CN113832485B - 电催化氧化环醇/环酮制备二元羧酸耦合产氢的方法 - Google Patents
电催化氧化环醇/环酮制备二元羧酸耦合产氢的方法 Download PDFInfo
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- CN113832485B CN113832485B CN202010499294.2A CN202010499294A CN113832485B CN 113832485 B CN113832485 B CN 113832485B CN 202010499294 A CN202010499294 A CN 202010499294A CN 113832485 B CN113832485 B CN 113832485B
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- transition metal
- nitrate
- salt
- dicarboxylic acid
- nickel
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- 238000000034 method Methods 0.000 title claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000001257 hydrogen Substances 0.000 title claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 8
- 230000008878 coupling Effects 0.000 title claims abstract description 6
- 238000010168 coupling process Methods 0.000 title claims abstract description 6
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 17
- 125000004122 cyclic group Chemical group 0.000 title abstract description 12
- 150000003997 cyclic ketones Chemical class 0.000 title abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 32
- 150000003624 transition metals Chemical class 0.000 claims abstract description 24
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000001361 adipic acid Substances 0.000 claims description 13
- 235000011037 adipic acid Nutrition 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- -1 transition metal salt Chemical class 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011943 nanocatalyst Substances 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 3
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 10
- 150000002576 ketones Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 5
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- JAQAHZMWBUQJTF-UHFFFAOYSA-N azanium fluoride trihydrofluoride Chemical compound [H+].[NH4+].F.F.[F-].[F-] JAQAHZMWBUQJTF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 3
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
