CN114774949B - Catalyst for preparing alcohol by electro-oxidation of methane, preparation method and application thereof - Google Patents
Catalyst for preparing alcohol by electro-oxidation of methane, preparation method and application thereof Download PDFInfo
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- CN114774949B CN114774949B CN202210584745.1A CN202210584745A CN114774949B CN 114774949 B CN114774949 B CN 114774949B CN 202210584745 A CN202210584745 A CN 202210584745A CN 114774949 B CN114774949 B CN 114774949B
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- graphene oxide
- hydrogel film
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- zinc
- nickel
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 276
- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 226
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000000017 hydrogel Substances 0.000 claims abstract description 138
- 239000011787 zinc oxide Substances 0.000 claims abstract description 113
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 98
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 58
- 230000003647 oxidation Effects 0.000 claims abstract description 52
- 239000000084 colloidal system Substances 0.000 claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 134
- 239000006185 dispersion Substances 0.000 claims description 97
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 87
- 239000007788 liquid Substances 0.000 claims description 80
- 239000000243 solution Substances 0.000 claims description 74
- 238000000034 method Methods 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 239000012528 membrane Substances 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 238000000151 deposition Methods 0.000 claims description 47
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 42
- 238000001652 electrophoretic deposition Methods 0.000 claims description 37
- 239000000725 suspension Substances 0.000 claims description 37
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 35
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 35
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 34
- 239000003792 electrolyte Substances 0.000 claims description 34
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 33
- 230000008021 deposition Effects 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 229910001868 water Inorganic materials 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- 238000007906 compression Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 25
- 230000006835 compression Effects 0.000 claims description 22
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000004327 boric acid Substances 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 150000003751 zinc Chemical class 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 229920002678 cellulose Polymers 0.000 claims description 14
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000003828 vacuum filtration Methods 0.000 claims description 14
- 150000002815 nickel Chemical class 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- -1 nickel acetylacetonate dihydrate Chemical class 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- MBBQAVVBESBLGH-UHFFFAOYSA-N methyl 4-bromo-3-hydroxybutanoate Chemical compound COC(=O)CC(O)CBr MBBQAVVBESBLGH-UHFFFAOYSA-N 0.000 claims description 3
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 3
- 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 3
- 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 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 3
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 3
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 246
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 160
- 229910000510 noble metal Inorganic materials 0.000 abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 284
- 239000001569 carbon dioxide Substances 0.000 description 142
- 229910002092 carbon dioxide Inorganic materials 0.000 description 142
- 239000000047 product Substances 0.000 description 41
- 239000008367 deionised water Substances 0.000 description 35
- 229910021641 deionized water Inorganic materials 0.000 description 35
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 33
- 239000004246 zinc acetate Substances 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 21
- 239000012298 atmosphere Substances 0.000 description 16
- 239000012046 mixed solvent Substances 0.000 description 15
- 238000001962 electrophoresis Methods 0.000 description 12
- 238000011056 performance test Methods 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 229910018661 Ni(OH) Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 2
- 229910002440 Co–Ni Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910002640 NiOOH Inorganic materials 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910002708 Au–Cu Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- 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
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- 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
- 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
- C25B11/067—Inorganic compound e.g. ITO, silica or titania
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing alcohol by electro-oxidation of methane, a preparation method and application thereof, and relates to the technical field of catalysts. The catalyst for preparing alcohol by methane electrooxidation comprises a hydrogel film formed by reducing graphene oxide and zinc oxide colloid, wherein the zinc oxide colloid is dispersed in a film layer of the hydrogel film, zirconium oxide and nickel are also loaded on the surface of the hydrogel film, so that a non-noble metal catalyst is obtained, and the catalyst for preparing alcohol by methane electrooxidation has high methanol/isopropanol selectivity at room temperature and can effectively inhibit deep oxidation.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for preparing alcohol by electro-oxidation of methane, a preparation method and application thereof.
Background
The earth crust of the world is filled with abundant natural gas resources, and the storage amount accounts for about 21% of the total energy of the earth. In recent years, unconventional natural gas resources such as shale gas, methane hydrate and the like are continuously explored, so that the natural gas becomes an ideal substitute for petroleum resources. Methane is the major component of natural gas (about 70-90% by volume). In view of the extremely high combustion enthalpy (-892 kJ/mol) and energy density of methane >1000kWh/m 3 ) Most natural gas resources are used for heating or catalytic oxidation in fuel cells to produce electrical energy. Carbon dioxide emissions and methane leaks induced by these modes of utilization will exacerbate the greenhouse effect. In contrast, the catalytic conversion of methane into high value-added chemical products has higher economic value and practicability.
Currently, methane thermocatalysis is the most mature methane catalytic conversion technology near commercialization, mainly comprising methane steam reforming, methane-carbon dioxide reforming, methane autothermal reforming, methane oxidative coupling, methane dehydroaromatization, methane conversion to olefins, aromatics, hydrogen, and the like. However, the above-mentioned thermocatalytic processes are all high energy consuming processes involving high temperature and high pressure (700-1000 ℃,10-40 atm) conditions. The product is mainly a deep oxidation product of carbon dioxide, water and the like except a small amount of short-chain olefin and aromatic hydrocarbon, and does not meet the requirement of low carbon. In contrast, the following features make electrocatalytic oxidation of methane the most promising route for alternative thermocatalytics:
(1) The electric field near the electrode surface can effectively activate the inert carbon-hydrogen (C-H) bonds of methane;
(2) The evolution and regeneration of the catalyst surface active species can be realized by regulating the potential, and the reaction rate and the product selectivity are regulated;
(3) The continuous flow electrolytic cell and the membrane electrode structure are optimized, and the product selectivity and the reaction rate can be regulated and controlled from the dynamic angle;
(4) Sustainable electricity such as solar energy, wind energy, nuclear energy and the like can obviously reduce the cost of electrocatalytic oxidation.
At present, the catalyst systems for mild methane electrooxidation mainly comprise: cobalt phthalocyanine (CoPc) single-atom catalyst for acid electrolyte, acid/alkali electrolyte, noble metal catalyst (Pt, au, pd, ru, rh) and noble metal alloy catalyst (Pd-Cu, pd-Ni, pd-Mn and Pd-Au-Cu) for proton-transporting solid electrolyte, ni/Ni (OH) for alkaline electrolyte 2 Heterojunction catalyst, composite metal oxide catalyst of neutral or alkaline electrolyte (V 2 O 5 /SnO 2 ，Rh/NiO/V 2 O 5 ，Rh/ZnO，TiO 2 /RuO 2 ，TiO 2 /RuO 2 /V 2 O 5 Co-Ni spinel Co 3 O 4 /ZrO 2 ，CuO/ZrO 2 ，CuO/CeO 2 Co-Ni spinel/ZrO 2 Etc.), homogeneous catalyst of concentrated sulfuric acid electrolyte (Na 2 PtIVCl 6 ，PdSO 4 And (V) -oxo dimer, organic mixed solvent electrolyte "tetrabutylammonium perchlorate/1Homogeneous catalysts of 2-difluorobenzene (TBAClO 4/1, 2-DFB) "(tetramethylporphyrin rhodium II radical (TMP) Rh II), and the like. The electrocatalytic oxidation of methane is mainly carried out at normal temperature and normal pressure (the operating temperature of a fuel cell system based on proton transfer solid electrolyte is 50-200 ℃), and the main products are partial oxidation products with high added value such as methanol, ethanol, n-propanol, isopropanol, acetone, formic acid, propionic acid and the like. Therefore, the mild reaction system and effective inhibition of deep oxidation are major advantages of electrocatalytic oxidation of methane.
However, most of the above catalysts use noble metal (Pt, pd, au, ru, rh) as a main active component or an important doping auxiliary agent, so that the cost of the catalyst for preparing alcohol by electro-oxidation of methane is too high, and the practical application value is lacking. In addition, the catalyst powder is usually mixed with a conductive agent (carbon black, etc.), a binder (Nafion solution, etc.), a solvent (water, ethanol, acetone, etc.), and then added dropwise to a conductive matrix material (carbon paper, carbon fiber cloth, glass carbon fiber, metal foam, conductive glass, etc.), and the performance degradation caused by the falling of the active component cannot be avoided. Therefore, the development of the catalyst for preparing alcohol by methane electrooxidation, which takes non-noble metal elements as active components, firmly connects matrix materials with the active components, can effectively inhibit deep oxidation at room temperature and mainly generates high-added-value products, has important significance.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a catalyst for preparing alcohol by methane electrooxidation and a preparation method thereof, and aims to prepare a catalyst which is non-noble metal, has high methanol/isopropanol selectivity at room temperature and can effectively inhibit deep oxidation of methane.
