US20240003017A1 - Electrochemical cells and electrochemical methods - Google Patents
Electrochemical cells and electrochemical methods Download PDFInfo
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- US20240003017A1 US20240003017A1 US18/465,427 US202318465427A US2024003017A1 US 20240003017 A1 US20240003017 A1 US 20240003017A1 US 202318465427 A US202318465427 A US 202318465427A US 2024003017 A1 US2024003017 A1 US 2024003017A1
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- 238000002848 electrochemical method Methods 0.000 title description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 63
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 55
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 46
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 46
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 32
- 230000009467 reduction Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 239000012530 fluid Substances 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 229910021389 graphene Inorganic materials 0.000 claims description 12
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- 239000010949 copper Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
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- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 3
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- 239000001273 butane Substances 0.000 claims description 2
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- 238000000576 coating method Methods 0.000 claims description 2
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- 239000001294 propane Substances 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 29
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- 150000002739 metals Chemical class 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- -1 e.g. Natural products 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 230000036647 reaction Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 101150013568 US16 gene Proteins 0.000 description 1
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- 150000001450 anions Chemical group 0.000 description 1
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- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
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- OIBMEBLCOQCFIT-UHFFFAOYSA-N ethanesulfonyl fluoride Chemical compound CCS(F)(=O)=O OIBMEBLCOQCFIT-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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Images
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
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- 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
-
- 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
-
- 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
Definitions
- This invention relates to electrochemical cells and methods for reducing carbon dioxide, oxidizing hydrocarbons, or a combination thereof.
- Carbon dioxide (CO 2 ) is the chief greenhouse gas that results in global warming and climate change.
- CO 2 is a highly desirable carbon feedstock that can also be used to produce large volumes of industrial chemicals and fuels, such as carbon monoxide (CO), methanol, ethylene, and formic acid.
- CO carbon monoxide
- methanol methanol
- ethylene ethylene
- formic acid a highly desirable carbon feedstock that can also be used to produce large volumes of industrial chemicals and fuels
- CO 2 carbon monoxide
- methanol methanol
- ethylene ethylene
- formic acid formic acid
- Equation (3) the overall cell reaction is provided according to Equation (3):
- thermodynamics potential 1.151 V.
- the high surface overpotential for the water oxidation reaction increases the cell voltage significantly.
- dehydrogenating hydrocarbons to olefins is an important commercial hydrocarbon conversion process because of the great demand for olefinic products for the manufacture of various chemical products such as detergents, high octane motor fuels, pharmaceutical products, plastics, synthetic rubbers, and other products well known to those skilled in the art.
- the process is traditionally carried at high temperatures, such as between 550° C. and 650° C., and in the presence of a metal-based catalyst. Due to the high temperature, the catalyst is quickly and easily coked, and the period of time during which the catalyst is stable is limited, in some instances to minutes or even seconds.
- the present invention overcomes one or more of the foregoing problems and other shortcomings, drawbacks, and challenges of conventional carbon dioxide reduction, conventional dehydrogenation of hydrocarbons to olefins, or combinations thereof. While the invention will be described in connection with certain embodiments, it will be understood that the invention is not limited to these embodiments. To the contrary, this invention includes all alternatives, modifications, and equivalents as may be included within the scope of the present invention.
- an electrochemical cell for reducing carbon dioxide comprises a cathode compartment including a cathode comprising a first conducting component that is active toward adsorption and reduction of CO 2 ; and an anode compartment including an anode comprising a second conducting component that is active toward adsorption and oxidation of a reducing agent.
- the reducing agent may include, but is not limited to, hydrogen, hydrocarbons, amines, alcohols, coal, pet-coke, biomass, lignin, or combinations thereof.
- the electrochemical cell may be employed in a method for reducing carbon dioxide.
- an electrochemical cell for dehydrogenating a hydrocarbon to an olefin comprises a cathode compartment including a cathode comprising a first conducting component that is active toward adsorption and reduction of an oxidizing agent; and an anode compartment including an anode comprising a second conducting component that is active toward adsorption and oxidation of a hydrocarbon to an olefin.
- the oxidizing agent may include, but is not limited to, oxygen, carbon dioxide, molecular halogens, metal ions, protons, or combinations thereof.
- a hydrophobic modifier is present on at least a portion of a surface of the second conducting component or both the first and second conducting components.
- the electrochemical cell may be employed in a method for dehydrogenating a hydrocarbon to an olefin.
- an electrochemical cell for reducing carbon dioxide and dehydrogenating a hydrocarbon to an olefin.
- the electrochemical cell comprises a cathode compartment including a cathode comprising a first conducting component that is active toward adsorption and reduction of CO 2 ; and an anode compartment including an anode comprising a second conducting component that is active toward adsorption and oxidation of a hydrocarbon to an olefin.
- a hydrophobic modifier is present on at least a portion of a surface of the second conducting component or both the first and second conducting components.
- a method for concurrently electrolytically reducing carbon dioxide and dehydrogenating a hydrocarbon to an olefin in an electrochemical cell comprising a cathode, an anode, and a separator is provided.
- the method includes exposing the cathode comprising a first conducting component to a carbon dioxide (CO 2 )-containing fluid at a first pressure and first temperature, wherein the first conducting component is active toward adsorption and oxidation of CO 2 ; exposing the anode comprising a second conducting component to a hydrocarbon-containing fluid at a second pressure and a second temperature, wherein the second conducting component is active toward adsorption and reduction of hydrocarbons via a dehydrogenation reaction, and wherein a hydrophobic modifier is present on at least a portion of a surface of the second conducting component.
- CO 2 carbon dioxide
- the method further includes applying a voltage between the cathode exposed to the CO 2 -containing fluid and the anode exposed to the hydrocarbon-containing fluid so as to facilitate adsorption of CO 2 onto the cathode and adsorption of the hydrocarbon onto the anode, wherein the voltage is sufficient to simultaneously oxidize the hydrocarbon via a dehydrogenation reaction and reduce the CO 2 .
