US20110237830A1 - Novel catalyst mixtures - Google Patents
Novel catalyst mixtures Download PDFInfo
- Publication number
- US20110237830A1 US20110237830A1 US12/830,338 US83033810A US2011237830A1 US 20110237830 A1 US20110237830 A1 US 20110237830A1 US 83033810 A US83033810 A US 83033810A US 2011237830 A1 US2011237830 A1 US 2011237830A1
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- United States
- Prior art keywords
- catalyst
- helper
- active element
- helper catalyst
- conversion
- Prior art date
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- Abandoned
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- 239000003054 catalyst Substances 0.000 title claims abstract description 142
- 239000000203 mixture Substances 0.000 title description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 113
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 25
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 235000019253 formic acid Nutrition 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 22
- 229910052737 gold Inorganic materials 0.000 claims description 19
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 16
- 229960003178 choline chloride Drugs 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- 229910052718 tin Inorganic materials 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 235000019743 Choline chloride Nutrition 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- FNPBHXSBDADRBT-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CCO FNPBHXSBDADRBT-UHFFFAOYSA-M 0.000 claims description 8
- 229910052745 lead Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052772 Samarium Inorganic materials 0.000 claims description 7
- 229910052771 Terbium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052753 mercury Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 229910052716 thallium Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000005496 phosphonium group Chemical group 0.000 claims description 4
- 229910052729 chemical element Inorganic materials 0.000 claims description 3
- 150000003003 phosphines Chemical class 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 3
- JJCWKVUUIFLXNZ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCO JJCWKVUUIFLXNZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 claims 4
- 235000008979 vitamin B4 Nutrition 0.000 claims 2
- 150000002891 organic anions Chemical class 0.000 claims 1
- 150000002892 organic cations Chemical class 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 description 19
- 239000010931 gold Substances 0.000 description 19
- 238000012552 review Methods 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000011135 tin Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- -1 CH3COO− Chemical compound 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
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- 239000000243 solution Substances 0.000 description 10
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- 238000002474 experimental method Methods 0.000 description 9
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 7
- 230000005518 electrochemistry Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004832 voltammetry Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- 239000002574 poison Substances 0.000 description 4
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
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- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 238000005984 hydrogenation reaction Methods 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013580 millipore water Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- CWLUFVAFWWNXJZ-UHFFFAOYSA-N 1-hydroxypyrrolidine Chemical class ON1CCCC1 CWLUFVAFWWNXJZ-UHFFFAOYSA-N 0.000 description 1
- FHCUSSBEGLCCHQ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CCO FHCUSSBEGLCCHQ-UHFFFAOYSA-M 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001295 alanines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008361 aminoacetonitriles Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- 150000001484 arginines Chemical class 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 150000001510 aspartic acids Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000003937 benzamidines Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000023266 generation of precursor metabolites and energy Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 235000008521 threonine Nutrition 0.000 description 1
- 150000003588 threonines Chemical class 0.000 description 1
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- 150000008648 triflates Chemical class 0.000 description 1
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Images
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0289—Sulfur
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/23—Carbon monoxide or syngas
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- 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
- C25B11/095—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 at least one of the compounds being organic
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- C25B3/03—Acyclic or carbocyclic hydrocarbons
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- C25B3/26—Reduction of carbon dioxide
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/004—CO or CO2
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Definitions
- the field of the invention is catalysis and catalysts.
- the catalysts of this invention are applicable, for example, to the electrochemical conversion of carbon dioxide into formic acid.
- an electrochemical cell contains an anode ( 50 ), a cathode ( 51 ) and an electrolyte ( 53 ) as indicated in FIG. 1 .
- Catalysts are placed on the anode, and or cathode and or in the electrolyte to promote desired chemical reactions.
- reactants or a solution containing reactants is fed into the cell.
- a voltage is applied between the anode and the cathode, to promote an electrochemical reaction.
- a reactant comprising CO 2 , carbonate or bicarbonate is fed into the cell.
- a voltage is applied to the cell and the CO 2 reacts to form new chemical compounds. Examples of cathode reactions in The Hori Review include
- catalysts comprising one or more of V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, C, In, Sn, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd have all shown activity for CO 2 conversion.
- Reviews include Ma, et al. (Catalysis Today, 148, 221-231, 2009) Hori (Modern Aspects of Electrochemistry, 42, 89-189, 2008), Gattrell, et al. (Journal of Electroanalytical Chemistry, 594, 1-19, 2006), DuBois (Encyclopedia of Electrochemistry, 7a, 202-225, 2006) and references therein.
