transition metal oxynitride (TMOxNy)- based catalyst, which typically exhibit FE values below 15%. In various embodiments a catalyst is provided, which includes: a first layer containing WO3; a second layer containing WOxNy; wherein x is about 1.2 to about 2.8; wherein y is about 0.2 to about 1.8; and wherein the sum of x and y is about 3. In various embodiments, x is equal to y. In various embodiments, x is about 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, or about 2.8. In various embodiments, y is about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, or about 1.8. In various embodiments, the first layer has substantially the same crystal structure as pure WO3. In various embodiments, the first layer has the same crystal structure as pure WO3. In various embodiments, the WO3 in the first layer is hexagonal WO3 (h-WO3). In various embodiments, the second layer includes an amorphous layer of WOxNy. In various embodiments, the catalyst has a Faradaic efficiency of at least about 25%. In various embodiments, the catalyst has a Faradaic efficiency of at least about 25, 30, 35, 36, 37, 38, 39, 40, or 41%, or more. In various embodiments, the catalyst has a Faradaic efficiency of at least about 25, 30, 35, 36, 37, 38, 39, 40, or 41%, or more in a process that uses the catalyst to produce NH3. In various embodiments, the catalyst exhibits a powder x-ray diffraction (PXRD) peak at 63.6° 2θ as measured using Co Kα radiation with a wavelength (λ) of 1.789 Å. In various embodiments, the second layer has a thickness of about 0.01 to about 10 nm. In various embodiments, the second layer has a thickness of about 0.01, 0.05, 0.10, 0.15, - 22 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, to about 10 nm. In various embodiments, the first layer is adjacent to and in contact with the second layer. The detailed procedures for the growth of WO3 nanosheet array on a piece of highly conductive carbon cloth with a microporous layer (MPL) are described, in accordance with various embodiments, in the Examples herein. This approach significantly shortens the reaction time to just 15 minutes, a marked improvement compared to the 24 - 48 hours required by conventional hydrothermal methods. Notably, this synthesis method enables direct growth of WO3 on the hydrophobic MPL side of the carbon cloth. Scanning electron microscope (SEM) was used to characterize the structure of the WO3 nanostructures. FIG.13A shows the nanosheet-like morphology of the as-prepared WO3, with the nanosheets predominantly aligned vertically but exhibiting random orientations. Each individual nanostructure appears as a thin, platelet-like crystal measuring a few tens to hundreds of nanometers in thickness and extending laterally on the order of hundreds of nanometers to a few micrometers. FIG.13B further reveals that each nanosheet is composed of an assembly of nanocrystals, suggesting a high surface area, which is highly beneficial for catalytic applications. The crystal structure of the WO3 was characterized with powder X-ray diffraction (PXRD). As shown in FIG.13C, the diffraction peaks of the as- prepared WO3 align well with hexagonal WO3 (h-WO3, JCPDS No.33-1387). To achieve selective surface nitridation of the h-WO3 nanosheet array while preserving the underlying WO3 crystal structure and the MPL layer on the carbon cloth, a room-temperature, non-equilibrium plasma-assisted surface nitridation approach was developed. This method utilizes a hydrogen/nitrogen mixture plasma, enabling the direct fabrication of the hybrid WOxNy/WO3 catalyst electrode with the designed HIC architecture at room temperature. This approach ensures precise control over nitridation while maintaining the structural integrity and electronic properties essential for efficient proton and electron transport. Briefly, the synthesized WO3 nanosheets on carbon cloth described above were used as the precursor, directly located in a H2/N2 dielectric barrier discharge (DBD) plasma chamber for the surface selective nitridation. Various plasma treatment conditions, including N2 plasma for 1 hour, first H2 plasma for half hour, followed by N2 plasma for 1 - 23 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) hour, H2/N2 (1:4) plasma for 1 hour, and H2/N2 plasma for 2 hours, were tested to optimize the surface nitridation. The resulting hybrid WOxNy/WO3 catalyst electrode was accordingly named as WO3-N2-1h, WO3-H2-0.5h-N2-1h, WO3-H2/N2-1h, and WO3-H2/N2-2h, respectively. SEM and PXRD were also used to study their morphology and crystal structural change after plasma treatment. By comparing FIGs.19A-19C (SEM as-prepared WO3) to FIGs.19D-19F (SEM post-nitridation), the WO3 nanostructures retain their morphology without significant changes under the applied plasma nitridation conditions. Note that a new peak at 63.6° with very low intensity appears on the PXRD spectra (FIG.13C) with WOxNy/WO3-H2/N2-2h having the highest intensity, indicating the formation of WOxNy (JCPDS No.89-4762). However, the diffraction peaks of h-WO3 remained largely unchanged across all the plasma nitridation conditions studied. This result suggests that the crystal structure of h-WO3 remains largely intact. To further investigate the atomic-scale structural changes of h-WO3 after nitridation, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) was utilized to image the WOxNy/WO3-H2/N2-2h catalyst, which exhibited the highest intensity of the new peak at 63.6° in the PXRD spectrum (FIG.13C). As shown in FIG.13D, the well-defined hexagonal crystal structure of h-WO3 was largely preserved, consistent with the bulk PXRD studies. However, a very thin (1–2 nm) amorphous surface layer appeared, which likely associated with the formation of WOxNy species, as confirmed by electron energy-loss spectroscopy (EELS). As shown in FIGs.20A- 20B, minimal nitrogen signals are observed in the bulk WO3, whereas a nitrogen-rich region is detected within the amorphous layer near the surface. All these structural characterizations demonstrated that the WO3 surface was selectively nitridated while preserving the bulk crystal structure, leading to the formation of the designed heterogeneous interfacial complexion (HIC) structure—an achievement that is difficult to realize using conventional high-temperature annealing nitridation methods. First, the h-WO3 crystal structure represents an intermediate phase within the WO3 family. At elevated temperatures, around 400 °C, h-WO3 transitions into monoclinic WO3 (m-WO3), the most thermodynamically stable form of WO3. In addition, even when using m-WO3 as a starting material for nitridation, a significant degradation of its crystal structure at 500 °C occurs—this is the temperature at which WOxNy/WN begins to emerge. These findings highlight a key advantage of the non-equilibrium plasma nitridation approach over traditional thermal nitridation methods, i.e., its ability to achieve selective surface nitridation while preserving the underlying WO3 crystal structure, which is crucial for maintaining proton - 24 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) intercalation and electronic transport properties. To gain insight into the composition and electronic structure of the amorphous WOxNy surface layer of the HIC structure, X-ray photoelectron spectroscopy (XPS), a surface-sensitive technique, was performed. As expected, there is no detectable N in the as- prepared h-WO3 sample, as shown in FIG.14A. After plasma-assisted surface nitridation, a distinct nitrogen signal is detected on the surface of all samples, further confirming the successful incorporation of nitrogen into the WO3 nanostructures. However, high-resolution XPS analysis (FIG.14B), as described below, reveals that none of the samples exhibit W3+- related peaks, indicating that the nitridation conditions did not lead to the formation of WN domains. This suggests that the nitridated surface likely consists of WOxNy rather than WN. The surface composition was further quantified based on the integrated peak areas in their respected XPS spectrum. The WO3-H2/N2-2h sample exhibits the highest nitrogen content of 14.3 at%, which remains significantly lower than that of any known tungsten oxynitride phases. This suggests that the amorphous HIC layer observed in FIG.13D is not composed solely of a uniform WOxNy phase. Instead, it likely consists of a heterogeneous mixture of WO3 and WOxNy domains, as schematically illustrated in