- the FIGURE is a diagrammatical view of a simplified electrolytic cell for reducing carbon dioxide (CO 2 ) that is configured for flow cell processing, in accordance with an embodiment of the present invention.
- the process may be called the “HYCO2chem process.”
- each of the half-reactions may be practiced independently, e.g., by substituting the hydrocarbon with a different reducing agent or by substituting CO 2 with a different oxidizing agent.
- the HYCO2chem process includes an electrochemical cell designed with an architecture that will control the transport of the species required for the oxidation/reduction reactions.
- the FIGURE is a diagrammatic depiction of a simplified electrochemical cell 10 configured for flow cell processing.
- the simplified electrochemical cell 10 comprises a cathodic chamber 15 containing a cathode electrode 20 , an anodic chamber 25 containing an anode electrode 30 , wherein the cathodic chamber 15 and the anodic chamber 25 are physically separated from each other by a separator 35 .
- the separator 35 allows the transport of ions between the anodic chamber 25 and the cathodic chamber 15 .
- the cathode electrode 20 and the anode electrode 30 are configured with an electrical connection therebetween via a cathode lead 42 and an anode lead 44 along with a voltage source 45 , which supplies a voltage or an electrical current to the electrochemical cell 10 .
- the cathodic chamber 15 comprises an inlet 50 by which an oxidizing agent-containing fluid 11 enters and an outlet 55 by which reduction product(s) and unreacted oxidizing agent 12 exit.
- the oxidizing agent may include, but is not limited to, carbon dioxide, oxygen, molecular halogens, metal ions, protons, or combinations thereof.
- the anodic chamber 25 comprises an inlet 60 by which a reducing agent-containing fluid 13 enters and an outlet 65 by which oxidation product(s) and unreacted reducing agent 14 exit.
- the reducing agent may include, but is not limited to, hydrogen, hydrocarbons, amines, alcohols, coal, pet-coke, biomass, lignin, or combinations thereof.
- Each of the cathodic and anodic chambers 15 , 25 may further comprise gas distributors 70 , 75 , respectively.
- the electrochemical cell 10 may be sealed at its upper and lower ends with an upper gasket 80 and a lower gasket 85 .
- the cathode electrode 20 comprises a conducting component that is active toward adsorption and reduction of CO 2 .
- CO 2 reduction products include single carbon species like carbon monoxide (CO), formic acid (HCO 2 H), methanol (CH 3 OH), and/or methane (CH 4 ), or C2 products like oxalic acid (HO 2 C—CO 2 H), glycolic acid (HO 2 C—CH 2 OH), ethanol (CH 3 CH 2 OH), ethane (CH 3 CH 3 ) and/or ethylene (CH 2 CH 2 ).
- CO 2 is reduced to produce at least ethylene, which takes place according to Equation 3 above.
- conducting component comprises an active catalyst selected from platinum (Pt), iridium (Ir), ruthenium (Ru), palladium (Pd), rhodium (Rh), nickel (Ni), cobalt (Co), iron (Fe), copper (Cu), silver (Ag), and their combinations.
- the active catalyst includes one or more platinum-group metals, which includes ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt).
- the metals can be co-deposited as alloys as described in U.S. Pat. Nos.
- the overlying layer of metal may incompletely cover the underlying layer of metal.
- the cathode electrode may be constructed as a high surface area material, so as to increase the available surface area for the cathodic conducting component.
- the conducting component and/or active catalyst of the cathode may be present in a form, e.g., nanoparticles, that provides a high surface area material.
- the cathode electrode may further include a substrate onto which the conducting component and/or active catalyst is applied.
- suitable substrates include conductive metals, carbon fibers, carbon paper, glassy carbon, carbon nanofibers, carbon nanotubes, graphene, metal nanoparticles, nickel, nickel gauze, Raney nickel, alloys, etc.
- Carbon dioxide feedstock is not particularly limited to any source and may be supplied to the carbon dioxide containing fluid as a pure gas or as a mixture of gases.
- Other inert gases e.g., a carrier gas
- a carrier gas can be present in the carbon dioxide containing fluid.
- the gas distributor 70 e.g., screen of metals
- the gas distributor 70 provides channels for the carbon dioxide to disperse and contact the cathode electrode 20 . If desired, any excess or unreacted carbon dioxide gas that exits the cathodic chamber 15 can be separated from the reduction product(s) and recirculated in the process.
- the anode electrode 30 comprises a conducting component that is active toward adsorption and oxidation of hydrocarbons via a dehydrogenation reaction.
- the conducting component of the anode electrode 30 comprises an active catalyst selected from platinum (Pt), iridium (Ir), ruthenium (Ru), palladium (Pd), rhodium (Rh), nickel (Ni), Cobalt (Co), iron (Fe), copper (Cu), and their combinations.
- the active catalyst includes one or more platinum-group metals, which includes ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt).
- the metals can be co-deposited as alloys as described in U.S. Pat.
- the overlying layer of metal may incompletely cover the underlying layer of metal.
- the anode electrode 30 may be constructed as a high surface area material, so as to increase the available surface area for the anodic conducting component. Accordingly, the conducting component and/or active catalyst of the anode may be present in a form, e.g., nanoparticles, that provides the high surface area material. Additionally, the anode electrode 30 may further include a substrate onto which the conducting component and/or active catalyst is applied. Non-limiting examples of suitable substrates include conductive metals, carbon fibers, carbon paper, glassy carbon, carbon nanofibers, graphene, carbon nanotubes, metal nanoparticles, nickel, nickel gauze, Raney nickel, alloys, etc.
- the hydrocarbon comprises ethane and its electrochemical dehydrogenation (i.e., oxidation) to ethylene will take place according to Equation (5).
