EP4136277A1 - Material auf kupfer- und antimonbasis und elektrode zur selektiven umwandlung von kohlendioxid in kohlenmonoxid - Google Patents

Material auf kupfer- und antimonbasis und elektrode zur selektiven umwandlung von kohlendioxid in kohlenmonoxid

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Publication number
EP4136277A1
EP4136277A1 EP21724756.8A EP21724756A EP4136277A1 EP 4136277 A1 EP4136277 A1 EP 4136277A1 EP 21724756 A EP21724756 A EP 21724756A EP 4136277 A1 EP4136277 A1 EP 4136277A1
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EP
European Patent Office
Prior art keywords
antimony
electrode
copper
carbon
electrocatalyst
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EP21724756.8A
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English (en)
French (fr)
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EP4136277B1 (de
EP4136277C0 (de
Inventor
Juqin ZENG
Angelica Monica CHIODONI
Telemaco RINO
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Fondazione Istituto Italiano di Tecnologia
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Fondazione Istituto Italiano di Tecnologia
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Classifications

    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/037—Electrodes made of particles
    • 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
    • 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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • 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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon

Definitions

  • the present invention relates to a copper and antimony based material, and an electrode obtained from this material, useful for the electrochemical reduction of carbon dioxide to carbon monoxide with high efficiency and selectivity.
  • CO2 reduction can occur according to several proton-coupled electron transfer processes. CO2 reduction reactions for the production of compounds containing a single carbon atom and the electrochemical evolution of 3 ⁇ 4 are reported below as R1-R5, together with their standard potentials:
  • the result of the process is usually a mixture of products, which is difficult or not easy to use industrially.
  • the parasitic reaction of hydrogen evolution usually occurs in higher yield than the reduction of CO2 in aqueous electrolyte.
  • electrode materials are required that can provide high CO2 conversion efficiency and at the same time high selectivity towards a specific reaction product, in particular towards CO; materials of this kind are generally known in electrochemistry as electrocatalysts.
  • gold (Au), silver (Ag) and palladium (Pd) are considered the best metal electrocatalysts to convert CO2 into CO; however, these metals cannot be used on an industrial scale for this purpose due to their high cost and low availability.
  • Patent application US 2019/0127866 A1 describes an electrocatalyst material for converting CO2 to ethanol, comprising nanoparticles of copper or alloys thereof supported by nanometer-sized tips (“nanospikes”) of carbon doped with nitrogen, boron or phosphorus.
  • Copper alloys indicated as useful by this document are all those of the element with one or more elements selected from those in the Groups 3-15 of the periodic table. Alloys indicated as preferred are those between copper and an element selected from Ni, Co, Zn, In, Ag and Sn.
  • the electrocatalysts of this document exhibit higher selectivity for CO2 electroreduction than H2 evolution with high faradic efficiency in ethanol production, with a yield in this compound of at least 60% of the mixture; other species, such as carbon monoxide, are thus produced with yields not exceeding 40%.
  • the preparation of the doped carbon nanospikes makes the process not straightforward.
  • the materials in this paper are produced by dissolving soluble Cu(II) and Sb(III) salts in a suspension of carbon black in ethanol, adding a base (KOH) to the suspension and allowing the system to react for 6 hours at a temperature of 80 °C obtained with an oil bath; the precipitate obtained is then washed with water and ethanol and finally dried. The mixture of powders thus obtained is then distributed on a carbon paper obtaining electrodes.
  • the object of the present invention is to overcome the problems of the prior art, and in particular to provide an electrocatalyst material which allows to obtain in the electrochemical reduction reaction of C0 2 a CO yield and a selectivity towards this compound higher than with the electrocatalysts of the prior art.
  • Another object of the invention is to make available a cost-effective process for large-scale production of this electrocatalyst.
  • an electrocatalyst material comprising copper(I) oxide (Cu 2 0) containing antimony, wherein the amount of antimony is between 5% to 30% by weight.
  • This material is used in a finely divided form to produce electrodes for the electrochemical reduction of CO2, wherein said material is combined with an electroconductive material.