FIGs.13A-13B. To carefully study the chemical configuration of the N in the HIC structures, high- resolution N 1s spectrum was collected and the N peaks were carefully deconvoluted. As shown in FIG.14A, the high-resolution N 1s peaks for WO3-H2/N2-2h and WO3-H2/N2-1h samples can be deconvoluted into three distinct peaks, whereas for the WO3-N2-1h and WO3- H2-0.5h-N2-1h samples, only two peaks were observed. Based on the previous literatures, the peaks in the range of 397.9-397.0 eV and 402.3 eV are assigned to W-N and N-O bonds, respectively. The assignment for the peak at 400.1 eV was inconsistent across studies. Some reports assigned it to N-W-O bond or to nitrogen vacancy (Nv) related. Nevertheless, the presence of the W-N peak suggests the successful formation of oxynitride species. Notably, this peak appears only in samples treated with an H2/N2 plasma and is absent in N2 plasma- treated samples. Additionally, sequential H2 plasma treatment followed by N2 plasma treatment did not produce the same effect, suggesting that NHx radicals formed in the H2/N2 plasma may play a role in accelerating surface nitridation. Furthermore, the intensity of the W-N peak in the WO3-H2/N2-1h sample is significantly lower than in the WO3-H2/N2-2h sample, indicating that longer treatment times facilitate more N-W bond formation. Despite this, all the samples show high peak densities corresponding to N-O bonds and N-W-O/Nv- related bonds. Interestingly, the peak associated with N-W-O/Nv-related bonds in the WO3- H2/N2-1h sample is even higher than in the WO3-H2/N2-2h sample. These results suggest a - 25 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) plasma nitridation pathway in which N-O and N-W-O/Nv-related species serve as intermediates in the formation of N-W bonds. The high-resolution W 4f spectrum shows characteristic peaks at 38.6 eV and 36.5 eV, which correspond to W6+ in the as-prepared WO3 sample (FIG.14B, bottom curve). After plasma-assisted surface nitridation, a negative shift of approximately 0.5 eV was observed for the WO3-H2/N2-2h, WO3-H2/N2-1h, and WO3-N2-1h samples, indicating a slight reduction in the oxidation state of W upon nitridation, which is consistent with the literatures. Two additional peaks at even lower binding energy (36.7 eV and 34.2 eV) were observed for the WO3-H2/N2-2h sample, which can be assigned to W5+ species. These results suggest that the electron density of the W centers in the nitridated samples is higher than that in the parent h- WO3, with WO3-H2/N2-2h exhibiting the highest electron density. It is reported that a higher electron density of the W centers facilities the formation of W-H* species. Without being bound by theory, the facile formation of W-H* species plays a crucial role in promoting N hydrogenation, facilitating the formation of nitrogen vacancies (N^) in the catalyst, and accelerating the eNRR catalytic cycles in WOxNy-based catalysts (FIGs.13A-3B). Furthermore, the coexistence of WO3 domains and the unique HIC architecture of the catalyst is expected to sustain proton intercalation, ensuring the continuous generation and delivery of active H* species to the WOxNy regions for the formation of W-H* FIG.11A). As a result, significantly enhanced eNRR activity is anticipated. The eNRR performance of the WOxNy/WO3 hybrid catalyst electrodes was evaluated and the correlation between their structural characteristics and catalytic activity was investigated. The eNRR was conducted in an acidic electrolyte (H2SO4, pH = 2) using a custom-designed N₂ flow electrolysis cell, as shown in FIG.19A. In this configuration, the WOxNy/WO3 hybrid catalysts were directly employed as gas diffusion electrodes (GDEs) to address the low solubility of N2 in water (0.71 mg/L). The electrolyte in the working electrode (WE) side of the cell was collected for quantification of ammonium (NH4+) and possible hydrazine (N2H4) byproduct using the indophenol blue UV-Vis spectroscopy method, the Watt-Chrisp method, and NMR spectroscopy as detailed in herein. The NH3 yield rate and Faradic efficiency (FE) for the nitrogen-ammonia conversion were calculated as detailed in herein. FIG.15A presents the NH3 yield rate and Faradaic efficiency (FE) of WOxNy/WO3 catalysts fabricated under various plasma treatment conditions at -0.15 V vs. RHE during the first half hour of electrolysis. The NH3 yield rate and FE of WOxNy /WO3-H2/N2-1h are lower than those of WO3-H2/N2-2h, which can be attributed to its reduced W-N content and the - 26 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) absence of W5+ species, as confirmed by the N 1s and W 4f XPS spectra. Similarly, the significantly lower performance of WO3-N2-1h and WOxNy/WO3-H2-0.5h-N2-1h is due to the lack of W-N bonds. Among all the samples, WO3-H2/N2-2h demonstrates the highest NH3 yield rate of 3.2 × 10-10 mol^cm-2^s-1, accompanied by a FE of 40.1%. This enhanced performance correlates with the fact that WO3-H2/N2-2h contains the highest number of W-N species and exhibits the highest electron density at the W centers, both of which facilitate the formation of W-H* species, as discussed previously. Notably, this FE surpasses all previously reported values for transition metal nitride- and oxynitride-based catalysts in aqueous electrolytes, which typically exhibit FE values below 15% (FIG.15B). The surprising and unexpecetd high FE of the WOxNy/WO3 catalysts indicates significantly lower HER competition. This is especially worth mentioning because HER is generally more dominant in acidic electrolytes compared to alkaline electrolytes. To verify that the detected ammonia originates exclusively from electrocatalytic N₂ reduction—and not from false contributions such as NH₃ or NH₄⁺ released from the carbon cloth (CC), electrolysis cell, electrolyte contamination, or the N₂ gas feed—two carefully designed control experiments were performed: (1) The direct use of the h-WO3 nanosheet array grown on carbon cloth via the microwave hydrothermal method (without subsequent plasma nitridation) as the working electrode to perform electrolysis at -0.15 V versus RHE under N2 flow, and (2) the use of the WOxNy/WO3-H2/N2-2h as the working electrode to run electrolysis under N2 flow but keeping the potential at open circuit potential (OCP). In both cases, no detectable NH4 + was produced as shown in FIG.15A and FIG.19A. These results not only demonstrate that h-WO3 alone is inactive for eNRR but also confirm that ammonia synthesis is exclusively driven by the electrochemical activity of the WOxNy/ WO3 catalyst. It has been reported that commercial N2 gas may contain non-negligible amounts of NOx and other impurities, which can be more readily catalytically reduced to NH3, potentially leading to false positive results in NH3 synthesis experiments. To ensure that NOx impurities in the N2 feed did not contribute to the observed results, we followed the protocol developed by Douglas et al. to remove the possible NOx in the N2 feed as illustrated in FIG.19B. Specifically, prior to introducing onto the back side of the GDE working electrode, the feed N2 gas was passed three purification traps to effectively eliminate any NOx impurities in the gas feed: (1) a KMnO4 oxidation trap to oxidize any NOx present in the N2 gas into soluble NO3-, (2) a KOH trap to remove the possibly formed NO3-, and (3) a 0.1 M H2SO4 solution to trap any residual NH3 in the N2 gas. As shown in FIG.20B, the NH3 yield obtained after NOx purification was approximately 8% lower than the yield achieved using only the NH3 trap - 27 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) without NOx purification. This difference falls within the experimental error range, confirming that under the conditions employed in this study, the observed NH3 yield is genuine and not significantly affected by possible NOx impurities in the N2 feed. To further confirm that the detected NH4 + originates from the electrocatalytic reduction of the feed N2 via the MvK mechanism, a 15N isotopic labeling experiment was conducted using 15N2 as the feed gas (as described herein and FIG.24). The resulting product was analyzed via 1H NMR spectroscopy, taking advantage of the distinct characteristic features between 15NH4 + and 14NH4 + in NMR spectra to verify the nitrogen source of the NH4+ product. As shown in FIG.15C, the 1H NMR spectrum of the electrolyte after eNRR electrolysis using the WOxNy/WO3-H2/N2-2h catalyst with 15N2 as the gas feed (top