- Equation (6) the overall electrochemical cell reaction, as shown in Equation (6), will take place at a cell voltage of 0.444 V, which represents a 61% reduction in the electrical energy when compared to the reaction shown in Equation (3).
- Other hydrocarbons e.g., methane, propane, butane, pentane, hexane, etc. can also be oxidized, but ethylene is shown as an example.
- the hydrocarbon comprises hexane and its electrochemical dehydrogenation (i.e., oxidation) to hexene will take place according to Equation (7).
- Equation (7) coupled with the reduction of CO 2 to ethylene, which is shown in Equation (1), will lead to the production of high value olefins (hexene and ethylene, simultaneously) while minimizing CO 2 emissions, as shown in Equation (8).
- the overall cell reaction will take place at a cell voltage of 0.376 V, according to the thermodynamics, which represents a 67% reduction in the electrical energy when compared to the reaction shown in Equation (3).
- the anode electrode further includes a hydrophobic modifier on at least a portion of a surface of the conducting component and/or active catalyst.
- the hydrophobic modifier includes an electrochemically reduced graphene oxide (ERGO) coating on the conducting component and/or active catalyst, which provides a hydrophobic-hydrophilic anodic surface.
- ERGO electrochemically reduced graphene oxide
- the hydrophobic modifier includes a graphene film (for example, synthesized by chemical vapor deposition).
- the hydrophobic material includes Teflon.
- the electrochemically reduced graphene oxide (ERGO)-coated anode electrode may be prepared by a one-step electrochemical synthesis on graphene oxide (GO) support.
- GO suspensions can be prepared by exfoliation of graphite by Hummers method or a modified Hummers method.
- the ERGO-coated anode electrode may be prepared by performing an electrochemical reduction of a GO-coated conducting component in an ionic solution (e.g., 0.1 M KCl) that includes a salt or a compound of the active catalyst.
- an ionic solution e.g., 0.1 M KCl
- graphene can be directly lifted on a membrane and/or separator and coated with the active catalyst for the oxidation of the hydrocarbon.
- graphene sheets can be bounded with Teflon, nafion, or another binder.
- Gas distribution channels e.g., screen of metals
- any excess or unreacted hydrocarbon that exits the anodic chamber 25 can be separated from the oxidation product(s) and recirculated in the process.
- the separator 35 may divide the cathodic and anodic chambers 15 , 25 , and physically separate the cathode electrode 20 and the anode electrode 30 .
- Exemplary separators include ion (e.g., proton or anion) exchange membranes, which are thin polymeric films that permit the passage of ions.
- the separator includes a proton conducting polymer comprising a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer.
- the sulfonated tetrafluoroethylene-based fluoropolymer-copolymer may be ethanesulfonyl fluoride, 2-[1-[difluoro-[(trifluoroethenyl)oxy]methyl]-1,2,2,2-tetrafluoroethoxy]-1,1,2,2,-tetrafluoro-, with tetrafluoroethylene, which is commercially available from the E. I. du Pont de Nemours and Company, under the tradename Nafion®.
- the electrochemical cell 10 can be operated at a constant voltage or a constant current. While the electrochemical cell 10 is shown in a flow cell configuration, which can operate continuously, the present invention is not limited thereto.
- the electrochemical cell 10 may incorporate the following features:
- the flow rate of the CO 2 and the hydrocarbon through the cathodic and anodic chambers 15 , 25 , respectively can be varied over a wide range, depending on a variety of factors, including but not limited to catalyst surface area, temperature, pressure, reduction efficiency of the CO 2 and oxidation efficiency of the hydrocarbon.
- the flow rate of CO 2 is in a range from about 1 L/min to about 2,000 L/min.
- the temperature of the cell can be in a range from about 25° C. to about 120° C.
- the pressure of the cell can be in a range from about 1 atm to about 100 atm.
- the humidity of the CO 2 -containing fluid and/or the hydrocarbon-containing fluid can be modulated to achieve a desired level.
- the humidity may be increased or decreased, and may be in a range from less than about 1% to about 100% Relative Humidity (RH) at the operating temperature of the electrochemical cell.
- RH Relative Humidity
- Graphite powder (C, grade #38), sulfuric acid (H 2 SO 4 , 96.3%), hydrochloric acid (HCl, 37.4%), potassium hydroxide (KOH, 85.0%+), potassium chloride (KCl, 99.6%), carbon dioxide (CO 2 ), ethane (C 2 H 6 ), and hexane (C 6 H 14 ) are obtainable from Fisher Scientific.
- Potassium permanganate (KMnO 4 , 98%), sodium nitrate (NaNO 3 , 98%+), hydrogen peroxide (H 2 O 2 , 29-32%), and chloroplatinic acid (H 2 PtCl 6 ⁇ 6 H 2 O) are obtainable from Alfa Aeaser.
- Graphene oxide may be prepared by the modified Hummers method.
- a typical procedure for the synthesis of the GO involves the following steps:
- the diluted mixture may then be washed with 5 wt % HCl, followed by centrifugation (Thermo Scientific Sorvall Legend X1 Centrifuge) at 4000 rpm for 10 min. This purification/washing process may be repeated as desired, e.g., 15 times.
- the remaining mixture may then be washed with deionized H 2 O, followed by centrifugation at 4000 rpm for 10 min.
- the deionized H 2 O washing process may be repeated as desired, e.g., 5 times, to obtain the GO slurry.
- the GO slurry may be dried at room temperature in a vacuum oven (about 25 in. of Hg vacuum) (Napco E Series, Model 5831) equipped with a vacuum pump (Gast, Model DDA-V191-AA) for 1 day to get GO powder.
- a GO dispersion may be prepared by sonication (Zenith Ultrasonic bath at 40 kHz) of the graphite oxide powder in deionized H 2 O for 30 min, followed by 10 min centrifugation at 1000 rpm. The concentration of the GO dispersion can be adjusted to about 0.2 mg/ml.
