WO2015148796A1 - Système et procédé de conversion électrochimique de dioxyde de carbone en monoxyde de carbone - Google Patents

Système et procédé de conversion électrochimique de dioxyde de carbone en monoxyde de carbone Download PDF

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WO2015148796A1
WO2015148796A1 PCT/US2015/022734 US2015022734W WO2015148796A1 WO 2015148796 A1 WO2015148796 A1 WO 2015148796A1 US 2015022734 W US2015022734 W US 2015022734W WO 2015148796 A1 WO2015148796 A1 WO 2015148796A1
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tin
electrolyte
ions
electrode
cathode
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PCT/US2015/022734
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Joel Rosenthal
Jonnathan Medina-Ramos
John L. DIMEGLIO
Thomas P. KEANE
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Joel Rosenthal
Jonnathan Medina-Ramos
Dimeglio John L
Keane Thomas P
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Priority to US15/129,701 priority Critical patent/US20170130347A1/en
Publication of WO2015148796A1 publication Critical patent/WO2015148796A1/fr

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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • 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
    • 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
    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used

Definitions

  • the present invention pertains to systems and processes useful for the electrochemical conversion of carbon dioxide to carbon monoxide.
  • Storage of solar and other sources of renewable electricity may be enabled by the endothermic production of chemical fuels such as H 2 or reduced carbon-containing compounds via the electrochemical reduction of H 2 0 or C0 2 , respectively.
  • chemical fuels such as H 2 or reduced carbon-containing compounds
  • the renewable production of liquid fuels provides a clear route to energy supply and distribution and addresses energy needs associated with transportation, which account for more than 20% of US energy demand.
  • liquid fuels are compatible with existing infrastructure for energy supply and distribution.
  • the societal importance and economic value of liquid fuel resources clearly highlights the need for new platforms that enable the sustainable generation of liquid fuels from C0 2 , and distinguishes C0 2 activation and reduction chemistry as a critical area of focus in the fields of renewable energy storage and molecular energy conversion.
  • CO can be reacted with H 2 0 via the water-gas shift (WGS) reaction to generate H 2 .
  • GSS water-gas shift
  • This CO/H 2 mixture (synthesis gas) can be used to generate synthetic petroleu m and liquid fuels using existi ng Fischer-Tropsch (FT) methods for di rect integration i nto existing energy storage and distribution networks.
  • Carbon monoxide is a valuable commodity chemical that is required for the production of many other products, including plastics, solvents and acids. It can also be used directly to prepare other valuable reagents such as hydrogen via the industrial Water- Gas-Shift process. Also, carbon monoxide is the principal feedstock for the industrial Fischer-Tropsch process, which allows for the large-scale production of synthetic petroleum.
  • Carbon dioxide is also a waste product from conventional power plants. Collection and sequestration of carbon dioxide is commonplace. The ability to convert this waste product to a commodity chemical such as carbon monoxide can offset the cost of sequestration and is of interest to current power producers. Moreover, an attractive strategy for storage of renewable energy resources such as solar or wind is electrochemical fuel synthesis from carbon dioxide. This technology has not yet been realized commercially due to the lack of electrode systems capable of driving the conversion of carbon dioxide to fuels or fuel precursors. Thus, it would be advantageous to develop technology which bridges this gap by allowing electricity from a photovoltaic assembly, wind turbine, etc. to be used to drive fuel production.
  • Carbon monoxide is required for commodity chemical synthesis, which includes some pharmaceuticals and other species that require hydroformylation chemistry. Since carbon monoxide is an expensive and toxic feedstock, the ability to generate small quantities of this chemical on demand allows it to be prepared as needed as opposed to relying on large stockpiles of carbon monoxide produced using conventional methods. This strategy would also reduce costs associated with safety and carbon monoxide use.
  • the present invention will permit the production of carbon monoxide, which is a valuable commodity chemical and fuel precursor, from atmospheric carbon dioxide or flue gas from a power plant. Since this energy storing process is driven electrochemically, the invention allows carbon monoxide production to be driven using conventional electric and/or renewable energy resources such as wind or solar, Taken together, this invention will permit storage of solar, wind or conventional electric energy by converting carbon dioxide to carbon monoxide and liquid fuels.