curve) displays five peaks. This spectrum closely matches a standard sample containing both 15NH4+ and 14NH4 +. The two characteristic peaks at δ = 6.85 and 6.99 ppm are attributed to 15NH4 +, while the three peaks at δ = 6.82, 6.93, and 7.03 ppm correspond to 14NH4+. The peak height for 15NH4 + peaks is much higher than those of 14NH4 + suggested that most of the detected NH4+ comes from electrocatalytic reduction of the 15N2 feed. The simultaneous detection of 15NH4+ and a small amount of 14NH4+ in 15N isotope labeling experiments has been used as an indication of MvK mechanism as both lattice nitrogen on the catalyst surface and the N₂ feed contribute to nitrogen turnover during eNRR. This is because the initial NH3 generation originates from the hydrogenation of lattice nitrogen on TMN and TMOxNy-based electrocatalysts. This suggests that NH3 can be produced at the start of electrolysis without the need for an external N2 feed, distinguishing this process from direct proton-coupled electron transfer (PCET) of adsorbate nitrogen. However, it is important to note that TMN and TMOxNy-based electrocatalysts can also generate NH3 without an external N₂ feed through electrochemically driven decomposition, rather than by hydrogenation of surface lattice nitrogen under acidic conditions. It has been reported that electrochemical-driven decomposition of TMN has led to false positives in discovering new electrocatalysts for eNRR. Therefore, the detection of 14NH4 + in the NMR does not yet confirm that the eNRR is proceeding via the MvK mechanism. Further evidence is required to demonstrate that 14NH4 + is not a result of electrochemical-driven decomposition of the catalyst in acidic electrolytes. To determine whether the detected 14NH4 + originated from the hydrogenation of surface lattice nitrogen or from the electrochemically driven decomposition of the catalyst in acidic electrolytes—and thereby unambiguously confirm that the WOxNy/WO3 catalyst follows the MvK mechanism during eNRR—a detailed XPS study of the catalyst after - 28 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) electrolysis was conducted. If the detected NH3 was due to decomposition, a concurrent loss of N and W on the WOxNy surface would be expected. On the other hand, if the detected 14NH4+ was originated from hydrogenation of the surface lattice N, no W loss should be observed. As shown in FIGs.18A-18D and FIG.21, after electrolysis, W5+ in the catalyst was converted to W6+, while the total W signal remained nearly unchanged, indicating minimal decomposition. This suggests that the 14NH4 + detected by NMR under N2 purging originates from the initial hydrogenation of lattice nitrogen in WOxNy rather than from its decomposition. Taken together, all the experimental results confirm that the eNRR facilitated by the WOxNy/WO3-H2/N2-2h catalyst follows a MvK mechanism. In this work, we refer to it as the HIC-enhanced MvK mechanism, owing to the unique structure and properties of the heterogeneous interfacial complexion (HIC) in the catalyst. After electrolysis, it was noticed that the total N content decreased, and the N-W and N-O species decreased more than that of the N-W-O species (FIGs.18A-18D). The decrease of the N species is consistent to the observation of decreased NH3 yield rate with extended electrolysis (FIG.22), which is commonly observed in TMN/TMNxOy based eNRR. While the exact cause of the decreased NH3 yield rate remains under investigation, the significant decrease in N-W species may suggest that re-filling the nitrogen vacancies (Nv) during eNRR may be still a limiting factor. Methods of Using NE-EPC Systems In another aspect, the disclosure provides a method of generating a chemical species, comprising contacting a plasma with the NE-EPC systems of the disclosure. In certain embodiments, the chemical species is ammonia (NH3). In certain embodiments, the chemical species is hydrogen (H2). In certain embodiments, the chemical species is carbon monoxide (CO). In certain embodiments, the chemical species is methanol (CH3OH). In certain embodiments, the method of generating a chemical species comprises a reduction reaction. In certain embodiments, the chemical species is a reduced chemical species. In certain embodiments, the reduced chemical species is NH3. In certain embodiments, the chemical species is generated under ambient conditions. In certain embodiments, the reduction reaction has a specific yield of at least 1 x 10-10 mol•cm-2s-1 (hydrogen atom transportation membrane). In certain embodiments, the plasma is derived from nitrogen (N2). In certain embodiments, the plasma has a frequency ranging from about 0 GHz to about 10 GHz. In - 29 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) certain embodiments, the plasma has a gas temperature ranging from about 300 K to about 1,000 K. In certain embodiments, the plasma has an electron temperature ranging from about 1 eV to about 100 eV. In certain embodiments, the plasma has a pressure ranging from about 20 Torr to about 760 Torr. In certain embodiments, the plasma is enhanced by contacting one or more electrodes with at least one dielectric material. In certain embodiments, the dielectric material is a piezoelectric material. In certain embodiments, the dielectric material is a ferroelectric material. In certain embodiments, the dielectric material is a pyroelectric material. In certain embodiments, the dielectric material is flat. In certain embodiments, the dielectric material is porous. In certain embodiments, the dielectric material is microstructured. In certain embodiments, the dielectric material is nanostructured. In certain embodiments, the plasma is generated by a discharge. In certain embodiments, the discharge is a direct current (DC) discharge. In certain embodiments, the discharge is a alternating current (AC) discharge. In certain embodiments, the discharge is a radio frequency (RF) discharge. In certain embodiments, the discharge is a microwave (MW) frequency discharge. In certain embodiments, the discharge with a duration in the range of about 1 nanosecond to about 1 microsecond. In certain embodiments, the faradic efficiency of the NE-EPC system is at least about 5%. In certain embodiments, the methods of the disclosure (e.g., use of the NE-EPC system of the disclosure) permits ammonia production of at least 30 nmol/s^cm2. In certain embodiments, the methods of the disclosure permits ammonia production of at least 100 nmol/s^cm2In certain embodiments, the methods of the disclosure permits ammonia production of at least 1,000 nmol/s^cm2. EXAMPLES Various embodiments of the present application can be better understood by reference to the following Examples which are offered by way of illustration. The scope of the present application is not limited to the Examples given herein. Example 1: Non-equilibrium electrochemical plasma electrocatalysis (NE-EPC) system design In one aspect, the disclosure relates to the development of a strategy to overcome the - 30 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) fundamental challenges impeding practical green ammonia production. The approach described herein leverages the efficient N2 activation by plasma and the facile activation of water by electrochemistry. These two initially incompatible systems are integrated by constructing a non-equilibrium electrochemical plasma electrocatalysis (NE-EPC) system, enabling efficient green synthesis of NH3 at ambient pressures and room temperature, as well as higher temperatures. In certain embodiments, the two major competing reactions (i.e. water activation and N2 activation) occur in different locations and chambers as shown in FIGs.11-12. This allows for independent control and optimization of the reaction, enabling a system-level optimization in tandem. Specifically, a hydrogen atom selective membrane (i.e., hydrogen atom transportation membrane), including metal based- and the multifunctional transition metal oxide (TMO)-based hydrogen-selective membrane has been described herein, which plays a crucial role in constructing the non-equilibrium electrochemical plasma catalysis (NE-EPC) system of the disclosure. The features of the electrochemical system of the disclosure are described herein. Spatial/Temporal Separation avoids competition of the active sites In one aspect, spatial and/or temporal separation of the coupled reactions (i.e., water activation and N2 activation) avoids active