Another object of the present invention is to provide a method for preparing alcohol by electrooxidation of methane, which uses the catalyst to perform electrooxidation, and has the advantages of low cost and high reaction efficiency.
The invention is realized in the following way:
in a first aspect, the invention provides a catalyst for preparing alcohol by electrooxidation of methane, which consists of a hydrogel film formed by reducing graphene oxide and zinc oxide, wherein the zinc oxide is dispersed in a film layer of the hydrogel film, and zirconium oxide and nickel are loaded on the surface of the hydrogel film. The zinc oxide is uniformly dispersed between layers of the hydrogel film by utilizing a hydrogel film formed by reducing graphene oxide and zinc oxide, and zirconium oxide and nickel are deposited on the surface of the hydrogel film to prepare the non-noble metal catalyst, and meanwhile, the catalyst is a catalyst for preparing alcohol by electro-oxidation of methane, which has high methanol/isopropanol selectivity at room temperature and can effectively inhibit deep oxidation.
In an alternative embodiment, the ratio of the total mass of the reduced graphene oxide to the zinc oxide in the catalyst is 60-95% and the ratio of the total mass of the zirconium oxide to the nickel is 5-40% in terms of mass fraction;
preferably, the total mass ratio of the reduced graphene oxide to the zinc oxide is 75-85%, and the total mass ratio of the zirconium oxide to the nickel is 15-25%;
preferably, the mass ratio of zinc oxide to reduced graphene oxide is 1 (0.5-50); more preferably 4:3 to 3:4;
Preferably, the mass ratio of zirconia to nickel is 1 (4-20); more preferably 1, (4-6);
preferably, the hydrogel film is subjected to capillary compression.
The ratio of each component in the catalyst is optimized, so that the performance of the catalyst is further improved, such as the selectivity of methanol/isopropanol is improved, and the occurrence of deep oxidation is restrained.
In a second aspect, the present invention provides a method for preparing a catalyst according to the foregoing embodiment, comprising:
preparing a zinc oxide-reduced graphene oxide hydrogel film by taking reduced graphene oxide dispersion liquid and zinc oxide colloid solution as raw materials;
zirconium oxide and nickel are deposited on the zinc oxide-reduced graphene oxide hydrogel film.
The preparation method provided by the embodiment of the invention utilizes the hydrogel film formed by reducing graphene oxide and zinc oxide to uniformly disperse zinc oxide among layers of the hydrogel film, and deposits zirconium oxide and nickel on the surface of the hydrogel film to prepare the non-noble metal catalyst, and meanwhile, the catalyst is a catalyst for preparing alcohol by methane electrooxidation, which has high methanol/isopropanol selectivity at room temperature and can effectively inhibit deep oxidation.
In an alternative embodiment, the zinc oxide-reduced graphene oxide hydrogel film is prepared by a process comprising: mixing the reduced graphene oxide dispersion liquid and the zinc oxide colloid solution, and performing vacuum suction filtration to form a hydrogel film, wherein the preparation of the hydrogel film by the method is simple and easy to implement;
Preferably, vacuum filtration is performed by using a mixed cellulose ester microporous filter membrane;
preferably, the formed hydrogel film is peeled off the filter membrane and is fed into water to remove residual impurities.
In an alternative embodiment, the preparation process of the reduced graphene oxide dispersion liquid comprises: uniformly mixing graphene oxide dispersion liquid, ammonia water and hydrazine hydrate, and reacting for 0.5-4 h at the temperature of 70-100 ℃;
preferably, the concentration of the graphene oxide dispersion liquid is 0.05mg/mL-0.5mg/mL, ammonia water is aqueous solution with ammonia content of 25-28wt%, hydrazine hydrate is aqueous solution with hydrazine hydrate content of 80-90wt%, the volume ratio of the ammonia water to the graphene oxide dispersion liquid is 1 (100-1000), and the volume ratio of the hydrazine hydrate to the graphene oxide dispersion liquid is 1 (1000-10000);
preferably, the preparation process of the graphene oxide dispersion liquid comprises the following steps: and diluting the graphene oxide with water, performing ultrasonic stripping, and centrifuging to remove the non-stripped part, thereby obtaining the graphene oxide dispersion liquid meeting the concentration requirement.
In the preparation process of the reduced graphene oxide dispersion liquid provided by the embodiment of the invention, the concentration and the dosage of ammonia water and hydrazine hydrate are controlled to promote reduction of graphene oxide, so that the uniform reduced graphene oxide dispersion liquid is obtained.
In an alternative embodiment, the zinc oxide colloid solution is prepared by a process comprising: dropwise adding zinc salt aqueous solution into alkaline precipitant aqueous solution, reacting for 0.5-5 h at 50-90 ℃, cooling and diluting to 0.05-0.5 mg/mL;
preferably, the concentration of the zinc salt aqueous solution is 1mM-10mM, and the mass ratio of the zinc salt to the alkaline precipitant adopted in the reaction is 1 (2-5);
preferably, the zinc salt is selected from at least one of zinc acetate dihydrate, zinc nitrate hexahydrate, zinc chloride, zinc acetylacetonate hydrate and zinc sulfate heptahydrate;
preferably, the alkaline precipitant is selected from at least one of sodium hydroxide, potassium hydroxide and aqueous ammonia.
According to the preparation method of the zinc oxide colloidal solution, disclosed by the embodiment of the invention, zinc salt aqueous solution is dropwise added into alkaline precipitant aqueous solution to form the zinc oxide colloidal solution, and the reaction is fully carried out by controlling the reaction conditions, so that uniform colloidal solution is obtained.
In an alternative embodiment, the zinc oxide-reduced graphene oxide hydrogel film is subjected to capillary compression prior to depositing the zirconium oxide and nickel on the zinc oxide-reduced graphene oxide hydrogel film; capillary compression is carried out on the zinc oxide-reduced graphene oxide hydrogel film so as to improve the conductivity of the catalyst and the catalytic activity of the catalyst.
Preferably, the capillary compression process comprises: soaking the zinc oxide-reduced graphene oxide hydrogel film in a mixed solution formed by water and N-methylpyrrolidone for 8-15 h, taking out, and vacuum drying at 40-90 ℃ for 4-20h to compress the film; and (3) soaking the compressed zinc oxide-reduced graphene oxide hydrogel film in water again to enable NMP remained between layers to be replaced by H2O again, so as to obtain ZnO-rGO hydrogel films with different compression degrees.
Preferably, the volume ratio of water to N-methylpyrrolidone is (0-19): 1;
more preferably, the volume ratio of water to N-methylpyrrolidone is (2-3): 1;
more preferably, the vacuum drying temperature is 50-70 ℃ and the vacuum drying time is 6-10 h.
In an alternative embodiment, the method of electrophoretic deposition is used for depositing zirconium oxide and nickel on the zinc oxide-reduced graphene oxide hydrogel film, and the method is simple and easy to implement, and can be used for depositing zirconium oxide and nickel with higher purity on the zinc oxide-reduced graphene oxide hydrogel film.
Preferably, the process of electrophoretic deposition comprises: dispersing nickel salt, zirconia powder, a surfactant and a buffer agent in water to form a suspension, taking a zinc oxide-reduced graphene oxide hydrogel film as a cathode, and immersing the cathode and the anode in the suspension for electrophoretic deposition;
Preferably, the concentration of the nickel salt material in the suspension is 0.5M to 5M and the concentration of the zirconia is 1mg/mL to 20mg/mL;
preferably, the surfactant is sodium dodecyl sulfate, the buffer is boric acid, the mass ratio of zirconia to sodium dodecyl sulfate is (5-50): 1, and the mass ratio of zirconia to boric acid is (0.5-5);
preferably, the nickel salt is selected from at least one of nickel chloride hexahydrate, nickel nitrate hexahydrate, nickel acetate tetrahydrate and nickel acetylacetonate dihydrate;
preferably, the zirconia powder has an average particle diameter of 5nm to 20nm;
preferably, the anode is a carbon rod.