  • the invention in a second aspect thereof, relates to a process for the production of the electrocatalyst material, comprising the following steps: a) dissolving a copper(II) salt and an antimony(III) salt in a solvent selected from ethanol, ethylene glycol, acetylacetone, diethylamine, ethylenediamine, oleylamine, N,N-dimethylformamide, mixtures of these solvents with each other, with water or with aqueous solutions of D-glucose, hydrazine hydrate, amino acids or sodium carboxymethylcellulose, obtaining a solution; b) heating the solution in a microwave oven at a temperature between 180 and 230 °C for a time between 1 and 10 minutes; c) separating the precipitate from the solution and its drying.
  • a solvent selected from ethanol, ethylene glycol, acetylacetone, diethylamine, ethylenediamine, oleylamine, N,N-dimethylformamide, mixture
  • FIG. 1 shows photomicrographs obtained by field effect scanning electron microscope (FESEM) of various materials of the invention and three comparison materials;
  • XRD X-ray diffraction
  • - Fig. 3 shows spectra obtained by X-ray photoelectron spectroscopy (XPS) for Cu and Sb on a sample of the invention
  • Fig. 4 represents in a schematic form an electrolytic cell used to carry out the CO2 reduction tests reported in the Examples section;
  • the inventors have found that copper(I) oxide (CU2O, cuprous oxide) containing antimony in an amount between 5 and 30% by weight, when used to produce an electrode, enables the electrochemical reduction of CO2 to CO to be achieved with higher values of faradic efficiency and selectivity than known materials.
  • the compounds of the invention enable these results to be obtained by employing copper and antimony, which are inexpensive and widely available components.
  • the Cu 2 0/Sb materials of the invention have a Sb content between 5 and 30% by weight; preferred are the materials having a Sb content between 17.2 and 23.9% by weight.
  • Fig. 1 shows images obtained by field effect scanning electron microscope (FESEM) of samples of the invention with increasing Sb content (Figs. 1(b) to l(i)) and, for comparison, of three samples produced following the same method as the samples of the invention but containing only copper (Fig. 1(a)), only antimony (Fig. l(k)), and a sample not of the invention containing an amount of antimony of 36% (Fig. l(j)); in particular, the weight percentage amount of Sb in the samples of the invention prepared as described in Example 1, determined by chemical analysis, is as follows:
  • the materials of the invention with a Sb content of up to 26.4% by weight have a similar morphology to one another, and comprise powders in the form of essentially spherical particles with very narrow size distribution (all particles have a size of about 5 pm), composed of tightly packed nanoparticles.
  • Sb-rich particles and the formation of an isolated phase consisting of crystalline Sb 0 3 are observed (octahedral particles in Fig. l(j), to be compared with the image of pure antimony oxide in Fig. l(k)).
  • Energy dispersive X-ray spectroscopy (EDX) analysis indicates that Sb is uniformly distributed in the samples of the invention.
  • XRD analysis confirms that the material is essentially copper oxide.
  • Fig. 2 are shown, from top to bottom, the diffractograms for the sample containing only copper (diffractogram indicated with (Cu)), of the samples of the invention with increasing concentration of antimony (diffractograms from A to H), and of the sample containing 36% by weight of antimony (diffractogram indicated with (NI), which stands for "not of the invention”), respectively.
  • Figure 3 shows the typical spectra of the sample containing 17.2% by weight of Sb. From the XPS measurement (Fig. 3a) it appears that antimony is present in the sample in the form of Sb 3+ ions, as highlighted by the intense peaks relative to Sb 3ds /2 and Sb 3d 3/2 centred at 530.06 eV and 539.45 eV, respectively.
  • Fig. 3b shows instead the region of the XPS spectrum corresponding to the Cu 2p doublet; since the Cu 2p peak is difficult to deconvolve due to the overlap of numerous peaks, the Auger CuLMM region is also acquired (inset in Figure 3b).
  • the kinetic energy of the peak is 916.8 eV, which corresponds to Cu + .
  • the modified Auger parameter is about 1848.8 eV, which correlates with an average oxidation state of Cu(I). It is therefore evident that copper is present in the samples in the form of Cu + ion.
  • the electrocatalyst materials of the invention are poor electrical conductors per se, they are used in combination with conductive materials for the production of electrodes for C0 2 reduction.
  • the conductive material is in turn in the form of powders or other finely divided form.
  • a carbon-based material is generally used for this purpose, thanks to its low catalytic activity, for example carbon black, graphite, graphene, carbon nanotubes or mixtures thereof; the preferred conductive material is carbon black.
  • the electrocatalyst material of the invention and the conductive material are used in weight ratios between 9:1 and 19:1.
  • the mixture between the electrocatalyst material of the invention and the conductive material is distributed on a support, which may in turn be conductive or non-conductive.
  • a support which may in turn be conductive or non-conductive.
  • preferred supports are conductive carbon paper, conductive carbon cloth and metal mesh. Stabilization of the powder mixture on the support can be achieved with ionomers, i.e., ion conductive polymers, which form a containing and conductive film on the powders.