site competition. The positions of the active sites responsible for electrochemically generating active hydrogen are distinct from the sites dedicated to N2 activation, hydrogenation, and NH3 generation. This separation eliminates the competition for catalytic sites on the surfaces for H2 activation in previous reported plasma- enhanced NH3 synthesis where H2 was used as the hydrogen resource, or for water and proton activation, which would lead to overwhelming hydrogen evolution reaction (HER) in electrochemical cells. This separation ensures unimpeded access for N2 to the catalytic sites for eNRR. Simultaneously, it guarantees an ample supply of hydrogen resources for eNRR, thanks to the mixed electron-hydrogen transportation property of the hydrogen atom selective membranes. It is worth noting that TMO based hydrogen atom selective membranes also compare favorably with metal-based hydrogen atom membranes. The spatial/temporal separation allows independently optimization of the environments for the reactions at each side of the membrane for efficient green NH3 production. In another aspect, spatial and/or temporal separation of the coupled reactions (i.e., water activation and N2 activation) permits independent optimization for efficient NH3 production. Spatial and/or temporal separation enables plasma-enhanced N2 activation and hydrogenation of the activated N2 to the NH3 product in an electrolyte-free and hydrogen gas- - 31 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) free environment. Specifically, inert N2 can be effectively activated by N2 plasma under optimized conditions, transforming into highly reactive vibrational nitrogen (N2 (^)) and atomic N as the reactants for NH3 generation. Simultaneously, water molecules are electrochemically activated into protons or active H atoms, which are transported through the membrane, and become available for the hydrogenation of the activated N2 (^) and atomic N. The use of highly active N2 (^) and H atoms as reactants, rather than the extremely inert N2 molecules, leads to membrane surface nitridation and significant decrease in activation energy of the process combined with the use of protons or active H atoms as reactants, instead of the relatively inert H2O molecules as hydrogen resources, the system, thereby substantially boosting the ammonia synthesis efficiency. Enhanced Selective NH3 Synthesis In another aspect, the system(s) (e.g., membranes and/or NE-EPC) and/or methods of the present disclosure facilitate the one-step, highly selective synthesis of NH3 with remarkable yield and Faradaic efficiency, while minimizing the production of undesirable byproducts such as NOx and H2O2. Product Protection Mechanism In another aspect, the vertically aligned and densely packed TMO nanostructures on the surface of the membranes of the disclosure not only offer large surface area for efficient NH3 production, but also provide safeguarding of the NH3 products, protecting them from plasma-induced decomposition. Extending catalyst cycle life-time for sustainable and stable NH3 synthesis Transition metal nitrides (TMNs) and Transition metal oxynitrides (TMOxNy) are a class of catalysts for electrochemical N2 fixation. Unlike other catalysts, where Proton- Coupled Electron Transfer (PCET) pathway is widely accepted as the catalytic reaction mechanism for eNRR, TMN catalysts, in contrast, proceeds via a Mars-van Krevelen (MvK) catalytic reaction pathway. Specifically, the lattice N atoms on the surface of TMNs are first hydrogenated to produce NH3, leaving N vacancies behind. These N vacancies are subsequently refilled by the dissolved N2 from the electrolyte. Reduction of the absorbed nitrogen (N2) forms the second NH3 molecule and regenerates the lattice N atoms, completing the catalytic cycles. This mechanism largely breaks the scaling relationships of N and H - 32 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) intermediates during electrochemical nitrogen reduction reaction (eNRR), since the catalytic sites for eNRR (N sites) and for hydrogen evolution (HER) sites (transition metal sites) in TMN based catalysts are different. Having different catalytic sites is favorable for simultaneous suppressing HER and promoting eNRR for high efficient and selective NH3 synthesis. However, a challenge regarding the approach described herein is the endurance of TMN-based catalysts. In the present NE-EPC systems, the use of highly reactive and non- equilibrium N and N2 (^) produced by plasma, instead of inert N2, facilitates replenishment of the lattice N vacancies on the catalytic surfaces enabling continued stable NH3 production. The fast replenishment diminishes the issue of their migration into the bulk of the catalysts. The new mechanism, which is denoted as plasma assisted Mars-Van Krevelen (PA-MvK) mechanism, is shown in FIG.11. In addition, the possible poison by O, OH, and solvated protons from electrolytes are naturally avoided, since the sites for plasma enhanced eNRR are in an electrolyte-free environment. Example 2: Exemplary membrane compositions and electrochemical cells of the disclosure and methods of use thereof In certain embodiments, the hydrogen atom transportation membranes of the disclosure, and NE-EPC systems comprising the same, are prepared by microwave enabled growth of WO3 on a porous carbon support (FIGs.1-2). In certain embodiments, the membranes are prepared by microwave irradiation of precursors with (NH4)2SO4 (FIG.1) or Na2SO4 (FIG.2) as the capping agent. In certain embodiments, the microwave irradiation method enables one step, one pot direct growth of WO3 structures in combination with additional heteroatom doping elements (e.g., Ru) to further enhance catalytic performance of the membranes of the disclosure in NE-EPC systems of the disclosure (FIGs.3-8). Selected preliminary results include evaluation of ex situ N2 plasma treatment to generate tungsten oxynitride layer as the catalytic layer on the tungsten oxide (WO3) membrane surface in a single chamber (i.e., eNRR). In certain embodiments, eNRR of a plasma treated catalytic substrate of the disclosure comprising WOxNy demonstrated a NH3 yield about 200 times greater than that which was observed using a Ni3N membrane (FIG.15A). Thus, preliminary results demonstrated that N2 plasma treatment of a WO3 surface generates catalytic centers for NH3 synthesis and shows that eNRR activity of the WOxNy-WO3 decreases over time (FIG.15A) due to the slow refilling of the nitrogen vacancies by the inert N2, which is depicted in FIG.11. - 33 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) Example 3: Fast fabrication of WO3 nanosheet array on carbon cloth with the microporous layer (MPL) via a microwave hydrothermal method A microwave hydrothermal method was applied to fabricate the WO3 nanosheet array directly on a carbon cloth support with the microporous layer (MPL). The recipe for the fabrication was slightly modified from the work by Gao et al., "High-performance energy- storage devices based on WO3 nanowire arrays/carbon cloth integrated electrodes," Journal of Materials Chemistry A 2013, 1 (24), 7167-7173. In brief, 1.25 mmol of sodium tungstate dihydrate (Na2WO4^2H2O) was dissolved in deionized water (10 mL) under vigorous stirring for 20 min. Subsequently a 3M HCl aqueous solution was slowly dropped into the solution until the pH value of the solution reached 1.2 to form a yellowish transparent solution. Then, 3.5 mmol oxalic acid (H2C2O4) was added into the above mixture and diluted to 25 mL, which resulted in the formation of the H2C2O4 precursor. For the next step, the as-prepared 4 mL H2WO4 precursor was transferred into a microwave tube, and then 0.1 g of Na2SO4 was added to the solution to control the structure. A piece of carbon cloth (0.75cm × 0.75 cm in size) with the MPL (Hydro-LAT 1400, Fuel Cells ETC), which was ultrasonically cleaned by deionized water and alcohol in sequence, was put into the microwave tube and sealed, and maintained at 180 °C for 15 minutes by microwave oven (Discover SP, CEM). After the autoclave cooled down to room temperature, the WO3 membrane was taken out and rinsed with deionized water several times and dried at 70 °C in ambient. Example 4: Plasma assisted surface nitridation of the WO3 nanosheet array The as-fabricated WO₃ nanosheet arrays on carbon cloth support were treated with 16-torr N₂ and N₂/H₂ plasma for different durations, as specified in the sample