CN116180133A - Nickel-based metal organic framework/graphite felt electrode material and preparation method and application thereof - Google Patents
Nickel-based metal organic framework/graphite felt electrode material and preparation method and application thereof Download PDFInfo
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- CN116180133A CN116180133A CN202310140508.0A CN202310140508A CN116180133A CN 116180133 A CN116180133 A CN 116180133A CN 202310140508 A CN202310140508 A CN 202310140508A CN 116180133 A CN116180133 A CN 116180133A
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- graphite felt
- nickel
- electrode material
- pyridine
- based metal
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 102
- 239000010439 graphite Substances 0.000 title claims abstract description 102
- 239000007772 electrode material Substances 0.000 title claims abstract description 69
- 239000013099 nickel-based metal-organic framework Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 57
- -1 pyridine alcohols Chemical class 0.000 claims abstract description 44
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000002815 homogeneous catalyst Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 59
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 229910052759 nickel Inorganic materials 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- 239000000376 reactant Substances 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 239000013110 organic ligand Substances 0.000 claims description 17
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 229920006395 saturated elastomer Polymers 0.000 claims description 16
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 150000002815 nickel Chemical class 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 11
- 238000004729 solvothermal method Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 claims description 5
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- FZTIWOBQQYPTCJ-UHFFFAOYSA-N 4-[4-(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(O)=O)C=C1 FZTIWOBQQYPTCJ-UHFFFAOYSA-N 0.000 claims 1
- 239000007805 chemical reaction reactant Substances 0.000 claims 1
- 230000006837 decompression Effects 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 abstract description 7
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 25
- 239000008151 electrolyte solution Substances 0.000 description 17
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- SHNUBALDGXWUJI-UHFFFAOYSA-N pyridin-2-ylmethanol Chemical compound OCC1=CC=CC=N1 SHNUBALDGXWUJI-UHFFFAOYSA-N 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 7
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- MVQVNTPHUGQQHK-UHFFFAOYSA-N 3-pyridinemethanol Chemical compound OCC1=CC=CN=C1 MVQVNTPHUGQQHK-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- PTMBWNZJOQBTBK-UHFFFAOYSA-N pyridin-4-ylmethanol Chemical compound OCC1=CC=NC=C1 PTMBWNZJOQBTBK-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- BXGYBSJAZFGIPX-UHFFFAOYSA-N 2-pyridin-2-ylethanol Chemical compound OCCC1=CC=CC=N1 BXGYBSJAZFGIPX-UHFFFAOYSA-N 0.000 description 3
- BPSNETAIJADFTO-UHFFFAOYSA-N 2-pyridinylacetic acid Chemical compound OC(=O)CC1=CC=CC=N1 BPSNETAIJADFTO-UHFFFAOYSA-N 0.000 description 3
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 235000001968 nicotinic acid Nutrition 0.000 description 3
- 239000011664 nicotinic acid Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 3
- AZYKGQOIAGPVCK-UHFFFAOYSA-N 3-pyridin-1-ium-2-ylpropanoate Chemical compound OC(=O)CCC1=CC=CC=N1 AZYKGQOIAGPVCK-UHFFFAOYSA-N 0.000 description 2
- FVZXYJDGVYLMDB-UHFFFAOYSA-N 3-pyridin-2-ylpropan-1-ol Chemical compound OCCCC1=CC=CC=N1 FVZXYJDGVYLMDB-UHFFFAOYSA-N 0.000 description 2
- UGNSMKDDFAUGFT-UHFFFAOYSA-N 4,4-dimethyl-2-phenyl-5h-1,3-oxazole Chemical compound CC1(C)COC(C=2C=CC=CC=2)=N1 UGNSMKDDFAUGFT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- RCBVKBFIWMOMHF-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium;pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1.O[Cr](=O)(=O)O[Cr](O)(=O)=O RCBVKBFIWMOMHF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CRBHXDCYXIISFC-UHFFFAOYSA-N 2-(Trimethylammonio)ethanolate Chemical compound C[N+](C)(C)CC[O-] CRBHXDCYXIISFC-UHFFFAOYSA-N 0.000 description 1
- BZFGKBQHQJVAHS-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C(F)(F)F)=C1 BZFGKBQHQJVAHS-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000006809 Jones oxidation reaction Methods 0.000 description 1
- DKUPFNXIBNYFDK-UHFFFAOYSA-N [Ni+2].O.O.O.O.O.O.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [Ni+2].O.O.O.O.O.O.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] DKUPFNXIBNYFDK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- 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
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a nickel-based metal organic framework/graphite felt electrode material, a preparation method and application thereof. The electrode material can be well applied to the preparation of pyridine acid compounds by electrocatalytic oxidation of pyridine alcohols or pyridine aldehydes, nickel-based metal organic framework nano sheets are used as heterogeneous catalysts, nitrogen-oxygen free radicals are used as homogeneous catalysts, and the corresponding pyridine acid compounds are obtained by electrocatalytic oxidation of pyridine alcohols or pyridine aldehydes under constant potential. The electrode material does not use noble metal, has low cost, simple preparation method, larger specific surface area and good stability, has excellent performance in electrocatalytic oxidation of pyridine alcohols or pyridine aldehydes compounds, and has current density far superior to unmodified graphite felt.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a nickel-based metal organic framework/graphite felt electrode material, a preparation method thereof and application thereof in preparing pyridine acid compounds by electrocatalytic oxidation of pyridine alcohols or pyridine aldehydes.
Background
The oxidation reaction of pyridinols or pyridinaldehydes compounds to pyridinic compounds is an important reaction in organic synthesis, and is widely applied to the fields of food additives, pharmaceutical chemicals and the like. At present, jones oxidation (CrO) is mainly adopted in the production process for preparing pyridine acid compounds by using pyridine alcohols or pyridine aldehydes compounds as raw materials 3 /H 2 SO 4 ) Kolin oxidation (CrO) 3 /py 2 ) PDC (pyridinium dichromate) oxidation, and the like. The oxidizing agent used in the oxidation method has high activity, so that peroxidation occurs, carbonyl is peroxidized to form carboxyl, the selectivity of the reaction is reduced, and the heavy metal chromium contained in the oxidizing agent can cause serious damage to the ecological environment, so that the oxidizing agent is a process with high pollution. In addition, the reaction conditions often require high temperatures or pressures and the reaction time is long, thereby limiting the application of such processes in industrial production. Thus, finding a method for efficiently, mildly, pollution-free, and easy to handle oxidation of pyridinols or pyridinaldehydes to pyridinics has long been a challenge in organic synthesis.