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- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 description 1
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical compound O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WAOWQLJJQBDGQC-UHFFFAOYSA-N tetraazanium;tetrafluoride Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[F-].[F-].[F-].[F-] WAOWQLJJQBDGQC-UHFFFAOYSA-N 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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Abstract
本发明涉及一种电催化氧化环醇/环酮制备二元羧酸耦合产氢的方法，具体步骤包括：使用过渡金属磷化物纳米电催化剂分别作为阴极催化剂和阳极催化剂，并且将环醇/环酮加入到电解质水溶液中，组装成电解池；在0.3V至10V的电压下，恒电压反应1小时至20小时。与传统硝酸氧化环醇/环酮制备二元羧酸工艺相比，本发明使用通过简单方法制备的过渡金属磷化物纳米电催化剂作为阳极和阴极，在室温和常压下施加恒定电压直接合成二元羧酸，不仅不产生N2O等有毒有害气体，还实现联产氢气，同时本发明还拓宽了过渡金属磷化物类电极材料在电催化有机合成领域的应用范围。
Description
技术领域
本发明涉及电催化有机合成及制氢技术领域，具体涉及一种电催化氧化环醇/环酮制备二元羧酸耦合产氢的方法。
背景技术
氢能是公认的清洁能源，作为低碳和零碳能源正在脱颖而出。当今世界开发新能源迫在眉睫，原因是所用的能源如石油、天然气、煤、石油气均属于不可再生资源，地球上存量有限，而人类生存又时刻离不开能源，因此必须寻找新的能源。随着化石燃料耗量的日益增加，其储量日益减少，终有一天，这些资源、能源将要枯竭，这就迫切需要寻找一种不依赖化石燃料的储量丰富的新的含能体能源。氢正是这样一种在常规能源危机的出现和开发新的二次能源时，人们期待的新的二次能源。氢位于元素周期表之首，原子序数为1，常温常压下为气态，超低温高压下为液态，是一种理想的新的合能体能源。世界各国正在研究如何能大量而廉价的生产氢，电解水制氢方法有较大的研究前景，然而缓慢的析氧反应往往限制了制氢效率，虽然目前已经开发出多种具有促进析氧反应动力学的电催化剂，但是仍然难以与析氢反应所需要的效率匹配，导致能量转换效率低下。因此，用热力学上更有利的电氧化反应取代阳极的析氧反应，在阳极产生增值化学品取代氧气，同时耦合制氢成为了新的研究方向。
二元羧酸是一类重要的工业原料，主要用做聚合物的单体。尤其是己二酸，是合成尼龙和工程塑料的重要原料，同时也是固体饮料、果冻的添加剂，医药、酵母提纯、杀虫剂、合成革等的原料，具有较大的工业价值。传统己二酸的制备工艺需要利用苯、苯酚、环己烷为原料制备环己醇和环己酮，再使用浓硝酸氧化为己二酸。该方法工艺成熟，产物纯度高，但对设备防腐要求高，硝酸用量大，成本高，并且产生N2O气体，对环境造成污染。随着我国环保的日益加强，开发新型绿色的己二酸生产工艺愈加迫切。
专利CN104226317A公布了一类合金催化剂TM100-xREx的制备，在温度为130℃至150℃，空气压力为1MPa至3MPa的条件下催化氧化环己烷或KA油制备己二酸的方法。美国专利5455375和日本专利6279350公开了一种采用环氧环己烷制备己二酸的方法，所述方法使用环氧环己烷水解生成1,2-二醇环己烷和环氧环己烷，再经过硝酸氧化制得己二酸。该方法使用强酸作为氧化剂，容易腐蚀反应设备，反应所产生的氮氧化物副产物也对环境造成污染，不符合绿色化学的要求。
水是一种来源丰富、成本低廉的绿色溶剂和氧源。利用水在阳极氧化产生的活性氧来氧化环己醇(酮)制备己二酸不仅不产生有害气体，还实现了阴极联产高纯度氢气，使得本发明具有很高的环境和经济价值。
发明内容
技术问题
为了解决背景技术中的问题而做出本发明，本发明的目的是提供一种电催化环醇(酮)制备二元羧酸的方法。
技术方案
根据本发明，提供一种电催化环醇(酮)制备二元羧酸的方法，包括：使用过渡金属磷化物纳米电催化剂分别作为阴极催化剂和阳极催化剂，并且将环醇(酮)加入到电解质水溶液中，组装成电解池；在0.3V至10V的电压下，恒电压反应1小时至20小时。
根据本发明所述的电催化环醇(酮)制备二元羧酸的方法，其中，所述恒电压反应时间优选为3小时至15小时。