names. The plasma was generated in a home-made DBD cell, powered by a 20-kHz, 13-kV AC power supply. After plasma treatment, the composition, oxidation states, and morphology of the samples were analyzed by a range of surface characterization techniques, including X-ray photoelectron spectroscope (XPS), scanning electron microscope (SEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). Example 5: Characterization of the Electrocatalysts The morphology of the WO3 and WOxNy/WO3 was analyzed by field emission scanning electron microscope (FE-SEM) (Hitachi S-4800 and JSM-7900F, JEOL, Japan) at 15 kV. The crystalline structures were investigated by X ray diffraction (XRD, a Rigaku - 34 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) Miniflex 6G) with a Co Kα radiation (λ = 1.789 Å). The surface chemical states and compositions were measured by X-ray photoelectron spectroscope (XPS, Thermo, K-Alpha, USA) with a monochromatic Al Kα radiation (hv = 1486.6 eV). All spectra were calibrated using the binding energy of C 1s (284.8 eV) as a reference. High-angle annular dark-field scanning transmission electron microscopy (HAADF- STEM) was acquired on an aberration-corrected JEOL NEOARM operating at 200 kV using a convergence semi-angle of 28 mrad. Any electron energy loss spectroscopy (EELS) data was acquired on an aberration corrected FEI Titan microscope operating at 300 kV using a convergence semi-angle of 19.3 mrad. A 0.1 eV/channel dispersion was used during dual EELS data acquisition, wherein the low loss contains the zero-loss peak and the high loss contains both the O K-edge and N K-edge simultaneously. A full-width half maximum of the zero-loss peak registers an energy resolution of 1.0 eV. STEM samples were prepared using a solution-casting technique. The initial sample powders were dispersed in isopropyl alcohol and sonicated. Thereafter, the solution was applied to conventional lacey carbon TEM foil grids. Example 6: Assessment of eNRR performance of the WOxNy/WO3 hybrid catalyst electrodes All the electrochemical measurements were performed using a CHI 760 C Potentiostat (CH Instruments, USA). Ag/AgCl (sat. KCl) and Pt wire were used as reference (RE) and counter electrodes (CE), respectively. The applied potentials measured against the Ag/AgCl reference electrode in saturated KCl were converted to the reversible hydrogen electrode (RHE) using the equation: RHE = EAg/AgCl + 0.197 V + 0.059×pH (eq1) Example 7: eNRR setup The eNRR performance of the WOxNy/WO3 hybrid catalyst electrodes was evaluated using a CH Instruments 760E Potentiostat with a homemade designed N2 flow electrolysis cell as shown in FIG.19A. This cell consists of a proton exchange membrane (Nafion 117, Dupont), a piece of Pt plate, Ag/AgCl (saturated KCl) electrode, which act as the counter electrode (CE), and reference electrode, respectively. The working electrode (WE) is the as- prepared WOxNy/WO3 hybrid catalyst electrodes with a size of 0.7 × 0.7 cm, which were directly used as a catalytic gas-diffusion electrode (GDE) for eNRR to alleviate the low solubility issue of N2 in water-based electrolytes (0.71 mg/mL). To eliminate potential NO^ - 35 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) and NH₃ contamination in the N₂ gas, pressurized N₂ (flow rate: 2.5 mL/min) from the gas tank was passed through three traps arranged in series before being introduced to the backside of the GDE (the side without catalyst coating) for eNRR (FIG.19B). The three purification traps included: (1) A KMnO₄ oxidation trap to oxidize any NO3 present in the N₂ gas into soluble NO₃⁻. (2) A KOH trap to remove the possibly formed NO3⁻. (3) A 0.1 M H₂SO₄ solution to trap any residual NH₃ in the N₂ gas. After purification, the N₂ gas was purged onto the backside of the GDE to initiate eNRR and the excess gas was purged back to the electrolyte to avoid the loss of the produced NH3 carried over by the N2 flow during the eNRR. The WE side and the CE side were separated by a Nafion 117 membrane (Fuel cell store). The electrolysis was performed for 0.5 h with constant potential in a H2SO4 solution (pH=2) as the electrolyte. The electrolyte in the WE side of the cell was collected for ammonium (NH3) and hydrazine (N2H4) detection using the indophenol blue UV-Vis spectroscopy method and NMR spectroscopy as detailed herein. The NH3 yield rate and the Faradic efficiency for the nitrogen-ammonia conversion were calculated as detailed in herein. Example 8: Determination of NH4 + via the indophenol blue method The concentration of the produced NH4+ was spectrophotometrically determined by the indophenol blue method. Typically, 1 mL of electrolyzed electrolyte was transferred from the electrochemical cell to a clean vial. Then 1 mL of solution containing 1M NaOH with 5 wt% salicylic acid and 5 wt% sodium citrate was added to the vial. Then 0.5 mL of 5 wt% NaClO aqueous solution and 0.1 mL of 1 wt% sodium nitroprusside solution was sequentially dropwise added to the mixture. After reacting for 2 h, the UV-vis spectrum was collected from 750 nm to 500 nm. Calibration curve was made using NH4Cl standard (BTC) diluted to 0.4, 0.8, 1.2, 1.6 ppm (NH4+ concentration) with the fresh electrolyte. Calibration curve was made at each time the electrolyzed electrolytes were measured. Example 9: Determination of N2H4 N2H4 was determined by Watt and Chrisp colorimetric method. In brief, the color reagent was obtained by mixing concentrated HCl (30 mL), C2H5OH (300 mL) and C9H11NO (5.99 g). And 5 mL electrolyte was taken from the cathodic chamber and added into 5 mL above as-prepared color reagent. After standing for 15 minutes, the absorption spectrum of the solution was collected in the wavelength range of 420-500 nm, and the peak appears at 455 nm. The calibration curve was measured using the absorbance of N2H4 solution with different concentrations. Calibration curve displays good linear relationship of absorbance - 36 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) with N2H4 concentrations (y = 1.0158x + 0.1519, R2 = 0.9991) by taking the mean of three times independent calibration. Example 10: 15N2 isotope label experiment and NMR Analysis: Before starting the nitrogen reduction reaction (NRR) experiment using ¹⁵N-labeled nitrogen, the system was purged with argon gas three times over a total of 30 minutes to remove any residual air. After purging, the argon supply was turned off, and the balloon was evacuated by pump before being filled with ¹⁵N₂ gas. The electrolysis was then conducted at - 0.15 V vs RHE for 30 minutes. Following electrolysis, the electrolyte was collected for further analysis of the ¹⁵N-labeled products. For NMR sample preparation, the pH of the electrolyte was adjusted to 4.5, maleic acid was added as an internal standard, and DMSO-d₆ was used to lock the sample. NH4 + detection via NMR was performed using the excitation sculpting water suppression (zgesgp pulse sequence) on a Bruker 500 MHz Avance III HD spectrometer. To improve the signal- to-noise ratio, the following parameters were optimized: frequency offset (O1P), size of the free induction decay (FID) (TD), pre-scan delay (D1), and the number of scans (NS). While O1P varied from experiment to experiment, TD was set to 16,378, D1 to 1 s, and NS to 16,378. Before starting the NRR experiment using 15N-labeled nitrogen, the system was purged with argon gas three times over a total of 30 minutes to remove residual air. Afterward, the argon supply was shut off, and the balloon was evacuated by pump and subsequently filled with 15N₂ gas. The electrolysis was then carried out at -0.15V vs RHE for 30 minutes. Finally, the electrolyte was collected for further analysis of the 15N-labeled products. NMR samples were prepared in the particular way: after electrolysis pH was adjusted to 4.5, maleic acid was added as internal standard, and DMSO-d6 to lock. NH4 + detection via NMR was performed using the excitation sculpting water suppression (zgesgp pulse sequence) on Bruker 500 MHz Avance III HD spectrometer. For better signal-to-noise ratio the following parameters were optimized: frequency offset (O1P), size of FID (TD), pre-scan delay (D1), and number of scans (NS). While O1P was varied from experiment-to- experiment TD was set to 16378, D1 to 1 s, and NS to 16378. Example 11: Calculation of NH3 yield rate and Faradic efficiency for ammonia production The NH3 yield rate was calculated by Eq.2: - 37 