WO2016030749A1 - Électrodes, procédés de fabrication d'électrodes et procédés d'utilisation d'électrodes - Google Patents
Électrodes, procédés de fabrication d'électrodes et procédés d'utilisation d'électrodes Download PDFInfo
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- WO2016030749A1 WO2016030749A1 PCT/IB2015/001687 IB2015001687W WO2016030749A1 WO 2016030749 A1 WO2016030749 A1 WO 2016030749A1 IB 2015001687 W IB2015001687 W IB 2015001687W WO 2016030749 A1 WO2016030749 A1 WO 2016030749A1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Definitions
- the electricity generated from renewable resources can convert atmospheric/industrially sourced carbon dioxide generated in refineries and power plants, where there is a significant potential to not only ensure the protection of the environment but also safeguard global economic security.
- renewable resources such as wind, geothermal, and photovoltaic technologies
- the direct formation of CO2 reduction products in electrochemical cells can provide a continuous supply of high-energy carrier fuels at small/medium scales.
- the construction of the electrocatalysts that can efficiently activate stable CO2 molecules to specific product with high selectivity has proven to be a significant challenge.
- Embodiments of the present disclosure provide for converting CO2 to CO and formic acid, electrodes, devices including electrodes, methods of making electrodes, and the like.
- An embodiment of the present disclosure provides a method of converting CO2 to CO and formic acid, among others, that includes: exposing CO2 and H 2 0 to a cathode to form formic acid and O2 at an anode, wherein the cathode includes a substrate having a material thereon.
- the material thereon can be selected from the group consisting of indium, tin, zinc, nickel, gallium, carbon, and a combination thereof.
- the substrate can be selected from the group consisting of copper, tin, indium, iron, nickel, cobalt, gold, platinum, titanium, niobium, tantalum, molybdenum, tungsten, zinc, nickel, gallium, and a combination thereof.
- An embodiment of the present disclosure provides for a device, among others, that includes: an anode; and a cathode, wherein the cathode includes a substrate having a material thereon.
- the material thereon can be selected from the group consisting of indium, tin, zinc, nickel, gallium, carbon, and a combination thereof.
- the substrate can be selected from the group consisting of copper, tin, indium, iron, nickel, cobalt, gold, platinum, titanium, niobium, tantalum, molybdenum, tungsten, zinc, gallium, carbon, and a combination thereof.
- An embodiment of the present disclosure provides for a cathode, among others, that includes: a substrate having a material thereon.
- the material thereon can be selected from the group consisting of indium, tin, zinc, nickel, gallium, carbon, and a combination thereof.
- the substrate can be selected from the group consisting of copper, tin, indium, iron, nickel, cobalt, gold, platinum, titanium, niobium, tantalum, molybdenum, tungsten, zinc, gallium, carbon, and a combination thereof.
- the material can include indium and the substrate can include indium, and formation of formic acid can be preferentially formed relative to CO and 3 ⁇ 4.
- the material can include indium and the substrate can include copper, and formation of CO can be preferentially formed relative to formic acid and 3 ⁇ 4.
- the substrate can be oxidized.
- the material can be a nanoparticle or a microparticle or both.
- FIG. 1.1 A illustrates the comparison of the current density profiles for OD-Cu and Cu-In, chronoamperometric analyses as shown in Fig. L IB illustrates OD-Cu and Fig. L LC illustrates Cu-In, and the long-term stability test for the Cu-In catalyst at -0.6 V vs. RHE in 0.1 M KHCO 3 /CO 2 .
- Fig L ID illustrates electrolysis with long controlled potentials in 0.1 M KHCO 3 /CO 2 at -0.6 V vs. RHE.
- Fig. 1.2 A illustrates an SEM image
- Fig. 1.2B illustrates HR-TEM image of Cu-In with FFT images from the bulk and the surface (inset).
- Fig. 1.2C illustrates EDS element mapping of the selected area, showing In and Cu
- Fig. 1.3A illustrates XRD profiles and Fig. 1.3B illustrates In 3d and Cu 2p XPS spectra of the Cu-In sample.
- Fig. 1.4A illustrates the comparison of current density profiles for OD-Cu and Cu-Sn
- Fig. 1.4B chronoamperometric analysis for the Cu-Sn catalyst in 0.1 M
- Fig. 2.1 A illustrates the chronoamperometric electrolysis profiles and Fig. 2.