Metal organic framework Materials (MOFs) are organic-inorganic hybrid materials with intramolecular pores formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds. The MOFs material has the characteristics of large specific surface area, multiple holes and the like, and the MOFs material is loaded on the graphite felt substrate in situ by adopting a one-step solvothermal method by utilizing the characteristics of large specific surface area, multiple holes and the like, and does not need to use an additional adhesive, and is matched with the nitroxide free radical to carry out indirect electrocatalytic oxidation, so that the reduction of the dosage of the nitroxide free radical and the improvement of electrocatalytic performance are realized.
Disclosure of Invention
Aiming at the technical problems of environmental pollution, high cost, complex synthesis, non-mild production conditions and the like existing in the existing aldehyde or ketone organic compound synthesis process, the invention aims to provide a nickel-based metal organic framework/graphite felt electrode material, a preparation method thereof and application thereof in preparing pyridine acid compounds by electrocatalytically oxidizing pyridine alcohols or pyridine aldehydes, wherein nickel-based metal organic framework nano sheets are used as heterogeneous catalysts, nitrogen oxide radicals are used as homogeneous catalysts, and the corresponding pyridine acid compounds are obtained by electrocatalytically oxidizing the pyridine alcohols or the pyridine aldehydes under constant potential.
The preparation method of the nickel-based metal organic frame/graphite felt electrode material is characterized in that metal nickel salt and aryl acid organic ligands are used as raw materials, a graphite felt is used as a base material, hydrothermal reaction is carried out in a solvent, and a three-dimensional flaky nickel-based metal organic frame array is loaded on the surface of a graphite felt substrate through a solvothermal method, so that the nickel-based metal organic frame/graphite felt electrode material is prepared; wherein the molar ratio of the metal nickel salt to the aryl acid organic ligand is 1-1.5:1, preferably 1.1-1.2:1, and the molar dosage of the metal nickel salt is 0.02-0.2 mmol/cm based on the size area of the graphite felt substrate material 2 Preferably 0.08 to 0.12mmol/cm 2 。
The preparation method of the nickel-based metal organic framework/graphite felt electrode material is characterized in that the aryl acid organic ligand is terephthalic acid, 4 '-biphenyl, [1,1':4', 1' -terphenyl ] -4,4 '-dicarboxylic acid or 2, 6-naphthalene dicarboxylic acid, preferably 4,4' -biphenyl; the metal nickel salt is nickel nitrate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate or nickel sulfate hexahydrate, preferably nickel nitrate hexahydrate.
The preparation method of the nickel-based metal organic framework/graphite felt electrode material is characterized by comprising the following steps of:
1) Pretreating the graphite felt to remove impurities on the surface of the graphite felt substrate; dissolving metal nickel salt and aryl acid organic ligand in a solvent, and uniformly dispersing by ultrasonic to obtain a precursor solution;
2) And (3) adding the precursor solution and the pretreated graphite felt in the step (1) into a hydrothermal kettle, performing hydrothermal reaction for 8-16 hours at 100-170 ℃, cooling to room temperature after the reaction is finished, taking out the graphite felt, respectively washing the graphite felt with distilled water and ethanol for 2-3 times, and performing forced air drying at 50-80 ℃ to obtain the nickel-based metal organic frame/graphite felt electrode material.
The preparation method of the nickel-based metal organic framework/graphite felt electrode material is characterized in that in the step 1), the pretreatment process of the graphite felt is as follows: and sequentially and respectively carrying out ultrasonic treatment on the graphite felt in nitric acid, acetone, absolute ethyl alcohol and deionized water for 30-120 min to remove impurities on the surface of a graphite felt substrate and improve the load strength, taking out the graphite felt, and then washing and drying the graphite felt by using the deionized water to obtain the pretreated graphite felt for standby.
The preparation method of the nickel-based metal organic framework/graphite felt electrode material is characterized in that the solvent is deionized water, anhydrous ethanol and N, N-dimethylformamide, and the volume ratio of the deionized water to the anhydrous ethanol to the N, N-dimethylformamide is 1:0.5-2:5-80; the concentration of the metal nickel salt in the precursor solution is 10-30mmol/L, preferably 10-20mmol/L; the concentration of the aryl acid organic ligand in the precursor solution is 10-30mmol/L, preferably 10-20mmol/L.
The invention relates to an application of a nickel-based metal organic frame/graphite felt electrode material in preparing pyridine acid compounds by electrocatalytic oxidation of pyridine alcohols or pyridine aldehydes, which is characterized in that a flow type double-groove electric reactor is adopted, an anode groove and a cathode groove are separated by a proton exchange membrane, the nickel-based metal organic frame/graphite felt electrode material is used as a working electrode of the anode groove, foam nickel is used as a cathode, a saturated Ag/AgCl electrode is used as a reference electrode, pyridine alcohols or pyridine aldehydes reactants are dissolved in a solvent to be used as an anode liquid, nitrogen-oxygen free radicals are added into the anode liquid to be used as a homogeneous catalyst, a weak alkaline solution is used as a cathode liquid, the voltage between the reference electrode and the working electrode is 0.6-0.8V at a certain temperature, the electrocatalytic alcohol oxidation reaction is carried out for 8-60 minutes, after the reaction is finished, the anode groove reaction liquid is cooled, the pH value of the reaction liquid is regulated to be 2-4, then the organic solvent is added for extraction, and the organic layer is taken for reduced pressure distillation after layering, the corresponding pyridine acid compounds are obtained, and the reaction equation is as follows:
the application of the nickel-based metal organic framework/graphite felt electrode material in preparing pyridine acid compounds by electrocatalytic oxidation of pyridine alcohols or pyridine aldehydes is characterized in that the concentration of a reaction raw material pyridine alcohol substrate in an anode solution is 10-300mmol/L, preferably 50-200mmol/L;
the solvent used for the anode liquid is divided into a main solvent and a secondary solvent, wherein the main solvent is a weak alkaline solution, is selected from aqueous solution of sodium bicarbonate, sodium carbonate, potassium bicarbonate or potassium carbonate, preferably sodium carbonate aqueous solution, and has the concentration of 0.1-2.0mol/L; the secondary solvent is one of acetonitrile, dichloromethane, chloroform or carbon tetrachloride, and the volume ratio of the primary solvent to the secondary solvent is 9:1-1:1; the catholyte is selected from aqueous solutions of sodium bicarbonate, sodium carbonate, potassium bicarbonate or potassium carbonate, preferably aqueous sodium carbonate, at a concentration of 0.1-2.0mol/L. In the electrocatalytic alcohol oxidation reaction process, the catholyte in the cathode tank is pumped out and then returned to the cathode tank again for circulating flow, and the anolyte in the anode tank is pumped out and then returned to the anode tank again for circulating flow.