In an alternative embodiment, a direct current pulse power supply deposition method is adopted in the electrophoretic deposition process, the average current density is controlled to be 1A/dm 2-10A/dm 2, the duty ratio is 5-95%, the pulse frequency is 50Hz-2000 Hz, the stirring speed is 200-1000 rpm, the suspension temperature is 20-90 ℃, and the deposition time is 0.5-40 min;
preferably, the average current density is controlled to be 3A/dm 2-8A/dm 2, the duty ratio is 40% -80%, the pulse frequency is 100Hz-1200Hz, the stirring speed is 400rpm-600rpm, the suspension temperature is 50 ℃ -70 ℃, and the deposition time is 10min-30min. By further controlling the parameters of the electrophoretic deposition process, it is advantageous to promote the deposition of the zirconia carrying nickel on the cathode.
In a third aspect, the present invention provides a method for preparing alcohol by electro-oxidation of methane, which uses the catalyst of any one of the previous embodiments or the catalyst prepared by the preparation method of any one of the previous embodiments as an electrocatalytic anode working electrode, has high methanol/isopropanol selectivity, and can effectively inhibit deep oxidation.
Preferably, a graphite carbon rod is used as a cathode counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, each electrode is placed in an alkaline electrolyte of an H-type double-chamber electrolytic cell, methane is introduced into the alkaline electrolyte for electrocatalytic oxidation, and constant potential reaction is carried out for 2-4 hours under the condition of 0.5-1.0V of potential interval;
preferably, the alkaline electrolyte is selected from Na 2 CO 3 、K 2 CO 3 Any one of NaOH and KOH, wherein the mass concentration of the alkaline electrolyte is 0.3M-1.0M;
preferably, the reaction pressure is normal pressure, the reaction temperature is room temperature, and the methane gas flow rate is 25mL/min-35mL/min.
The embodiment of the invention has the following beneficial effects: the zinc oxide is uniformly dispersed between layers of the hydrogel film by utilizing a hydrogel film formed by reducing graphene oxide and zinc oxide, and zirconium oxide and nickel are deposited on the surface of the hydrogel film to prepare the non-noble metal catalyst, and meanwhile, the catalyst is a catalyst for preparing alcohol by electro-oxidation of methane, which has high methanol/isopropanol selectivity at room temperature and can effectively inhibit deep oxidation.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a ZnO-rGO hydrogel film;
FIG. 2 shows Ni-ZrO after deposition by DC pulse electrophoresis 2 ZnO-rGO hydrogel film;
FIG. 3 Ni-ZrO under various atmospheres 2 Linear sweep voltammogram when ZnO-rGO is used as a catalyst for preparing alcohol by electro-oxidation of methane;
FIG. 4 shows the results of the test of methane oxidation performance of the catalysts prepared in example 1 and examples 12-15;
FIG. 5 shows the results of the test of methane oxidation performance of the catalysts prepared in example 1 and examples 16-19;
FIG. 6 shows the results of the test of methane oxidation performance of the catalysts prepared in example 1 and examples 20-22;
FIG. 7 is a cyclic voltammogram of the catalyst prepared in comparative example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides a preparation method of a catalyst, which can be used for preparing alcohol by electro-oxidation of methane and comprises the following steps:
s1, preparing reduced graphene oxide dispersion liquid
Uniformly mixing Graphene Oxide (GO) dispersion liquid, ammonia water and hydrazine hydrate, and reacting for 0.5-4 hours at the temperature of 70-100 ℃ to obtain reduced graphene oxide (rGO) dispersion liquid, wherein stirring is kept in the preparation process.
In order to further control the sufficient reduction of the graphene oxide, the concentration of the graphene oxide dispersion liquid is 0.05mg/mL-0.5mg/mL (such as 0.05mg/mL, 0.1mg/mL, 0.2mg/mL, 0.3mg/mL, 0.4mg/mL and 0.5 mg/mL), ammonia water is an aqueous solution with the ammonia content of 25-28wt%, hydrazine hydrate is an aqueous solution with the hydrazine content of 80-90wt%, the volume ratio of the ammonia water to the graphene oxide dispersion liquid is 1 (100-1000), the volume ratio of the hydrazine hydrate to the graphene oxide dispersion liquid is 1 (1000-10000), the raw materials of the hydrazine hydrate and the ammonia water are solutions in the preparation process, and the consumption of the two reducing agents is far less than that of the graphene oxide dispersion liquid, so that the concentration of the prepared reduced graphene oxide dispersion liquid is approximately the same as that of the graphene oxide dispersion liquid.
Specifically, the preparation process of the graphene oxide dispersion liquid comprises the following steps: and diluting the graphene oxide with water, performing ultrasonic stripping, and centrifuging to remove the non-stripped part, thereby obtaining the graphene oxide dispersion liquid meeting the concentration requirement.
S2, preparing zinc oxide colloid solution
The preparation process of the zinc oxide colloid solution comprises the following steps: and (3) dropwise adding the zinc salt aqueous solution into an alkaline precipitant aqueous solution, reacting for 0.5-5 h at 50-90 ℃, cooling and diluting to 0.05-0.5 mg/mL, wherein the diluted final concentration is approximately the same as the final concentration of the reduced graphene oxide dispersion, and the mass ratio of the reduced graphene oxide to the zinc oxide can be determined by controlling the volumes of the two raw materials. Specifically, zinc salt aqueous solution is dripped into alkaline precipitant aqueous solution to generate zinc hydroxide precipitate, zinc oxide colloid is formed through hydrolysis and crosslinking, and the zinc oxide colloid is not pure zinc oxide or zinc hydroxide, but colloid formed through water crosslinking.
In a preferred embodiment, the concentration of the zinc salt aqueous solution is 1mM-10mM, the mass ratio of the zinc salt to the alkaline precipitant adopted in the reaction is 1 (2-5), and the zinc salt and the alkaline precipitant are controlled to promote the hydrolysis and crosslinking to obtain the zinc oxide colloid.
In some embodiments, the zinc salt is selected from zinc acetate dihydrate (Zn (CH 3 COO) 2 ·2H 2 O), zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), zinc chloride (ZnCl) 2 ) Zinc acetylacetonate hydrate (Zn (C) 5 H 7 O 2 ) 2 ·xH 2 O) and zinc sulfate heptahydrate (ZnSO) 4 ·7H 2 At least one of the O) can be one or more of water-soluble zinc salts. The alkaline precipitant is selected from sodium hydroxide (NaOH), potassium hydroxide (KOH) and ammonia water (NH) 3 ·H 2 O,25% -28%), which may be one kind or plural kinds.
S3, preparing zinc oxide-reduced graphene oxide hydrogel film
Preparing a zinc oxide-reduced graphene oxide hydrogel film by taking reduced graphene oxide dispersion liquid and zinc oxide colloid solution as raw materials, wherein the volume ratio of the zinc oxide colloid solution to the reduced graphene oxide dispersion liquid is controlled to be 1 (0.5-50).
In some embodiments, the zinc oxide-reduced graphene oxide hydrogel film is prepared by a process comprising: mixing the reduced graphene oxide dispersion liquid and the zinc oxide colloid solution, and performing vacuum suction filtration to form a hydrogel film; such as vacuum filtration using a mixed cellulose ester microporous filter. After suction filtration, water, solvent and other components are filtered, and the reduced graphene oxide and zinc oxide form a self-supporting ZnO-rGO hydrogel film on the filter membrane.
In some embodiments, the formed hydrogel film is peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
S4, performing capillary compression on the zinc oxide-reduced graphene oxide hydrogel film
Before depositing zirconia and nickel on the zinc oxide-reduced graphene oxide hydrogel film, capillary compression is performed on the zinc oxide-reduced graphene oxide hydrogel film so as to improve the conductivity of the catalyst and the catalytic activity of the catalyst.
In some embodiments, the process of capillary compression includes: soaking a zinc oxide-reduced graphene oxide hydrogel film in a mixed solution formed by water and N-methylpyrrolidone (NMP) for 8-15 h, so that the water in the hydrogel film is completely replaced by the mixed solvent; after taking out, fixing the film by using two cover slips, and vacuum drying for 4-20H at 40-90 ℃ to ensure that H in the mixed solvent 2 O is completely volatilized, and NMP remains in the hydrogel film layer, so that the ZnO-rGO film is compressed to different degrees. Soaking the compressed zinc oxide-reduced graphene oxide hydrogel film in water again to make the NMP remained between layers be H 2 O is replaced again, so that ZnO-rGO hydrogel films with different compression degrees are obtained.
It should be noted that N-methylpyrrolidone may be replaced with a conventional solvent having a viscosity higher than water and a volatility lower than water.