- the Bell Report “The major obstacle preventing efficient conversion of carbon dioxide into energy - bearing products is the lack of catalyst” with sufficient activity at low overpotentials and high electron conversion efficiencies.
- the overpotential is associated with lost energy of the process and so one needs the overpotential to be as low as possible. Yet, according to The Bell Report “ Electron conversion efficiencies of greater than 50 percent can be obtained, but at the expense of very high overpotentials” This limitation needs to be overcome before practical processes can be obtained.
- the '134 patent also considers the use of salt (NaCl) as a secondary “catalyst” for CO 2 reduction in the gas phase but salt does not lower the overpotential for the reaction.
- a second disadvantage of many of the catalysts is that they also have low electron conversion efficiency. Electron conversion efficiencies over 50% are needed for practical catalyst systems.
- the invention provides a novel catalyst mixture that can overcome one or more of the limitations of low rates, high overpotentials and low electron conversion efficiencies (i.e. selectivities) for catalytic reactions and high powers for sensors.
- the catalyst mixture includes at least one Catalytically Active Element, and at least one Helper Catalyst.
- the Catalytically Active Element and the Helper Catalyst are combined the rate and/or selectivity of a chemical reaction can be enhanced over the rate seen in the absence of the Helper Catalyst.
- the overpotential for electrochemical conversion of carbon-dioxide can be substantially reduced and the current efficiency (i.e. selectivity) for CO 2 conversion can be substantially increased.
- the invention is not limited to catalysts for CO 2 conversion.
- catalysts that include Catalytically Active Elements and Helper Catalysts might enhance the rate of a wide variety of chemical reactions.
- Reaction types include: homogeneously catalyzed reactions, heterogeneously catalyzed reactions, chemical reactions in chemical plants, chemical reactions in power plants, chemical reactions in pollution control equipment and devices, chemical reactions in fuel cells, chemical reactions in sensors.
- the invention includes all of these examples.
- the invention also includes processes using these catalysts.
- FIG. 1 is a diagram of a typical electrochemical cell.
- FIG. 2 is a schematic of how the potential of the system moves as it proceeds along the reaction coordinate in the absence of the ionic liquid if the system goes through a (CO 2 ) ⁇ intermediate
- the reaction coordinate indicates the fraction of the reaction that has completed.
- a high potential for (CO 2 ) ⁇ formation can create a high overpotential for the reaction.
- FIG. 3 illustrates how the potential could change when a helper catalyst is used.
- the reaction could go through a CO 2 -EMIM complex rather than a (CO 2 ) ⁇ substantially lowering the overpotential for the reaction.
- FIGS. 4A , 4 B and 4 C illustrate some of the cations that may be used to form a complex with (CO 2 ) ⁇
- FIGS. 5A and 5B illustrates some of the anions that may stabilize the (CO 2 ) ⁇ anion.
- FIG. 6 illustrates some of the neutral molecules that may be used to form a complex with (CO 2 ) ⁇
- FIG. 7 shows a schematic of a cell used for the experiments in Examples 1, 2, 3, 4 and 5.
- FIG. 8 shows comparison of the cyclic voltametry for a blank scan where the catalyst was synthesized as in Example 1 where i) the EMIM-BF4 was sparged with argon and ii) a scan where the EMIM-BF4 was sparged with CO 2 . Notice the large negative peak associated with CO 2 formation
- FIG. 9 shows a series of Broad Band Sum Frequency Generation (BB-SFG) taken sequentially as the potential in the cell was scanned from +0. to ⁇ 1.2 with respect to SHE.
- BB-SFG Broad Band Sum Frequency Generation
- FIG. 10 shows a CO stripping experiment done by holding the potential at ⁇ 0.6 V for 10 or 30 minutes and them measuring the size of the CO stripping peak between 1.2 and 1.5 V with respect to RHE.
- FIG. 11 shows a comparison of the cyclic voltametry for a blank scan where the catalyst was synthesized as in Example 3 where i) the water-choline iodide mixture was sparged with argon and ii) a scan where the water-choline iodide mixture was sparged with CO 2 .
- FIG. 12 shows a comparison of the cyclic voltametry for a blank scan where the catalyst was synthesized as in Example 4 where i) the water-choline chloride mixture was sparged with argon and ii) a scan where the water-choline chloride mixture was sparged with CO 2 .