- Glassy carbon electrodes may be first polished with 1 ⁇ m and 0.05 ⁇ m polishing alumina and rinsed with deionized water, and finally sonicated in deionized water for about 10 min to remove any alumina particles. After drying with an Argon flow, the polished GCEs may be used as representative substrates for electrochemical reduction of graphene oxide (ERGO) to form ERGO-catalyst nanocomposites. To prepare the nanocomposites, 20 ⁇ l of the GO dispersion may be first dropped on the polished GCEs. Drying at room temperature for about 1 h forms GO films on the GCEs.
- ERGO graphene oxide
- a one-step electrochemical reduction process may then be performed in 0.1 M KCl solution in the presence of 5 mM H 2 PtCl 6 ⁇ 6 H 2 O at ⁇ 1.1 V vs. Ag/AgCl for 5 min with 60 rpm stirring for producing a pure electrochemically reduced graphene oxide (ERGO) electrode and an EGRO-Ni electrode, respectively.
- ERGO electrochemically reduced graphene oxide
- a platinum foil e.g., 2 cm ⁇ 1 cm
- a membrane electrode assembly may be built using the Graphene-Pt nanocomposite as the anode electrode or as both the anode and cathode electrode, using NAFION® as the membrane separator.
- the MEA may be assembled into the electrochemical cell 10 as depicted in the FIGURE.
- Toray TGP-H-030 carbon paper may be used as gas diffusion layers in both the anodic and cathodic chambers.
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Abstract
An electrochemical cell and method for reducing carbon dioxide and/or dehydrogenating a hydrocarbon to an olefin are provided. The electrochemical cell includes a cathode having a first conducting component that is active toward adsorption and reduction of an oxidizing agent such as CO2; and an anode having a second conducting component that is active toward adsorption and oxidation of a reducing agent such as a hydrocarbon. Additionally, a hydrophobic modifier is present on at least a portion of a surface of the second conducting component or both the first and second conducting components. The method includes exposing the cathode to a CO2-containing fluid; exposing the anode to a hydrocarbon-containing fluid; and applying a voltage between the cathode exposed to the CO2-containing fluid and the anode exposed to the hydrocarbon-containing fluid, wherein the voltage is sufficient to simultaneously oxidize the hydrocarbon via a dehydrogenation reaction and reduce the CO2.
Description
- This application is a Divisional Application which claims priority to, and the benefit of the filing date of, U.S. National Stage application Ser. No. 15/570,848, filed on Oct. 31, 2017, which claims priority to, and benefit of the filing date of, PCT Application No. PCT/US16/29950, filed on Apr. 29, 2016, which claims priority to, and benefit of the filing date of, U.S. Provisional Application No. 62/157,103, filed May 5, 2015, the disclosures of which are hereby incorporated by reference herein in their entireties.
- This invention relates to electrochemical cells and methods for reducing carbon dioxide, oxidizing hydrocarbons, or a combination thereof.
- Carbon dioxide (CO2) is the chief greenhouse gas that results in global warming and climate change. However, CO2 is a highly desirable carbon feedstock that can also be used to produce large volumes of industrial chemicals and fuels, such as carbon monoxide (CO), methanol, ethylene, and formic acid. While the conversion of CO2 to useful fuels has been proposed and explored through different routes (e.g., photochemical, biochemical, and electrochemical conversion), many of these routes suffer from low efficiencies or occur under extreme temperatures and pressures.
- With respect to electrochemical conversion, it has been demonstrated that the electrochemical reduction of CO2 can produce CO, methane, formic acid, etc. using solid oxide electrolyte-type electrolyzers at 800° C. to 1000° C. operating temperature, and liquid electrolyte-type electrolyzers have been demonstrated operating around room temperature. Various metal catalysts and coordination complexes have been studied for the electrochemical reduction of CO2 in liquid electrolytes.
- Even though the electrochemical reduction of CO2 is a promising candidate process for CO2 recycling and synthetic fuel production, it encounters technical challenges, such as high operating voltage and low conversion yields that affect the economics and the implementation of the process.
- With respect to high operating voltages, typically in the electrochemical process, CO2 is reduced at the cathode while water is oxidized at the anode. The overpotential for the oxidation of water increases the cell voltage. For example, the reduction of carbon dioxide to ethylene takes place at 0.079 V vs. standard hydrogen electrode (SHE) according to Equation (1) (*All the half cell electrode potentials listed herein are reduction electrode potentials vs. SHE V (electrolysis cell)):
- While the oxidation of water takes place at 1.23 V vs. SHE according to Equation (2):
- Accordingly, the overall cell reaction is provided according to Equation (3):
-
2CO2+2H2O→3O2+C2H4 (3) - with a thermodynamics potential of 1.151 V. However, the high surface overpotential for the water oxidation reaction increases the cell voltage significantly.
- With respect to low conversion, reduction of protons can also occur at the cathode (see Equation (4)), which can thereby compete with the desired reduction of CO2 and lead to low conversions of CO2.
- Accordingly, prior electrochemical methods of reducing CO2 are hampered with high-energy consumption (high operating voltage), low conversion to high value products, and low selectivity, which prevent the implementation of the process.
- Similarly, dehydrogenating hydrocarbons to olefins is an important commercial hydrocarbon conversion process because of the great demand for olefinic products for the manufacture of various chemical products such as detergents, high octane motor fuels, pharmaceutical products, plastics, synthetic rubbers, and other products well known to those skilled in the art. The process is traditionally carried at high temperatures, such as between 550° C. and 650° C., and in the presence of a metal-based catalyst. Due to the high temperature, the catalyst is quickly and easily coked, and the period of time during which the catalyst is stable is limited, in some instances to minutes or even seconds. While the stability of the catalyst can be somewhat improved by using it in a form of a fluidized bed, traditional catalytic dehydrogenation of hydrocarbons has other drawbacks and deficiencies besides problems with stability. For example, in traditional catalytic dehydrogenation many catalysts cannot withstand many cycles of regeneration and heat integration without substantial loss of activity and selectivity. The ability of catalysts to promote selective reactions (i.e., reactions leading to the formation of the desired final product) is also limited in traditional processes, and the share of thermal, non-selective reactions (i.e., reactions leading to the formation of the products other than the desired product) is often larger than desired.