In some embodiments, the volume ratio of water to N-methylpyrrolidone is (0-19): 1; preferably, the volume ratio of water to N-methylpyrrolidone is (2-3): 1, the vacuum drying temperature is 50-70 ℃, and the vacuum drying time is 6-10 hours. By controlling the operation parameters in the capillary compression process, the compression degree is favorably regulated and controlled, so that the compression degree is not too large or too small, and the performance of the catalyst is favorably further improved.
S5, depositing zirconia and nickel
Zirconium oxide and nickel are deposited on the zinc oxide-reduced graphene oxide hydrogel film, and the specific deposition method is not limited. In some embodiments, the method of electrophoretic deposition may be used to deposit zirconia and nickel on zinc oxide-reduced graphene oxide hydrogel films, nickel not referring to elemental form, but rather to a complex nickel component in a doped state.
Specifically, the process of electrophoretic deposition includes: nickel salt, zirconia powder, surfactant and buffer are dispersed in water to form a suspension, a zinc oxide-reduced graphene oxide hydrogel film is used as a cathode, and the cathode and the anode are immersed in the suspension for electrophoretic deposition. The surfactant may be, but is not limited to, sodium dodecyl sulfate and the buffer may be, but is not limited to, boric acid.
In some embodiments, nickel salt, zirconia powder, sodium Dodecyl Sulfate (SDS), and boric acid are dispersed in water to form a suspension in which the nickel salt has an amount concentration of 0.5M to 5M and the zirconia has a concentration of 1mg/mL to 20mg/mL; the mass ratio of the zirconia to the sodium dodecyl sulfate is (5-50): 1, and the mass ratio of the zirconia to the boric acid is (1) (0.5-5). The deposition of nickel and zirconia onto the hydrogel film is promoted by controlling the amount of raw materials.
Specifically, the nickel salt is at least one selected from nickel chloride hexahydrate, nickel nitrate hexahydrate, nickel acetate tetrahydrate and nickel acetylacetonate dihydrate, and can be one or more of soluble nickel salts; the average grain diameter of the zirconia powder is 5nm-20nm, and the zirconia powder is a nano-scale powder raw material; the anode may be a carbon rod.
In some embodiments, a direct current pulse power supply deposition method is adopted in the electrophoretic deposition process, the average current density is controlled to be 1A/dm 2-10A/dm 2, the duty ratio is 5-95%, the pulse frequency is 50Hz-2000 Hz, the stirring speed is 200-1000 rpm, the suspension temperature is 20-90 ℃, and the deposition time is 0.5-40 min; preferably, the average current density is controlled to be 3A/dm 2-8A/dm 2, the duty ratio is 40% -80%, the pulse frequency is 100Hz-1200Hz, the stirring speed is 400rpm-600rpm, the suspension temperature is 50 ℃ -70 ℃, and the deposition time is 10min-30min. By controlling the power supply parameters in the electrophoretic deposition process, the method is beneficial to promoting the deposition of the zirconia carrying nickel on the cathode.
The embodiment of the invention also provides a catalyst for preparing alcohol by electro-oxidation of methane, which is prepared by the preparation method. The catalyst consists of a hydrogel film formed by reducing graphene oxide and zinc oxide, wherein the zinc oxide is dispersed in a film layer of the hydrogel film, and zirconium oxide and nickel are loaded on the surface of the hydrogel film. The catalyst does not contain noble metal, and is a catalyst for preparing alcohol by methane electrooxidation, which has high methanol/isopropanol selectivity at room temperature and can effectively inhibit deep oxidation.
Further, in terms of mass fraction, the total mass ratio of the reduced graphene oxide and zinc oxide in the catalyst is 60% -95%, and the total mass ratio of the zirconium oxide and nickel is 5% -40%; preferably, the total mass ratio of the reduced graphene oxide and the zinc oxide is 75% -85%, and the total mass ratio of the zirconium oxide and the nickel is 15% -25%. The mass ratio of the zinc oxide to the reduced graphene oxide is 1 (0.5-50); preferably 4:3 to 3:4; the mass ratio of the zirconia to the nickel is 1 (4-20); preferably 1 (4-6). The catalyst performance is further improved by optimizing the proportion of each component in the catalyst.
The embodiment of the invention also provides a method for preparing alcohol by electro-oxidation of methane, which takes the catalyst as an electrocatalytic anode working electrode to perform electrocatalytic.
In the actual operation process, a graphite carbon rod is used as a cathode counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, each electrode is placed in alkaline electrolyte (the volume of electrolyte in an anode chamber is 60 mL) of an H-type double-chamber electrolytic cell, methane is introduced into the alkaline electrolyte for electrocatalytic oxidation, and constant potential reaction is carried out for 2-4H under the condition of 0.5-1.0V in potential interval, so that the reaction is fully carried out.
Specifically, the alkaline electrolyte is selected from Na 2 CO 3 、K 2 CO 3 Any one of NaOH and KOH, wherein the mass concentration of the alkaline electrolyte is 0.3M-1.0M; the reaction pressure is normal pressure, the reaction temperature is room temperature, and the flow rate of methane gas is 25mL/min-35mL/min. Atmospheric room temperature is a conventional understanding of pressureIs at a standard atmospheric pressure and a temperature of 25 ℃.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a preparation method of a catalyst, which comprises the following steps:
(1) Graphene oxide is prepared according to the Hummers method, and deionized water is injected into the prepared graphene oxide to obtain GO dispersion liquid with the concentration of 0.2mg/mL. 100mL of the GO dispersion was mixed with ammonia and hydrazine hydrate. Wherein the volume ratio of ammonia water to GO dispersion liquid is 1:1000, the volume ratio of hydrazine hydrate to GO dispersion liquid is 1:10000, and the mixture is heated at 80 ℃ under reflux for 1h to obtain rGO dispersion liquid.
(2) And slowly injecting the zinc acetate solution into the NaOH solution by using a syringe pump, wherein the concentration of zinc acetate in the mixed solution is 1mM, the mass concentration ratio of zinc acetate to NaOH is 1:4, uniformly stirring, heating at 80 ℃ for 1h to obtain a ZnO colloid solution, and adding deionized water to dilute to the target concentration of 0.2mg/mL.
And (3) injection: the method for measuring the concentration of the ZnO colloid solution comprises the following steps: taking out one slide glass, weighing the slide glass with the mass of m 1 1mL of the ZnO colloidal solution was drawn out by a pipette and dropped onto a slide glass. The slide was moved to a 100deg.C oven until the moisture was completely evaporated, at which point the slide mass was weighed to be m 2 The concentration of the ZnO colloid solution is (m) 2 -m 1 )mg/mL。
(3) ZnO colloid solution and rGO dispersion (100 mL) are mixed according to the volume ratio of 1:1, and are subjected to vacuum filtration through a mixed cellulose ester microporous filter membrane to form a self-supporting ZnO-rGO hydrogel membrane (shown in figure 1). The membrane was peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
(4) Placing the ZnO-rGO hydrogel film in H 2 In an O/NMP mixed solvent for 12H, wherein H 2 The volume ratio of O to NMP was 9:1, and the membrane was then fixed using two coverslips and dried in vacuo at 40℃for 4h for capillary compression. And immersing the compressed ZnO-rGO film in deionized water for 0.5h to obtain the capillary compressed ZnO-rGO hydrogel film.
(5) According to Ni (NO) 3 ) 2 ·6H 2 The mass concentration of O is 1M, the concentration of nano zirconia powder is 5mg/mL, the concentration ratio of zirconia to SDS is 10:1, and the concentration ratio of zirconia to boric acid is 1:2. The capillary compressed ZnO-rGO hydrogel film is used as a cathode, a carbon rod is used as an anode and is connected to a direct current power supply, and the capillary compressed ZnO-rGO hydrogel film is immersed in the suspension to carry out direct current pulse electrophoresis deposition. Electrophoretic deposition conditions: average current density 3A/dm 2 The catalyst for preparing alcohol by electro-oxidation of methane is obtained by the steps of the duty ratio of 80 percent, the pulse frequency of 1200Hz, the stirring speed of 1000rpm, the electrophoretic deposition suspension at 60 ℃ and the deposition time of 40min and is named as Ni-ZrO 2 ZnO-rGO-1 (shown in FIG. 2).