- FIG. 13 shows a comparison of the cyclic voltametry for a blank scan where the catalyst was synthesized as in Example 5 where i) the water-choline chloride mixture was sparged with argon and ii) a scan where the water-choline chloride mixture was sparged with CO 2 .
- FIG. 14 shows a schematic of the sensor.
- FIG. 15 shows a schematic of where EMBF4 is placed on the sensor.
- FIG. 16 shows the current measured when the voltage on the sensor was exposed to various gases, the applied voltage on the sensor was swept from 0 to 5 volts at 0.1 V/sec.
- FIG. 17 shows the resistance of the sensor, in nitrogen and in carbon dioxide. The resistance was determined by measuring the voltage needed to maintain a current of 1 microamp. Time is the time from when the current was applied.
- any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least two units between any lower value and any higher value.
- concentration of a component or value of a process variable such as, for example, size, angle size, pressure, time and the like, is, for example, from 1 to 90, specifically from 20 to 80, more specifically from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc., are expressly enumerated in this specification.
- one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
- electrochemical conversion of CO 2 refers to any electrochemical process, where carbon dioxide, carbonate, or bicarbonate is converted into another chemical substance in any step of the process.
- CV refers to a cyclic voltamogram or cyclic voltammetry.
- Cathode Overpotential refers to the overpotential on the cathode of an electrochemical cell.
- Anode Overpotential refers to the overpotential on the anode of an electrochemical cell.
- Electrode Conversion Efficiency refers to selectivity of an electrochemical reaction. More precisely, it is defined as the fraction of the current that is supplied to the cell that goes to the production of a desired product.
- Catalytically Active Element refers to any chemical element that can serve as a catalyst for the electrochemical conversion of CO 2 .
- Helper Catalyst refers to any organic molecule or mixture of organic molecules that does at least one of the following:
- Active Element refers to any mixture that includes one or more Catalytically Active Element and at least one Helper Catalyst
- Ionic Liquid refers to salts or ionic compounds that form stable liquids at temperatures below 200° C.
- Deep Eutectic Solvent refers to an ionic solvent that includes of a mixture which forms a eutectic with a melting point lower than that of the individual components.
- the invention relates generally to Active Element, Helper Catalyst Mixtures where the mixture does at least one of the following:
- such mixtures can lower the overpotential for CO 2 conversion to a value less than the overpotentials seen when the same Catalytically Active Element is used without the Helper Catalyst.
- catalysts include one or more of V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Sn, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd all show activity for CO 2 conversion.
- Products include one or more of CO, OH ⁇ , HCO ⁇ , H 2 CO, (HCO 2 ) ⁇ , H 2 CO 2 , CH 3 OH, CH 4 , C 2 H 4 , CH 3 CH 2 OH, CH 3 COO ⁇ , CH 3 COOH, C 2 H 6 , CH 4 , O 2 , H 2 (COOH) 2 , (COO ⁇ ) 2 .
- V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Sn, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd are each examples of Catalytically Active Elements but the invention is not limited to this list of chemical elements.
- Possible products of the reaction are include one or more of CO, OH ⁇ , HCO ⁇ , H 2 CO, (HCO 2 ) ⁇ , H 2 CO 2 , CH 3 OH, CH 4 , C 2 H 4 , CH 3 CH 2 OH, CH 3 COO ⁇ , CH 3 COOH, C 2 H 6 , CH 4 , O 2 , H 2 (COOH) 2 , (COO ⁇ ) 2 , but the invention is not limited to this list of products.
- FIGS. 2 and 3 illustrate one possible mechanism by which a Helper Catalyst can enhance the rate of CO 2 conversion.
- Chandrasekaran, et al. Surface Science, 185, 495-514, 1987
- the high overpotentials for CO 2 conversion occur because the first step in the electroreduction of CO 2 is the formation of a (CO 2 ) intermediate. It takes energy to form the intermediate as illustrated in FIG. 2 . This results in a high overpotential for the reaction.
- FIG. 3 illustrates what might happen if a solution containing 1-ethyl-3-methylimidazolium (EMIM + ) cations is added to the mixture.
- EMIM + might be able to form a complex with the (CO 2 ) ⁇ intermediate. In that case, the reaction could proceed via the EMIM + -(CO 2 ) ⁇ complex instead of going through a bare (CO 2 ) ⁇ intermediate as illustrated in FIG. 3 . If the energy to form the EMIM + -(CO 2 ) ⁇ complex is less than the energy to form the (CO 2 ) ⁇ intermediate, the overpotential to for CO 2 conversion could be substantially reduced. Therefore any substance including EMIM + cations could act as a Helper Catalyst for CO 2 conversion.
