WO2022045816A1 - Catalyseur de réduction utilisant une paire acide-base de lewis frustrée graphitique (gflp) et système de réduction l'utilisant - Google Patents

Catalyseur de réduction utilisant une paire acide-base de lewis frustrée graphitique (gflp) et système de réduction l'utilisant Download PDF

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WO2022045816A1
WO2022045816A1 PCT/KR2021/011490 KR2021011490W WO2022045816A1 WO 2022045816 A1 WO2022045816 A1 WO 2022045816A1 KR 2021011490 W KR2021011490 W KR 2021011490W WO 2022045816 A1 WO2022045816 A1 WO 2022045816A1
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lewis acid
gflp
catalyst
carbon
reduction
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Korean (ko)
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권태혁
김현탁
강석주
박재현
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울산과학기술원
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Priority claimed from KR1020200110606A external-priority patent/KR102427852B1/ko
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Publication of WO2022045816A1 publication Critical patent/WO2022045816A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • 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 in the gas phase
    • 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
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a catalyst for N 2 reduction using a graffiti incomplete Lewis acid-base pair (GFLP), and more particularly, to a catalyst for reducing N 2 by inducing a multi-active site in the N 2 molecule to synthesize clean ammonia (NH 3 ) It relates to a high-performance and high-durability catalyst.
  • the present invention relates to a carbon dioxide reduction battery system in seawater using a graphic incomplete Lewis acid-base pair catalyst, and more particularly, to reduce dissolved carbon dioxide in seawater to multi-carbon compounds such as ethanol and propanol, and increase the pH It relates to a battery system capable of preventing seawater acidification.
  • Ammonia (NH 3 ) is safe and easy to store, and since it can be used not only as a raw material for urea fertilizers and pharmaceuticals, but also as a carrier of hydrogen ions, which is spotlighted as a next-generation transportation fuel, various studies on production and utilization methods are being conducted.
  • the 'Haber-Bosch process' which is currently commercialized ammonia production process, it is operated under conditions of high temperature of 500 °C or higher and high pressure of 15 ⁇ 25 MPa to break the triple bond of nitrogen, and it is used as a precursor. Since hydrogen must be supplied, there is a major disadvantage in energy and cost consumption.
  • the core of ammonia synthesis is the nitrogen fixation process that dissociates the stable triple bond of N 2 as an inert gas. It is being actively pursued worldwide.
  • Such a rare metal-based N 2 reduction reaction requires only one active nitrogen site and is accompanied by an endothermic reaction. Due to competition with Hydrogen Evolution Reaction (HER), there is a fundamental limitation in that the N 2 -ammonia conversion efficiency remains at 1 to 10%. Therefore, there is a need to develop a new strategy and material for inducing a multi-active site.
  • HER Hydrogen Evolution Reaction
  • Such an electrocatalyst provides an activation site for converting CO 2 by electron-deficient metal-center or electron-rich diatomic species and electrochemically converts CO 2 into methane, It can be converted into industrial raw materials such as methanol, formic acid and acetic acid.
  • the catalyst for N 2 reduction according to the present invention is to solve the above problems, and an object of the present invention is to reduce a reduction reaction by introducing a heterogeneous element or a Lewis acid and a base as a pair on a graphene framework using an ultrasonic spray synthesis method. It is to provide a catalyst capable of efficiently reducing N 2 to ammonia using a catalyst having an increased active site for the purpose.
  • the carbon dioxide reduction battery system in seawater according to the present invention is to solve the above problems, and an object of the present invention is to reduce reaction by introducing a heterogeneous element or a Lewis acid and a base as a pair on a graphene framework using an ultrasonic spray synthesis method To provide a battery system that can efficiently reduce carbon dioxide using a catalyst having an increased active site for
  • a graphic incomplete Lewis acid - base pair ( It provides a catalyst for N 2 reduction using GFLP).
  • a cathode composed of carbon nanomaterials in which Lewis acid and base components are paired with each other and introduced into the molecule
  • seawater electrolyte including,
  • the carbon dioxide dissolved in the seawater reacts with Lewis acid and base components of the carbon nanomaterial of the negative electrode,
  • GFLP Graffitially incomplete Lewis acid-base pair
  • the catalyst according to the present invention has excellent economic feasibility by overcoming the limitations of durability and catalyst reforming of conventional catalysts without using expensive rare metals, as well as in competition with Hydrogen Evolution Reaction (HER). With high conversion efficiency, N 2 -Ammonia reduction reaction may be induced to exhibit excellent yield.