  • the invention relates to a process for the production of the electrocatalyst material, which consists of steps a) to c) above.
  • Step a) consists in dissolving a copper(II) salt and an antimony(III) salt in a solvent selected from ethanol, ethylene glycol, acetyl acetone, diethylamine, ethylenediamine, oleylamine, N,N-dimethylformamide, mixtures of these solvents with each other, with water or with aqueous solutions of D-glucose, hydrazine hydrate, amino acids and sodium carboxymethylcellulose.
  • a solvent selected from ethanol, ethylene glycol, acetyl acetone, diethylamine, ethylenediamine, oleylamine, N,N-dimethylformamide, mixtures of these solvents with each other, with water or with aqueous solutions of D-glucose, hydrazine hydrate, amino acids and sodium carboxymethylcellulose.
  • the most suitable salts for the purposes of the invention are acetates, sulfates and nitrates of both metals.
  • the starting salts are weighed to obtain the desired weight ratio of Cu:Sb, and thus the desired weight ratio of CU2O to Sb; the calculations necessary to determine the quantities to be used of the starting salts, given a desired final composition, are of simple executability for the average chemist.
  • the solution thus formed is heated in a microwave oven, within a sealed container of suitable material (e.g., Teflon) at a temperature between 180 and 230 °C for a time between 1 and 10 minutes.
  • suitable material e.g., Teflon
  • microwave heating in the presence of the aforementioned solvents results in the reduction of the Cu 2+ ion of the starting copper salt to Cu + ion present in the CU2O oxide.
  • ethylene glycol glycol functions as both a solvent and a reducing agent, and increasing temperature can increase its reducing capacity. Normally a temperature between 180 °C and 230 °C is suitable for the formation of Cu + from Cu 2+ in the given solution.
  • the precipitate formed in the microwave heating is separated from the liquid phase, e g., by filtration or centrifugation, washed with ethanol, and dried, e.g., by treatment in an oven at a temperature between 50 and 100 °C under vacuum or in an inert atmosphere.
  • the process of the invention differs from that of the article by Li et al. cited above in that microwave heating is used instead of conventional heating, that as said results in the reduction of the Cu 2+ ion of the starting copper salt and the formation of the CU2O phase.
  • Nafion ® 117 solution (Sigma-Aldrich, catalogue no. 31175-20-9; Nafion is a registered trademark of E. I. du Pont de Nemours and Company), purity: ⁇ 5% in a mixture of lower aliphatic alcohols and water
  • Electron microscope images and energy dispersive X-ray spectroscopy (EDX) analyses were obtained with a FESEM Supra 40 (Zeiss) equipped with a detector (Oxford Instruments Si(Li)) for energy dispersive X-ray spectroscopy (EDX) analyses.
  • XRD diffractograms were recorded in the 2Q 25-80° range with a step (2Q) of 0.017° and a counting time of 0.45 seconds.
  • Analyses of gaseous products derived from CO2 electroreduction were performed in real time with an INFICON Fusion ® microgascromatograph (pGC) equipped with two channels with a 10 m Rt-Molsieve 5A column and an 8 m Rt-Q-Bond column, respectively, and thermal conductivity microdetectors (micro-TCD).
  • pGC INFICON Fusion ® microgascromatograph
  • This example relates to the synthesis of the materials of the invention.
  • Example 1 Seven samples of materials of the invention with different Sb contents were prepared using copper acetate and antimony acetate as precursors, used in the amounts shown in Table 1. The samples of the invention are indicated as A-H. For comparison, a sample from copper acetate alone (sample referred to as “Cu” in the table), a sample from antimony acetate alone (sample “Sb”), and a sample of mixed Cu/Sb composition not of the invention (sample “NT’) were also produced in the identical manner described below.
  • Cu copper acetate alone
  • Sb sample from antimony acetate alone
  • NT sample of mixed Cu/Sb composition not of the invention
  • the last column of the table shows the values of Sb content in each of the samples of the invention, obtained by ICP- OES analysis (the data for the Cu and Sb samples are not shown because naturally in these two cases the analysis for the determination of the percentage content of Sb was not carried out).
  • Table 1 The indicated amounts of precursors were dissolved in 40 ml of ethylene glycol and 5 ml of double distilled H 2 0 (resistivity about 18 MW ⁇ ah). Each solution was then transferred to a Teflon container (volume 100 mL). The Teflon container was sealed, placed in a microwave oven (Milestone, STARTSynth, HPR-1000-10S segment with temperature and pressure control), heated to 220 °C and then maintained at this temperature by powering the oven with a maximum power of 900 W for a total irradiation time of 2 minutes. After cooling to room temperature, the suspended product in each container was separated by centrifugation and washed twice with double-distilled FhO and subsequently once with ethanol. Each powder sample was finally dried under vacuum at 60 °C overnight.