所述电解质水溶液可以包括：氢氧化钠、氢氧化钾、氢氧化锂、氢氧化钙、碳酸氢钾、碳酸钾、碳酸氢钠、碳酸钠、硫酸钠、硫酸钾、硫酸锂、硫酸锌、硫酸镁、硝酸钠、硝酸钾、硝酸锂、硝酸锌、硝酸钙、硝酸镁、硝酸铝中的一种或多种物质的水溶液。
所述电解质水溶液的浓度可以为10mg/mL至1000mg/mL，优选为5
mg/mL至100mg/mL。
所述环醇(酮)可以包括：环己醇、环己酮、环戊醇、环戊酮、环丁醇、环丁酮中的一种或多种。
所述二元羧酸可以包括：己二酸、戊二酸、丁二酸，以及三种酸相对应的锂盐、钠盐、钾盐、钙盐、镁盐、铝盐中的一种或多种。
根据本发明所述的电催化环醇(酮)制备二元羧酸的方法，其中，所述过渡金属磷化物纳米电催化剂通过以下方法制备，具体步骤包括：1)在水热反应釜中制备包含过渡金属盐、导向剂的水热反应液；2)将导电基底用分析纯的无水乙醇、分析纯的丙酮和去离子水各超声洗涤15分钟至30分钟，然后浸泡在上述水热反应液中；3)在恒温条件下通过水热法反应以在所述导电基底上合成过渡金属纳米阵列之后，将其取出，用去离子水将表面冲洗干净，并在60℃下干燥，制得导电基底负载的过渡金属磷化物前体；4)将所述导电基底负载的过渡金属磷化物前体与磷源同时放置在石英舟中，并转入管式炉中；5)在200℃至400℃的温度下，在惰性气氛中磷化2小时至5小时，制得过渡金属磷化物纳米电催化剂。
在步骤1)中，所述过渡金属盐可以包括：硝酸钴、氯化钴、硫酸钴、硝酸镍、氯化镍、硫酸镍、硝酸铁，氯化铁、硫酸亚铁、硝酸锰、硝酸铜、氯化铜、氯化钒、硝酸铝、氯化铝中的一种或多种。例如，所述过渡金属盐可以为硝酸镍、硝酸钴、硝酸锰、硝酸铁中的一种或多种。
所述导向剂可以包括：四氟化铵、尿素、六亚甲基四胺中的一种或多种。
所述过渡金属盐的浓度可以为1mg/mL至30mg/mL，所述导向剂的浓度可以为1mg/mL至50mg/mL，所述过渡金属盐与所述导向剂的比例可以为：1mg/mL至30mg/mL：0mg/mL至50mg/mL。
在步骤2)中，所述导电基底可以包括：碳布、碳纸、泡沫镍、镍片、镍网、泡沫铜、铜片、铜网、钛片、钛网、不锈钢片、不锈钢网、ITO导电玻璃、FTO导电玻璃中的一种或多种。例如，所述导电基底可以为碳布、泡沫镍、镍片、钛片中的一种或多种。
在步骤3)中，所述恒温条件可以为80℃至150℃。所述水热法反应可以进行6小时至24小时。
所述磷源可以包括：次亚磷酸钠、次亚磷酸钾、红磷、磷化氢中的一种或多种。
所述惰性气氛可以包括氦气、氖气、氩气等。
有益效果
与传统硝酸氧化环醇(酮)制备二元羧酸工艺相比，本发明采用电催化方法，使用通过简单方法制备的过渡金属磷化物纳米电催化剂作为阳极和阴极，在室温和常压下施加恒定电压直接合成二元羧酸，且产物收率高，不仅不产生N2O等有毒有害气体，还实现联产氢气，适用于工业化生产，同时本发明还拓宽了过渡金属磷化物类电极材料在电催化有机合成领域的应用范围。
附图说明
图1示出了根据本发明的电催化氧化环醇/环酮制备二元羧酸耦合产氢的方法的示意图；
图2是本发明的实施例1中得到的多孔网状磷化镍纳米电催化剂的扫描电镜图；
图3是本发明的实施例1中得到的多孔网状磷化镍纳米电催化剂的线性扫描伏安曲线；
图4是本发明的实施例1中得到的过渡金属磷化物纳米电催化剂在恒定电压下反应5小时的液相色谱测试结果；
图5是本发明实施例3中使用催化剂在恒定电压下反应5小时的液相色谱测试结果。
具体实施方式
下面，结合具体实施例来对本发明做进一步的说明，下述各实施例仅用于举例说明本发明，而对本发明的保护范围不起限制作用。
实施例1
将碳布分别在分析纯的无水乙醇、分析纯的丙酮、去离子水中各超声15分钟以去除表面杂质。制备25mL的包含1.5g的尿素、0.9g的四氟化氨和0.5g的硝酸镍的水溶液作为水热反应液，将碳布浸泡在配置的水热反应液中，在110℃下恒温反应8小时，取出、用去离子水洗涤并干燥，得到前体材料。将制备的前体材料与100mg的次亚磷酸钠一同放入石英舟内，并转入管式炉中。在氩气氛围下，在300℃下磷化2小时，得到多孔网状磷化镍纳米电催化剂。该多孔网状磷化镍纳米电催化剂的扫描电镜图示于图2中。
制备20mL的包含0.5mg的环己醇的1M的氢氧化钾溶液作为电解液，将上面制备的多孔网状磷化镍纳米电催化剂同时作为阳极和阴极，Ag/AgCl电极作为参比电极，并搭建三电极体系。在0.4V的恒定电压下连续搅拌反应5小时。取样加入1∶1的稀盐酸溶液(1M)并调节pH至弱酸性，使用液相色谱对己二酸进行定量鉴定，收率为73％。
实施例2
将泡沫镍分别在分析纯的无水乙醇、分析纯的丙酮、去离子水中各超声15分钟以去除表面杂质。制备25mL的包含1.5g的尿素、0.9g的四氟化氨、0.5g的硝酸钴和0.5g的硝酸镍的水溶液作为水热反应液，将泡沫镍浸泡在配置的水热反应液中，在120℃下恒温反应8小时，取出、用去离子水洗涤并干燥，得到前体材料。将制备的前体与100mg的次亚磷酸钾一同放入石英舟内，并转入管式炉中。在氩气氛围下，在300℃下磷化2小时，得到磷化钴镍纳米电催化剂。