  • the GFLP catalyst system according to the present invention is excellent in economic feasibility by using a catalyst that overcomes the limitations of durability and catalyst reforming of conventional catalysts without using expensive rare metals as an anode.
  • the battery system according to the present invention not only uses a catalyst as a cathode that overcomes the limitations of durability and catalyst reforming of conventional catalysts without using expensive rare metals, but also has excellent economic feasibility and reduces dissolved carbon dioxide in seawater by 80% With the above efficiency, it can be converted into multi-carbon compounds such as ethanol and propanol.
  • FIG. 1 is a diagram showing the dynamic covalent bonding of a heteroelement-doped GFLP structure and an N 2 molecule and properties thereof according to an embodiment of the present invention
  • D 31 P MAS NMR spectra of TMP at BN-GFLP.
  • E 1 H MAS NMR spectrum of pyrrole adsorbed to BN-GFLP).
  • FIG. 2 is a graph showing control of nitrogen doping concentration (A) and boron doping concentration (B) in graphene nanopowder according to an embodiment of the present invention.
  • FIG 3 is a graph showing HR-TEM and EDS results using a GFLP catalyst according to an embodiment of the present invention.
  • FIG 4 is a graph for the electrochemical reduction of N 2 molecules using a GFLP catalyst according to an embodiment of the present invention.
  • FIG. 5 is a photograph (top) of an ammonia titration experiment through an indophenol protocol using a GFLP catalyst according to an embodiment of the present invention and a UV-visible absorption spectrum according to the concentration of ammonium ion (middle left) and standard The curve (middle right) and the Faraday efficiency equation (bottom) are shown.
  • FIG. 7 shows the ultrasonic spray synthesis method and characteristics of the BN-GFLP structure according to an embodiment of the present invention
  • FIG 8 is a graph showing the electrochemical reduction of carbon dioxide in the BN-GFLP electrode in seawater according to an embodiment of the present invention.
  • FIG. 9 is a graph showing the CO 2 R performance of the negative electrode physically mixed with B-GN and N-GN in the seawater carbon dioxide reduction battery system according to an embodiment of the present invention.
  • Figure 10 confirms the electrical energy storage and stability during CO 2 R in the seawater carbon dioxide reduction battery system according to an embodiment of the present invention
  • (A) a schematic diagram of a jig-type CBS system.
  • Figure 11 shows the DFT calculation of the BN-GFLP catalyst for CO 2 R according to an embodiment of the present invention.
  • FIG. 12 is a graph showing HPLC and ESI-MS results of a BN-GFLP catalyst according to an embodiment of the present invention.
  • FIG. 13 is a graph showing the quantitative CO 2 reduction efficiency for the reduction product of the BN-GFLP catalyst according to an embodiment of the present invention and the selectivity (selectivity, 95%) for the multi-carbon (C 2+ ) product.
  • a catalyst for N 2 reduction using a graphic incomplete Lewis acid-base pair (GFLP) according to an embodiment of the present invention
  • Nitrogen forms a covalent bond with each of the Lewis acid and the base to secure multiple active sites, and the N 2 is reduced to ammonia (NH 3 ) through an exothermic reaction.
  • the graphic incomplete Lewis acid-base pair (GFLP) catalyst according to the present invention has a structure in which a heterogeneous element is doped on graphene, and more specifically, a Lewis acid and a base component in a graphene molecule are arranged in pairs. characterized.
  • FLP Fieldrated Lewis Pair
  • A an acid
  • Base an electron of a base
  • the Lewis acid and base pair is an incompletely bonded Lewis pair ( Frustrated Lewis Pairs (FLPs) are formed, whereby their respective activities can be maintained.
  • Frustrated Lewis Pairs FLPs
  • the FLP (Frustrated Lewis Pair) is bound to a carbon nanomaterial, that is, a graphic framework, and ⁇ -electron from the graphic framework is continuously applied to the active site of the FLP.
  • a carbon nanomaterial that is, a graphic framework
  • ⁇ -electron from the graphic framework is continuously applied to the active site of the FLP.