- Catalytically Active Element that can catalyze reactions of (CO 2 ) in order to get high rates of CO 2 conversion.
- Catalysts include at least one of the following Catalytically Active Elements have been previously reported to be active for electrochemical conversion of CO 2
- FIG. 3 could be drawn for any molecule that could form a complex with (CO 2 ) ⁇ .
- solutions including one or more of: ionic liquids, deep eutectic solvents, amines, and phosphines, including specifically imidazoniums, pyridiniums, pyrrolidiniums, phosphoniums, ammoniums sulfoniums, prolinates, methioninates, form complexes with CO 2 . Consequently, they may serve as Helper Catalysts. Also Davis Jr, et al.
- salts that show ionic properties. Specific examples include compounds including one or more of Acetocholines, alanines, aminoacetonitriles, methylammoniums, arginines, aspartic acids, threonines, chloroformamidiniums, thiouroniums, quinoliniums, pyrrolidinols, serinols, benzamidines, sulfamates, acetates, carbamates, triflates, and cyanides. These salts may act as helper catalysts. These examples are meant for illustrative purposes only, and are not meant to limit the scope of the invention.
- helper catalyst not every substance that forms a complex with (CO 2 ) ⁇ will act as a helper catalyst.
- Masel (Chemical Kinetics and Catalysis, Wiley 2001, p717-720), notes that when an intermediate binds to a catalyst, the reactivity of the intermediate decreases. If the intermediate bonds too strongly to the catalyst, the intermediate will become unreactive, so the substance will not be effective. This provides a key limitation on substances that act as helper catalysts.
- the helper catalyst cannot form too strong of a bond with the (CO 2 ) ⁇ that the (CO 2 ) ⁇ is unreactive toward the Catalytically Active Element.
- the substance to form a complex with the (CO 2 ) ⁇ so is that the complex is stable (i.e. has a negative free energy of formation) at potentials less negative than ⁇ 1 V with respect to SHE.
- the complex should not be so stable, that the free energy of the reaction between the complex and the Catalytically Active Element is more positive than about 3 kcal/mol.
- Zhao, et al. (The Journal of Supercritical Fluids, 32, 287-291, 2004) examined CO 2 conversion over copper in 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) but FIG. 3 in Zhao et al shows that the BMIM-PF6 did NOT lower the overpotential for the reaction (i.e. the BMIM-PF6 did not act as a Helper Catalyst)/ This may be because the BMIM-PF6 formed such a strong bond to the (CO 2 ) ⁇ that the CO 2 was unreactive with the copper.
- BMIM-PF6 1-n-butyl-3-methylimidazolium hexafluorophosphate
- BMIM-Br 1-butyl-3-methylimidazolium bromide
- Solutions consisting of one or more of the cations in FIG. 4 , the anions in FIG. 5 , the neutral species in FIG. 6 , where R1, R2 and R3 include H, OH or any ligand containing at least on carbon atom are believed to form complexes with CO 2 or (CO 2 ⁇ .
- Specific examples include: imidazoniums, pyridiniums, pyrrolidiniums, phosphoniums, ammoniums and sulfoniums, prolinates, methioninates. All of these examples might be able to be used as Helper Catalysts for CO 2 conversion and are specifically included in the invention. These examples are meant for illustrative purposes only, and are not meant to limit the scope of the invention.
- Helper Catalyst could be in any one of the following forms i) a solvent for the reaction, ii) an electrolyte, iii) an additive to any component of the system, or iv) something that is bound to at least one of the catalysts in a system.
- a solvent for the reaction ii) an electrolyte
- iii) an additive to any component of the system iii) an additive to any component of the system
- something that is bound to at least one of the catalysts in a system iv
- Helper Catalyst Those trained in the state of the art should recognize that one might only need a tiny amount of the Helper Catalyst to have a significant effect. Catalytic reactions often occur on distinct active sites. The active site concentration can be very low so in principle a small amount of Helper Catalyst can have a significant effect on the rate. One can obtain an estimate of how little of the helper catalyst would be needed to change the reaction from Pease et al, JACS 47, 1235 (1925)'s study of the effect of carbon monoxide (CO) on the rate of ethylene hydrogenation on copper. This paper is incorporated into this disclosure by reference.