  • One aspect of the invention provides an electrolytic system for conversion of carbon dioxide to carbon monoxide, the system comprising an electrode comprised of tin and a source of electrical current in electrical communication with the electrode.
  • the electrode comprised of tin may be a cathode and the system may further comprise an anode comprised of platinum (or other suitable anode material such as an iridium oxide, ruthenium oxide, iron oxide, cobalt oxide, nickel oxide and/or mixed metal oxide) and an electrolyte (e.g., an ionic liquid or an organic electrolyte containing one or more salts dissolved therein) in fluid communication with at least one of the cathode comprised of tin or the anode comprised of platinum.
  • the cathode may be in fluid communication with a first electrolyte, the anode is in fluid communication with a second electrolyte, and the first electrolyte and the second electrolyte are the same as or different from each other.
  • Another aspect of the invention provides an electrolytic system for conversion of carbon dioxide to carbon monoxide, wherein the system comprises a cathode comprised of tin, an anode comprised of platinum (or other suitable anode material), an electrolyte (e.g., an ionic liquid or an organic electrolyte) in fluid communication with at least one of the cathode and the anode, and a source of electrical current in electrical communication with the cathode and the anode.
  • the cathode and the anode are present in a single compartment.
  • the cathode is present in a first compartment, the anode is present in a second compartment, and the first and second compartment are separated by an ion conducting bridge such as a porous glass frit or polymeric membrane.
  • the cathode may be in fluid communication with a first electrolyte, the anode may be in fluid communication with a second electrolyte, and the first electrolyte and the second electrolyte may be the same as or different from each other.
  • an electrolyte which is an ionic liquid that may comprise one of trifluoromethanesulfonate (triflate) ions, borate ions, phosphate ions, imidazolium ions, pyridinium ions, pyrrolidinium ions, ammonium ions, phosphonium ions, halides and combinations thereof.
  • the electrolyte may also be an organic liquid comprising one of acetonitrile, dimethylformamide, dimethyl sulfoxide, carbonates, bistriflimide, triflate, tosylate and combinations thereof.
  • the electrolyte is comprised of at least one organic solvent (such as acetonitrile) and at least one imidazolium salt (such as a 1,3-dialkyl imidazolium salt).
  • Yet another aspect of the invention provides a method for electrochemically converting carbon dioxide to carbon monoxide, wherein the method comprises electrolyzing carbon dioxide in an electrolytic system comprising an electrode comprised of tin and a source of electrical current in electrical communication with the electrode.
  • the electrolytic system may further comprise an anode comprised of platinum, an electrolyte in fluid communication with at least one of the cathode and the anode, and a source of electrical current in electrical communication with the cathode and the anode, whereby carbon dioxide may be continuously introduced into the electrolytic system.
  • Yet another aspect of the invention provides a method of making an electrode comprised of tin, wherein the method comprises electrodepositing a tin-containing material onto a surface of an inert electrode substrate and wherein the method may further comprise reducing a solution comprising a precursor to the tin-containing material (such as a tin(II) salt).
  • the inert electrode substrate may be a nickel electrode or other conducting electrode.
  • the invention provides an electrode comprised of tin.
  • Figure la shows a single cell arrangement of an electrolytic system
  • Figure lb shows a dual cell arrangement of an electrolytic system.
  • Figure 2a shows a cyclic voltammogram (CV) for a nickel electrode in a solution of 1.0 M hydrochloric acid (HCI) containing 20 mM Sn 2+
  • Figure 2b shows an SEM image of the tin modified nickel electrode.
  • Figure 3a shows a cyclic voltammogram (CV) for a tin modified nickel electrode in a MeCN solution containing 20 mM tin (II) triflate ([Sn(OTf) 2 ]) + 100 mM tetrabutylammonium hexafluorophosphate (TBAPF 6 ), and Figure 3b shows an SEM image of the tin modified nickel electrode.