- IB illustrates their Faradaic efficiencies using the Culn electrode in C0 2 -saturated 0.1 M
- Fig. 2.2A illustrates the XRD profiles and Fig. 2.2B illustrates SEM images of the as-prepared and after-electrolysis Culn electrodes.
- Fig. 2.3A-B illustrate XPS spectra of (Fig. 2.3 A) Cu 2p and (Fig. 2.3B) In 3d for as-prepared and after-electrolysis Culn samples.
- the present disclosure is not limited to particular materials, reagents, reaction materials, manufacturing processes, dimensions, frequency ranges, applications, or the like, as such can vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only, and is not intended to be limiting. It is also possible in the present disclosure that steps can be executed in different sequence, where this is logically possible. It is also possible that the embodiments of the present disclosure can be applied to additional embodiments involving measurements beyond the examples described herein, which are not intended to be limiting. It is furthermore possible that the embodiments of the present disclosure can be combined or integrated with other measurement techniques beyond the examples described herein, which are not intended to be limiting.
- Embodiments of the present disclosure provide for converting CO 2 to CO and formic acid, electrodes, devices including electrodes, methods of making electrodes, and the like.
- Embodiments of the present disclosure are advantageous in that they can provide for improved efficiencies for forming formic acid and/or CO in reducing CO 2 in the presence of water.
- embodiments can provide for improved CO 2 reduction efficiency as compared to hydrogen evolution efficiency.
- embodiments can provide superior selectivity of CO 2 reduction products over the proton reduction product (H 2 ).
- the cathode can have an increased surface area, which improves current density profiles. Additional details are provided in the Example(s).
- an embodiment of the present disclosure provides for a method for converting CO 2 to CO and formic acid.
- an electrochemical or photoelectrochemical cell, system, or device can be used to react CO2 (e.g., provided (e.g. bubbling) to the system or cell using a gas handling system) and H 2 O (e.g., under negatively applied potentials) to produce CO and formic acid.
- the reaction can take place at ambient temperature and pressure but can also be conducted at higher or lower temperatures and/or pressures.
- a cathode can be used that includes a substrate having a material thereon.
- the substrate can be copper, tin, indium, iron, nickel, cobalt, gold, platinum, titanium, niobium, tantalum, molybdenum, tungsten, zinc, gallium, and carbon, and alloys, and oxidized forms thereof.
- the material can be disposed on about 5 to 75 % of the surface of the substrate.
- the material can be disposed on the substrate using a technique such as electrodeposition, electrophoretic deposition, and drop-casting.
- the material can be one that has a high hydrogen overpotential (e.g., about 500 mV, at 25 °C, 1 atm).
- the material can be a metal, metal alloy, metal oxide, or a metal hydroxide.
- the material can be indium, tin, zinc, gallium, nickel and carbon and a combination thereof, or alloys, oxides, mixed oxides, or hydroxides thereof.
- the alloy can include Cu-In alloys.
- the material can be in the form of a sheet or foil disposed on the substrate.
- the material can include particles of the material such as
- microparticles microparticles, nanoparticles, or a mixture thereof.
- the alloy can be formed by the electrochemical deposition of one metal onto another, for example, indium (In) on copper (Cu), to make Cu-In alloy catalyst, as shown in Example 2.
- the alloy can be formed from a mixed oxide to form the alloy, for example Culn0 2 , can be reduced to Cu-In alloy, as shown in Example 1.
- formation of formic acid is preferred selectively over the formation of CO and 3 ⁇ 4.
- formation of CO is preferred over the formation of formic acid and 3 ⁇ 4. Consequently, one can design the cathode for CO 2 reduction to generate a desired product(s). See the Examples for more details.
- other products can be produced such as methanol, methane, and higher hydrocarbons by changing the reactants and/or conditions.
- methane can be generated by using Cu nanoparticles supported on glassy carbon as a cathode in 0.1 M aHC03.
- Ethanol, methanol and higher hydrocarbons can be produced by further reduction of CO, which is the sole product in our system.
- An exemplary embodiment of the present disclosure includes a glass electrolysis cell comprising of two chambers separated by a ceramic frit or ionic membrane, where the cell includes the cathode provided herein, an anode, an electrolyte, a reference electrode, and a gas inlet/outlet for gas sample analyzer.
- the anode can include an anode that is appropriate for the desired application.
- the anode can include nickel based anodes, cobalt based anodes, and iron based anodes.