- In view of the foregoing, there is a need for new electrochemical cells, as well as new electrochemical methods for reducing CO2, for the dehydrogenation of hydrocarbons to corresponding olefins, or combinations thereof.
- The present invention overcomes one or more of the foregoing problems and other shortcomings, drawbacks, and challenges of conventional carbon dioxide reduction, conventional dehydrogenation of hydrocarbons to olefins, or combinations thereof. While the invention will be described in connection with certain embodiments, it will be understood that the invention is not limited to these embodiments. To the contrary, this invention includes all alternatives, modifications, and equivalents as may be included within the scope of the present invention.
- According to an embodiment of the present invention, an electrochemical cell for reducing carbon dioxide is provided. The electrochemical cell comprises a cathode compartment including a cathode comprising a first conducting component that is active toward adsorption and reduction of CO2; and an anode compartment including an anode comprising a second conducting component that is active toward adsorption and oxidation of a reducing agent. The reducing agent may include, but is not limited to, hydrogen, hydrocarbons, amines, alcohols, coal, pet-coke, biomass, lignin, or combinations thereof. The electrochemical cell may be employed in a method for reducing carbon dioxide.
- According to another embodiment of the present invention, an electrochemical cell for dehydrogenating a hydrocarbon to an olefin is provided. The electrochemical cell comprises a cathode compartment including a cathode comprising a first conducting component that is active toward adsorption and reduction of an oxidizing agent; and an anode compartment including an anode comprising a second conducting component that is active toward adsorption and oxidation of a hydrocarbon to an olefin. The oxidizing agent may include, but is not limited to, oxygen, carbon dioxide, molecular halogens, metal ions, protons, or combinations thereof. Additionally, a hydrophobic modifier is present on at least a portion of a surface of the second conducting component or both the first and second conducting components. The electrochemical cell may be employed in a method for dehydrogenating a hydrocarbon to an olefin.
- According to another embodiment of the present invention, an electrochemical cell for reducing carbon dioxide and dehydrogenating a hydrocarbon to an olefin is provided. The electrochemical cell comprises a cathode compartment including a cathode comprising a first conducting component that is active toward adsorption and reduction of CO2; and an anode compartment including an anode comprising a second conducting component that is active toward adsorption and oxidation of a hydrocarbon to an olefin. Additionally, a hydrophobic modifier is present on at least a portion of a surface of the second conducting component or both the first and second conducting components.
- According to an embodiment of the present invention, a method for concurrently electrolytically reducing carbon dioxide and dehydrogenating a hydrocarbon to an olefin in an electrochemical cell comprising a cathode, an anode, and a separator is provided. The method includes exposing the cathode comprising a first conducting component to a carbon dioxide (CO2)-containing fluid at a first pressure and first temperature, wherein the first conducting component is active toward adsorption and oxidation of CO2; exposing the anode comprising a second conducting component to a hydrocarbon-containing fluid at a second pressure and a second temperature, wherein the second conducting component is active toward adsorption and reduction of hydrocarbons via a dehydrogenation reaction, and wherein a hydrophobic modifier is present on at least a portion of a surface of the second conducting component. The method further includes applying a voltage between the cathode exposed to the CO2-containing fluid and the anode exposed to the hydrocarbon-containing fluid so as to facilitate adsorption of CO2 onto the cathode and adsorption of the hydrocarbon onto the anode, wherein the voltage is sufficient to simultaneously oxidize the hydrocarbon via a dehydrogenation reaction and reduce the CO2.
- The accompanying drawing, which is incorporated in and constitutes a part of this specification, illustrates embodiments of the present invention and, together with a general description of the invention given above, and the detailed description of the embodiments given below, serves to explain the principles of the present invention.
- The FIGURE is a diagrammatical view of a simplified electrolytic cell for reducing carbon dioxide (CO2) that is configured for flow cell processing, in accordance with an embodiment of the present invention.
- An electrochemical method and electrochemical cell for reducing CO2, dehydrogenating a hydrocarbon to an olefin, or a combination thereof are disclosed in various embodiments. However, one skilled in the relevant art will recognize that the various embodiments may be practiced without one or more of the specific details or with other replacement and/or additional methods, materials, or components. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of various embodiments of the present invention.
- Similarly, for purposes of explanation, specific numbers, materials, and configurations are set forth in order to provide a thorough understanding. Nevertheless, the embodiments of the present invention may be practiced without specific details. Furthermore, it is understood that the illustrative representations are not necessarily drawn to scale.
- Reference throughout this specification to “one embodiment” or “an embodiment” or variation thereof means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention, but does not denote that they are present in every embodiment. Thus, the appearances of the phrases such as “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily referring to the same embodiment of the invention. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. Various additional layers and/or structures may be included and/or described features may be omitted in other embodiments.
- Additionally, it is to be understood that “a” or “an” may mean “one or more” unless explicitly stated otherwise.
- Various operations will be described as multiple discrete operations in turn, in a manner that is most helpful in understanding the invention. However, the order of description should not be construed as to imply that these operations are necessarily order dependent. In particular, these operations need not be performed in the order of presentation. Operations described may be performed in a different order than the described embodiment.
- Various additional operations may be performed and/or described operations may be omitted in additional embodiments.