  • CV cyclic voltammogram
  • Figure 4a and Figure 4b show CV traces recorded for Sn-modified and bare nickel electrodes in acetonitrile (MeCN) containing 100 mM TBAPF 6 or 100 mM l-butyl-3- methylimidazolium trifluoromethane sulfonate ([BMIM]OTf), under an atmosphere of N 2 or C0 2 , for tin-based carbon monoxide evolving catalysts (Sn-CMECs) prepared in organic (MeCN) and aqueous Sn 2+ solutions, respectively.
  • Figure 4c shows the representative total current density (j to t) profiles for Sn-CMEC at -1.95 V in MeCN, for the results of Figure 4a and Figure 4b.
  • Figure 5 shows Tafel plots for Sn-CMEC on nickel electrodes.
  • Tin (chemical symbol: Sn) represents an attractive material for development of heterogeneous C0 2 reduction catalysts, as this metal is relatively non-toxic and has a small environmental impact. Moreover, the ability of Sn to drive electrochemical conversion of C0 2 to CO would represent an important development in the fields of C0 2 electrocatalysis and renewable energy conversion.
  • Cathodes useful in the present invention are electrodes containing metallic tin (Sn°) or metastable materials such as SnO and Sn0 2 .
  • the cathode may, for example, be a tin modified electrode wherein a Sn° and/or Sn 2+ / Sn 4+ containing film(s) has been deposited on a substrate, such as a nickel substrate.
  • the tin film may be deposited electrochemically or via other chemical means including electroless plating, sputtering, CVD (Chemical Vapor Deposition), ALD (Atomic Layer Deposition) and the like. Tin bulk electrodes may also be utilized.
  • Anodes useful in the present invention include electrodes comprised of platinum or metal oxide-based materials, such as iridium oxides, ruthenium oxides, iron oxides, cobalt oxides, nickel oxides and the like (including mixed metal oxides).
  • the platinum may, for example, be in the form of platinum black.
  • Platinum black (Pt black) is a fine powder of platinum with good catalytic properties.
  • Platinized anodes wherein an electrode substrate (such as a carbon substrate or metallic substrate, such as a platinum or titanium substrate, which could be in the form of a mesh or screen) is covered with a thin film of platinum black are particularly useful. In common practice, the platinum black is either sprayed or hot pressed onto the substrate. A suspension of platinum black and carbon powder in an aqueous solution may, for example, be applied to the substrate surface. Electrodeposition (electroplating) techniques may also be employed to provide a platinized anode.
  • the working electrodes employed for the electrolytic system of the invention may, for example, include either a tin plate, a piece of tin foil or a tin-modified electrode as the cathode and a platinized mesh as the anode.
  • Tin foil electrodes may be preconditioned, for example, by sequential sonication in acetone, deionized water and acetonitrile.
  • Tin plates may be preconditioned, for example, by polishing with a slurry of 0.05 micron alumina powder in water. Residual alumina may be rinsed from the tin surface with Millipore water, and the plate then sonicated in Millipore water for five minutes prior to use.
  • Tin-modified cathodes include cathodes having a surface layer containing tin on top of a conducting support other than metallic tin and may be prepared, for example, by submersing any conducting support such as a glassy carbon support, graphite support, carbon fiber support, carbon paper support, or carbon cloth support or a metallic support such as a nickel plate, nickel foil or a piece of metal in an acidic solution containing any water soluble tin(II) salt such as tin(II) chloride (0.5 to 40 mM) and a protic acid such as hydrochloric acid (0.2 to 2 M).
  • any conducting support such as a glassy carbon support, graphite support, carbon fiber support, carbon paper support, or carbon cloth support or a metallic support such as a nickel plate, nickel foil or a piece of metal
  • a metallic support such as a nickel plate, nickel foil or a piece of metal in an acidic solution containing any water soluble tin(II) salt such as tin(II)
  • the soluble tin(II) salt functions as a precursor to the tin-containing film deposited on the surface of the conducting support, wherein the tin(II) salt gets reduced during electrolysis.