- CO carbon monoxide
- Example 1 The upper limit is illustrated in Example 1 below where the Active Element, Helper Catalyst Mixture has approximately 99.999% by weight of Helper Catalyst, and the helper catalyst can be an order of magnitude more concentrated.
- the range of Helper Catalyst concentrations for the invention here may be 0.0000062% to 99.9999%
- FIG. 3 only considered the electrochemical conversion of CO 2 , but the method is general.
- energy is needed to create a key intermediate in a reaction sequence. Examples include: homogeneously catalyzed reactions, heterogeneously catalyzed reactions, chemical reactions in chemical plants, chemical reactions in power plants, chemical reactions in pollution control equipment and devices, chemical reactions in safety equipment, chemical reactions in fuel cells, and chemical reactions in sensors.
- Theoretically if one could find a Helper Catalyst that forms a complex with a key intermediate the rate of the reaction should increase. All of these examples are within the scope of the invention.
- Specific examples of specific processes that may benefit with Helper Catalysts include the electrochemical process to produce products including one or more of Cl 2 , Br 2 , I 2 , NaOH, KOH, NaClO, NaClO 3 , KClO 3 , CF 3 COOH.
- the Helper Catalyst could enhance the rate of a reaction even if it does not form a complex with a key intermediate.
- Examples of possible mechanisms of action include the Helper Catalyst i) lowering the energy to form a key intermediate by any means ii) donating or accepting electrons or atoms or ligands, iii) weakening bonds or otherwise making them easier to break, iv) stabilizing excited states, v) stabilizing transition states, vi) holding the reactants in close proximity or in the right configuration to react vii) block side reactions.
- the invention is not limited to just the catalyst. Instead it includes any process or device that uses an Active Element, Helper Catalyst Mixture as a catalyst. Fuel cells are sensors are specifically included in the invention.
- EMIM-BF 4 1-ethyl-3-Methylimidazoilum Tetrafluoroborate
- the cell consisted of a Three neck flask ( 101 ), to hold the anode ( 108 ), and the cathode ( 109 ).
- the reference electrode ( 103 ) was fitted with a vycor frit to prevent any of the reference electrode solution from contaminating the ionic liquid in the capillary.
- the reference electrode was calibrated against the Fc/Fc + redox couple.
- a conversion factor of +535 was used convert our potential axis to reference the Standard Hydrogen Electrode (SHE).
- a 25 ⁇ 25 mm Platinum gauze (size 52) ( 113 ) was connected to the anode while a 0.33 cm 2 polycrystalline gold plug ( 115 ) was connected to the cathode.
- a catalyst ink comprising a Catalytically Active Element platinum was first prepared as follows: First 0.0056 grams of Johnson-Matthey Hispec 1000 platinum black purchased from Alfa-Aesar was mixed with 1 grams of milipore water and sonicating for 10 minutes to produce a solution containing a 5.6 mg/ml suspension of platinum black in Millipore water. A 25 ⁇ l drop of the ink was placed on the gold plug and allowed to dry under a heat lamp for 20 min, and subsequently allowed to dry in air for an additional hour. This yielded a catalyst with 0.00014 grams of Catalytically Active Element, a platinum, on a gold plug. The gold plug was mounted into the three neck flask ( 101 ).
- EMIM-BF 4 EMD chemicals
- concentration of water in the ionic liquid after this procedure was found to be ca. 90 mM by conducting a Karl-Fischer titration. (i.e. the ionic liquid contained 99.9999% of helper catalyst) 13 grams of the EMIM-BF 4 was added to the vessel, creating an Active Element, Helper Catalyst Mixture that contained about 99.999% of the Helper Catalyst.
- the geometry was such that the gold plug formed a meniscus with the EMIM-BF 4
- Next ultra-high-purity (UHP) Argon was fed through the sparging tube ( 104 ) and glass frit ( 112 ) for 2 hours at 200 sccm to further remove any moisture picked up by contact with the air.
- the cathode was connected to the working electrode connection in a SI 1287 Solatron electrical interface, the anode was connected to the counter electrode connection and the reference electrode was connected to the reference electrode connection on the Solartron. Then the potential on the cathode was swept from ⁇ 1.5 V versus a standard hydrogen electrode (SHE) to 1V vs. SHE and then back to ⁇ 1.5 volts versus SHE thirty times at a scan rate of 50 mV/s. The current produced during the last scan is labeled as the “blank” scan in FIG. 8 .
- SHE standard hydrogen electrode
- BB-SFG broad-band sum frequency generation
- Tables 1 compares these results to results from the previous literature.