- To confront one or more of the limitations of prior art methods, a new process is provided that enables the concurrent oxidation of a hydrocarbon and the reduction of carbon dioxide (CO2) to high value products; the process may be called the “HYCO2chem process.” However, each of the half-reactions may be practiced independently, e.g., by substituting the hydrocarbon with a different reducing agent or by substituting CO2 with a different oxidizing agent. Thus, in an embodiment, the HYCO2chem process includes an electrochemical cell designed with an architecture that will control the transport of the species required for the oxidation/reduction reactions. The FIGURE is a diagrammatic depiction of a simplified electrochemical cell 10 configured for flow cell processing. The simplified electrochemical cell 10 comprises a
cathodic chamber 15 containing acathode electrode 20, ananodic chamber 25 containing ananode electrode 30, wherein thecathodic chamber 15 and theanodic chamber 25 are physically separated from each other by aseparator 35. However, while also serving as a physical barrier between thecathode electrode 20 and theanode electrode 30, theseparator 35 allows the transport of ions between theanodic chamber 25 and thecathodic chamber 15. Thecathode electrode 20 and theanode electrode 30 are configured with an electrical connection therebetween via acathode lead 42 and ananode lead 44 along with avoltage source 45, which supplies a voltage or an electrical current to the electrochemical cell 10. - The
cathodic chamber 15 comprises aninlet 50 by which an oxidizing agent-containingfluid 11 enters and anoutlet 55 by which reduction product(s) andunreacted oxidizing agent 12 exit. The oxidizing agent may include, but is not limited to, carbon dioxide, oxygen, molecular halogens, metal ions, protons, or combinations thereof. Similarly, theanodic chamber 25 comprises aninlet 60 by which a reducing agent-containingfluid 13 enters and anoutlet 65 by which oxidation product(s) and unreacted reducingagent 14 exit. The reducing agent may include, but is not limited to, hydrogen, hydrocarbons, amines, alcohols, coal, pet-coke, biomass, lignin, or combinations thereof. Each of the cathodic andanodic chambers gas distributors upper gasket 80 and alower gasket 85. - Cathode
- In accordance with an embodiment of the present invention, the
cathode electrode 20 comprises a conducting component that is active toward adsorption and reduction of CO2. Non-limiting examples of CO2 reduction products include single carbon species like carbon monoxide (CO), formic acid (HCO2H), methanol (CH3OH), and/or methane (CH4), or C2 products like oxalic acid (HO2C—CO2H), glycolic acid (HO2C—CH2OH), ethanol (CH3CH2OH), ethane (CH3CH3) and/or ethylene (CH2CH2). In accordance with an embodiment, CO2 is reduced to produce at least ethylene, which takes place according to Equation 3 above. - In one embodiment, conducting component comprises an active catalyst selected from platinum (Pt), iridium (Ir), ruthenium (Ru), palladium (Pd), rhodium (Rh), nickel (Ni), cobalt (Co), iron (Fe), copper (Cu), silver (Ag), and their combinations. In another embodiment, the active catalyst includes one or more platinum-group metals, which includes ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt). When a combination of one or more metals is used for the conducting component of the
cathode electrode 20, the metals can be co-deposited as alloys as described in U.S. Pat. Nos. 7,485,211 and 7,803,264, and/or by layers as described in U.S. Pat. No. 8,216,956, wherein the entirety of these disclosures are incorporated by reference herein in their entirety. In one embodiment, where the metals are layered, the overlying layer of metal may incompletely cover the underlying layer of metal. - In accordance with an embodiment of the present invention, the cathode electrode may be constructed as a high surface area material, so as to increase the available surface area for the cathodic conducting component. Accordingly, the conducting component and/or active catalyst of the cathode may be present in a form, e.g., nanoparticles, that provides a high surface area material. Additionally, the cathode electrode may further include a substrate onto which the conducting component and/or active catalyst is applied. Non-limiting examples of suitable substrates include conductive metals, carbon fibers, carbon paper, glassy carbon, carbon nanofibers, carbon nanotubes, graphene, metal nanoparticles, nickel, nickel gauze, Raney nickel, alloys, etc.
- Carbon dioxide feedstock is not particularly limited to any source and may be supplied to the carbon dioxide containing fluid as a pure gas or as a mixture of gases. Other inert gases (e.g., a carrier gas) can be present in the carbon dioxide containing fluid.
- To enhance the distribution of carbon dioxide in the
cathodic chamber 15, the gas distributor 70 (e.g., screen of metals) provides channels for the carbon dioxide to disperse and contact thecathode electrode 20. If desired, any excess or unreacted carbon dioxide gas that exits thecathodic chamber 15 can be separated from the reduction product(s) and recirculated in the process. - Anode
- In accordance with an embodiment of the present invention, the
anode electrode 30 comprises a conducting component that is active toward adsorption and oxidation of hydrocarbons via a dehydrogenation reaction. - In one embodiment, the conducting component of the
anode electrode 30 comprises an active catalyst selected from platinum (Pt), iridium (Ir), ruthenium (Ru), palladium (Pd), rhodium (Rh), nickel (Ni), Cobalt (Co), iron (Fe), copper (Cu), and their combinations. In another embodiment, the active catalyst includes one or more platinum-group metals, which includes ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt). When a combination of one or more metals is used for the conducting component of theanode electrode 30, the metals can be co-deposited as alloys as described in U.S. Pat. Nos. 7,485,211 and 7,803,264, and/or by layers as described in U.S. Pat. No. 8,216,956, wherein the entirety of these disclosures are incorporated by reference herein in their entirety. In one embodiment, where the metals are layered, the overlying layer of metal may incompletely cover the underlying layer of metal. - In accordance with an embodiment of the present invention, the
anode electrode 30 may be constructed as a high surface area material, so as to increase the available surface area for the anodic conducting component. Accordingly, the conducting component and/or active catalyst of the anode may be present in a form, e.g., nanoparticles, that provides the high surface area material. Additionally, theanode electrode 30 may further include a substrate onto which the conducting component and/or active catalyst is applied. Non-limiting examples of suitable substrates include conductive metals, carbon fibers, carbon paper, glassy carbon, carbon nanofibers, graphene, carbon nanotubes, metal nanoparticles, nickel, nickel gauze, Raney nickel, alloys, etc. - In an embodiment, the hydrocarbon comprises ethane and its electrochemical dehydrogenation (i.e., oxidation) to ethylene will take place according to Equation (5).