The application of the nickel-based metal organic framework/graphite felt electrode material in preparing pyridine acid compounds by electrocatalytic oxidation of pyridine alcohols or pyridine aldehydes is characterized in that the nitroxide free radical is selected from 4-acetamido-2, 6-tetramethyl piperidine-1-nitroxide free radical, and the concentration of the nitroxide free radical in an anode solution is 0.2-2.2 g/L.
The application of the nickel-based metal organic framework/graphite felt electrode material in preparing pyridine acid compounds by electrocatalytic oxidation of pyridine alcohols or pyridine aldehydes is characterized in that the voltage between an anode and a cathode is 2-10V, and the reaction temperature is 20-60 ℃; the organic solvent for extraction is dichloromethane, chloroform or ethyl acetate.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1) Compared with other noble metal-containing electrode materials, the nickel-based metal organic frame electrode material prepared by the method is in a three-dimensional nano sheet structure, and the nano sheet is thin and has large specific surface area, so that metal active sites can be fully exposed, the catalytic activity and stability of the electrocatalytic alcohol oxidation reaction are obviously improved, the current density of the nickel-based metal organic frame electrode material is far better than that of an unmodified graphite felt electrode material, the problems that the dosage of nitrogen and oxygen free radicals is large, the yield is low, the selectivity is low, the space-time yield is low and the like are urgently needed to be solved are solved on the basis of environmental friendliness, and the nickel-based metal organic frame electrode material has good industrial application prospect.
2) The electrode material can be prepared by one-step solvothermal method, and complicated preparation steps are not needed;
3) Compared with other electrode materials with a catalyst supported by a binder, the synthesis method of the invention has the advantages that the nickel-based organic frame material is directly supported on the graphite felt by a solvothermal method, the binder is not needed, the nickel-based organic frame material is firmly combined with the graphite felt, and the nickel-based organic frame material is stable in an organic solvent, is not easy to fall off from the graphite felt, and has good stability and long service life;
4) The reaction related by the invention is carried out at normal temperature and normal pressure, and the applied voltage of the reaction is low, the safety is high, and the energy consumption is low;
5) Compared with the method for controlling the current, the method shortens the reaction time and simultaneously has higher raw material conversion rate and product selectivity;
6) The reaction liquid and the waste liquid do not contain heavy metal ions, so that the post-treatment of products and the waste liquid treatment are more convenient;
7) The invention has wide range of applicable pyridinol or pyridinaldehyde compounds, is also applicable to green oxidation of other alcohol compounds, and has strong adaptability.
Drawings
FIGS. 1 and 2 are each a scanning electron microscope image at 1 μm of the electrode material obtained in example 1;
FIG. 3 and FIG. 4 are each a scanning electron microscope image at 1 μm of the electrode material obtained in example 2;
FIG. 5 and FIG. 6 are each a scanning electron microscope image at 1 μm of the electrode material obtained in example 3;
FIG. 7 is a graph showing the concentration of each substance over time in the reaction of electrocatalytically oxidizing 2-pyridinemethanol to 2-pyridinecarboxylic acid according to example 1.
FIG. 8 is a graph comparing the space time yields of electrocatalytically oxidizing 2-pyridinemethanol using a nickel-based metal organic frame/graphite felt electrode material and a blank graphite felt electrode, respectively, for example 1 and comparative example 7.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1: preparation of 2-picolinic acid by electrocatalytic oxidation of 2-pyridinemethanol with organic ligand terephthalic acid and nickel-based metal organic frame/graphite felt electrode material with nickel salt hexahydrate nickel nitrate
1) And sequentially and respectively ultrasonically treating graphite felt with the size of 3cm and 3.5cm in nitric acid (the concentration is 8mol/L, the same applies below), acetone, absolute ethyl alcohol and deionized water for 60 minutes to remove impurities on the surface of a graphite felt substrate. Then washing with a large amount of deionized water, and finally drying at 70 ℃ for later use.