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) ^^ேுయ ൌ ^^ேுర శ^ൈ^ ^^ೌ^ൈ௧ (Eq.2) where C[NH4 +] in the WE side, V is the volume of the electrolyte, Scat is the catalyst electrode area, t is the electrolysis duration. The Faradic efficiency for the nitrogen-ammonia conversion was calculated by Eq. (Eq.3): ^^^^ ൌ ଷൈ^^ேுర శ^ൈ^ൈி ொ (Eq.3) where Q is the constant (96485 C mol-1). Enumerated Embodiments The following enumerated embodiments are provided, the numbering of which is not to be construed as designating levels of importance: Embodiment 1 provides a hydrogen atom transportation membrane comprising: i) a transition metal oxide (TMO) standalone membrane, or ii) a porous support and a TMO membrane, wherein the TMO membrane is embedded in the porous support or deposited on a surface of the porous support. Embodiment 2 provides the hydrogen atom transportation membrane of embodiment 1, wherein the TMO comprises a plasma catalyst layer. Embodiment 3 provides the hydrogen atom transportation membrane of any one of embodiments 1-2, wherein the porous support comprises at least one selected from the group consisting of a conductive metal- or metal-oxide-based membrane, a nonconductive ceramics-based membrane, a polymer-based membrane, and a carbon-based membrane, or combinations thereof. Embodiment 4 provides the hydrogen atom transportation membrane of any one of embodiments 1-3, wherein the porous support is surface modified, optionally wherein surface modification improves hydrophobicity or hydrophilicity. Embodiment 5 provides the hydrogen atom transportation membrane of any one of embodiments 1-4, wherein the TMO comprises a proton intercalatable TMO or a polymer composite thereof, a metal nanoparticle composite, a carbon nanomaterial composite, a metal nanoparticle polymer composite, a carbon nanomaterial composite, or a metal nanoparticle and carbon nanomaterial polymer thereof. - 38 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) Embodiment 6 provides the hydrogen atom transportation membrane of any one of embodiments 1-5, wherein the TMO comprises at least one selected from the group consisting of WO3, MoO3, TiO2, VO2, Nb2O5, ZrO2, HfO2, and MnO2. Embodiment 7 provides the hydrogen atom transportation membrane of any one of embodiments 1-6, wherein the proton intercalatable TMO comprises at least one hybrid TMO selected from the group consisting of, but not limited to, (WO3)m-(WO2)n, (Nb2O5)m-(WO3)n, (MoO3)m -(VO2)n, (Nb2O5)m-(TiO2)n, (Nb2O5)m-(NbO2)n, (Nb2O5)m-(WO2)n, MomVOn, and WmNbOn, and wherein m and n are each independently an integer selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Embodiment 8 provides the hydrogen atom transportation membrane of any one of embodiments 5-7, wherein the polymer composite comprises at least one polymer comprising at least one of sulfonated tetrafluoroethylene, polyaniline, polypyrrole, and polyacrylate. Embodiment 9 provides the hydrogen atom transportation membrane of any one of embodiments 5-7, wherein the composite comprises at least one metal nanostructure comprising at least one of Pd, Ni, Pt, and Ru. Embodiment 10 provides the hydrogen atom transportation membrane of any one of embodiments 1-9, wherein the TMO is doped with at least one element selected from the group consisting of P, S, N, B, Se, Ru, Mo, Nb, Ti, V, Fe, Co, Ni, Sb, Mn, Rh, Re, Cu, Pt, Ir, Au, Ag, Ge, Pt, Zr, and Zn. Embodiment 11 provides the hydrogen atom transportation membrane of any one of embodiments 1-10, wherein the hydrogen atom transportation membrane further comprises at least one additional metal catalyst embedded in the TMO, or deposited on the surface thereof, optionally wherein the at least one additional metal catalyst is selected from the group consisting of a transition metal nitride (TMN), a transition metal oxynitride (TMON), and a nitrogen (N) doped TMO. Embodiment 12 provides the hydrogen atom transportation membrane of any one of embodiments 1-11, wherein the TMN, TMON, or (N)-doped TMO comprises at least one metal selected from the group consisting of Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, and Sm. Embodiment 13 provides a non-equilibrium electrochemical plasma catalysis (NE- EPC) system comprising: (a) an electrochemical cell; (b) a plasma catalytic reaction chamber; and (c) a hydrogen atom transportation membrane comprising a porous carbon support, a transition metal oxide (TMO) layer, and a plasma catalyst layer, - 39 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) wherein the electrochemical cell and plasma catalytic reaction chamber are connected through, and separated by, the hydrogen atom transportation membrane. Embodiment 14 provides the system of any one of embodiments 13, wherein the system further comprises a water streaming chamber. Embodiment 15 provides the system of any one of embodiments 13 or 14, wherein the electrochemical cell comprises an anode and a cathode and at least one of the following applies: (a) the anode comprises a water streaming oxidation anode; (b) the cathode comprises a transition metal nitride (TMN); and (c) the cathode is in contact with the plasma catalytic reaction chamber. Embodiment 16 provides the system of any one of embodiments 13-15, wherein the hydrogen atom transportation membrane further comprises a transition metal-based hydrogen atom transportation membrane comprising at least one of Pd, Ni, V, and Nb. Embodiment 17 provides the system of any one of embodiments 13-16, wherein the hydrogen atom transportation membrane comprises the membrane of any one of embodiments 1-13. Embodiment 18 provides the system of any one of embodiments 13-17, wherein the TMO layer further comprises one or more substantially vertically aligned nanostructures, optionally wherein the nanostructures are selected from the group consisting of nanosheets, nanorods, and nanospikes. Embodiment 19 provides the system of any one of embodiments 13-18, further comprising a plasma source comprising one or more electrodes and one or more reactants, optionally wherein the reactant is at least one selected from the group consisting of nitrogen (N2), hydrogen (H2), methane (CH4), and carbon dioxide (CO2). Embodiment 20 provides the system of any one of embodiments 13-19, wherein the TMO layer further comprises a heteroatom-doped transition metal oxide (TMO). Embodiment 21 provides the system of any one of embodiments 13-20, wherein the TMO comprises WO3. Embodiment 22 provides the system of any one of embodiments 13-21, wherein the hydrogen transportation membrane has a thickness ranging from about 100 nm to about 25 µm. Embodiment 23 provides the system of any one of embodiments 13-22, wherein the plasma catalyst layer comprises at least one transition metal nitride (TMN) or transition metal - 40 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) oxynitride (TMON) catalyst, wherein the TMN or TMON comprises at least one metal selected from the group consisting of Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, and Sm. Embodiment 24 provides the system of any one of embodiments 13-23, wherein the TMO doped with about 0.5% Ru, P, S, N, B, Se, Mo, Nb, Ti, V, Fe, Co, Ni, Sb, Mn, Rh, Re, Cu, Pt, Ir, Au, Ag, Ge, Pt, Zr, or Zn by weight. Embodiment 25 provides the system of any one of embodiments 13-24, wherein the plasma catalytic reaction chamber further comprises a plasma control unit or plasma control chamber. Embodiment 26 provides the system of any one of embodiments 13-25, wherein an electrical current is used to generate the source of plasma. Embodiment 27 provides the system of any one of embodiments 26, wherein the current ranges from about 100 µA to about 1000 mA, optionally wherein the current ranges from about 1 mA to about 1000 mA. Embodiment 28 provides the system of any one of embodiments 13-27, wherein water is a proton donor of the electrochemical cell. Embodiment 29 provides the system of any one of embodiments 13-28, wherein the hydrogen atom transportation membrane is a cathode in the electrochemical cell, optionally wherein the electrochemical cell comprises a metal anode. Embodiment 30 provides the system of any one of embodiments 13-29, wherein the electrochemical cell comprises a liquid electrolyte that has a pH less than 5. Embodiment 31 provides the system of any one of embodiments 30, wherein the liquid electrolyte comprises one or more inorganic acids, alkaline, or alkaline earth metal salts, optionally wherein the liquid