  • the catalyst has less restrictions in the selection of Acidic and Basic dopants by using the ultrasonic spray synthesis method (USC), which is a unique dual atom introduction method, and is quantum mechanical by cavitation by high frequency in the ultrasonic nozzle.
  • USC ultrasonic spray synthesis method
  • high activation energy 5000 °C, 2000 atm
  • reaction and atomic bonding are possible within a few microseconds, and diatoms can be uniformly introduced throughout the graphene molecule.
  • the Lewis acid component may be one selected from the group consisting of boron, tin, zinc, copper, bismuth, molybdenum, tungsten and vanadium, and the Lewis base component is nitrogen, oxygen, sulfur, phosphorus , selenium, tellurium, may be one selected from the group consisting of arsenic and antimony, but is not limited thereto.
  • the Lewis acid component is specifically bis (pinacolato) diboron (Bis (pinacolato) diboron), it is preferable to use a metal chloride (Metal chloride), etc.
  • the Lewis base component is specifically as a gaseous phase, N 2 , It is preferable to use O 2 , but is not limited thereto.
  • the carbon nanomaterial may use graphene, reduced graphene oxide (rGO), carbon nanotubes, carbon nanofibers, graphite, or activated carbon, but is not limited thereto .
  • rGO reduced graphene oxide
  • carbon nanotubes carbon nanofibers
  • graphite graphite
  • activated carbon but is not limited thereto .
  • the metal used for the positive electrode may be sodium, lithium, nickel, manganese, or alloys and oxides of the above metals, but is not limited thereto.
  • the graffiti incomplete Lewis acid-base pair (GFLP) according to the present invention can exhibit superior performance than conventional metal and non-metal catalysts, it can be used as various electrochemical devices such as fuel cells, supercapacitors, and dye-sensitized solar cells as well as batteries. applicable.
  • a cathode composed of carbon nanomaterials in which Lewis acid and base components are paired with each other and introduced into the molecule
  • electrolyte including,
  • N 2 dissolved in the electrolyte reacts with Lewis acid and base components of the carbon nanomaterial of the negative electrode
  • N 2 is reduced to ammonia while securing multiple active sites by forming a dynamic covalent bond with a Lewis acid and a Lewis base, respectively.
  • the battery system according to the present invention is characterized in that it uses the above-mentioned graffiti incomplete Lewis acid-base pair (GFLP) catalyst prepared using ultrasonic spray synthesis (USC) as an anode.
  • GFLP graffiti incomplete Lewis acid-base pair
  • USC ultrasonic spray synthesis
  • the carbon nanomaterial introduced into the molecule by pairing the Lewis acid and the base component with each other exhibits N 2 R selectivity due to a high chemical potential for the hydrogenation reaction, so that the reduction reaction can be performed.
  • the electrolyte may be HNO 3 , H 2 SO 4 , Li 2 SO 4 , K 2 SO 4 , LiOH, NaOH, or the like, but is not limited thereto.
  • graphene nanopowder 15 mg was added to NMP (30 mL) and sonicated with an ultrasonic probe (750 W, 20 kHz, Sonics and Materials Inc., USA) for 2 hours. to form a spray solution of 0.5 mg mL -1 .
  • the spray solution was directly used to synthesize N-GN using N 2 gas as a Lewis base dopant through USC.
  • Lewis acid dopant or bis(pinacolato)diboron) (30 mg) as a boron dopant was used in the GN spray prepared above. It was added to the solution (0.5 mg mL -1 , 30 mL) and sonicated for 1 hour to prepare a precursor solution.
  • Simultaneously pumped spray coating was performed with an ExactaCoat system fixed with an impact ultrasonic nozzle (Sono-Tek Co.).
  • the prepared precursor solution was sequentially supplied to an ultrasonic nozzle (180 kHz) system at a spray rate of 0.3 mL min -1 . Adjust the nozzle-to-substrate distance to 10 cm, and use compressed N 2 or Ar gas pressure (3.0 psi) under the conditions of a temperature of 150 °C, a spray rate of 20 mm s -1 5 cm x 5 cm, thickness: ⁇ 4.1 mm). Then, the prepared product was cooled to room temperature and washed with water, ethanol and acetone to remove unreacted precursors and impurities. The residual solvent was evaporated in a vacuum oven at 200 °C for 24 h.