制备20mL的包含1mg的环己酮的1M的氢氧化钾溶液作为电解液，将上面制备的磷化钴镍纳米电催化剂同时作为阳极和阴极，Ag/AgCl电极作为参比电极，并搭建三电极体系。在0.45V的恒定电压下连续搅拌反应5小时。取样加入1∶1的稀盐酸溶液(1M)并调节pH至弱酸性，使用液相色谱对己二酸进行定量鉴定，收率为76％。
实施例3
将镍片分别在分析纯的无水乙醇、分析纯的丙酮、去离子水中各超声15分钟以去除表面杂质。制备25mL的包含1.5g的六亚甲基四胺、0.9g的四氟化氨、0.5g的硝酸钴和0.2g的硝酸锰的水溶液作为水热反应液，将镍片浸泡在配置的水热反应液中，在120℃下恒温反应8小时，取出、用去离子水洗涤并干燥，得到前体材料。将制备的前体材料与100mg的红磷一同放入石英舟内，并转入管式炉中。在氩气氛围下，在350℃下磷化2小时，得到磷化钴锰纳米电催化剂。
制备20mL的包含1mg的环戊醇的1M的氢氧化钾溶液作为电解液，将上面制备的磷化钴锰纳米电催化剂同时作为阳极和阴极，Ag/AgCl电极作为参比电极，并搭建三电极体系。在0.45V的恒定电压下连续搅拌反应5小时。取样加入1∶1的稀盐酸溶液(1M)并调节pH至弱酸性，使用液相色谱对戊二酸进行定量鉴定，收率为71％。
实施例4
将钛片分别在分析纯的无水乙醇、分析纯的丙酮、去离子水中各超声15分钟以去除表面杂质。制备25mL的包含1.5g的六亚甲基四胺、0.9g的四氟化氨、0.5g的硝酸镍和0.2g的硝酸铁的水溶液作为水热反应液，将钛片浸泡在配置的水热反应液中，在110℃下恒温反应6小时，取出、用去离子水洗涤并干燥，得到前体材料。将制备的前体材料与100mg的次亚磷酸钠一同放入石英舟内，并转入管式炉中。在氩气氛围下，在350℃下磷化2小时，得到磷化镍铁纳米电催化剂。
制备20mL的包含0.6mg的环戊酮的1M的氢氧化钾溶液作为电解液，将上面制备的磷化镍铁纳米电催化剂同时作为阳极和阴极，Ag/AgCl电极作为参比电极，并搭建三电极体系。在0.4V的恒定电压下连续搅拌反应5小时。取样加入1∶1的稀盐酸溶液(1M)并调节pH至弱酸性，使用液相色谱对戊二酸进行定量鉴定，收率为77％。
Claims (8)
1.一种电催化氧化环己酮制备二元羧酸耦合产氢的方法，具体步骤包括：使用过渡金属磷化物纳米电催化剂分别作为阴极催化剂和阳极催化剂，并且将环己酮加入到电解质水溶液中，组装成电解池；在0.3V至10V的电压下，恒电压反应1小时至20小时，
其中，所述二元羧酸的收率为76％，
其中，所述过渡金属磷化物纳米电催化剂由过渡金属盐制备，所述过渡金属盐包括：硝酸钴、氯化钴、硫酸钴、硝酸镍、氯化镍、硫酸镍、硝酸铁，氯化铁、硫酸亚铁、硝酸锰、硝酸铜、氯化铜、氯化钒、硝酸铝、氯化铝中的一种或多种。
2.根据权利要求1所述的方法，其特征在于，所述电解质水溶液包括：氢氧化钠、氢氧化钾、氢氧化锂、氢氧化钙、碳酸氢钾、碳酸钾、碳酸氢钠、碳酸钠、硫酸钠、硫酸钾、硫酸锂、硫酸锌、硫酸镁、硝酸钠、硝酸钾、硝酸锂、硝酸锌、硝酸钙、硝酸镁、硝酸铝中的一种或多种的水溶液，所述电解质水溶液的浓度为10mg/mL至1000mg/mL。
3.根据权利要求1所述的方法，其特征在于，所述二元羧酸包括：己二酸以及己二酸相对应的锂盐、钠盐、钾盐、钙盐、镁盐、铝盐中的一种或多种。
4.根据权利要求1所述的方法，其特征在于，所述过渡金属磷化物纳米电催化剂的制备方法包括：1)在水热反应釜中制备包含所述过渡金属盐、导向剂的水热反应液；2)将导电基底用分析纯的无水乙醇、分析纯的丙酮和去离子水各超声洗涤15分钟至30分钟，然后浸泡在上述水热反应液中；3)在恒温条件下通过水热法反应以在所述导电基底上合成过渡金属纳米阵列之后，将其取出，用去离子水将表面冲洗干净，并在60℃下干燥，制得导电基底负载的过渡金属磷化物前体；4)将所述导电基底负载的过渡金属磷化物前体与磷源同时放置在石英舟中，并转入管式炉中；5)在200℃至400℃的温度下，在惰性气氛中磷化2小时至5小时。
5.根据权利要求4所述的方法，其特征在于，所述导电基底包括：碳布、碳纸、泡沫镍、镍片、镍网、泡沫铜、铜片、铜网、钛片、钛网、不锈钢片、不锈钢网、ITO导电玻璃、FTO导电玻璃中的一种或多种。
6.根据权利要求4所述的方法，其特征在于，所述导向剂包括：氟化铵、尿素、六亚甲基四胺中的一种或多种。
7.根据权利要求4所述的方法，其特征在于，所述过渡金属盐与所述导向剂的比例为：1-30mg/mL：0-50mg/mL。
8.根据权利要求4所述的方法，其特征在于，所述磷源包括：次亚磷酸钠、次亚磷酸钾、红磷、磷化氢中的一种或多种。
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