  • the conducting substrate may then be preconditioned by cycling the applied potential (10 cycles) from 0 to -0.66 V vs. standard calomel electrode (SCE) at a sweep rate of 100 mV/sec. Controlled potential electrolysis at -0.49 V vs SCE may be carried out on the quiescent solution until ⁇ 1 C of charge is passed for each square centimeter of submersed substrate.
  • the tin-modified electrode may then be sequentially rinsed with 1 M hydrochloric acid, illipore water, and acetonitrile prior to being dried under a gentle stream of nitrogen.
  • tin-modified cathodes may be prepared, for example, by submersing any conducting support such as a glassy carbon support, nickel plate, nickel foil or a piece of metal in an organic solvent solution (e.g., an acetonitrile, dimethylformamide or other polar organic solvent solution) containing any soluble tin(II) compound such as tin(II) triflate (0.5 to 40 mM) and a supporting electrolyte such as a quaternary ammonium hexafluorophosphate (e.g., tetrabutylammonium hexafluorophosphate) (0.02 to 2 M) or an ionic liquid such as an imidazolium salt-based ionic liquid (1 to 200 mM)(in particular, a 1,3-dialkyl imidazolium triflate).
  • organic solvent solution e.g., an acetonitrile, dimethylformamide or other polar organic solvent solution
  • the conducting substrate may then be preconditioned by cycling the applied potential ( 10 cycles) from -0.26 to -2.26 V vs. SCE at a sweep rate of 100 mV/sec. Controlled potential electrolysis at -1.56 V vs SCE may be carried out on the quiescent solution until ⁇ 1 coulomb ⁇ of charge is passed for each square centimeter of submersed substrate.
  • a thin tin-containing film derived from soluble tin (II) compound as a precursor may be electrodeposited to a desired total thickness, for example, from 0.2 to 4 C/cm 3 .
  • the tin-modified electrode may then be sequentially rinsed with acetonitrile prior to being dried under a gentle stream of nitrogen.
  • the plating of tin onto the conducting substrate can be achieved in situ, under a C0 2 atmosphere, at an applied potential around -1.96 V vs. an SCE electrode.
  • the tin-modified cathode may be prepared ex situ in a quiescent polar organic solvent solution (e.g., MeCN solution) containing soluble tin(II) salt and a quaternary ammonium hexafluorophosphate, under a nitrogen atomosphere, by holding the potential around -1.56 V vs. SCE electrode until about 1.0 C of charge is passed for each square centimeter of submersed substrate,
  • a quiescent polar organic solvent solution e.g., MeCN solution
  • soluble tin(II) salt and a quaternary ammonium hexafluorophosphate under a nitrogen atomosphere
  • a tin-modified electrode suitable for use in electrochemically converting carbon dioxide to carbon monoxide may be made by a method comprising contacting an inert electrode substrate with a solution comprised of at least one tin(II) salt and polarizing the inert electrode substrate at a potential effective to electrodeposit a tin-containing material onto a surface of the inert electrode substrate.
  • Such electrodeposition may be performed either ex situ or in situ.
  • the atmosphere above the solution may be an inert atmosphere (e.g., a nitrogen atmosphere) or a C0 2 atmosphere.
  • the solution may comprise one or more polar organic solvents, such as acetonitrile.
  • the solution may be an aqueous solution.
  • the solution may further comprise an acid, in particular a strong protic acid such as HCI (e.g., at a concentration of 0.2 to 2 M).
  • the tin(II) salt may be a triflate, nitrate, carboxylate (e.g., acetate), halide or sulfate salt or the like.
  • the concentration of tin (II) salt in solution may be 0.5 to 50 mM, for example.
  • the solution may additionally comprise a quaternary ammonium phosphate, such as tetrabutylammonium phosphate, typically at a concentration of 10 to 500 mM.
  • the solution may alternatively comprise an ionic liquid, in particular an imidazolium-based ionic liquid (e.g., a 1,3-disubstituted imidazolium salt, such as a triflate or tetrafluoroborate salt of a 1,3-dialkyl imidazolium), typically at a concentration of 1 to 300 mM.