electrolyte comprises sulfuric acid. Embodiment 32 provides the system of any one of embodiments 30 or 31, wherein the liquid electrolyte comprises an aqueous solution. Embodiment 33 provides a method of generating a chemical species, comprising contacting a plasma with the system of any one of embodiments 13-32 to form the chemical species. Embodiment 34 provides the method of embodiment 33, wherein the plasma is derived from nitrogen (N2). Embodiment 35 provides the method of embodiments 33 or 34, wherein the chemical species is selected from the group consisting of ammonia (NH3), hydrogen (H2), carbon monoxide (CO), and methanol (CH3OH). - 41 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) Embodiment 36 provides the method of any one of embodiments 33-35, wherein at least one of the following applies: (a) the plasma has a frequency ranging from about 0 GHz to about 10 GHz; (b) the plasma has a gas temperature ranging from about 300 K to about 1,000 K; (c) the plasma has an electron temperature ranging from about 1 eV to about 100 eV; and (d) the plasma has a pressure ranging from about 20 Torr to about 760 Torr. Embodiment 37 provides the method of any one of embodiments 33-36, wherein the plasma is enhanced by contact with an electrode comprising at least one dielectric material selected from the group consisting of a piezoelectric material, a ferroelectric material, and a pyroelectric material, optionally wherein the electrode or dielectric material is flat or porous, and optionally wherein the electrode or dielectric material is microstructured or nanostructured. Embodiment 38 provides the method of any one of embodiments 33-37, wherein the chemical species is generated under ambient conditions. Embodiment 39 provides the method of any one of embodiments 33-38, wherein the plasma is generated by a discharge selected from the group consisting of direct current (DC) discharge, alternating current (AC) discharge, radio frequency (RF) discharge, and microwave (MW) frequency discharge, or a combination of thereof, optionally wherein the discharge occurs with a duration in the range of about 1 nanosecond to about 1 microsecond. Embodiment 40 provides the method of any one of embodiments 33-39, wherein the system has a Faradaic efficiency of at least about 5%. Embodiment 41 provides a catalyst comprising: a first layer comprising WO3; a second layer comprising WOxNy; wherein x is about 1.2 to about 2.8; wherein y is about 0.2 to about 1.8; and wherein the sum of x and y is about 3. Embodiment 42 provides the catalyst of embodiment 41, wherein the first layer has substantially the same crystal structure as pure WO3. Embodiment 43 provides the catalyst of any one of embodiments 41-42, wherein the WO3 in the first layer is hexagonal WO3 (h-WO3). Embodiment 44 provides the catalyst of any one of embodiments 41-43, wherein the WO3 in the first layer is h'-hexagonal WO3 (h'-WO3). - 42 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) Embodiment 45 provides the catalyst of any one of embodiments 41-44, wherein the second layer comprises an amorphous layer of WOxNy. Embodiment 46 provides the catalyst of any one of embodiments 41-45, wherein the catalyst has a Faradaic efficiency of at least 25%. Embodiment 47 provides the catalyst of any one of embodiments 41-46, wherein the catalyst exhibits a powder x-ray diffraction (PXRD) peak at 63.6° 2θ as measured using Co Kα radiation with a wavelength (λ) of 1.789 Å. Embodiment 48 provides the catalyst of any one of embodiments 41-47, wherein the second layer has a thickness of about 0.01 to about 10 nm. Embodiment 49 provides the catalyst of any one of embodiments 41-48, wherein the first layer is adjacent to and in contact with the second layer. The terms and expressions employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present application. Thus, it should be understood that although the present application describes specific embodiments and optional features, modification and variation of the compositions, methods, and concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of embodiments of the present application. - 43 - 55799713.4

Claims

Attorney Docket No.370602-7078WO1 (00278) CLAIMS What is claimed is: 1. A hydrogen atom transportation membrane comprising: i) a transition metal oxide (TMO) standalone membrane, or ii) a porous support and a TMO membrane, wherein the TMO membrane is embedded in the porous support or deposited on a surface of the porous support.
2. The hydrogen atom transportation membrane of claim 1, wherein the TMO comprises a plasma catalyst layer.
3. The hydrogen atom transportation membrane of claim 1, wherein the porous support comprises at least one selected from the group consisting of a conductive metal- or metal- oxide-based membrane, a nonconductive ceramics-based membrane, a polymer-based membrane, and a carbon-based membrane, or combinations thereof.
4. The hydrogen atom transportation membrane of claim 3, wherein the porous support is surface modified, optionally wherein surface modification improves hydrophobicity or hydrophilicity.
5. The hydrogen atom transportation membrane of any one of claims 1-4, wherein the TMO comprises a proton intercalatable TMO or a polymer composite thereof, a metal nanoparticle composite, a carbon nanomaterial composite, a metal nanoparticle polymer composite, a carbon nanomaterial composite, or a metal nanoparticle and carbon nanomaterial polymer thereof.
6. The hydrogen atom transportation membrane of any one of claims 1-5, wherein the TMO comprises at least one selected from the group consisting of WO3, MoO3, TiO2, VO2, Nb2O5, ZrO2, HfO2, and MnO2.
7. The hydrogen atom transportation membrane of any one of claims 1-6, wherein the proton intercalatable TMO comprises at least one hybrid TMO selected from the group consisting of, but not limited to, (WO3)m-(WO2)n, (Nb2O5)m-(WO3)n, (MoO3)m -(VO2)n, - 44 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278) (Nb2O5)m-(TiO2)n, (Nb2O5)m-(NbO2)n, (Nb2O5)m-(WO2)n, MomVOn, and WmNbOn, and wherein m and n are each independently an integer selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.
8. The hydrogen atom transportation membrane of any one of claims 5-7, wherein the polymer composite comprises at least one polymer comprising at least one of sulfonated tetrafluoroethylene, polyaniline, polypyrrole, and polyacrylate.
9. The hydrogen atom transportation membrane of any one of claims 5-7, wherein the composite comprises at least one metal nanostructure comprising at least one of Pd, Ni, Pt, and Ru.
10. The hydrogen atom transportation membrane of any one of claims 1-9, wherein the TMO is doped with at least one element selected from the group consisting of P, S, N, B, Se, Ru, Mo, Nb, Ti, V, Fe, Co, Ni, Sb, Mn, Rh, Re, Cu, Pt, Ir, Au, Ag, Ge, Pt, Zr, and Zn.
11. The hydrogen atom transportation membrane of any one of claims 1-10, wherein the hydrogen atom transportation membrane further comprises at least one additional metal catalyst embedded in the TMO, or deposited on the surface thereof, optionally wherein the at least one additional metal catalyst is selected from the group consisting of a transition metal nitride (TMN), a transition metal oxynitride (TMON), and a nitrogen (N) doped TMO.
12. The hydrogen atom transportation membrane of claim 11, wherein the TMN, TMON, or (N)-doped TMO comprises at least one metal selected from the group consisting of Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, and Sm.
13. A non-equilibrium electrochemical plasma catalysis (NE-EPC) system comprising: (a) an electrochemical cell; (b) a plasma catalytic reaction chamber; and (c) a hydrogen atom transportation membrane comprising a porous carbon support, a transition metal oxide (TMO) layer, and a plasma catalyst layer, wherein the electrochemical cell and plasma catalytic reaction chamber are connected through, and separated by, the hydrogen atom transportation membrane. - 45 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278)
14. The system of claim 13, wherein the system further comprises a water streaming chamber.
15. The system of claim 13 or 14, wherein the electrochemical cell comprises an anode and a cathode and at least one of the following applies: (a) the anode comprises a water streaming oxidation anode; (b) the cathode comprises a transition metal nitride (TMN); and (c) the cathode is in contact with the plasma catalytic reaction chamber.