- Accordingly, the overall electrochemical cell reaction, as shown in Equation (6), will take place at a cell voltage of 0.444 V, which represents a 61% reduction in the electrical energy when compared to the reaction shown in Equation (3). Other hydrocarbons, e.g., methane, propane, butane, pentane, hexane, etc. can also be oxidized, but ethylene is shown as an example.
-
6C2H6+2CO2→7C2H4+4H2O (6) - As another non-limiting example, the hydrocarbon comprises hexane and its electrochemical dehydrogenation (i.e., oxidation) to hexene will take place according to Equation (7).
- Accordingly, the reaction shown in Equation (7) coupled with the reduction of CO2 to ethylene, which is shown in Equation (1), will lead to the production of high value olefins (hexene and ethylene, simultaneously) while minimizing CO2 emissions, as shown in Equation (8). In this case, the overall cell reaction will take place at a cell voltage of 0.376 V, according to the thermodynamics, which represents a 67% reduction in the electrical energy when compared to the reaction shown in Equation (3).
-
6C6H14+2CO2→6C6H12+C2H4+4H2O (8) - The key to achieve the selective electrochemical dehydrogenation of the hydrocarbons is minimizing the presence of water that can lead to the parasitic oxidation of the hydrocarbons towards CO2, which may be shown for ethane by the reverse reaction of Equation (1), for example. This parasitic oxidation of hydrocarbons is one of the reasons why electrochemical dehydrogenation of hydrocarbons has been studied at high temperature using ceramic type electrolytes. According to embodiments of the present invention, the anode electrode further includes a hydrophobic modifier on at least a portion of a surface of the conducting component and/or active catalyst. In an embodiment, the hydrophobic modifier includes an electrochemically reduced graphene oxide (ERGO) coating on the conducting component and/or active catalyst, which provides a hydrophobic-hydrophilic anodic surface. In another embodiment, the hydrophobic modifier includes a graphene film (for example, synthesized by chemical vapor deposition). In another environment, the hydrophobic material includes Teflon.
- Thus according to an embodiment, the electrochemically reduced graphene oxide (ERGO)-coated anode electrode may be prepared by a one-step electrochemical synthesis on graphene oxide (GO) support. GO suspensions can be prepared by exfoliation of graphite by Hummers method or a modified Hummers method. The ERGO-coated anode electrode may be prepared by performing an electrochemical reduction of a GO-coated conducting component in an ionic solution (e.g., 0.1 M KCl) that includes a salt or a compound of the active catalyst.
- According to an embodiment, graphene can be directly lifted on a membrane and/or separator and coated with the active catalyst for the oxidation of the hydrocarbon.
- In another environment, graphene sheets can be bounded with Teflon, nafion, or another binder.
- Gas distribution channels (e.g., screen of metals) can be added to the anodic chamber to enhance the distribution of the gas among the
anodic chamber 25. If desired, any excess or unreacted hydrocarbon that exits theanodic chamber 25 can be separated from the oxidation product(s) and recirculated in the process. - Separator
- In accordance with another embodiment, when present, the
separator 35 may divide the cathodic andanodic chambers cathode electrode 20 and theanode electrode 30. Exemplary separators include ion (e.g., proton or anion) exchange membranes, which are thin polymeric films that permit the passage of ions. In one embodiment, the separator includes a proton conducting polymer comprising a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer. For example, the sulfonated tetrafluoroethylene-based fluoropolymer-copolymer may be ethanesulfonyl fluoride, 2-[1-[difluoro-[(trifluoroethenyl)oxy]methyl]-1,2,2,2-tetrafluoroethoxy]-1,1,2,2,-tetrafluoro-, with tetrafluoroethylene, which is commercially available from the E. I. du Pont de Nemours and Company, under the tradename Nafion®. - In accordance with embodiments of the present invention, the electrochemical cell 10 can be operated at a constant voltage or a constant current. While the electrochemical cell 10 is shown in a flow cell configuration, which can operate continuously, the present invention is not limited thereto.
- The electrochemical cell 10 may incorporate the following features:
- A. Flow Rate Controllers
- In accordance with embodiments of the present invention, the flow rate of the CO2 and the hydrocarbon through the cathodic and
anodic chambers - B. Temperature Controllers
- In accordance with embodiments of the present invention, the temperature of the cell can be in a range from about 25° C. to about 120° C.
- C. Pressure Controllers
- In accordance with embodiments of the present invention, the pressure of the cell can be in a range from about 1 atm to about 100 atm.
- D. Humidifiers.
- In accordance with embodiments of the present invention, the humidity of the CO2-containing fluid and/or the hydrocarbon-containing fluid can be modulated to achieve a desired level. For example, the humidity may be increased or decreased, and may be in a range from less than about 1% to about 100% Relative Humidity (RH) at the operating temperature of the electrochemical cell.
- Materials and methods: Graphite powder (C, grade #38), sulfuric acid (H2SO4, 96.3%), hydrochloric acid (HCl, 37.4%), potassium hydroxide (KOH, 85.0%+), potassium chloride (KCl, 99.6%), carbon dioxide (CO2), ethane (C2H6), and hexane (C6H14) are obtainable from Fisher Scientific. Potassium permanganate (KMnO4, 98%), sodium nitrate (NaNO3, 98%+), hydrogen peroxide (H2O2, 29-32%), and chloroplatinic acid (H2PtCl6·6 H2O) are obtainable from Alfa Aeaser.