Performance test: ni-ZrO using electrode clamps 2 The ZnO-rGO-1 hydrogel film was immobilized as the anode working electrode. Graphite carbon rod as cathode counter electrode, saturated Calomel Electrode (SCE) as reference electrode, na with concentration of 0.5M in H-type double-chamber electrolytic cell 2 CO 3 In alkaline electrolyte (anode chamber electrolyte volume 60 mL). Methane was introduced at 30mL/min and evaluated by the potentiostatic method at a potential of 0.7V (vs. SCE) for 3 hours.
Concentration test shows that: taking the electrolyte after the reaction, and using a gas chromatography FID detector to compare signal parameters of a standard substance, so as to determine the concentration of methanol and isopropanol; CO 2 As a gas phase product: introducing the tail gas after reaction into gas chromatography, and comparing signal parameters of standard substances by means of a gas chromatography TCD detector to obtain CO 2 Concentration in the tail gas. CO 2 Concentration reaction time tail gas volumetric flow rate = CO 2 Volume generation, CO 2 Volume conversion to CO 2 Mass (according to the "volume-mass" relationship), finally CO 2 The mass divided by the volume of the electrolyte is CO 2 The concentration is reduced.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 12.61 mug/mL and 8.23 mug/mL, respectively, CO 2 The reduced concentration was 1.73. Mu.g/mL. Methanol, isopropanol and CO 2 Selectivity of 46.66%,48.70% and 4.64%, respectively, demonstrating the ability to effectively inhibit deep oxidation product CO 2 And can obtain multi-carbon high added value products.
FIG. 3 shows Ni-ZrO under various atmospheres 2 As can be seen from FIG. 3, the linear sweep voltammogram of ZnO-rGO as catalyst for the electrooxidation of methane to alcohols: CH in the potential interval 0.55V-0.75V (vs. SCE) 4 The current density in the atmosphere is obviously improved compared with that in the He atmosphere, which proves that the catalyst has methane electrooxidation activity. And the potential interval is greater than 0.75V (vs. SCE), CH 4 The decrease in current density in the atmosphere can be attributed to the inhibition of the oxygen evolution reaction by the electro-oxidation reaction of methane at the catalyst surface. Calculated: the methane conversion rate was 270.67. Mu.g/h.
Introducing He atmosphere in the test provides a blank control by comparing CH 4 And detecting whether the catalyst has oxidation activity and active potential interval on methane or not according to the difference of the line scanning voltammetry curves under the atmosphere and the He atmosphere. FIG. 3 is He atmosphere and CH 4 Ni-ZrO under atmosphere 2 Linear sweep voltammogram of the ZnO-rGO catalyst. The following explanation is given to fig. 3:
under He atmosphere:
0V-0.55V (vs. sce) potential interval: no obvious current signal and no reactivity;
a potential interval of 0.55V-0.75V (vs. sce): the oxidation peaks were present and the following reactions occurred:
catalyst surface Ni oxidation reaction:
Ni+OH-→Ni-OH ads +e - ；
Ni-OH ads →(OH-Ni)；
(OH-Ni)+OH-→Ni(OH) 2,ads +e - ；
Ni(OH) 2 +OH-→NiOOH+H 2 O+e - ；
0.75V (vs. sce): oxygen evolution reaction: 4OH- & gtO 2 +2H 2 O+4e - 。
On CH 4 The atmosphere is as follows:
0V-0.55V (vs. sce) potential interval: no obvious current signal and no reactivity;
a potential interval of 0.55V-0.75V (vs. sce): catalyst surface Ni oxidation reaction:
Ni+OH-→Ni-OH ads +e - ；
Ni-OH ads →(OH-Ni)；
(OH-Ni)+OH-→Ni(OH) 2,ads +e - ；
Ni(OH) 2 +OH-→NiOOH+H 2 O+e - 。
the methane oxidation reaction occurs at an increased current compared to the He atmosphere:
CH 4 +CO 3 2- →CH 3 OH+CO 2 +2e - (methanol);
CH 3 OH+CO 3 2- →HCHO+CO 2 +H 2 O+2e - ；
CH 4 +CH 3 OH+CO 3 2- →CH 3 CH 2 OH+CO 2 +H 2 O+2e - ；
CH 3 CH 2 OH+CO 3 2- →CH 3 CHO+CO 2 +H 2 O+2e - ；
CH 4 +HCHO+CO 3 2- →CH 3 CHO+CO 2 +H 2 O+2e - ；
CH 3 OH+HCHO→CH 3 CHO+H 2 O；
CH 3 CHO+CH 4 →CH 3 CH(OH)CH 3 (isopropanol).
0.75V (vs. sce): oxygen evolution reaction: 4OH- & gtO 2 +2H 2 O+4e-；
Methane deep oxidation reaction: CH (CH) 4 +8OH-→CO 2 +6H 2 O+4e-。
Obviously, under the condition of identical number of transferred electrons, CH 4 The deep oxidation reaction requires more OH to be consumed - And the above OH - Instead of free hydroxide anions in the electrolyte, the surface of the catalyst adsorbs activated OH - . Thus, on the catalyst surface OH - In the case of a limited number and the same, the CH is introduced 4 Resulting in a part of the surface OH - Participate in CH 4 The deep oxidation reaction, rather than the oxygen evolution reaction, reduces the number of transferred electrons. This is associated with CH when the potential interval is greater than 0.75V (vs. SCE) 4 The current density in the atmosphere is instead lower than in the He atmosphere.
Example 2
The embodiment provides a preparation method of a catalyst, which comprises the following steps:
(1) 100mL of GO dispersion with a concentration of 0.2mg/mL was mixed well with ammonia and hydrazine hydrate. Wherein the volume ratio of ammonia water to GO dispersion liquid is 2.8:1000, the volume ratio of hydrazine hydrate to GO dispersion liquid is 5.1:10000, and the mixture is heated at 90 ℃ in a reflux way for 0.5h to obtain rGO dispersion liquid.
(2) And slowly injecting the zinc acetate solution into the NaOH solution by using a syringe pump, wherein the concentration of zinc acetate in the mixed solution is 7.5mM, the mass concentration ratio of zinc acetate to NaOH is 1:4, uniformly stirring, heating at 60 ℃ for 2 hours to obtain a ZnO colloid solution, and adding deionized water to dilute to the target concentration of 0.2mg/mL.
(3) ZnO colloid solution and rGO dispersion (100 mL) are mixed according to the volume ratio of 2:1, and are subjected to vacuum filtration through a mixed cellulose ester microporous filter membrane to form a self-supporting ZnO-rGO hydrogel membrane. The membrane was peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
(4) Placing the ZnO-rGO hydrogel film in H 2 In an O/NMP mixed solvent for 12H, wherein H 2 The O to NMP volume ratio was 7:3, and the membrane was then fixed using two coverslips and dried in vacuo at 50℃for 8h for capillary compression. And immersing the compressed ZnO-rGO film in deionized water for 0.5h to obtain the capillary compressed ZnO-rGO hydrogel film.
(5) According to Ni (NO) 3 ) 2 ·6H 2 The mass concentration of O is 0.5M, the concentration of nano zirconia powder is 10mg/mL, the concentration ratio of zirconia to SDS is 20:1, and the concentration ratio of zirconia to boric acid is 1:1. The capillary compressed ZnO-rGO hydrogel film is used as a cathode, a carbon rod is used as an anode and is connected to a direct current power supply, and the capillary compressed ZnO-rGO hydrogel film is immersed in the suspension to carry out direct current pulse electrophoresis deposition. Electrophoretic deposition conditions: average current density 5A/dm 2 The duty cycle is 80%, the pulse frequency is 2000Hz, the stirring speed is 1000rpm, and the electrophoretic deposition suspension is carried outThe catalyst for preparing alcohol by methane electrooxidation is obtained after deposition time of 10min at 30 ℃ and is named as Ni-ZrO 2 /ZnO-rGO-2。
Performance test: ni-ZrO using electrode clamps 2 The ZnO-rGO-2 hydrogel film was immobilized as the anode working electrode. Graphite carbon rod as cathode counter electrode, saturated Calomel Electrode (SCE) as reference electrode, na with concentration of 0.5M in H-type double-chamber electrolytic cell 2 CO 3 In alkaline electrolyte. Methane was introduced at 30mL/min and evaluated by the potentiostatic method at a potential of 1.0V (vs. SCE) for 3 hours. The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 1.93 mug/mL and 1.35 mug/mL, respectively, CO 2 Reduced concentration of 0.52. Mu.g/mL, methanol, isopropanol and CO 2 The selectivities of (c) are 43.19%,48.33% and 8.48%, respectively: the methane conversion rate was 44.75. Mu.g/h.