2) Respectively weighing 330mg of nickel nitrate hexahydrate and 166mg of terephthalic acid, and adding the nickel nitrate hexahydrate and the 166mg of terephthalic acid into a mixed solution composed of 3mL of absolute ethyl alcohol, 3mL of deionized water and 60mL of N, N-dimethylformamide to obtain a precursor solution;
3) Adding the pretreated graphite felt and the precursor solution into a 100mL polytetrafluoroethylene lining, performing ultrasonic dispersion for 10 minutes, loading the lining into a stainless steel reaction kettle, and performing solvothermal reaction for 12 hours at 130 ℃;
4) And taking out the graphite felt after the reaction kettle is cooled to room temperature, washing with deionized water and ethanol for 2 times respectively, and drying in a blast drying oven at 70 ℃ for 12 hours to obtain the graphite felt electrode material loaded with the nickel-based metal organic framework catalyst, wherein SEM scanning electron microscope images are shown in figures 1 and 2. It can be seen that the nickel-based metal organic framework catalyst on the graphite felt is in the shape of nano-sheets, and the thickness of the sheets is thinner and the size is uniform. The BET specific surface area of the catalyst material obtained was measured and found to be 342m 2 /g。
The electrode material obtained in the example 1 is applied to electrocatalytic oxidation of 2-pyridinemethanol to prepare 2-pyridinecarboxylic acid, and the specific method is as follows:
controlled by potentiostat, using a flow-type double-tank electric reactor (volume 330 cm) 3 The same applies below), the anode tank and the cathode tank have volumes of 100mL and are separated by a proton exchange membrane, 70mL of 1mol/L sodium carbonate aqueous solution and 30mL of acetonitrile mixed solution (the feeding volume ratio of the main solvent to the secondary solvent is 7:3) are used as the electrolyte solution of the anode tank, and 100mL of 1mol/L sodium carbonate aqueous solution is used as the electrolyte solution of the cathode tank; taking the prepared electrode material as a working electrode in an anode tank of the electrolytic tank; in the cathode groove of the electric reactor, foam nickel is used as a counter electrode; using a saturated Ag/AgCl electrode as a reference electrode;
s1: taking 0.55g (5 mmol) of 2-pyridine methanol as a reactant, adding the reactant into a mixed solvent consisting of 70mL of 1mol/L sodium carbonate solution and 30mL of acetonitrile, adding 10.6mg of 4-acetamido-2, 6-tetramethylpiperidine-1-nitroxide free radical (ACT) into an anode cell electrolyte solution, and carrying out ultrasonic treatment for 5min to fully dissolve and uniformly mix the reactant;
s2: placing the anode tank electrolyte in a water bath at 30 ℃, keeping the temperature constant, using magnetic stirring, and placing the cathode tank electrolyte and the flowing double-tank electric reactor in room temperature;
s3: the flow rate was controlled to be 100mL/min (i.e., catholyte was continuously flowed into and out of the cathode tank at a flow rate of 100mL/min for circulating flow of catholyte in the cathode tank, anolyte was simultaneously flowed into and out of the anode tank at a flow rate of 100mL/min for circulating flow of anolyte in the anode tank, the following examples were identical.) the potential was controlled to be 0.8V using a saturated Ag/AgCl reference electrode, at which time the current control range was 2-5A, and the voltage applied between anode and cathode was 2-10V. Stopping the reaction when the total amount of the applied charges reaches 2000 ℃, wherein the reaction time is 700s;
s4: sampling and analyzing the electrolyte of the anode tank in the step S3, cooling to room temperature, acidifying to pH=3 by using 3mol/L hydrochloric acid, extracting and layering by ethyl acetate, evaporating and separating the ethyl acetate after taking the upper layer, and using HPLCTracking, when the reaction reaches 700s, the conversion rate of the raw materials reaches 98%, the selectivity of the 2-picolinic acid exceeds 99%, and the space-time yield reaches 8.32 kg/(m) 3 H) the unit kg of space-time yield is the mass unit of the target product, m 3 Is the volume unit of the anode cell, h is the unit of reaction time. As the reaction time goes on, the kinetic graph of 2-pyridinemethanol oxidation is shown in FIG. 7, and it can be seen from the graph that the raw material 2-pyridinemethanol gradually decreases and the product 2-pyridineformaldehyde gradually increases as the reaction time increases.
Example 2: preparation of 2-picolinic acid by electrocatalytic oxidation of 2-pyridylaldehyde by using nickel-based metal organic frame/graphite felt electrode material with 4,4' -biphthalic acid as organic ligand and nickel nitrate hexahydrate as metal nickel salt
1) And sequentially and respectively ultrasonically treating graphite felt with the size of 3cm x 3.5cm in nitric acid, acetone, absolute ethyl alcohol and deionized water for 60 minutes to remove impurities on the surface of a graphite felt substrate. Then washing with a large amount of deionized water, and finally drying at 70 ℃ for later use.
2) Respectively weighing 320mg of nickel nitrate hexahydrate and 242mg of 4,4' -biphenyl dicarboxylic acid, and adding into a mixed solution composed of 7mL of absolute ethyl alcohol, 7mL of deionized water and 50mLN, N-dimethylformamide to obtain a precursor solution;
3) Adding the pretreated graphite felt and the precursor solution into a 100mL polytetrafluoroethylene lining, performing ultrasonic dispersion for 20 minutes, loading the lining into a stainless steel reaction kettle, and performing solvothermal reaction for 12 hours at 140 ℃;
4) And taking out the graphite felt after the reaction kettle is cooled to room temperature, washing with deionized water and ethanol for 3 times respectively, and drying in a forced air drying oven at 80 ℃ for 12 hours to obtain the graphite felt electrode material loaded with the nickel-based metal-organic framework catalyst, wherein SEM scanning electron microscope images are shown in figures 3 and 4. It can be seen that the nickel-based metal organic framework catalyst on the graphite felt is in the shape of nano-sheets, and the thickness of the sheets is thinner and the size is uniform.
The electrode material obtained in the example 2 is applied to electrocatalytic oxidation of 2-pyridylaldehyde to prepare 2-picolinic acid, and the specific method is as follows:
the method is controlled by a potentiostat, a flowing double-tank electric reactor is adopted for reaction, the volumes of an anode tank and a cathode tank are 100mL and are separated by a proton exchange membrane, 90mL of 2mol/L sodium carbonate aqueous solution and 10mL of acetonitrile mixed solution (the feeding volume ratio of a main solvent to a secondary solvent is 9:1) are used as electrolyte solution of the anode tank, and 100mL of 2mol/L sodium carbonate aqueous solution is used as electrolyte solution of a cathode chamber; taking the prepared electrode material as a working electrode in an anode tank of the electrolytic tank; in the cathode groove of the electric reactor, foam nickel is used as a counter electrode; using a saturated Ag/AgCl electrode as a reference electrode;
s1: taking 0.107g (1 mmol) of 2-pyridine formaldehyde as a reactant, adding the reactant into a mixed solvent consisting of 90mL of 1mol/L sodium carbonate solution and 10mL of acetonitrile, adding 53mg of 4-acetamido-2, 6-tetramethylpiperidine-1-nitroxide free radical (ACT) into an anode cell electrolytic solution, and performing ultrasonic treatment for 5min to fully dissolve and uniformly mix the reactant;
s2: placing the anode tank electrolyte in a water bath at 50 ℃, keeping the temperature constant, using magnetic stirring, and placing the cathode tank electrolyte and the flowing double-tank electric reactor in room temperature;
s3: the flow rate was controlled to 100mL/min, the potential was controlled to 0.6V using saturated Ag/AgCl, the current control range was 0.5-1.5A, and the voltage applied between anode and cathode was 2-10V. Stopping the reaction when the total amount of the applied charges reaches 200 ℃, wherein the reaction time is 300s;
s4: sampling and analyzing the electrolyte of the anode tank in the step S3, cooling to room temperature, acidifying to pH=3 by using 3mol/L hydrochloric acid, extracting and layering by using dichloromethane, evaporating and separating dichloromethane after taking the lower layer, tracking by using HPLC, when the reaction reaches 300S, the raw material conversion rate reaches 97%, the selectivity of 2-picolinic acid reaches 99%, and the space-time yield reaches 3.74 kg/(m) 3 ·h)。
Example 3: preparation of 4-picolinic acid by electrocatalytic oxidation of 4-picolinic acid by using [1,1':4',1 '-terphenyl ] -4, 4' -dicarboxylic acid as organic ligand and nickel-based metal organic framework/graphite felt electrode material with nickel salt of nickel nitrate hexahydrate
1) And sequentially and respectively ultrasonically treating graphite felt with the size of 3cm x 3.5cm in nitric acid, acetone, absolute ethyl alcohol and deionized water for 60 minutes to remove impurities on the surface of a graphite felt substrate. Then washing with a large amount of deionized water, and finally drying at 70 ℃ for later use.
