EP4136277B1 - Matériau à base de cuivre et d'antimoine et électrode pour la conversion sélective de dioxyde de carbone en monoxyde de carbone - Google Patents

Matériau à base de cuivre et d'antimoine et électrode pour la conversion sélective de dioxyde de carbone en monoxyde de carbone Download PDF

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EP4136277B1
EP4136277B1 EP21724756.8A EP21724756A EP4136277B1 EP 4136277 B1 EP4136277 B1 EP 4136277B1 EP 21724756 A EP21724756 A EP 21724756A EP 4136277 B1 EP4136277 B1 EP 4136277B1
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antimony
electrode
copper
carbon
electrocatalyst
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EP4136277A1 (fr
EP4136277C0 (fr
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Juqin ZENG
Angelica Monica CHIODONI
Telemaco RINO
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Fondazione Istituto Italiano di Tecnologia
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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
    • 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
    • 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
    • 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.
  • 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 CO 2 in aqueous electrolyte.
  • electrode materials are required that can provide high CO 2 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 CO 2 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 CO 2 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 CO 2 electroreduction than H 2 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 CO 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 O) 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 CO 2 , wherein said material is combined with an electroconductive material.
  • the invention relates to a process for the production of the electrocatalyst material, comprising the following steps:
  • the inventors have found that copper(I) oxide (Cu 2 O, cuprous oxide) containing antimony in an amount between 5 and 30% by weight, when used to produce an electrode, enables the electrochemical reduction of CO 2 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 materials of the invention will generally be referred to in the following by the notation CuzO/Sb, regardless of the specific composition.
  • the Cu 2 O/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 1(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. 1(k) ), and a sample not of the invention containing an amount of antimony of 36% ( Fig.
  • FESEM field effect scanning electron microscope
  • 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: - Fig. 1(b) : 5.2; - Fig. 1(c) : 9.4; - Fig. 1(d) : 13.6; - Fig. 1(e) : 17.2; - Fig. 1(f) : 20.1; - Fig. 1(g) : 23.9; - Fig. 1(h) : 25.2 - Fig. 1(i) : 26.4.
  • 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 ⁇ m), composed of tightly packed nanoparticles.
  • Sb-rich particles and the formation of an isolated phase consisting of crystalline Sb 2 O 3 are observed (octahedral particles in Fig. 1(j) , to be compared with the image of pure antimony oxide in Fig. 1(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.
  • FIG. 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 3d 5/2 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 CO 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.
  • Examples of 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.
  • ionomers i.e., ion conductive polymers
  • 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, 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 and sodium carboxymethylcellulose.
  • 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 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 CuzO 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 Cu 2 O 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 Cu 2 O phase.
  • 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 2 ⁇ 25-80° range with a step (20) of 0.017° and a counting time of 0.45 seconds.
  • This example relates to the synthesis of the materials 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 Sample Amount of precursor (mg) Sb content (% by weight) Cu(OAc) 2 ⁇ xH 2 O Sb(OAc) 3 Cu 900 0 / A 900 164 5.2 B 900 246 9.4 C 900 295 13.6 D 900 328 17.2 E 900 410 20.1 F 900 470 23.9 G 900 492 25.2 H 900 600 26.4 NI 900 820 36.0 Sb 0 900 /
  • the indicated amounts of precursors were dissolved in 40 ml of ethylene glycol and 5 ml of double distilled H 2 O (resistivity about 18 M ⁇ •cm). 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 H 2 O 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 CO 2 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 ⁇ l of Nafion ® 117 solution and 320 ⁇ l 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 CO 2 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 ® N117 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 KHCO 3 was used as the electrolyte solution.
  • gaseous CO 2 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
  • the E Sb electrode does not produce CO at either test potential.
  • the Cu electrode has poor selectivity for CO, with FE CO values below 10%.
  • the comparison E NI 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 CO 2 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 H 2 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 H 2 , taken when the reduction process has reached steady state, are reported at all evaluated potentials.
  • FE H2 values remain low ( ⁇ 9%) from -0.69 V to -1.09 V. No other gas phase products other than CO and H 2 were detected. Liquid products (e.g., HCOOH) were not quantified, but can be assumed to be present in very small or negligible amounts, since the total faradic efficiency for CO and H 2 measured in all tests is around 100%.
  • Liquid products e.g., HCOOH
  • the electrocatalyst materials of the invention catalyze the electrochemical reduction of CO 2 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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Claims (12)