Example 3
The embodiment provides a preparation method of a catalyst, which comprises the following steps:
(1) 100mL of GO dispersion with a concentration of 0.2mg/mL was mixed well with ammonia and hydrazine hydrate. Wherein, the volume ratio of ammonia water to GO dispersion liquid is 5.6:1000, the volume ratio of hydrazine hydrate to GO dispersion liquid is 1.7:10000, and the rGO dispersion liquid is obtained by reflux heating for 2 hours at 100 ℃.
(2) And slowly injecting the zinc acetate solution into the NaOH solution by using a syringe pump, wherein the concentration of zinc acetate in the mixed solution is 1mM, the mass concentration ratio of zinc acetate to NaOH is 1:2, uniformly stirring, heating at 90 ℃ for 0.5h to obtain a ZnO colloid solution, and adding deionized water to dilute to the target concentration of 0.2mg/mL.
(3) ZnO colloid solution and rGO dispersion (100 mL) are mixed according to the volume ratio of 1:50, and are subjected to vacuum filtration through a mixed cellulose ester microporous filter membrane to form a self-supporting ZnO-rGO hydrogel membrane. The membrane was peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
(4) Placing the ZnO-rGO hydrogel film in H 2 In an O/NMP mixed solvent for 12H, wherein H 2 O to NMP volume ratio of 7:3, followed by fixing the membrane with two coverslips, vacuum drying at 75deg.C for 8h for capillary actionAnd (5) compressing. And immersing the compressed ZnO-rGO film in deionized water for 0.5h to obtain the capillary compressed ZnO-rGO hydrogel film.
(5) According to Ni (NO) 3 ) 2 ·6H 2 The mass concentration of O is 1M, the concentration of nano zirconia powder is 20mg/mL, the concentration ratio of zirconia to SDS is 40:1, and the concentration ratio of zirconia to boric acid is 1:1. The capillary compressed ZnO-rGO hydrogel film is used as a cathode, a carbon rod is used as an anode and is connected to a direct current power supply, and the capillary compressed ZnO-rGO hydrogel film is immersed in the suspension to carry out direct current pulse electrophoresis deposition. Electrophoretic deposition conditions: average current density 5A/dm 2 The catalyst for preparing alcohol by electro-oxidation of methane is obtained by the method that the duty ratio is 40 percent, the pulse frequency is 1200Hz, the stirring speed is 200rpm, the electrophoretic deposition suspension is 90 ℃, and the deposition time is 40 minutes and is named as Ni-ZrO 2 /ZnO-rGO-3。
Performance test: ni-ZrO using electrode clamps 2 The ZnO-rGO-3 hydrogel film was immobilized as the anode working electrode. Graphite carbon rod as cathode counter electrode, saturated Calomel Electrode (SCE) as reference electrode, na with concentration of 0.5M in H-type double-chamber electrolytic cell 2 CO 3 In alkaline electrolyte. Methane was introduced at 30mL/min and evaluated by the potentiostatic method at a potential of 0.5V (vs. SCE) for 3 hours. The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 4.82 mug/mL and 3.28 mug/mL, respectively, CO 2 Reduced concentration of 0.35 μg/mL, methanol, isopropanol and CO 2 The selectivities of (a) are 46.70%,50.82% and 2.48%, respectively: the methane conversion rate was 103.37. Mu.g/h.
Example 4
The embodiment provides a preparation method of a catalyst, which comprises the following steps:
(1) Uniformly mixing 100mL of GO dispersion liquid with the concentration of 0.2mg/mL with ammonia water and hydrazine hydrate, wherein the volume ratio of the ammonia water to the GO dispersion liquid is 5.6:1000, the volume ratio of the hydrazine hydrate to the GO dispersion liquid is 7:10000, and carrying out reflux heating at 80 ℃ for 1h to obtain rGO dispersion liquid.
(2) And slowly injecting the zinc acetate solution into the NaOH solution by using a syringe pump, wherein the concentration of zinc acetate in the mixed solution is 5mM, the mass concentration ratio of the zinc acetate to the NaOH is 1:4.5, uniformly stirring, heating at 60 ℃ for 0.5h to obtain a ZnO colloid solution, and adding deionized water to dilute to the target concentration of 0.2mg/mL.
(3) ZnO colloid solution and rGO dispersion (100 mL) are mixed according to the volume ratio of 1:25, and are subjected to vacuum filtration through a mixed cellulose ester microporous filter membrane to form a self-supporting ZnO-rGO hydrogel membrane. The membrane was peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
(4) Placing the ZnO-rGO hydrogel film in H 2 In an O/NMP mixed solvent for 12H, wherein H 2 The volume ratio of O to NMP was 19:1, and the membrane was then fixed using two coverslips and dried in vacuo at 60℃for 12h for capillary compression. And immersing the compressed ZnO-rGO film in deionized water for 0.5h to obtain the capillary compressed ZnO-rGO hydrogel film.
(5) According to Ni (NO) 3 ) 2 ·6H 2 The mass concentration of O is 5M, the concentration of nano zirconia powder is 15mg/mL, the concentration ratio of zirconia to SDS is 50:1, and the concentration ratio of zirconia to boric acid is 3:2. The capillary compressed ZnO-rGO hydrogel film is used as a cathode, a carbon rod is used as an anode and is connected to a direct current power supply, and the capillary compressed ZnO-rGO hydrogel film is immersed in the suspension to carry out direct current pulse electrophoresis deposition. Electrophoretic deposition conditions: average current density 10A/dm 2 The catalyst for preparing alcohol by electro-oxidation of methane is obtained by the steps of 80 percent of duty ratio, 1200Hz of pulse frequency, 500rpm of stirring speed, 60 ℃ of electrophoretic deposition suspension and 10 minutes of deposition time and is named as Ni-ZrO 2 /ZnO-rGO-4。
Performance test: ni-ZrO using electrode clamps 2 The ZnO-rGO-4 hydrogel film was immobilized as the anode working electrode. Graphite carbon rod as cathode counter electrode, saturated Calomel Electrode (SCE) as reference electrode, na with concentration of 0.5M in H-type double-chamber electrolytic cell 2 CO 3 In alkaline electrolyte. Methane was introduced at 30mL/min and evaluated by the potentiostatic method at a potential of 0.65V (vs. SCE) for 3 hours. The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 25.14 mug/mL and 18.64 mug/mL, respectively, CO 2 Reduced concentration of 2.99. Mu.g/mL, methanol, isopropanol and CO 2 The selectivities of (a) are 44.01%,52.19% and 3.80%, respectively. Calculated: the methane conversion rate was 572.07. Mu.g/h.
Example 5
The embodiment provides a preparation method of a catalyst, which comprises the following steps:
(1) Uniformly mixing 100mL of GO dispersion liquid with the concentration of 0.2mg/mL with ammonia water and hydrazine hydrate, wherein the volume ratio of the ammonia water to the GO dispersion liquid is 8.4:1000, the volume ratio of the hydrazine hydrate to the GO dispersion liquid is 1:10000, and carrying out reflux heating for 3h at 70 ℃ to obtain rGO dispersion liquid.
(2) And slowly injecting the zinc acetate solution into the NaOH solution by using a syringe pump, wherein the concentration of zinc acetate in the mixed solution is 1mM, the mass concentration ratio of the zinc acetate to the NaOH is 1:4.5, uniformly stirring, heating at 80 ℃ for 0.5h to obtain a ZnO colloid solution, and adding deionized water to dilute to the target concentration of 0.2mg/mL.
(3) ZnO colloid solution and rGO dispersion (100 mL) are mixed according to the volume ratio of 1:1, and are subjected to vacuum filtration through a mixed cellulose ester microporous filter membrane to form a self-supporting ZnO-rGO hydrogel membrane. The membrane was peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
(4) Placing the ZnO-rGO hydrogel film in H 2 In an O/NMP mixed solvent for 12H, wherein H 2 The O to NMP volume ratio was 3:7, and the membrane was then fixed using two coverslips and dried in vacuo at 90℃for 4h for capillary compression. And immersing the compressed ZnO-rGO film in deionized water for 0.5h to obtain the capillary compressed ZnO-rGO hydrogel film.