- the table shows the actual cathode potential. More negative cathode potentials correspond to higher overpotentials. More precisely the overpotential is the difference between the thermodynamic potential for the reaction (about ⁇ 0.2 V with respect to SHE) and the actual cathode potential. The values of the cathode overpotential are also given in the table. Notice that the addition of the Helper Catalyst has reduced the cathode overpotential (i.e. lost work) on platinum by a factor of 4.5 and improved the selectivity to nearly 100%.
- Table 2 indicates the cathode potential needed to convert CO 2 . Notice that all of the values are more negative than ⁇ 0.9 V. By comparison, FIG. 8 shows that CO 2 conversion starts at ⁇ 0.2 V with respect to RHE, when the Active Element, Helper Catalyst Mixture is used as a catalyst. More negative cathode potentials correspond to higher overpotentials. This is further confirmation Active Element, Helper Catalyst Mixtures are advantageous for CO 2 conversion.
- FIG. 9 shows a series of BB-SFG spectra taken during the reaction. Notice the peak at 2350 cm ⁇ 1 . This peak corresponds to the formation of a stable complex between the Helper Catalyst and (CO 2 ) ⁇ . It is significant that the peak starts at ⁇ 0.1 with respect to SHE. According to The Hori Review, (CO 2 ) ⁇ is thermodynamically unstable unless the potential is more negative than ⁇ 1.2 V with respect to SHE on platinum. Yet FIG. 9 shows that the complex between EMIM-BF 4 and (CO 2 ) ⁇ is stable at ⁇ 0.1 V with respect to SHE.
- (CO 2 ) ⁇ is the rate determining step in CO 2 conversion to CO, OH ⁇ , HCO ⁇ , H 2 CO, (HCO 2 ) ⁇ , H 2 CO 3 , CH 3 OH, CH 4 , C 2 H 4 , CH 3 CH 2 OH, CH 3 COO ⁇ , CH 3 COOH, C 2 H 6 , CH 4 , O 2 , H 2 , (COOH) 2 , (COO ⁇ ) 2 on V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Sn, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd.
- the (CO 2 ) ⁇ is thermodynamically unstable at low potentials, which leads to a high overpotential for the reaction as indicated in FIG. 2 .
- the data in FIG. 9 shows that one can form the EMIM-BF4-(CO 2 ) complex at low potentials.
- the complex is thermodynamically.
- the reaction can follow a low energy pathway for CO 2 conversion to CO, OH ⁇ , HCO ⁇ , H 2 CO, (HCO 2 ) ⁇ , H 2 CO 2 , CH 3 OH, CH 4 , C 2 H 4 , CH 3 CH 2 OH, CH 3 COO ⁇ , CH 3 COOH, C 2 H 6 , CH 4 , O 2 , H 2 , (COOH) 2 , (COO ⁇ ) 2 on V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Sn, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd as indicated in FIG. 3 .
- This example shows that water additions speed the formation of CO.
- the experiment used the Cell and procedures in Example 1, with the following exception: a solution containing 98.55% EMIM-BF4 and 0.45% water was substituted for the 99.9999% EMIM-BF4 used in Example 1, the potential was held for 10 or 30 minutes at ⁇ 0.6V with respect to RHE, and then the potential was ramped positively at 50 mV/sec.
- FIG. 10 shows the result. Notice the peak at between 1.2 and 1.5 eV. This is the peak associated with CO formation and is much larger than in example 1. Thus the addition of water has accelerated the formation of CO presumably by acting as a reactant.
- Example 2 The experiment used the cell and procedures in Example 1, with the following exceptions: ii) A 10.3% by weight of a Helper Catalyst, choline iodide in water solution was substituted for the 1-ethyl-3-methylimidazolium tetrafluoroborate and ii) a 0.25 cm 2 Pd foil purchased from Alfa Aesar was substituted for the gold plug and platinum black on the cathode, and a silver/silver chloride reference was used.
- FIG. 11 shows a CV taken under these conditions.
- the data in Table 2 indicates that one needs to use a voltage more negative that ⁇ 1.2 V to convert CO 2 on palladium in the absence of the Helper Catalyst.
- the helper catalyst has lowered the overpotential for CO 2 formation by about 0.5 V.
- the next example is to demonstrate that the invention can be practiced using a third Helper Catalyst, choline chloride.
- Example 3 The experiment used the Cell and procedures in Example 3, with the following exception: a 6.5% by weight choline chloride in water solution was substituted for choline iodide solution.