  • an imidazolium-based ionic liquid e.g., a 1,3-disubstituted imidazolium salt, such as a triflate or tetrafluoroborate salt of a 1,3-dialkyl imidazolium
  • the potential applied during electrodeposition may, for example, be from -0.1 V to -3.0 V versus SCE. Controlled potential electrolysis (CPE) may be employed.
  • CPE Controlled potential electrolysis
  • the electrolysis device of the invention can be comprised of either a single or dual cell configuration, as shown in Figures la and lb, respectively.
  • the cathode, anode and reference electrodes are all immersed in a single housing containing an electrolyte solution.
  • the dual cell configuration incorporates an ion conducting bridge such as a glass or sulfonated tetrafluoroethylene based fluoropolymer (e.g., Nafion ® ) membrane, which separates the cathode from the anode and is generally more efficient for carbon monoxide electrosynthesis.
  • an ion conducting bridge such as a glass or sulfonated tetrafluoroethylene based fluoropolymer (e.g., Nafion ® ) membrane, which separates the cathode from the anode and is generally more efficient for carbon monoxide electrosynthesis.
  • the ion conducting bridge may be configured to be liquid permeable but to substantially prevent gas flow or transport from the cathode side of the ion conducting bridge to the anode side of the ion conducting bridge and vice versa, including substantially preventing the flow of gas dissolved in the electrolyte or after nucleation of gas bubbles.
  • a reference electrode e.g., a Ag/AgCI or SCE reference electrode
  • the electrolytic cell may be configured to be pressurized, to permit the desired electrolysis of carbon dioxide to yield carbon monoxide to proceed at a pressure above atmospheric pressure.
  • the electrolyzer may be filled with an electrolyte solution that is comprised as follows. Acetonitrile containing 0-0.10 M tetrabutylammonium hexafluorophosphate or other quaternary ammonium salt(s) and 10- 100 mM of one or more imidazolium-based ionic liquid additive such as the triflate (and/or tetrafluoroborate, chloride, bromide, and/or acetate) salts of 1,3-disubstituted imidazolium (such as l-ethyl-3-methyl imidazolium salts and l-butyl-3-methyl imidazolium salts, in particular l-ethyl-3-methyl imidazolium triflate, l-ethyl-3-methyl imidazolium tetrafluoroborate, l-butyl-3-methyl imidazolium triflate, and l-butyl-3-methyl imidazolium
  • dimethylformamide, dimethyl sulfoxide, carbonates (e.g., ethylene carbonate, propylene carbonate, dialkyl carbonate), dimethyl sulfone, sulfolane, gamma butyrolactone, nitriles (propionitrile and buyronitrile, for example), esters (e.g., methyl acetate) and other polar organic solvents and mixtures thereof can be substituted for acetonitrile. Observed current densities and efficiencies are typically optimal in acetonitrile, however. If an ionic liquid additive is employed, the quaternary ammonium hexafluorophosphate can be excluded from the electrolytic cell .
  • the 1,3-disubstituted imidazolium may be an imidazolium that is substituted at the 1 and 3 positions with substituents (which may be the same as or different from each other) selected from the group consisting of alkyl groups (e.g., C1-C8 alkyl groups including methyl, ethyl, propyl, butyl, octyl and isomers thereof), aryl groups and halogenated derivatives thereof.
  • the 2 position of the imidazolium may be similarly substituted, as in 1- butyl-2,3-dimethylimidazolium (BMMIM).
  • BMMIM 1- butyl-2,3-dimethylimidazolium
  • the heterocyclic ring of the imidazolium may be substituted with one or more halogens.
  • Illustrative suitable imidazolium species include 1- ethyl-3-methylimidazolium (EMIM), l-butyl-3-methylimidazolium (BMIM), 1,3- dimethylimidazolium, l-methyl-3-propylimidazolium, or any other 1,3-dialkyl or 1,3-diaryl substituted imidazolium.