  • GN including Ar gas carrier
  • N-GN including N 2 gas carrier
  • B-GN including Ar gas carrier
  • BN-GFLP including N 2 gas carrier
  • X-ray photoelectron spectroscopy showed that the prepared carbon nanomaterial was 3.1 at% B in B-GN, 4.1 at% N in N-GN, and 6.8 at% B and 4.2 in BN-GFLP. It was confirmed that a high heteroatom doping concentration of at% N was achieved.
  • the heteroatom doped GNs exhibited paramagnetic properties of less than 10 K due to the presence of radical defects from the doped B and N as measured by electron paramagnetic resonance (EPR) spectroscopy.
  • This radical defect of BN-GFLP contributes to accelerate the first adsorption step of CO 2 to its surface.
  • Lewis Acid (LA) and Lewis Base (LB) of BN-GFLP are characterized by magic angle radiation nuclear magnetic resonance (MAS NMR).
  • MAS NMR magic angle radiation nuclear magnetic resonance
  • ⁇ 31 P peak at 55.04 ppm appeared when TMPO was chemisorbed on the LA boron site of BN-GFLP, which corresponds to a Lewis acidity ranging from 50 to 55 ppm.
  • the Br ⁇ nsted acid peak of BN-GFLP appeared at -8.79 and -15.69 ppm by the adsorbed TMP, but the signal was weak.
  • pyrrole was used as a probe for 1 H MAS NMR to determine basicity (see Figure 1E).
  • the strong peak at 5.95 ppm is assigned to the proton of the aromatic pyrrole ring.
  • pyrrole adsorbed to the BN-GFLP sample was 1 H at the shoulder peak at about 13.89 ppm due to hydrogen bonding interaction with the LB nitrogen in BN-GFLP.
  • a large chemical shift was observed. This result is similar to the chemical shift observed in KX zeolite, which is known as a superbasic material.
  • the heteroatom doping content of GN was controlled by the N 2 pressure (see FIG. 2A ) and the concentration of boron dopant (see FIG. 2B ).
  • the N doping content of GN in X-ray photoelectron spectroscopy (XPS) analysis was reduced from 0.76 at% (0.5 psi) to 4.10 at% (3.0 psi) according to the pressure of the impact N 2 carrier gas in USC. could be precisely controlled.
  • XPS X-ray photoelectron spectroscopy
  • Electrochemical analysis was performed to confirm the N 2 reduction characteristics of the catalyst prepared in Example 1 (see FIGS. 3 and 4 ).
  • BN-GFLP morphology and elemental analysis of BN-GFLP were performed through high-resolution transmission electron microscopy (HR-TEM) and energy dispersive X-ray spectroscopy (EDS) mapping. It can be seen that wrinkling and sheet pattern characteristic of graphene can be seen in A of FIG. 3, and in B, C, D and E, the elements of carbon, boron, nitrogen and oxygen are homogeneously distributed in molecular units, respectively.
  • HR-TEM transmission electron microscopy
  • EDS energy dispersive X-ray spectroscopy
  • Example 4 electrochemical analysis was performed using the BN-GFLP prepared in Example 1 as an anode, carbon felt as a substrate, and 1M HNO 3 (aq) as an electrolyte.
  • the pressure of N 2 was set to about 1,000 Torr (1.3 atm), and the galvanostatic discharge current was set to 0.2 mA.
  • the average N 2 reduction voltage was measured to be 2.69 V (vs Na/Na + ), and as a result, it was confirmed that the N 2 reduction conversion rate was about 70.8% (see the left of FIG. 4 ).
  • the conventional rare metal-based N 2 reduction catalyst exhibited an N 2 reduction conversion of about 9 to 12%, whereas the catalyst according to the present invention exhibited an excellent conversion rate without using a metal.
  • Table 1 compares the N 2 reduction conversion of the rare metal-based catalyst and the catalyst according to the present invention.
  • the BN-GN (BN-GFLP) catalyst of the FLP structure according to the present invention exhibited a higher Faraday efficiency value than a noble metal or a rare earth metal, and showed an excellent yield.
  • high Faraday efficiency and yield were exhibited even in a metal-free catalyst that does not use a metal, and in particular, the yield was about 6.5 times superior to that of a graphene (Fe-N-C) catalyst doped with iron and nitrogen.
  • the BN-GN (BN-GFLP) of the FLP structure according to the present invention can exhibit better N 2 R efficiency through the synergistic effect of LA and LB.