2) Respectively weighing 360mg of nickel nitrate hexahydrate and 318mg of [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid, and adding the nickel nitrate hexahydrate and the 1', 1' -terphenyl ] -4, 4' -dicarboxylic acid into a mixed solution consisting of 5mL of absolute ethyl alcohol, 5mL of deionized water and 60mL of N, N-dimethylformamide to obtain a precursor solution;
3) Adding the pretreated graphite felt and the precursor solution into a 100mL polytetrafluoroethylene lining, performing ultrasonic dispersion for 40 minutes, loading the lining into a stainless steel reaction kettle, and performing solvothermal reaction for 8 hours at 170 ℃;
4) And taking out the graphite felt after the reaction kettle is cooled to room temperature, washing with deionized water and ethanol for 3 times respectively, and drying in a forced air drying oven at 80 ℃ for 12 hours to obtain the graphite felt electrode material loaded with the nickel-based metal-organic framework catalyst, wherein SEM scanning electron microscope images are shown in figures 5 and 6. It can be seen that the nickel-based metal organic framework catalyst on the graphite felt is in the shape of nano-sheets, and the thickness of the sheets is thinner and the size is uniform.
The electrode material obtained in example 3 is applied to electrocatalytic oxidation of 4-pyridinemethanol to prepare 4-pyridinecarboxylic acid, and the specific method is as follows:
the method is controlled by a potentiostat, a flowing double-tank electric reactor is adopted for reaction, the volumes of an anode tank and a cathode tank are 100mL and are separated by a proton exchange membrane, 50mL of 1mol/L sodium carbonate aqueous solution and 50mL of acetonitrile mixed solution (the feeding volume ratio of a main solvent to a secondary solvent is 1:1) are used as electrolyte solution of the anode tank, and 100mL of 1mol/L sodium carbonate aqueous solution is used as electrolyte solution of a cathode chamber; taking the prepared electrode material as a working electrode in an anode tank of the electrolytic tank; in the cathode groove of the electric reactor, foam nickel is used as a counter electrode; using a saturated Ag/AgCl electrode as a reference electrode;
s1: taking 3.27g (30 mmol) of 4-pyridine methanol as a reactant, adding the reactant into a mixed solvent consisting of 50mL of 1mol/L sodium carbonate solution and 50mL of acetonitrile, adding 213mg of 4-acetamido-2, 6-tetramethylpiperidine-1-nitroxide free radical (ACT) into an anode cell electrolytic solution, and performing ultrasonic treatment for 5min to fully dissolve and uniformly mix the reactant;
s2: placing the anode tank electrolyte in a water bath at 40 ℃, keeping the temperature constant, using magnetic stirring, and placing the cathode tank electrolyte and the flowing double-tank electric reactor in room temperature;
s3: the flow rate was controlled at 160mL/min, the potential was controlled at 0.7V using a saturated Ag/AgCl reference electrode, at which time the current control range was 2-5A and the voltage applied between anode and cathode was 2-10V. Stopping the reaction when the total amount of the applied charges reaches 12000 ℃, and reacting for 3600s;
s4: sampling and analyzing the electrolyte of the anode tank in the step S3, cooling to room temperature, acidifying to pH=3 by using 3mol/L hydrochloric acid, extracting and layering by ethyl acetate, evaporating and separating the ethyl acetate after taking the upper layer, tracking by using HPLC, when the reaction reaches 3600S, the conversion rate of the raw material reaches 97%, the selectivity of 4-picolinic acid reaches 99%, and the space-time yield reaches 9.52 kg/(m) 3 ·h)。
Example 4: preparation of 3-picolinic acid by electrocatalytic oxidation of 3-pyridinemethanol with organic ligand of 4,4' -biphthalic acid and nickel-based metal organic frame/graphite felt electrode material of nickel chloride hexahydrate as metal nickel salt
1) And sequentially and respectively ultrasonically treating graphite felt with the size of 3cm x 3.5cm in nitric acid, acetone, absolute ethyl alcohol and deionized water for 60 minutes to remove impurities on the surface of a graphite felt substrate. Then washing with a large amount of deionized water, and finally drying at 70 ℃ for later use.
2) Respectively weighing 250mg of nickel chloride hexahydrate and 242mg of 4,4' -biphenyl dicarboxylic acid, and adding into a mixed solution consisting of 1mL of absolute ethyl alcohol, 1mL of deionized water and 80mLN, N-dimethylformamide to obtain a precursor solution;
3) Adding the pretreated graphite felt and the precursor solution into a 100mL polytetrafluoroethylene lining, performing ultrasonic dispersion for 40 minutes, loading the lining into a stainless steel reaction kettle, and performing solvothermal reaction for 16 hours at 100 ℃;
4) And (3) taking out the graphite felt after the reaction kettle is cooled to room temperature, respectively washing with deionized water and ethanol for 3 times, and drying in a blast drying oven at 80 ℃ for 12 hours to obtain the graphite felt electrode material loaded with the nickel-based metal organic framework catalyst.