- Graphene-platinum nanocomposites synthesis: Graphene oxide (GO) may be prepared by the modified Hummers method. A typical procedure for the synthesis of the GO involves the following steps:
- a). 3 g of graphite powder and 1.5 g of NaNO3 may be dissolved in a 400 mL beaker containing 100 mL of H2SO4 placed in an icewater bath. 12 g of KMnO4 may be gradually added to the mixture in 1 h while stirring at 200 rpm with a 25.4 mm×9.5 mm magnetic stirring bar, and the resulting mixture may be continuously stirred at 200 rpm at room temperature overnight.
- b). 150 mL of deionized H2O may be slowly added to the stirred mixture, and the diluted mixture may be further stirred at 200 rpm for 1 day. Afterwards, 15 mL of H2O2 may be added to the diluted mixture and stirred for an additional 2 hours.
- c). The diluted mixture may then be washed with 5 wt % HCl, followed by centrifugation (Thermo Scientific Sorvall Legend X1 Centrifuge) at 4000 rpm for 10 min. This purification/washing process may be repeated as desired, e.g., 15 times. The remaining mixture may then be washed with deionized H2O, followed by centrifugation at 4000 rpm for 10 min. The deionized H2O washing process may be repeated as desired, e.g., 5 times, to obtain the GO slurry.
- d). The GO slurry may be dried at room temperature in a vacuum oven (about 25 in. of Hg vacuum) (Napco E Series, Model 5831) equipped with a vacuum pump (Gast, Model DDA-V191-AA) for 1 day to get GO powder. A GO dispersion may be prepared by sonication (Zenith Ultrasonic bath at 40 kHz) of the graphite oxide powder in deionized H2O for 30 min, followed by 10 min centrifugation at 1000 rpm. The concentration of the GO dispersion can be adjusted to about 0.2 mg/ml.
- e). Glassy carbon electrodes (GCE, 5.0 mm diameter) may be first polished with 1 μm and 0.05 μm polishing alumina and rinsed with deionized water, and finally sonicated in deionized water for about 10 min to remove any alumina particles. After drying with an Argon flow, the polished GCEs may be used as representative substrates for electrochemical reduction of graphene oxide (ERGO) to form ERGO-catalyst nanocomposites. To prepare the nanocomposites, 20 μl of the GO dispersion may be first dropped on the polished GCEs. Drying at room temperature for about 1 h forms GO films on the GCEs. A one-step electrochemical reduction process may then be performed in 0.1 M KCl solution in the presence of 5 mM H2PtCl6·6 H2O at −1.1 V vs. Ag/AgCl for 5 min with 60 rpm stirring for producing a pure electrochemically reduced graphene oxide (ERGO) electrode and an EGRO-Ni electrode, respectively. A platinum foil (e.g., 2 cm×1 cm) may be used as a counter electrode.
- A membrane electrode assembly (MEA) may be built using the Graphene-Pt nanocomposite as the anode electrode or as both the anode and cathode electrode, using NAFION® as the membrane separator. The MEA may be assembled into the electrochemical cell 10 as depicted in the FIGURE. Toray TGP-H-030 carbon paper may be used as gas diffusion layers in both the anodic and cathodic chambers.
- While the present invention was illustrated by the description of one or more embodiments thereof, and while the embodiments have been described in considerable detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative product and method, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept embraced by the following claims.
Claims (12)
1. An electrochemical cell for reducing carbon dioxide, comprising:
a cathode compartment including a cathode comprising a first conducting component that is active toward adsorption and reduction of CO2;
an anode compartment including an anode comprising a second conducting component that is active toward adsorption and oxidation of a hydrocarbon, wherein the second conducting component is layered on an anode substrate surface, an overlying layer of the second conducting component incompletely covering an underlying layer of the second conducting component, and a hydrophobic modifier comprising an electrochemically reduced graphene oxide coating is present on both the first conducting component and the second conducting component;
a separator comprising an ion exchange membrane that physically separates the anode and cathode compartments and permits the passage of ions therebetween; and
wherein a hydrophobic modifier is present on at least a portion of a surface of the second conducting component, or both the first and second conducting components.
2. The electrochemical cell of claim 1 , wherein the second conducting component comprises a material selected from the group consisting of platinum (Pt), iridium (Ir), ruthenium (Ru), palladium (Pd), rhodium (Rh), nickel (Ni), cobalt (Co), iron (Fe), copper (Cu), and their combinations.
3. The electrochemical cell of claim 1 , wherein the second conducting component comprises platinum.
4. The electrochemical cell of claim 1 , wherein the hydrocarbon is selected from gaseous methane, ethane, propane, butane, pentane, and hexane.
5. The electrochemical cell of claim 1 , wherein the first conducting component is coupled to a substrate.
6. The electrochemical cell of claim 1 , wherein the first conducting component comprises a first nanoparticle.
7. The electrochemical cell of claim 6 , wherein the second conducting component comprises a second nanoparticle.
8. The electrochemical cell of claim 1 , wherein the second conducting component comprises a first nanoparticle.
9. The electrochemical cell of claim 1 , wherein the first conducting component comprises a material is selected from the group consisting of platinum (Pt), iridium (Ir), ruthenium (Ru), palladium (Pd), rhodium (Rh), osmium (Os), nickel (Ni), cobalt (Co), iron (Fe), copper (Cu), and their combinations.
10. The electrochemical cell of claim 1 , wherein the electrochemical cell is configured to adsorb CO2 onto the cathode and adsorb the hydrocarbon onto the anode in response to applying a voltage between the cathode exposed to a first fluid comprising CO2 and the anode exposed to a second fluid comprising the hydrocarbon.
11. The electrochemical cell of claim 10 , wherein the voltage is sufficient to simultaneously oxidize the hydrocarbon to a first olefin and reduce the CO2 to form a second olefin.
12. The electrochemical cell of claim 11 , wherein the oxidation of the hydrocarbon is configured to occur via a dehydrogenation reaction.
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