- FIG. 12 shows a comparison of the cyclic voltametry for a blank scan where i) the water-choline chloride mixture was sparged with argon and ii) a scan where the water-choline iodide mixture was sparged with CO 2 . Notice the negative going peaks starting at about ⁇ 0.6. This shows that CO 2 is being reduced at ⁇ 0.6 V.
- Table 2 indicates that one needs to use a voltage more negative than ⁇ 1.2 V is needed to convert CO 2 on palladium in the absence of the Helper Catalyst. Thus, the overpotential for CO 2 conversion has been lowered by 0.6 V by the Helper Catalyst.
- the next example is to demonstrate that the invention can be practiced using a third metal, nickel.
- Example 4 The experiment used the Cell and procedures in Example 4, with the following exception: a nickel foil from Alfa Aesar was substituted for the palladium foil.
- FIG. 13 shows a comparison of the cyclic voltametry for a blank scan where i) the water-choline chloride mixture was sparged with argon and ii) a scan where the water-choline chloride mixture was sparged with CO 2 . Notice the negative going peaks starting at about ⁇ 0.6. This shows that CO 2 is being reduced at ⁇ 0.6 V.
- Table 2 indicates that one needs to use a voltage more negative than ⁇ 1.48 V is needed to convert CO 2 on nickel in the absence of the Helper Catalyst. Thus, the Helper Catalyst has lowered the overpotential for CO 2 conversion.
- helper catalyst is very effective in improving the selectivity of the reaction.
- the Hori Review reports that hydrogen is the major product during carbon dioxide reduction on nickel in aqueous solutions. The hydrolysis shows 1.4% selectivity to formic acid, and no selectivity to carbon monoxide.
- analysis of the reaction products by CV indicate that carbon monoxide is the major product during CO 2 conversion on nickel in the presence of the Helper Catalyst. There may be some formate formation. However, no hydrogen is detected. This example shows that the helper catalyst has tremendiously enhanced the selectivity of the reaction toward CO and formate.
- the sensor will be a simple electrochemical device where an in an Active Element, Helper Catalyst Mixture is placed on an anode and cathode in an electrochemical device, then the resistance of the sensor is measured. If there no CO 2 present, the resistance will be high, but not infinite because of leakage currents. When CO 2 is present, the Active Element, Helper Catalyst Mixture may catalyze the conversion of CO 2 . That allows more current to flow through the sensor. Consequently, the sensor resistance decreases. As a result, the sensor may be used to detect carbon dioxide.
- An example sensor was fabricated on a substrate made from a 100 mm Silicon wafer (Silicon Quest, 500 ⁇ m thick, ⁇ 100> oriented, 1-5 ⁇ cm nominal resistivity) which was purchased with a 500 nm thermal oxide layer.
- a substrate made from a 100 mm Silicon wafer (Silicon Quest, 500 ⁇ m thick, ⁇ 100> oriented, 1-5 ⁇ cm nominal resistivity) which was purchased with a 500 nm thermal oxide layer.
- 170 ⁇ chromium was deposited by DC magnetron sputtering ( ⁇ 10 ⁇ 2 Ton of argon background pressure).
- 1000 ⁇ of a Catalytically Active element, gold was deposited on the chromium and the electrode was patterned via a standard lift-off photolithography process to yield the device shown schematically in FIG. 14 .
- the device consisted of an anode ( 200 ) and cathode ( 201 ) separated by a 6 ⁇ m gap, wherein the anode and cathode were coated with a Catalytically Active element, gold. At this point the sensor could not detect CO 2 .
- EMIM BF 4 ( 202 ) was added over the junction as shown FIG. 15 .
- the device was mounted into a sensor test cell with wires running from the anode and cathode.
- the anode and cathode were connected to a SI 1287 Solatron electrical interface, and the catalysts were condition by sweeping from o volts to 5 volts at 0.1 V/sec and then back again. The process was repeated 16 times. Then the sensor was exposed to either nitrogen, oxygen, dry air or pure CO 2 , and the sweeps were recorded. The last sweep is shown in FIG. 16 . Notice that there is a sizable peak at an applied voltage of 4 volts in pure CO 2 . That peak is associated with the electrochemical conversion of CO 2 .
- the peak is absent, when the sensor is exposed to oxygen or nitrogen, but it is clearly seen when the sensor is exposed to air containing less than 400 ppm of CO 2 . Further the peak grows as the CO 2 concentration increases. Thus, the sensor can be used to detect the presence of CO 2 .