  • the N 2 R selectivity and ammonia product were determined using an electrochemical mass spectrometry (DEMS) system and an Indophenol protocol.
  • DEMS electrochemical mass spectrometry
  • the indophenol protocol is a general-purpose ammonia titration method that quantifies ammonia by measuring the absorbance of indophenol produced by adding phenol-nitrofurside sodium solution and sodium hypochlorite solution and reacting with ammonium ions (NH 4 + ). As a method, specifically, it is shown in Scheme 1 below.
  • FIG. 5 it is a photograph (top) of an ammonia titration experiment through the indophenol protocol, and a UV-visible absorption spectrum (middle left) and standard curve (middle right) according to the concentration of ammonium ion.
  • the accuracy of titration is 99.4%, which is a reliable level, and the nitrogen-ammonia conversion efficiency was calculated by applying the ammonium ion concentration of the sample measured through the indophenol protocol to the Faradaic efficiency equation (below). .
  • N 2 R nitrogen reduction reaction
  • a carbon dioxide reduction battery system in seawater using a graphic incomplete Lewis acid-base pair (GFLP) catalyst according to an embodiment of the present invention
  • a cathode composed of carbon nanomaterials in which Lewis acid and base components are paired with each other and introduced into the molecule
  • seawater electrolyte including,
  • the carbon dioxide dissolved in the seawater reacts with Lewis acid and base components of the carbon nanomaterial of the negative electrode,
  • the carbon dioxide reduction battery (CO 2 Reduction Battery in Seawater, CBS) system uses a graphic incomplete Lewis acid-base pair (GFLP) catalyst prepared using ultrasonic spray synthesis (USC) as a negative electrode. It is characterized in that (see FIG. 7).
  • GFLP graphic incomplete Lewis acid-base pair
  • USC ultrasonic spray synthesis
  • methanol is basically CO 2 + 6H + + 6e -
  • ethanol is CO 2 + 12H + + 12e -
  • propanol is CO 2 + 18H +
  • the electrochemical reaction of + 18e - produces a reduction product, and in the case of multi-carbon products (ethanol, propanol), the reaction can proceed after the spontaneous generation of the C 2 O 3 intermediate in which the first intermediate CO and the second CO 2 are combined. there is.
  • the pH of the acidified seawater may exhibit an effect of increasing from about 6.4 to 8.0.
  • a catalyst for carbon dioxide reduction using a graphic incomplete Lewis acid-base pair (GFLP) according to an embodiment of the present invention
  • carbon dioxide is reduced by allowing oxygen of carbon dioxide to form a covalent bond with the Lewis acid and carbon of carbon dioxide to form a covalent bond with the Lewis base.
  • the catalyst for carbon dioxide reduction using a graffiti incomplete Lewis acid-base pair (BN-GFLP) doped with heteroelements of boron and nitrogen is a CO 2 reduction catalyst and a cathode of a carbon dioxide reduction battery at the same time.
  • BN-GFLP graffiti incomplete Lewis acid-base pair
  • the BN-GFLP negative electrode reduces CO 2
  • the reduction product is analyzed by high performance liquid chromatography (HPLC) and electrospray ionization mass spectroscopy (ESI-MS) to reduce the CO 2 product (methanol , ethanol and propanol) can be identified (see FIG. 12 ).
  • Example 4 Evaluation of CO 2 R Selectivity of a CO 2 Reduced Seawater Battery System (CBS)
  • a Swagelok-type CBS system consisting of a modified 2465-type coin cell with Na-ion superionic conductor membrane (NaSICON) capable of forming an aprotic electrolyte-based seawater hybrid system was fabricated.
  • the CBS can be connected to a pressure measuring system to continuously measure the change in internal CO 2 gas pressure during the discharge process.
  • the single-heteroatom-doped catalyst B-GN showed a high CO2 reduction but similar overpotential to the control (GN), whereas the N-GN single catalyst electrode had a low overpotential but similar CO2 consumption to the control. appeared to be From these results, it was found that LA enhances the catalytic activity, whereas LB can increase the reaction rate.
  • BN-GFLP of the FLP structure can increase the CO 2 R efficiency through the synergistic effect of LA and LB.
  • physically mixed N-GN and B-GN showed a completely different CO 2 R performance from BN-GFLP (see FIG. 9 ).