(5) According to Ni (NO) 3 ) 2 ·6H 2 The mass concentration of O is 0.5M, the concentration of nano zirconia powder is 5mg/mL, the concentration ratio of zirconia to SDS is 5:1, and the concentration ratio of zirconia to boric acid is 1:5. The capillary compressed ZnO-rGO hydrogel film is used as a cathode, a carbon rod is used as an anode and is connected to a direct current power supply, and the capillary compressed ZnO-rGO hydrogel film is immersed in the suspension to carry out direct current pulse electrophoresis deposition. Electrophoretic deposition conditions: average current density 8A/dm 2 The catalyst for preparing alcohol by electro-oxidation of methane is obtained by the method that the duty ratio is 40%, the pulse frequency is 2000Hz, the stirring speed is 600rpm, the electrophoretic deposition suspension is 30 ℃ and the deposition time is 20min, and is named as Ni-ZrO 2 /ZnO-rGO-5。
Performance test: ni-ZrO using electrode clamps 2 The ZnO-rGO-5 hydrogel film was immobilized as the anode working electrode. Graphite carbon rod as cathode counter electrode, saturated Calomel Electrode (SCE) as reference electrode, na with concentration of 0.5M in H-type double-chamber electrolytic cell 2 CO 3 In alkaline electrolyte. Methane was introduced at 30mL/min and evaluated by the potentiostatic method at a potential of 0.6V (vs. SCE) for 3 hours. The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 9.51 mug/mL and 5.61 mug/mL, respectively, CO 2 The reduced concentration was 0.87. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (2) are 49.74%,46.94% and 3.32%, respectively: the methane conversion rate was 191.45. Mu.g/h.
Example 6
The embodiment provides a preparation method of a catalyst, which comprises the following steps:
(1) Uniformly mixing 100mL of GO dispersion liquid with the concentration of 0.2mg/mL with ammonia water and hydrazine hydrate, wherein the volume ratio of the ammonia water to the GO dispersion liquid is 5.6:1000, the volume ratio of the hydrazine hydrate to the GO dispersion liquid is 5.1:10000, and carrying out reflux heating at 90 ℃ for 2h to obtain rGO dispersion liquid.
(2) And slowly injecting the zinc acetate solution into the NaOH solution by using a syringe pump, wherein the concentration of zinc acetate in the mixed solution is 7.5mM, the mass concentration ratio of zinc acetate to NaOH is 1:5, uniformly stirring the mixture, heating the mixture at 50 ℃ for 3.5 hours to obtain a ZnO colloid solution, and adding deionized water to dilute the ZnO colloid solution to the target concentration of 0.2mg/mL.
(3) ZnO colloid solution and rGO dispersion (100 mL) are mixed according to the volume ratio of 1:50, and are subjected to vacuum filtration through a mixed cellulose ester microporous filter membrane to form a self-supporting ZnO-rGO hydrogel membrane. The membrane was peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
(4) Placing the ZnO-rGO hydrogel film in H 2 In an O/NMP mixed solvent for 12H, wherein H 2 The O to NMP volume ratio was 7:3, and the membrane was then fixed using two coverslips and dried in vacuo at 50℃for 12h for capillary compression. Soaking the compressed ZnO-rGO membrane in deionized water for 0.5h to obtain capillary compressed ZnO-rGO waterGel films.
(5) According to Ni (NO) 3 ) 2 ·6H 2 The mass concentration of O is 2.5M, the concentration of nano zirconia powder is 20mg/mL, the concentration ratio of zirconia to SDS is 20:1, and the concentration ratio of zirconia to boric acid is 1:1. The capillary compressed ZnO-rGO hydrogel film is used as a cathode, a carbon rod is used as an anode and is connected to a direct current power supply, and the capillary compressed ZnO-rGO hydrogel film is immersed in the suspension to carry out direct current pulse electrophoresis deposition. Electrophoretic deposition conditions: average current density 8A/dm 2 The catalyst for preparing alcohol by electro-oxidation of methane is obtained by the steps of duty ratio of 95%, pulse frequency of 50Hz, stirring speed of 500rpm, electrophoretic deposition of suspension at 70 ℃ and deposition time of 20min and is named as Ni-ZrO 2 /ZnO-rGO-6。
Performance test: ni-ZrO using electrode clamps 2 The ZnO-rGO-6 hydrogel film was immobilized as the anode working electrode. Graphite carbon rod as cathode counter electrode, saturated Calomel Electrode (SCE) as reference electrode, na with concentration of 0.5M in H-type double-chamber electrolytic cell 2 CO 3 In alkaline electrolyte. Methane was introduced at 30mL/min and evaluated by the potentiostatic method at a potential of 0.7V (vs. SCE) for 3 hours. The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 17.64 mug/mL and 14.29 mug/mL, respectively, CO 2 The reduced concentration was 2.79. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (a) are 41.49%,53.75% and 4.76%, respectively: the methane conversion rate was 425.81. Mu.g/h.
Example 7
The embodiment provides a preparation method of a catalyst, which comprises the following steps:
(1) Uniformly mixing 100mL of GO dispersion liquid with the concentration of 0.2mg/mL with ammonia water and hydrazine hydrate, wherein the volume ratio of the ammonia water to the GO dispersion liquid is 1:1000, the volume ratio of the hydrazine hydrate to the GO dispersion liquid is 1:10000, and carrying out reflux heating for 4h at 70 ℃ to obtain rGO dispersion liquid.
(2) And slowly injecting the zinc acetate solution into the NaOH solution by using a syringe pump, wherein the concentration of zinc acetate in the mixed solution is 7.5mM, the mass concentration ratio of zinc acetate to NaOH is 1:3, uniformly stirring the mixture, heating the mixture at 50 ℃ for 2 hours to obtain a ZnO colloid solution, and adding deionized water to dilute the ZnO colloid solution to the target concentration of 0.2mg/mL.
(3) ZnO colloid solution and rGO dispersion (100 mL) are mixed according to the volume ratio of 1:1, and are subjected to vacuum filtration through a mixed cellulose ester microporous filter membrane to form a self-supporting ZnO-rGO hydrogel membrane. The membrane was peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
(4) Placing the ZnO-rGO hydrogel film in H 2 In an O/NMP mixed solvent for 12H, wherein H 2 The O to NMP volume ratio was 0:10, and the membrane was then fixed using two coverslips and dried in vacuo at 50℃for 8h for capillary compression. And immersing the compressed ZnO-rGO film in deionized water for 0.5h to obtain the capillary compressed ZnO-rGO hydrogel film.
(5) According to Ni (NO) 3 ) 2 ·6H 2 The mass concentration of O is 0.5M, the concentration of nano zirconia powder is 10mg/mL, the concentration ratio of zirconia to SDS is 40:1, and the concentration ratio of zirconia to boric acid is 2:1. The capillary compressed ZnO-rGO hydrogel film is used as a cathode, a carbon rod is used as an anode and is connected to a direct current power supply, and the capillary compressed ZnO-rGO hydrogel film is immersed in the suspension to carry out direct current pulse electrophoresis deposition. Electrophoretic deposition conditions: average current density 3A/dm 2 The catalyst for preparing alcohol by electro-oxidation of methane is obtained by the method that the duty ratio is 40 percent, the pulse frequency is 2000Hz, the stirring speed is 500rpm, the electrophoretic deposition suspension is 50 ℃, the deposition time is 0.5min, and the catalyst is named as Ni-ZrO 2 /ZnO-rGO-7。
Performance test: ni-ZrO using electrode clamps 2 The ZnO-rGO-7 hydrogel film was immobilized as the anode working electrode. Graphite carbon rod as cathode counter electrode, saturated Calomel Electrode (SCE) as reference electrode, na with concentration of 0.5M in H-type double-chamber electrolytic cell 2 CO 3 In alkaline electrolyte. Methane was introduced at 30mL/min and evaluated by the potentiostatic method at a potential of 0.5V (vs. SCE) for 3 hours. The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 3.37 mug/mL and 2.22 mug/mL, respectively, CO 2 The reduced concentration was 0.29. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivity of (2) was 47.25%,49.79% and 2.96%, respectively. Calculated: the methane conversion rate was 71.42. Mu.g +.h。
Example 8
The embodiment provides a preparation method of a catalyst, which comprises the following steps:
(1) Uniformly mixing 100mL of GO dispersion liquid with the concentration of 0.2mg/mL with ammonia water and hydrazine hydrate, wherein the volume ratio of the ammonia water to the GO dispersion liquid is 1:100, the volume ratio of the hydrazine hydrate to the GO dispersion liquid is 5.1:10000, and carrying out reflux heating for 0.5h at 95 ℃ to obtain rGO dispersion liquid.