The electrode material obtained in example 4 is applied to electrocatalytic oxidation of 3-pyridinemethanol to prepare 3-pyridinecarboxylic acid, and the specific method is as follows:
the method is controlled by a potentiostat, a flowing double-tank electric reactor is adopted for reaction, the volumes of an anode tank and a cathode tank are 100mL and are separated by a proton exchange membrane, 60mL of 0.1mol/L sodium carbonate aqueous solution and 40mL of acetonitrile mixed solution (the feeding volume ratio of a main solvent to a secondary solvent is 3:2) are used as electrolyte of the anode tank, and 100mL of 0.1mol/L sodium carbonate aqueous solution is used as electrolyte of a cathode chamber; taking the prepared electrode material as a working electrode in an anode tank of the electrolytic tank; in the cathode groove of the electric reactor, foam nickel is used as a counter electrode; using a saturated Ag/AgCl electrode as a reference electrode;
s1: taking 1.09g (10 mmol) of 3-pyridine methanol as a reactant, adding the reactant into a mixed solvent consisting of 60mL of 1mol/L sodium carbonate solution and 40mL of acetonitrile, adding 106mg of 4-acetamido-2, 6-tetramethylpiperidine-1-nitroxide free radical (ACT) into an anode cell electrolytic solution, and performing ultrasonic treatment for 5min to fully dissolve and uniformly mix the reactant;
s2: placing the anode tank electrolyte in a water bath at 20 ℃, keeping the temperature constant, using magnetic stirring, and placing the cathode tank electrolyte and the flowing double-tank electric reactor in room temperature;
s3: the flow rate was controlled at 100mL/min, the potential was controlled at 0.8V using a saturated Ag/AgCl reference electrode, at which time the current control range was 1.5-4.5A, and the voltage applied between anode and cathode was 2-10V. Stopping the reaction when the total amount of the applied charges reaches 4000 ℃, wherein the reaction time is 1500s;
s4: sampling and analyzing the electrolyte of the anode tank in the step S3, cooling to room temperature, acidifying to pH=3 by using 3mol/L hydrochloric acid, extracting and layering by ethyl acetate, evaporating and separating the ethyl acetate after taking the upper layer, tracking by using HPLC, and when the reaction reaches 1500S, the raw material conversion rate reaches 95%, the 3-picolinic acid selectivity reaches 99%, and the space-time yield reaches 7.46 kg/(m) 3 ·h)。
Example 5: preparation of 2-pyridine acetic acid by electrocatalytic oxidation of 2-pyridine ethanol with organic ligand 4,4' -biphthalic acid and nickel-based metal organic frame/graphite felt electrode material with nickel (II) acetate tetrahydrate as metal nickel salt
1) And sequentially and respectively ultrasonically treating graphite felt with the size of 3cm x 3.5cm in nitric acid, acetone, absolute ethyl alcohol and deionized water for 60 minutes to remove impurities on the surface of a graphite felt substrate. Then washing with a large amount of deionized water, and finally drying at 70 ℃ for later use.
2) Respectively weighing 300mg of nickel (II) acetate tetrahydrate, 242mg of 4,4' -biphenyl dicarboxylic acid, and adding into a mixed solution composed of 3mL of absolute ethyl alcohol, 3mL of deionized water and 60mLN, N-dimethylformamide to obtain a precursor solution;
3) Adding the pretreated graphite felt and the precursor solution into a 100mL polytetrafluoroethylene lining, performing ultrasonic dispersion for 40 minutes, loading the lining into a stainless steel reaction kettle, and performing solvothermal reaction for 12 hours at 120 ℃;
4) And (3) taking out the graphite felt after the reaction kettle is cooled to room temperature, respectively washing with deionized water and ethanol for 3 times, and drying in a blast drying oven at 70 ℃ for 12 hours to obtain the graphite felt electrode material loaded with the nickel-based metal organic framework catalyst.
The electrode material obtained in example 5 is applied to electrocatalytic oxidation of 2-pyridine ethanol to prepare 2-pyridine acetic acid, and the specific method is as follows:
the method is controlled by a potentiostat, a flowing double-tank electric reactor is adopted for reaction, the volumes of an anode tank and a cathode tank are 100mL and are separated by a proton exchange membrane, 70mL of 1mol/L sodium carbonate aqueous solution and 30mL of dichloromethane mixed solution (the feeding volume ratio of a main solvent to a secondary solvent is 3:2) are used as electrolyte solution of the anode tank, and 100mL of 1mol/L sodium carbonate aqueous solution is used as electrolyte solution of a cathode chamber; taking the prepared electrode material as a working electrode in an anode tank of the electrolytic tank; in the cathode groove of the electric reactor, foam nickel is used as a counter electrode; using a saturated Ag/AgCl electrode as a reference electrode;
s1: taking 0.615g (5 mmol) of 2-pyridine ethanol as a reactant, adding the reactant into a mixed solvent consisting of 70mL of 1mol/L sodium carbonate solution and 30mL of dichloromethane, adding 106mg of 4-acetamido-2, 6-tetramethylpiperidine-1-nitroxide free radical (ACT) into an anode cell electrolytic solution, and performing ultrasonic treatment for 5min to fully dissolve and uniformly mix the reactant;
s2: placing the anode tank electrolyte in a water bath at 30 ℃, keeping the temperature constant, using magnetic stirring, and placing the cathode tank electrolyte and the flowing double-tank electric reactor in room temperature;
s3: the flow rate was controlled at 150mL/min, the potential was controlled at 0.8V using saturated Ag/AgCl, the current control range was 2-4A, and the voltage applied between anode and cathode was 2-10V. Stopping the reaction when the total amount of the applied charges reaches 2000 ℃, wherein the reaction time is 700s;
s4: sampling and analyzing the electrolyte of the anode tank in the step S3, cooling to room temperature, acidifying to pH=3 by using 3mol/L hydrochloric acid, extracting and layering by ethyl acetate, evaporating and separating the ethyl acetate after taking the upper layer, tracking by using HPLC, and when the reaction reaches 700S, the raw material conversion rate reaches 98%, the selectivity of 2-pyridine acetic acid reaches 99%, and the space-time yield reaches 9.30 kg/(m) 3 ·h)。
Example 6: preparation of 2-pyridine propionic acid by electrocatalytic oxidation of 2-pyridine propanol with organic ligand terephthalic acid and nickel-based metal organic frame/graphite felt electrode material with nickel chloride hexahydrate as metal nickel salt
1) And sequentially and respectively ultrasonically treating graphite felt with the size of 3cm x 3.5cm in nitric acid, acetone, absolute ethyl alcohol and deionized water for 60 minutes to remove impurities on the surface of a graphite felt substrate. Then washing with a large amount of deionized water, and finally drying at 70 ℃ for later use.