- the electrolyte can be an aqueous medium containing an acidic electrolyte (e.g., citric acid, perchloric acid, hydroiodic acid, nitric acid, sulfuric acid, bromic acid, etc.) or basic electrolyte (e.g., hydroxides, sodium amide, sodium hydride, etc.), simple salts, KC1, NaCl, KHCO 3 , and NaHC03, and non-aqueous electrolytes which may comprise nBu 4 PF6 (TBHP) in MeCN solution, and a combination thereof.
- an acidic electrolyte e.g., citric acid, perchloric acid, hydroiodic acid, nitric acid, sulfuric acid, bromic acid, etc.
- basic electrolyte e.g., hydroxides, sodium amide, sodium hydride, etc.
- simple salts KC1, NaCl, KHCO 3 , and NaHC03
- non-aqueous electrolytes which may
- the simple salts can include an anion (e.g., chloride, fluoride, sulfate, nitrate, nitrite, phosphate, acetate, etc.) and a cation (e.g., sodium, potassium, magnesium, iron, calcium, ammonium, etc.) such as KHCO 3 , NaCl, KC1, LiCl, CaCl 2 , or Na 2 S0 4 .
- the electrolytes may be employed at various pH levels depending upon the system, reactants, and products to be generated.
- the challenge in the electrochemical reduction of aqueous carbon dioxide is in designing a highly selective, energy efficient, and non-precious metal electrocatalyst that minimizes the competitive reduction of proton to form hydrogen during aqueous CO 2 conversion.
- a non-noble metal electrocatalyst based on a copper-indium (Cu-In) alloy that selectively converts CO 2 to CO with a low overpotential is reported.
- oxide-derived (OD-)Cu electrodes were first prepared.
- Cu foils 200 ⁇ in thickness, 99.99%,
- Electrodes were cut to the desired electrode size (1 x3 cm) and cleaned for several seconds in 1 M HC1.
- the electrodes were rinsed with Milli-Q water (18.2 ⁇ cm @ 25 °C) and dried under ambient conditions. To acquire a smooth and uniform electrode surface, the electrodes were dried with Kimwipes soon after rinsing to avoid any partial oxidation of the electrodes from air.
- the cleaned electrodes were placed vertically in a ceramic crucible and thermally oxidized at 773 K for 2 h under static air in a muffle furnace.
- the Cu-In electrode was prepared through the in situ electrochemical reduction of the thermally oxidized Cu electrodes in 0.05 M In 2 (SO4)3/0.4 M citric acid at a current density of -10 mA for 90 min ( ⁇ 18 C cm ⁇ 2 ).
- the measured binding energies were calibrated based on the C Is binding energy at 284.8 eV.
- the samples were analyzed using transmission electron microscopy (TEM) to study the morphology, crystal structure, and the elemental distributions of Cu and In in the Cu-In crystals.
- TEM analysis of the samples was performed using a TitanG2 80-300 CT from FEI Instruments that was equipped with a field-emission-gun and a GIF Tridiem863 energy-filter from Gatan, Inc. Moreover, the analysis was conducted by the operating the microscope with a beam energy of 300 keV. Note that the TEM specimens were prepared by placing a small amount of samples on holey carbon-coated nickel (Ni) grids with a mesh size of 300.
- a custom-made electrochemical cell was employed, and a BioLogic ® VMP3 potentiostat was utilized. Three electrodes were used to monitor the current-potential response of the working electrode.
- a Pt wire and an Ag/AgCl electrode (in saturated KC1) were employed as a counter electrode and as a reference electrode, respectively.
- the counter electrode was isolated with a ceramic frit, so that the product crossover was effectively suppressed.
- 0.1 M KHCO 3 99.99%, metal basis, Sigma-Aldrich
- Oxide-derived (OD)-Cu substrate was obtained by thermally oxidizing a Cu metal sheet at 773 K for 2 h in static air. [13] This treatment led to the formation of a hairy CuO nanowire structure on CU2O-CU layers, [13] resulting in a surface roughness factor that was increased 140-fold compared to that of the pristine Cu sheet as measured by cyclic voltammetry.
- the Cu-In electrode was then prepared through electrochemical reduction of the OD-Cu in 2-electrode system with a solution containing 0.05 M InS0 4 and 0.4 M citric acid at a current density of -3.3 mA cnf 2 for 90 min ( ⁇ 18 C cm 2 ). This deposition of In underwent a rather complex reduction process, in which both reduction of the Cu oxide and deposition of In occurred. The surface roughness was further improved to double of OD-Cu.