  • EMIM 1- ethyl-3-methylimidazolium
  • BMIM l-butyl-3-methylimidazolium
  • 1,3- dimethylimidazolium 1,3- dimethylimidazolium
  • l-methyl-3-propylimidazolium or any other 1,3-dialkyl or 1,3-diaryl substituted imidazolium.
  • the present invention may also be practiced using a pure ionic liquid as the electrolyte. Under these conditions, acetonitrile (or another non-ionic, polar organic solvent) and an ammonium salt are unnecessary.
  • Imidazolium-based ionic liquids containing either triflate, tetrafluoroborate or hexafluorophosphate counter-anions e.g., imidazolium triflates, imadazolium tetrafluoroborates, imidazolium hexafluorophosphates
  • Suitable ionic liquids may, for example, generally consist of bulky and asymmetric organic cations such as imidazolium cations (e.g., l-alkyl-3-methylimidazolium), pyridinium cations (e.g., 1-al kylpyridinium cations), pyrrolidinium cations (e.g., N-methyl-N-alkylpyrrolidinium cations) and ammonium ions.
  • the cation may also be a phosphonium cation .
  • anions may be employed, including simple halides (e.g., chloride, bromide, fluoride), inorganic anions such as tetrafluoroborate and hexafluorophosphate, and large organic anions like triflate, bistriflimide or tosylate.
  • simple halides e.g., chloride, bromide, fluoride
  • inorganic anions such as tetrafluoroborate and hexafluorophosphate
  • large organic anions like triflate, bistriflimide or tosylate.
  • the solution and head space may be sparged with carbon dioxide at 1 atm for approximately 30 minutes, after which time the electrolysis is initiated.
  • Electrolysis may be carried out by applying a potential suitable to achieve the desired electrochemical conversion of carbon dioxide to carbon monoxide.
  • the potential may be from -1 to -3 V versus SCE.
  • Generation of CO is monitored by either manual injection or direct flow into a gas chromatograph . On a commercial scale, CO can be separated from the headspace using a standard gas diffusion electrode or other gas sorption technology.
  • a source of electrical current is in electrical communication with the cathode and the anode.
  • the power source may implement a variable voltage source.
  • the source of electrical current may be operational to generate an electrical potential between the anode and the cathode.
  • the electrical potential may be a DC voltage.
  • the electrolytic system of the present invention may comprise a carbon dioxide source.
  • the carbon dioxide source is generally operational to provide carbon dioxide (as a gas, for example) to a cell comprising the cathode, anode and electrolyte, which may be comprised of one, two or more compartments (chambers).
  • the carbon dioxide is bubbled directly into the compartment containing the cathode.
  • the electrolysis can be carried out either under isolation or under a steady flow of carbon dioxide. Under the latter conditions, current densities for CO production are measured to be roughly as high as 10 mA/cm 2 , which is comparable to or better than existing technologies.
  • the electrochemical system of the invention has been found to be robust and is capable of demonstrating steady current densities for longer than 8 - 10 hours.
  • the faradaic efficiency for CO formation using the present invention may be approximately 70-80 % and the energy efficiency for carbon dioxide reduction may be approximately 70 %. When taken together, the stability as well as the faradic and energy efficiencies are superior or comparable to previously known electrolytic systems that utilize inexpensive cathode materials (e.g. Bi-C EC).
  • a Sn containing material was electrodeposited onto an inert electrode substrate and the reduction of an aqueous solution of 20 imM SnCI 2 containing 1.0 M HCI using a nickel electrode produces the CV trace shown in Figure 2a, which is characterized by a broad reduction cathodic wave.
  • Controlled potential electrolysis was carried out at -0.49 V versus the standard calomel electrode (SCE; all potentials are referenced to this electrode) for quiescent acidic Sn 2+ solutions until ⁇ 1 C/cm 2 had been passed, leading to electrodeposition of a grey, non-lustrous material on the nickel surface.
  • Nickel was used as the working electrode to ensure that the base conducting substrate supported negligible background activity for C0 2 reduction .