2) Respectively weighing 250mg of nickel chloride hexahydrate and 166mg of terephthalic acid, and adding the nickel chloride hexahydrate and the 166mg of terephthalic acid into a mixed solution composed of 3mL of absolute ethyl alcohol, 3mL of deionized water and 60mL of N-dimethylformamide to obtain a precursor solution;
3) Adding the pretreated graphite felt and the precursor solution into a 100mL polytetrafluoroethylene lining, performing ultrasonic dispersion for 10 minutes, loading the lining into a stainless steel reaction kettle, and performing solvothermal reaction for 12 hours at 120 ℃;
4) And (3) taking out the graphite felt after the reaction kettle is cooled to room temperature, respectively washing with deionized water and ethanol for 3 times, and drying in a blast drying oven at 70 ℃ for 12 hours to obtain the graphite felt electrode material loaded with the nickel-based metal organic framework catalyst.
The electrode material obtained in example 6 is applied to electrocatalytic oxidation of 2-pyridinium propanol to prepare 2-pyridinium propionic acid, and the specific method is as follows:
the method is controlled by a potentiostat, a flowing double-tank electric reactor is adopted for reaction, the volumes of an anode tank and a cathode tank are 100mL and are separated by a proton exchange membrane, 70mL of 1mol/L sodium carbonate aqueous solution and 30mL of acetonitrile mixed solution (the feeding volume ratio of a main solvent to a secondary solvent is 3:2) are used as electrolyte solution of the anode tank, and 100mL of 1mol/L sodium carbonate aqueous solution is used as electrolyte solution of a cathode chamber; taking the prepared electrode material as a working electrode in an anode tank of the electrolytic tank; in the cathode groove of the electric reactor, foam nickel is used as a counter electrode; using a saturated Ag/AgCl electrode as a reference electrode;
s1: taking 0.685g (5 mmol) of 2-pyridine propanol as a reactant, adding the reactant into a mixed solvent consisting of 70mL of 1mol/L sodium carbonate solution and 30mL of acetonitrile, adding 106mg of 4-acetamido-2, 6-tetramethylpiperidine-1-nitroxide free radical (ACT) into an anode cell electrolyte solution, and performing ultrasonic treatment for 5min to fully dissolve and uniformly mix the reactant;
s2: placing the anode tank electrolyte in a water bath at 30 ℃, keeping the temperature constant, using magnetic stirring, and placing the cathode tank electrolyte and the flowing double-tank electric reactor in room temperature;
s3: the flow rate was controlled at 120mL/min, the potential was controlled at 0.8V using saturated Ag/AgCl, the current control range was 2-4A, and the voltage applied between anode and cathode was 2-10V. Stopping the reaction when the total amount of the applied charges reaches 2000 ℃, wherein the reaction time is 700s;
s4: sampling and analyzing the electrolyte of the anode tank in the step S3, cooling to room temperature, acidifying to pH=3 by using 3mol/L hydrochloric acid, extracting and layering by ethyl acetate, evaporating and separating the ethyl acetate after taking the upper layer, tracking by using HPLC, and when the reaction reaches 700S, the raw material conversion rate reaches 99%, the selectivity of 2-pyridine propionic acid reaches 99%, and the space-time yield reaches 10.46 kg/(m) 3 ·h)。
Comparative example 7: preparation of 2-picolinic acid by electrocatalytic oxidation of 2-picolinic alcohol from unmodified graphite felt electrode material
Directly applying the unmodified graphite felt electrode material to electrocatalytic oxidation of 2-pyridine methanol to prepare 2-pyridine carboxylic acid, wherein the specific method comprises the following steps:
the method is controlled by a potentiostat, a flowing double-tank electric reactor is adopted for reaction, the volumes of an anode tank and a cathode tank are 100mL and are separated by a proton exchange membrane, 70mL of 1mol/L sodium carbonate aqueous solution and 30mL of acetonitrile mixed solution (the feeding volume ratio of a main solvent to a secondary solvent is 7:3) are used as electrolyte of the anode tank, and 100mL of 1mol/L sodium carbonate aqueous solution is used as electrolyte of the cathode tank; in an anode tank of the electrolytic tank, an unmodified graphite felt electrode material is used as a working electrode; in the cathode groove of the electric reactor, foam nickel is used as a counter electrode; using a saturated Ag/AgCl electrode as a reference electrode;
s1: taking 0.55g (5 mmol) of 2-pyridine methanol as a reactant, adding the reactant into a mixed solvent consisting of 70mL of 1mol/L sodium carbonate solution and 30mL of acetonitrile, adding 21.3mg of 4-acetamido-2, 6-tetramethylpiperidine-1-nitroxide free radical (ACT) into an anode cell electrolyte solution, and carrying out ultrasonic treatment for 5min to fully dissolve and uniformly mix the reactant;
s2: placing the anode tank electrolyte in a water bath at 30 ℃, keeping the temperature constant, using magnetic stirring, and placing the cathode tank electrolyte and the flowing double-tank electric reactor in room temperature;
s3: the flow rate was controlled at 100mL/min, the potential was controlled at 0.8V using a saturated Ag/AgCl reference electrode, at which time the current control range was 0.5-1.5A, and the voltage applied between anode and cathode was 2-10V. Stopping the reaction when the total amount of the applied charges reaches 2000 ℃, wherein the reaction time is 1900s, and the current in the reaction process changes with time as shown in fig. 7;
s4: sampling and analyzing the electrolyte of the anode tank in the step S3, cooling to room temperature, acidifying to pH=3 by using 3mol/L hydrochloric acid, extracting and layering by ethyl acetate, evaporating and separating the ethyl acetate after taking the upper layer, tracking by using HPLC, and when the reaction reaches 1900S, the conversion rate of the raw material reaches 87%,2 percentPicolinic acid selectivity exceeding 95% and a space-time yield of 2.61 kg/(m) 3 ·h)。
The results of the reaction in electrocatalytic oxidation of pyridinols or pyridinaldehydes to pyridine compounds are shown in Table 1, comparing the above examples.