- Figs. 1.1A-D show the total current density (j ioi ) and FE at -0.3 to -0.7 V vs. RHE in 0.1 M KHC0 3 /C0 2 .
- Fig. 1.1A similar values for total current density,y to t, were obtained for OD-Cu and Cu-In in the same potential range and electrochemical conditions. These results indicate that the electron transfer rates are essentially identical in these electrodes; however, they exhibited a distinct difference in selectivity.
- the effects of the applied potentials on the FEs for OD-Cu and Cu-In are shown in Figs. LIB and LIC, respectively.
- OD-Cu began to convert CO 2 at a potential of -0.3 V vs. RHE, primarily generating 3 ⁇ 4 as the reaction product.
- the conversion of CO 2 to CO and HCOOH improved, reaching maximum FE of 40 and 30 %, respectively, at -0.6 V vs. RHE, consistent with the literature.
- the Cu-In electrode catalyzed the reduction of CO 2 at 0.3 V vs. RHE, to CO selectively (FE C o ⁇ 23%) while suppressing the formation of H 2 (FE H2 ⁇ 3%).
- Fig. 1.2A presents SEM image of the Cu-In structure.
- the microstructure consists of large irregularly shaped grains ranging from 100 to 500 nm in size. The large grains are formed as a result of the agglomeration of small nanoparticles ( ⁇ 50 nm), which are capped by a shell-like structure.
- High-resolution transmission electron micrographs (HR-TEM) and the corresponding calculated fast Fourier transform (FFT) patterns of the Cu-In samples after the CO 2 reduction experiments are shown in Fig. 1.2B.
- the nanostructure could be divided into two distinct regions: the bulk and the surface.
- the FFT pattern of the core clearly shows a highly crystalline structure
- the FFT pattern of the shell shows a deformed crystal structure, which may arise from the diffusion of In, with a large atomic radius (0.155 nm), into the smaller Cu (0.135 nm) lattice.
- Superimposed elemental maps of In and Cu are shown in Fig. 1.2C.
- the In appears primarely in a thin line about the periphery (surface) of the structure and as specs interspersed within the structure.
- the figure clearly shows that the surface is enriched with In with a thickness of ⁇ 3 nm.
- the XRD pattern of the Cu-In sample (Fig.
- the C0 2 reduction activity and the product selectivity depend on the nature of the electrolyte, temperature, pressure, the stabilization of the C0 2 ° radical, 1 and, most importantly, on the binding energy of CO, 15 which is a fundamental intermediate in the reduction of C0 2 , to the surface of the catalyst employed.
- Pt group metals initially reduce C0 2 to produce CO, which binds strongly to the surface, poisoning the electrode, preventing further C0 2 reactivity, and hydrogen (H 2 ) is generated as the main product from the competing reduction of water.
- Au 16 and Ag 17 bind CO weakly to release CO from the surface before further electron-proton coupled transfer occurs to generate hydrocarbons.
- Cu possesses an intermediate binding energy for CO, which provides not only successive electron/proton transfers but also offers the potential for C-C coupling as well to produce methane (CH 4 ), methanol (CH3OH) or ethanol
- ⁇ 2 ⁇ 3 (Aldrich 99.9%) was mixed with Na 2 C0 3 (Aldrich 99.999%) in a 1 : 1 molar ratio and then heated at 1273 to prepare Naln0 2 in a tube furnace (Nabertherm RS 80/300/13, tube I.D. 70 mm) under a high flow of nitrogen gas (1.5 L min -1 ).
- the Naln0 2 was reacted with CuCl in a 1 : 1 molar ratio and then heat treated at 673 for 12 h under flowing N 2 . 22
- Cu 2 0 (Aldrich >99.99%) was used as purchased.
- colloidal particles of each electrocatalyst ( ⁇ 0.5 g) were suspended using ultrasonication in reagent-grade acetone (50 ml) with a small amount of iodine ( ⁇ 50 mg). Homogenous films on carbon paper were obtained under an applied potential of 30 V for 3 min. The films were dried at 373 in vacuum for 12 h. The control experiment shows that the currents originated from the bare carbon paper electrode were negligible at the relevant potential range reported hereafter.