  • the samples of the invention were examined by scanning electron microscopy and EDX analysis to determine the morphology (also for Cu and Sb samples) and the antimony distribution, by X-ray diffraction to determine the crystal structure (also for Cu and Sb samples) and by XPS to determine the oxidation state of Cu and Sb; the results of the three analyses have been discussed above with reference to Figures 1, 2 and 3 respectively.
  • This example relates to the production of electrodes for electrochemical CO2 reduction using the materials of the invention (samples A-H) and the three comparison materials (samples Cu, Sb and NI).
  • Each electrode was prepared by mixing 10 mg of sample A-H, Cu, Sb or NI, 1 mg of carbon black from acetylene, 90 m ⁇ ofNafion ® 117 solution and 320 m ⁇ of isopropanol. Each mixture was sonicated for 30 minutes until a uniform suspension was obtained. Each suspension was then used to coat a carbon paper covered with a gas permeable layer (GDL; SIGRACET 28BC, SGL Technologies); the geometric area of each electrode was 1.5 cm 2 . The obtained electrode was dried at 60 °C overnight to evaporate the solvents. The electrocatalyst loading on each electrode was approximately 3.0 mg cm 2 .
  • the electrodes thus obtained are referred to in the following by the abbreviations E x , where the subscript x corresponds to the sample A-H, Cu, Sb or NI used for its production.
  • This example refers to the measurement of the CO2 reduction efficiency of the electrodes prepared in the previous Example.
  • Electrochemical measurements were performed with a cell having the configuration schematically shown in Fig. 4; the cell as a whole, 10, is shown in the figure enclosed by a discontinuous line.
  • the cell has two compartments separated by an ion exchange membrane 11 (Nafion ® NI 17 membrane, Sigma- Aldrich), and adopts a three- electrode configuration. Each compartment has a total volume of 10 ml and contains 7 ml of electrolyte, and thus 3 ml of headspace.
  • the reference electrode, 12, is an Ag/AgCl electrode (1 mm, lossless LF-1) that is inserted into the cathode compartment.
  • the counter electrode, 13, is a Pt foil (Goodfellow, 99.95%).
  • the working electrode i.e., the electrode of the invention
  • element 14 An aqueous solution of 0.1 M KHCO3 was used as the electrolyte solution.
  • gaseous CO2 is fed into both half-cells from the lower part of the two compartments, while the mixture of products on which the results are evaluated is extracted from the cathode compartment (on the right in the figure); most of this mixture is sent to the separation and purification stage (performed with methods known in the field and not described in this text), while a fraction of the mixture is sent to the analysis.
  • Chronoamperometric measurements were performed using a CHI760D electrochemical workstation (CH Instruments, Inc., USA).
  • FE faradic efficiency
  • FE (%) nNF/Q x 100
  • n is the number of electrons transferred in the faradic process (for the reduction of CO2 to CO and to H2, n is 2 as shown in the reactions R1 and R5 above)
  • N is the moles of a product generated in a specific reaction period
  • F is the faradic constant (96485.33 C/mol)
  • Q is the total charge in a specific reaction period.
  • the Es t , electrode does not produce CO at either test potential.
  • the Cu electrode has poor selectivity for CO, with FEco values below 10%.
  • the comparison ENI electrode shows poor selectivity values towards CO, probably because it is formed by a mixture containing only a small amount of active material together with a completely inactive material (antimony oxide).
  • the E A -E H electrodes of the invention exhibit high selectivity towards CO, with FEco above 80% for all A-H materials at -0.79 V.
  • D and E show excellent selectivity values for CO, of at least 90% at both potentials.
  • This example relates to the measurement of CO2 reduction with an electrode of the invention at various potentials.
  • the E D electrode which gave the best results in Example 3, was tested at five different potential values ranging from -0.69 V to -1.09 V. In each test, the evolution of CO and Eh over time was evaluated during tests lasting between one and two hours.
  • Figures 5(a) to 5(e) report tests performed at the following potentials: 5(a) -0.69 V; 5(b) -0.79 V; 5(c) -0.89 V; 5(d) -0.99 V; 5(e) -1.09 V.
  • the tests at -0.79 V and -0.99 V are the same as those whose results have already been reported in the previous example.
  • the results of these tests are provided in summary form in the graph in Fig. 5(f), in which the faradic efficiency values for CO and Eh, taken when the reduction process has reached steady state, are reported at all evaluated potentials.
  • the electrocatalyst materials of the invention catalyze the electrochemical reduction of CO2 with high selectivity toward CO.
  • the materials of the invention then offer further advantages.
  • antimony and copper, and the compounds thereof used as precursors in the process of the invention are inexpensive materials; moreover, the production of these materials is simple and easily scalable at an industrial level, also because it does not employ toxic or harmful products; the invention therefore offers a technically viable and competitive alternative to the use of metals such as Au, Ag and Pd.
  • the materials of the invention are in powder form, they can be used in reactors with various configurations as a gas diffusion electrode (GDE) and different sizes.
  • GDE gas diffusion electrode