- FIG. 17 shows that less voltage is needed to maintain the current when CO 2 is added to the cell. This shows that the sensor that include an Active Element, Helper Catalyst Mixture responds to the presence of CO 2 .
- Table 4 compares the sensor here to those in the previous literature. Notice that the new sensor uses orders of magnitude less energy than commercial CO 2 sensors. This is a key advantage for many applications.
- This example also illustrates that the invention can be practiced with a third active element, gold.
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AU2011276362A AU2011276362B2 (en) | 2010-07-04 | 2011-07-01 | Novel catalyst mixtures |
KR1020137002749A KR101801659B1 (ko) | 2010-07-04 | 2011-07-01 | 신규 촉매 혼합물 |
PCT/US2011/042809 WO2012006240A1 (fr) | 2010-07-04 | 2011-07-01 | Nouveaux mélanges de catalyseurs |
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JP2013518759A JP6059140B2 (ja) | 2010-07-04 | 2011-07-01 | 電気化学セル |
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CA2802893A CA2802893C (fr) | 2010-07-04 | 2011-07-01 | Nouveaux melanges de catalyseurs |
US13/445,887 US9012345B2 (en) | 2010-03-26 | 2012-04-12 | Electrocatalysts for carbon dioxide conversion |
US13/626,873 US8956990B2 (en) | 2010-03-26 | 2012-09-25 | Catalyst mixtures |
US13/775,245 US9193593B2 (en) | 2010-03-26 | 2013-02-24 | Hydrogenation of formic acid to formaldehyde |
US14/035,935 US9181625B2 (en) | 2010-03-26 | 2013-09-24 | Devices and processes for carbon dioxide conversion into useful fuels and chemicals |
US14/591,902 US9464359B2 (en) | 2010-03-26 | 2015-01-07 | Electrochemical devices comprising novel catalyst mixtures |
US14/592,246 US10023967B2 (en) | 2010-03-26 | 2015-01-08 | Electrochemical devices employing novel catalyst mixtures |
US14/684,145 US9555367B2 (en) | 2010-03-26 | 2015-04-10 | Electrocatalytic process for carbon dioxide conversion |
US14/704,934 US9481939B2 (en) | 2010-07-04 | 2015-05-05 | Electrochemical device for converting carbon dioxide to a reaction product |
US14/704,935 US9370773B2 (en) | 2010-07-04 | 2015-05-05 | Ion-conducting membranes |
US14/948,206 US9790161B2 (en) | 2010-03-26 | 2015-11-20 | Process for the sustainable production of acrylic acid |
JP2015232576A JP6254565B2 (ja) | 2010-03-26 | 2015-11-30 | 二酸化炭素を電気化学的に転換するための新規触媒混合物及び電気化学的装置 |
US15/090,477 US9580824B2 (en) | 2010-07-04 | 2016-04-04 | Ion-conducting membranes |
US15/158,227 US9945040B2 (en) | 2010-07-04 | 2016-05-18 | Catalyst layers and electrolyzers |
US15/226,894 US9957624B2 (en) | 2010-03-26 | 2016-08-02 | Electrochemical devices comprising novel catalyst mixtures |
US15/260,213 US10047446B2 (en) | 2010-07-04 | 2016-09-08 | Method and system for electrochemical production of formic acid from carbon dioxide |
JP2016238639A JP6449839B2 (ja) | 2010-07-04 | 2016-12-08 | 電気化学セル |
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Publication number | Publication date |
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JP2013525088A (ja) | 2013-06-20 |
EP2553147A1 (fr) | 2013-02-06 |
WO2011120021A1 (fr) | 2011-09-29 |
CA2794105C (fr) | 2018-07-10 |
US10023967B2 (en) | 2018-07-17 |
AU2011230545B2 (en) | 2016-02-11 |
AU2011230545A1 (en) | 2012-10-11 |
CN102892929B (zh) | 2016-09-14 |
CA2794105A1 (fr) | 2011-09-29 |
JP2016041427A (ja) | 2016-03-31 |
KR101721287B1 (ko) | 2017-03-29 |
JP6254565B2 (ja) | 2018-01-10 |
KR20130060185A (ko) | 2013-06-07 |
EP2553147B1 (fr) | 2022-05-18 |
AU2011230545C1 (en) | 2016-06-09 |
US20150122640A1 (en) | 2015-05-07 |
CN102892929A (zh) | 2013-01-23 |
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