- the as-prepared Cu oxide electrodes were first subjected to the C0 2 reduction conditions in 0.1 M HCO3 (99.99%, metal basis, Sigma- Aldrich) under chronopotentiometric conditions at -1.67 mA cnT 2 to obtain reduced electrodes.
- the KHCO3 electrolyte was saturated with a continuous flow of C0 2 (10 ml min 1 ), and the final pH was 6.8. Further experiments at different potentials were performed using the obtained reduced electrodes.
- an on-line gas analyzer H 2 , CO, CH 4 , C0 2 , C 2 H 6 , C 2 H 4
- an off-line gas chromatograph with a flame ionization detector CH 3 OH
- a high-performance liquid chromatography instrument HPLC, Agilent 1200 series
- XPS X-ray photoelectron spectroscopy
- Fig. 2.1A shows the total current density j tot ) and FE at different potentials from -0.4 to -0.8 V vs. RHE in 0.1 M KHC0 3 /C0 2 for 1 h.
- Fig. 2.1 A shows that the overall current density of the electrode increases with the applied potential, and a steady-state current was obtained at each potential when tested for at least 1 h.
- the chronoamperometric measurement at various potentials was conducted using the identical electrode, the stable currents were measured at each potential (for more than 5 h), demonstrating the excellent stability of the electrode.
- the product selectivities at different potentials are shown in Fig. 2.1B. The product distribution at a given potential remained almost unchanged during our
- the Culn electrode starts to convert C0 2 at approximately -0.4 V vs. RHE, generating CO with an FE of 1 1% while cogenerating H 2 as a main product (FE 45%). We could not capture the remaining products by HPLC and GC, probably associated with undesired metal redox reactions.
- the selectivity of the C0 2 reduction product was enhanced at applied potentials from -0.5 to -0.8 V vs. RHE.
- the FE for the C0 2 reduction products at -0.8 V vs. RHE reached ⁇ 90% (FEs of CO and HCOOH are 70 and 19%, respectively), whereas the H 2 selectivity was under 10%.
- Figs. 2.2A-B show the XRD profile and SEM image of the as-prepared and after-electrolysis Culn sample.
- the XRD pattern of the as-prepared sample in Fig. 2.2A shows the major pattern ascribable to Culn0 2 , along with the Naln0 2 precursor and ⁇ 2 ⁇ 3 as impurity phases.
- the surface states of the Culn0 2 and Culn electrodes were investigated by XPS, as shown in Figs. 2.3A-B.
- the broad Cu 2p 3 / 2 and Cu 2pi/ 2 peaks at 934.8 and 954.6 eV were attributed to Cu(II) surface oxide.
- the Cu(II) oxide species exhibit satellite peaks at 942.3 and 944.9 eV because of the partially filled Cu 3d 9 shells. 25
- the peaks positioned at 445.1 and 452.8 eV could be assigned to In 3ds/ 2 and In 3d3/ 2 , respectively.
- 26 Upon the reduction of Culn0 2 , a shift towards lower binding energies in both the Cu 2p and In 3d peaks were observed, exhibiting the Cu° and In 0 states, consistent with the XRD profile (Fig. 2.2 A).
- electrocatalytic reduction can further be improved using this strategy.
- ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, 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.
- a concentration range of "about 0.1% to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt% to about 5 wt%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range.
- the term "about” can include traditional rounding according to the measuring technique and the numerical value.
- the phrase "about 'x' to 'y'" includes “about 'x' to about 'y'".
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Abstract
La présente invention porte, dans des modes de réalisation, sur la conversion du CO2 en CO et en acide formique, sur des électrodes, sur des dispositifs comprenant des électrodes, sur des procédés de fabrication d'électrodes, et analogues.
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Cited By (4)
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US20210079543A1 (en) * | 2019-09-17 | 2021-03-18 | Kabushiki Kaisha Toshiba | Electrochemical reaction device |
WO2021016539A3 (fr) * | 2019-07-25 | 2021-04-08 | The Regents Of The University Of Michigan | Conversion de co2 avec une architecture de nanofils-nanoparticules |
US11053598B2 (en) | 2017-02-16 | 2021-07-06 | Honda Motor Co., Ltd. | Method for producing core shell nanoparticles |
CN115125587A (zh) * | 2022-07-22 | 2022-09-30 | 中南大学 | 一种硬质合金熔盐电解低碳分离钨钴、碳的装置及方法 |
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