  • the morphology of the deposited material was examined by scanning electron microscopy (SEM). As shown in Figure 2b, the electrode is coated by an array of micrometer sized crystallites. The surface of the electrodeposited material was also analyzed by x-ray photoelectron spectroscopy (XPS). High-resolution XPS spectra for the tin region reveal Sn 3d5/2 signals at 484.5 eV and 487 eV, which are in the range typical of Sn°, Sn 2+ and Sn 4+ oxides, respectively. XPS analyses indicate that reduction of acidic solutions of Sn + leads to deposition of a microcrystalline material containing metallic Sn°, Sn 2+ and Sn + that has incorporated a significant amount of oxygen.
  • Example 2 A Sn containing material was electrodeposited onto an inert electrode substrate and the reduction of an MeCN solution of 20 mM [Sn(OTf) 2 ] containing 0.1 M TBAPF 6 using a nickel electrode produces the CV trace shown in Figure 3a, which is characterized by a broad cathodic wave centered around -1.6 V vs. SCE. Controlled potential electrolysis (CPE) was carried out at -1.6 V vs. SCE for quiescent Sn 2+ solution until ⁇ 1 C/cm 2 had been passed, leading to electrodeposition of a grey, non-lustrous material on the nickel surface. Nickel was used as the working electrode to ensure that the base conducting substrate supported negligible background activity for C0 2 reduction.
  • CPE Controlled potential electrolysis
  • the morphology of the deposited material was examined by scanning electron microscopy (SEM). As shown in Figure 3b, the electrode is coated by a dense array of micrometer sized crystallites, The surface of the electrodeposited material was also analyzed by X-ray photoelectron spectroscopy (XPS). High-resolution XPS spectra for the tin region revealed a Sn 3d 5 2 signal at 488 eV, which is in the range typical of Sn 2+ and Sn 4+ oxides. XPS analyses indicate that reduction of an organic solution of Sn 2+ leads to deposition of a microcrystalline material containing primarily Sn 2+ and Sn + ions that has incorporated a significant amount of oxygen.
  • SEM scanning electron microscopy
  • Example 4 The ability of in situ Sn-modified electrodes to electrochemically activate C0 2 was assessed in MeCN, which supports a large electrochemical window and is commonly employed for C0 2 electrocatalysis. As shown in Figure 4b, scanning to negative potentials in C0 2 saturated solutions of MeCN containing 1.0 mM [Sn(OTf) 2 ] and 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF 6 ) shows a small current enhancement as compared to the corresponding experiment under N 2 . 1,3-Dialkyl substituted imidazolum based ionic liquids (ILs) can strongly interact with C0 2 and have found application for carbon sequestration.
  • ILs 1,3-Dialkyl substituted imidazolum based ionic liquids

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Abstract

L'invention concerne un système et un procédé qui permettent la conversion électrochimique sélective de dioxyde de carbone en monoxyde de carbone avec une efficacité énergétique élevée, au moyen d'une cathode constituée d'étain en combinaison avec une anode constituée de platine. Le système d'électrolyse peut être constitué d'une cellule à compartiment unique ou à deux compartiments et peut faire appel à un électrolyte organique ou à un électrolyte liquide ionique. L'invention permet le stockage d'énergie électrique solaire, éolienne ou classique par conversion de dioxyde de carbone en monoxyde de carbone et en combustibles liquides.
PCT/US2015/022734 2014-03-27 2015-03-26 Système et procédé de conversion électrochimique de dioxyde de carbone en monoxyde de carbone WO2015148796A1 (fr)

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CN110809649A (zh) * 2017-07-03 2020-02-18 科思创德国股份有限公司 用于制备碳酸二芳基酯的电化学方法
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CN114016069B (zh) * 2021-12-08 2023-11-24 昆明理工大学 一种氧化镓基液态金属催化剂的制备方法及应用

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US4801368A (en) * 1984-11-08 1989-01-31 Tokuyama Soda Kabushiki Kaisha Ni/Sn cathode having reduced hydrogen overvoltage
US20100193370A1 (en) * 2007-07-13 2010-08-05 Olah George A Electrolysis of carbon dioxide in aqueous media to carbon monoxide and hydrogen for production of methanol
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