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Catalysts (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
EP21724756.8A 2020-04-15 2021-04-14 Material auf kupfer- und antimonbasis und elektrode zur selektiven umwandlung von kohlendioxid in kohlenmonoxid Active EP4136277B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102020000007948A IT202000007948A1 (it) 2020-04-15 2020-04-15 Materiale ed elettrodo a base di rame e antimonio per la conversione selettiva di biossido di carbonio a monossido di carbonio
PCT/IB2021/053074 WO2021209920A1 (en) 2020-04-15 2021-04-14 Copper and antimony based material and electrode for the selective conversion of carbon dioxide to carbon monoxide

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EP4136277A1 true EP4136277A1 (de) 2023-02-22
EP4136277B1 EP4136277B1 (de) 2024-05-22
EP4136277C0 EP4136277C0 (de) 2024-05-22

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CN114293216B (zh) * 2021-11-25 2023-04-28 广州大学 一种CO2电化学还原制CO的Ni@NC-X电催化剂的制备方法
CN114799197B (zh) * 2022-04-13 2023-01-24 电子科技大学 铜锑单原子合金催化剂的制备方法和二氧化碳还原应用

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US10329677B2 (en) * 2016-11-01 2019-06-25 King Fahd University Of Petroleum And Minerals Method for electrochemical reduction of carbon dioxide

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IT202000007948A1 (it) 2021-10-15

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