  • LSV linear sweep voltammetry
  • a jig (Zig) type CBS cell was prepared. Under CO 2 bubbling, the jig-shaped CBS cell provided sufficient electrical energy to operate the light emitting diode (LED) device ( FIG. 10B ).
  • LED light emitting diode
  • CO 2 saturated seawater was prepared with CO 2 bubbling for 2 hours, and the pH was drastically reduced to 6.4.
  • the acidic seawater electrolyte was restored by the CO 2 R activity of the BN-GFLP cathode, and the pH gradually increased from 6.4 to 8.0 after 90 hours of CBS discharge ( FIG. 10C ).
  • the charge-discharge cycle stability of the CBS cell under CO 2 atmosphere was well maintained for 200 h with a lower discharge-charge overpotential than that of the GN catalyst ( FIG. 10D ).
  • the precipitation of CaCO 3 during the CO 2 R process in seawater can be caused by a local increase in pH, which is known to be a major stability problem of metallic CO 2 R catalysts.
  • CaCO 3 was not detected on the BN-GFLP surface, and only the C 2+ product was detected.
  • DFT density functional theory
  • BN-GFLP was confirmed to bind more strongly to CO 2 in the bidentate structures of NC and BO than in the monodentate structures of NC according to 11 B and 15 N MAS NMR analysis.
  • the bidentate structure can form carbon monoxide (CO) intermediates starting from CO 2 and HCO 3 ⁇ with a favorable Gibbs energy ( ⁇ G) of -1.4 eV.
  • ⁇ G Gibbs energy
  • Direct CC bond coupling between the CO intermediate and another CO 2 results in the formation of C 2 O 3 with a very stable ⁇ G of approximately -3.2 eV.
  • the energy levels of all species on BN-GFLP show Gibbs free binding energies favorable for the conversion of CO 2 to C 2+ such as ethanol and propanol.
  • a CO 2 reduction battery (CBS) system for reducing dissolved CO 2 in seawater was developed using a heteroelement doped graphic incomplete Lewis acid-base pair (GFLP) catalyst cathode according to the present invention, and 87.6% Faraday efficiency to recover acidic seawater.
  • the GFLP according to the present invention can provide a new double CO 2 bonding mode to provide a useful multi-carbon product in CO 2 R by exothermic CC coupling, and is environmentally friendly and can be used as an electrochemical catalyst in various fields Do.
  • the GFLP catalyst system according to the present invention is excellent in economic efficiency by using a catalyst that overcomes the limitations of durability and catalyst reforming of conventional catalysts without using expensive rare metals as a cathode.

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Abstract

La présente invention porte sur un catalyseur de réduction de N2 utilisant une paire acide-base de Lewis frustrée graphitique (GFLP) et, plus précisément, sur un catalyseur à haute performance et haute longévité pouvant synthétiser de l'ammoniac (NH3) propre en induisant un site multiactif dans une molécule de N2. De plus, la présente invention porte sur un système de batteries destiné à réduire le dioxyde de carbone dans l'eau de mer en utilisant un catalyseur à GFLP et, plus précisément, sur un système de batteries pouvant réduire le dioxyde de carbone dissous dans l'eau de mer en composés à plusieurs atomes de carbone comme l'éthanol et le propanol, et augmenter le pH pour empêcher ainsi l'acidification de l'eau de mer.
PCT/KR2021/011490 2020-08-31 2021-08-27 Catalyseur de réduction utilisant une paire acide-base de lewis frustrée graphitique (gflp) et système de réduction l'utilisant WO2022045816A1 (fr)

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KR1020200110604A KR102427845B1 (ko) 2020-08-31 2020-08-31 그래피틱 불완전 루이스 산-염기 쌍(gflp)을 이용한 질소 환원용 촉매제 및 이를 이용한 질소 환원 시스템
KR10-2020-0110604 2020-08-31
KR1020200110606A KR102427852B1 (ko) 2020-08-31 2020-08-31 그래피틱 불완전 루이스 산-염기 쌍(gflp)을 이용한 이산화탄소 환원용 촉매제 및 이를 이용한 해수 내 이산화탄소 환원 배터리 시스템
KR10-2020-0110606 2020-08-31

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CN114984982A (zh) * 2022-03-23 2022-09-02 安阳师范学院 一种高活性、高选择性、低价无毒的光热催化还原二氧化碳催化剂

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