16. The system of any one of claims 13-15, wherein the hydrogen atom transportation membrane further comprises a transition metal-based hydrogen atom transportation membrane comprising at least one of Pd, Ni, V, and Nb.
17. The system of any one of claims 13-16, wherein the hydrogen atom transportation membrane comprises the membrane of any one of claims 1-13.
18. The system of any one of claims 13-17, wherein the TMO layer further comprises one or more substantially vertically aligned nanostructures, optionally wherein the nanostructures are selected from the group consisting of nanosheets, nanorods, and nanospikes.
19. The system of any one of claims 13-18, further comprising a plasma source comprising one or more electrodes and one or more reactants, optionally wherein the reactant is at least one selected from the group consisting of nitrogen (N2), hydrogen (H2), methane (CH4), and carbon dioxide (CO2).
20. The system of any one of claims 13-19, wherein the TMO layer further comprises a heteroatom-doped transition metal oxide (TMO).
21. The system of any one of claims 13-20, wherein the TMO comprises WO3.
22. The system of any one of claims 13-21, wherein the hydrogen transportation membrane has a thickness ranging from about 100 nm to about 25 µm. - 46 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278)
23. The system of any one of claims 13-22, wherein the plasma catalyst layer comprises at least one transition metal nitride (TMN) or transition metal oxynitride (TMON) catalyst, wherein the TMN or TMON comprises at least one metal selected from the group consisting of Ru, Rh, Co, Mo, Nb, V, Ni, La, Ce, and Sm.
24. The system of any one of claims 13-23, wherein the TMO doped with about 0.5% Ru, P, S, N, B, Se, Mo, Nb, Ti, V, Fe, Co, Ni, Sb, Mn, Rh, Re, Cu, Pt, Ir, Au, Ag, Ge, Pt, Zr, or Zn by weight.
25. The system of any one of claims 13-24, wherein the plasma catalytic reaction chamber further comprises a plasma control unit or a plasma control chamber.
26. The system of any one of claims 13-25, wherein an electrical current is used to generate the plasma.
27. The system of claim 26, wherein the current ranges from about 100 µA to about 1000 mA, optionally wherein the current ranges from about 1 mA to about 1000 mA.
28. The system of any one of claims 13-27, wherein water is a proton donor of the electrochemical cell.
29. The system of any one of claims 13-28, wherein the hydrogen atom transportation membrane is a cathode in the electrochemical cell, optionally wherein the electrochemical cell comprises a metal anode.
30. The system of any one of claims 13-29, wherein the electrochemical cell comprises a liquid electrolyte that has a pH less than 5.
31. The system of claim 30, wherein the liquid electrolyte comprises one or more inorganic acids, alkaline, or alkaline earth metal salts, optionally wherein the liquid electrolyte comprises sulfuric acid. - 47 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278)
32. The system of claim 30 or 31, wherein the liquid electrolyte comprises an aqueous solution.
33. A method of generating a chemical species, comprising contacting a plasma with the system of any one of claims 13-32 to form the chemical species.
34. The method of claim 33, wherein the plasma is derived from nitrogen (N2).
35. The method of claim 33 or 34, wherein the chemical species is selected from the group consisting of ammonia (NH3), hydrogen (H2), carbon monoxide (CO), and methanol (CH3OH).
36. The method of any one of claims 33-35, wherein at least one of the following applies: (a) the plasma has a frequency ranging from about 0 GHz to about 10 GHz; (b) the plasma has a gas temperature ranging from about 300 K to about 1,000 K; (c) the plasma has an electron temperature ranging from about 1 eV to about 100 eV; and (d) the plasma has a pressure ranging from about 20 Torr to about 760 Torr.
37. The method of any one of claims 33-36, wherein the plasma is enhanced by contact with an electrode comprising at least one dielectric material selected from the group consisting of a piezoelectric material, a ferroelectric material, and a pyroelectric material, optionally wherein the electrode or dielectric material is flat or porous, and optionally wherein the electrode or dielectric material is microstructured or nanostructured.
38. The method of any one of claims 33-37, wherein the chemical species is generated under ambient conditions.
39. The method of any one of claims 33-38, wherein the plasma is generated by a discharge selected from the group consisting of direct current (DC) discharge, alternating current (AC) discharge, radio frequency (RF) discharge, and microwave (MW) frequency discharge, or a combination of thereof, optionally wherein the discharge occurs with a duration of about 1 nanosecond to about 1 microsecond. - 48 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278)
40. The method of any one of claims 33-39, wherein the system has a Faradic efficiency of at least about 5%.
41. A catalyst comprising: a first layer comprising WO3; a second layer comprising WOxNy; wherein x is about 1.2 to about 2.8; wherein y is about 0.2 to about 1.8; and wherein the sum of x and y is about 3.
42. The catalyst of claim 41, wherein the first layer has substantially the same crystal structure as pure WO3.
43. The catalyst of claim 41, wherein the WO3 in the first layer is hexagonal WO3 (h- WO3).
44. The catalyst of claim 41, wherein the WO3 in the first layer is h'-hexagonal WO3 (h'- WO3).
45. The catalyst of claim 41, wherein the second layer comprises an amorphous layer of WOxNy.
46. The catalyst of claim 41, wherein the catalyst has a Faradaic efficiency of at least 25%.
47. The catalyst of claim 41, wherein the catalyst exhibits a powder x-ray diffraction (PXRD) peak at 63.6° 2θ as measured using Co Kα radiation with a wavelength (λ) of 1.789 Å.
48. The catalyst of claim 41, wherein the second layer has a thickness of about 0.01 to about 10 nm. - 49 - 55799713.4 Attorney Docket No.370602-7078WO1 (00278)
49. The catalyst of claim 41, wherein the first layer is adjacent to and in contact with the second layer. - 50 - 55799713.4
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050241477A1 (en) * 2002-03-05 2005-11-03 Mundschau Michael V Hydrogen transport membranes
US20130160650A1 (en) * 2008-01-24 2013-06-27 Renaissance Energy Research Corporation Co2-facilitated transport membrane and method for producing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050241477A1 (en) * 2002-03-05 2005-11-03 Mundschau Michael V Hydrogen transport membranes
US20130160650A1 (en) * 2008-01-24 2013-06-27 Renaissance Energy Research Corporation Co2-facilitated transport membrane and method for producing the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LI QINGDONG, KUCUKOSMAN OGUZ KAAN, MA QINGQUAN, OUYANG JUNJIE, KUCHERYAVY PAVEL, GU HENGFEI, LONG CONOR L., ZHANG ZHIYUAN, YOUNG J: "Enhancement of Electrochemical Nitrogen Reduction Activity and Suppression of Hydrogen Evolution Reaction for Transition Metal Oxide Catalysts: The Role of Proton Intercalation and Heteroatom Doping", ACS CATALYSIS, vol. 14, no. 11, 7 June 2024 (2024-06-07), US , pages 8899 - 8912, XP093389452, ISSN: 2155-5435, DOI: 10.1021/acscatal.4c00223 *
OLOGUNAGBA DAMILOLA, KATTEL SHYAM: "Transition metal oxynitride catalysts for electrochemical reduction of nitrogen to ammonia", MATERIALS ADVANCES, vol. 2, no. 4, pages 1263 - 1270, XP093389443, ISSN: 2633-5409, DOI: 10.1039/d0ma00849d *

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