Comparing the nickel-based metal organic frame/graphite felt electrode material in example 1 with the unsupported graphite felt electrode material under the same reaction conditions, the use amount of 4-acetamido-2, 6-tetramethyl piperidine-1-nitroxide free radical (ACT) is reduced by half, the cost and the product separation difficulty are effectively reduced, the reaction time is shortened from 1900s to 700s, the conversion rate is improved from 87% to 99%, the product selectivity is improved from 95% to 99%, and the space-time yield is improved from 2.84 kg/(m) 3 H) lifting to 9.06 kg/(m) 3 ·h)。
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (10)
1. The preparation method of the nickel-based metal organic frame/graphite felt electrode material is characterized in that metal nickel salt and aryl acid organic ligands are used as raw materials, a graphite felt is used as a base material, a hydrothermal reaction is carried out in a solvent, and a three-dimensional flaky nickel-based metal organic frame array is loaded on the surface of a graphite felt base by a solvothermal method, so that the nickel-based metal organic frame/graphite felt electrode material is prepared; wherein the molar ratio of the metal nickel salt to the aryl acid organic ligand is 1-1.5:1, preferably 1.1-1.2:1, and the molar dosage of the metal nickel salt is 0.02-0.2 mmol/cm based on the size area of the graphite felt substrate material 2 Preferably 0.08 to 0.12mmol/cm 2 。
2. A method of preparing a nickel-based metal organic framework/graphite felt electrode material according to claim 1, characterized in that the aryl acid based organic ligand is terephthalic acid, 4 '-biphthalic acid, [1,1':4',1 "-terphenyl ] -4,4" -dicarboxylic acid or 2, 6-naphthalene dicarboxylic acid, preferably 4,4' -biphthalic acid; the metal nickel salt is nickel nitrate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate or nickel sulfate hexahydrate, preferably nickel nitrate hexahydrate.
3. The method for preparing the nickel-based metal organic framework/graphite felt electrode material according to claim 1, which is characterized by comprising the following steps:
1) Pretreating the graphite felt to remove impurities on the surface of the graphite felt substrate; dissolving metal nickel salt and aryl acid organic ligand in a solvent, and uniformly dispersing by ultrasonic to obtain a precursor solution;
2) And (3) adding the precursor solution and the pretreated graphite felt in the step (1) into a hydrothermal kettle, performing hydrothermal reaction for 8-16 hours at 100-170 ℃, cooling to room temperature after the reaction is finished, taking out the graphite felt, respectively washing the graphite felt with distilled water and ethanol for 2-3 times, and performing forced air drying at 50-80 ℃ to obtain the nickel-based metal organic frame/graphite felt electrode material.
4. The method for preparing the nickel-based metal organic frame/graphite felt electrode material according to claim 1, wherein in the step 1), the graphite felt is pretreated by the following steps: and sequentially and respectively carrying out ultrasonic treatment on the graphite felt in nitric acid, acetone, absolute ethyl alcohol and deionized water for 30-120 min to remove impurities on the surface of a graphite felt substrate and improve the load strength, taking out the graphite felt, and then washing and drying the graphite felt by using the deionized water to obtain the pretreated graphite felt for standby.
5. The preparation method of the nickel-based metal organic frame/graphite felt electrode material according to claim 1, wherein the solvent is deionized water, absolute ethyl alcohol and N, N-dimethylformamide, and the volume ratio of the deionized water to the absolute ethyl alcohol to the N, N-dimethylformamide is 1:0.5-2:5-80; the concentration of the metal nickel salt in the precursor solution is 10-30mmol/L, preferably 10-20mmol/L; the concentration of the aryl acid organic ligand in the precursor solution is 10-30mmol/L, preferably 10-20mmol/L.
6. A nickel-based metal organic framework/graphite felt electrode material prepared by the method of any one of claims 1 to 5.
7. The application of the nickel-based metal organic frame/graphite felt electrode material in preparing pyridine acid compounds by electrocatalytic oxidation of pyridine alcohols or pyridine aldehydes, as claimed in claim 1, characterized in that a flow double-tank electric reactor is adopted, an anode tank and a cathode tank are separated by a proton exchange membrane, the nickel-based metal organic frame/graphite felt electrode material is used as a working electrode of the anode tank, foam nickel is used as a cathode, a saturated Ag/AgCl electrode is used as a reference electrode, pyridine alcohols or pyridine aldehydes reactants are dissolved in a solvent to be used as an anode liquid, nitrogen oxide free radicals are added into the anode liquid to be used as a homogeneous catalyst, a weak alkaline solution is used as a cathode liquid, at a certain temperature, the voltage between the reference electrode and a working electrode is 0.6-0.8V, the electric catalytic alcohol oxidation reaction is carried out for 8-60 minutes, after the reaction is finished, the anode tank reaction liquid is cooled and the pH value of the reaction liquid is regulated to be 2-4, then organic solvent extraction is added, the organic layer is taken for distillation after standing and layering, the corresponding pyridine acid compounds are obtained by decompression, and the reaction equation is as follows:
8. use according to claim 7, characterized in that the concentration of the reaction starting material pyridinol or pyridinaldehyde substrate in the anolyte is 10-300mmol/L, preferably 50-200mmol/L;
the solvent used for the anode liquid is divided into a main solvent and a secondary solvent, wherein the main solvent is a weak alkaline solution, is selected from aqueous solution of sodium bicarbonate, sodium carbonate, potassium bicarbonate or potassium carbonate, preferably sodium carbonate aqueous solution, and has the concentration of 0.1-2.0mol/L; the secondary solvent is one of acetonitrile, dichloromethane, chloroform or carbon tetrachloride, and the volume ratio of the primary solvent to the secondary solvent is 9:1-1:1;
the catholyte is selected from sodium bicarbonate, sodium carbonate, potassium bicarbonate or potassium carbonate aqueous solution, preferably sodium carbonate aqueous solution, and the concentration of the catholyte is 0.1-2.0mol/L;
in the electrocatalytic alcohol oxidation reaction process, the catholyte in the cathode tank is pumped out and then returned to the cathode tank again for circulating flow, and the anolyte in the anode tank is pumped out and then returned to the anode tank again for circulating flow.
9. The use according to claim 7, characterized in that the nitroxide radical is selected from the group consisting of 4-acetamido-2, 6-tetramethylpiperidine-1-nitroxide radicals, which are present in the anolyte in a concentration of 0.2-2.2 g/L.
10. Use according to claim 7, characterized in that the voltage between anode and cathode is 2-10V and the reaction temperature is 20-60 ℃; the organic solvent for extraction is dichloromethane, chloroform or ethyl acetate.
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| CN117174923A (en) * | 2023-11-03 | 2023-12-05 | 杭州德海艾科能源科技有限公司 | Graphite felt for enhancing solid-liquid interface interaction and preparation method thereof |
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| CN117174923B (en) * | 2023-11-03 | 2024-02-06 | 杭州德海艾科能源科技有限公司 | Graphite felt for enhancing solid-liquid interface interaction and preparation method thereof |
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