  1. Matériau d'électrocatalyseur constitué d'oxyde de cuivre(I) (Cu2O) contenant de l'antimoine, dans lequel la quantité d'antimoine est entre 5 % et 30 % en poids.
  2. Matériau d'électrocatalyseur selon la revendication 1, dans lequel la quantité d'antimoine est entre 5,2 % et 26,4 % en poids.
  3. Matériau d'électrocatalyseur selon la revendication 2, dans lequel la quantité d'antimoine est entre 17,2 % et 23,9 % en poids.
  4. Électrode comprenant une poudre d'un matériau d'électrocatalyseur selon l'une quelconque des revendications 1 à 3 et un matériau conducteur déposé sur un support, dans un rapport en poids entre le matériau d'électrocatalyseur et le matériau conducteur d'entre 9:1 et 19:1.
  5. Électrode selon la revendication 4, dans laquelle le matériau conducteur se présente sous la forme d'une poudre.
  6. Électrode selon l'une quelconque des revendications 4 ou 5 dans laquelle le matériau conducteur est à base de carbone.
  7. Électrode selon la revendication 6, dans laquelle le matériau conducteur est choisi parmi le noir de carbone, le graphite, le graphène, les nanotubes de carbone et les mélanges de ceux-ci.
  8. Électrode selon l'une quelconque des revendications 4 à 7 dans laquelle le support est sélectionné parmi un papier de carbone conducteur, un tissu de carbone conducteur et un treillis métallique.
  9. Électrode selon l'une quelconque des revendications 4 à 8 dans laquelle la poudre du matériau d'électrocatalyseur et éventuellement du matériau conducteur sont stabilisées sur le support avec un ionomère.
  10. Processus pour la production du matériau d'électrocatalyseur selon l'une quelconque des revendications 1 à 3, comprenant les étapes suivantes :
    a) la dissolution d'un sel de cuivre(II) et d'un sel d'antimoine(III) dans un solvant sélectionné parmi l'éthanol, l'éthylène glycol, l'acétylacétone, la diéthylamine, l'éthylènediamine, l'oléylamine, le N,N-diméthylformamide, les mélanges de ces solvants les uns avec les autres, avec de l'eau ou avec des solutions aqueuses de D-glucose, d'hydrate d'hydrazine, d'acides aminés ou de carboxyméthylcellulose sodique, en obtenant une solution ;
    b) le chauffage de la solution dans un four à micro-ondes à une température entre 180 et 230 °C pendant une durée entre 1 et 10 minutes ;
    c) la séparation du précipité à partir de la solution et son séchage.
  11. Processus selon la revendication 10, dans lequel le sel de cuivre(II) est sélectionné parmi l'acétate, le sulfate et le nitrate, et le sel d'antimoine(III) est sélectionné parmi l'acétate, le sulfate et le nitrate.
  12. Procédé pour la réduction électrochimique sélective de CO2 en CO, comprenant l'utilisation d'une électrode selon l'une quelconque des revendications 4 à 9 à un potentiel entre -0,69 V et -1,09 V.
EP21724756.8A 2020-04-15 2021-04-14 Matériau à base de cuivre et d'antimoine et électrode pour la conversion sélective de dioxyde de carbone en monoxyde de carbone Active EP4136277B1 (fr)

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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 (fr) 2020-04-15 2021-04-14 Matériau à base de cuivre et d'antimoine et électrode pour la conversion sélective de dioxyde de carbone en monoxyde de carbone

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EP4136277A1 EP4136277A1 (fr) 2023-02-22
EP4136277B1 true EP4136277B1 (fr) 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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US20170314148A1 (en) 2016-05-02 2017-11-02 Ut-Battelle, Llc Electrochemical catalyst for conversion of co2 to ethanol
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EP4136277A1 (fr) 2023-02-22
US20230167563A1 (en) 2023-06-01
EP4136277C0 (fr) 2024-05-22
IT202000007948A1 (it) 2021-10-15

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