(2) And slowly injecting the zinc acetate solution into the NaOH solution by using a syringe pump, wherein the concentration of zinc acetate in the mixed solution is 3mM, the mass concentration ratio of the zinc acetate to the NaOH is 1:3, uniformly stirring, heating at 70 ℃ for 0.5h to obtain a ZnO colloid solution, and adding deionized water to dilute to the target concentration of 0.2mg/mL.
(3) ZnO colloid solution and rGO dispersion (100 mL) are mixed according to the volume ratio of 1:5, and are subjected to vacuum filtration through a mixed cellulose ester microporous filter membrane to form a self-supporting ZnO-rGO hydrogel membrane. The membrane was peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
(4) Placing the ZnO-rGO hydrogel film in H 2 In an O/NMP mixed solvent for 12H, wherein H 2 The O to NMP volume ratio was 7:3, and the membrane was then fixed using two coverslips and dried under vacuum at 75℃for 16h for capillary compression. And immersing the compressed ZnO-rGO film in deionized water for 0.5h to obtain the capillary compressed ZnO-rGO hydrogel film.
(5) According to Ni (NO) 3 ) 2 ·6H 2 The mass concentration of O is 5M, the concentration of nano zirconia powder is 10mg/mL, the concentration ratio of zirconia to SDS is 40:1, and the concentration ratio of zirconia to boric acid is 2:1. The capillary compressed ZnO-rGO hydrogel film is used as a cathode, a carbon rod is used as an anode and is connected to a direct current power supply, and the capillary compressed ZnO-rGO hydrogel film is immersed in the suspension to carry out direct current pulse electrophoresis deposition. Electrophoretic deposition conditions: average current density 1A/dm 2 The catalyst for preparing alcohol by electro-oxidation of methane is obtained by the steps of 5 percent of duty ratio, 50Hz of pulse frequency, 500rpm of stirring speed, 50 ℃ of electrophoretic deposition suspension and 10 minutes of deposition time and is named as Ni-ZrO 2 /ZnO-rGO-8。
Performance test: ni-ZrO using electrode clamps 2 The ZnO-rGO-8 hydrogel film was immobilized as the anode working electrode. Graphite carbon rod as cathode counter electrode, saturated Calomel Electrode (SCE) as reference electrode, na with concentration of 0.5M in H-type double-chamber electrolytic cell 2 CO 3 In alkaline electrolyte. Methane was introduced at 30mL/min and evaluated by the potentiostatic method at a potential of 0.65V (vs. SCE) for 3 hours. The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 22.77 mug/mL and 17.98 mug/mL, respectively, CO 2 The reduced concentration was 2.80. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (2) are 42.51%,53.69% and 3.80%, respectively. Calculated: the methane conversion rate was 536.41. Mu.g/h.
Example 9
The embodiment provides a preparation method of a catalyst, which comprises the following steps:
(1) Uniformly mixing 100mL of GO dispersion liquid with the concentration of 0.2mg/mL with ammonia water and hydrazine hydrate, wherein the volume ratio of the ammonia water to the GO dispersion liquid is 5.6:1000, the volume ratio of the hydrazine hydrate to the GO dispersion liquid is 1.7:10000, and carrying out reflux heating at 100 ℃ for 4 hours to obtain rGO dispersion liquid.
(2) And slowly injecting the zinc acetate solution into the NaOH solution by using a syringe pump, wherein the concentration of zinc acetate in the mixed solution is 3mM, the mass concentration ratio of the zinc acetate to the NaOH is 1:4, uniformly stirring, heating at 60 ℃ for 1h to obtain a ZnO colloid solution, and adding deionized water to dilute to the target concentration of 0.2mg/mL.
(3) ZnO colloid solution and rGO dispersion (100 mL) are mixed according to the volume ratio of 2:1, and are subjected to vacuum filtration through a mixed cellulose ester microporous filter membrane to form a self-supporting ZnO-rGO hydrogel membrane. The membrane was peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
(4) Placing the ZnO-rGO hydrogel film in H 2 In an O/NMP mixed solvent for 12H, wherein H 2 The O to NMP volume ratio was 5:5, and the membrane was then fixed using two coverslips and dried in vacuo at 90℃for 8h for capillary compression. And immersing the compressed ZnO-rGO film in deionized water for 0.5h to obtain the capillary compressed ZnO-rGO hydrogel film.
(5) According to Ni (NO) 3 ) 2 ·6H 2 The mass concentration of O is 0.5M, the concentration of nano zirconia powder is 15mg/mL, the concentration ratio of zirconia to SDS is 10:1, and the concentration ratio of zirconia to boric acid is 1:1. The capillary compressed ZnO-rGO hydrogel film is used as a cathode, a carbon rod is used as an anode and is connected to a direct current power supply, and the capillary compressed ZnO-rGO hydrogel film is immersed in the suspension to carry out direct current pulse electrophoresis deposition. Electrophoretic deposition conditions: average current density 3A/dm 2 The catalyst for preparing alcohol by electro-oxidation of methane is obtained by the steps of 80 percent of duty ratio, 1200Hz of pulse frequency, 1000rpm of stirring speed, 70 ℃ of electrophoretic deposition suspension and 40 minutes of deposition time, and is named as Ni-ZrO 2 /ZnO-rGO-9。
Performance test: ni-ZrO using electrode clamps 2 The ZnO-rGO-9 hydrogel film was immobilized as the anode working electrode. Graphite carbon rod as cathode counter electrode, saturated Calomel Electrode (SCE) as reference electrode, na with concentration of 0.5M in H-type double-chamber electrolytic cell 2 CO 3 In alkaline electrolyte. Methane was introduced at 30mL/min and evaluated by the potentiostatic method at a potential of 0.8V (vs. SCE) for 3 hours. The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 5.23 mug/mL and 4.29 mug/mL, respectively, CO 2 The reduced concentration was 1.08. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (2) are 40.62%,53.30% and 6.08%, respectively. Calculated: the methane conversion rate was 128.93. Mu.g/h.
Example 10
The embodiment provides a preparation method of a catalyst, which comprises the following steps:
(1) Uniformly mixing 100mL of GO dispersion liquid with the concentration of 0.2mg/mL with ammonia water and hydrazine hydrate, wherein the volume ratio of the ammonia water to the GO dispersion liquid is 2.8:1000, the volume ratio of the hydrazine hydrate to the GO dispersion liquid is 5.1:10000, and carrying out reflux heating for 4h at 95 ℃ to obtain rGO dispersion liquid.
(2) And slowly injecting the zinc acetate solution into the NaOH solution by using a syringe pump, wherein the concentration of zinc acetate in the mixed solution is 10mM, the mass concentration ratio of the zinc acetate to the NaOH is 1:4.5, uniformly stirring, heating at 70 ℃ for 2 hours to obtain a ZnO colloid solution, and adding deionized water to dilute to the target concentration of 0.2mg/mL.
(3) ZnO colloid solution and rGO dispersion (100 mL) are mixed according to the volume ratio of 1:25, and are subjected to vacuum filtration through a mixed cellulose ester microporous filter membrane to form a self-supporting ZnO-rGO hydrogel membrane. The membrane was peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
(4) Placing the ZnO-rGO hydrogel film in H 2 In an O/NMP mixed solvent for 12H, wherein H 2 The O to NMP volume ratio was 5:5, and the membrane was then fixed using two coverslips and dried in vacuo at 90℃for 20h for capillary compression. And immersing the compressed ZnO-rGO film in deionized water for 0.5h to obtain the capillary compressed ZnO-rGO hydrogel film.
(5) According to Ni (NO) 3 ) 2 ·6H 2 The mass concentration of O is 3.5M, the concentration of nano zirconia powder is 10mg/mL, the concentration ratio of zirconia to SDS is 10:1, and the concentration ratio of zirconia to boric acid is 1:2. The capillary compressed ZnO-rGO hydrogel film is used as a cathode, a carbon rod is used as an anode and is connected to a direct current power supply, and the capillary compressed ZnO-rGO hydrogel film is immersed in the suspension to carry out direct current pulse electrophoresis deposition. Electrophoretic deposition conditions: average current density 1A/dm 2 The catalyst for preparing alcohol by electro-oxidation of methane is obtained by the steps of duty ratio of 95%, pulse frequency of 600Hz, stirring speed of 1000rpm, electrophoretic deposition of suspension at 60 ℃ and deposition time of 10min and is named as Ni-ZrO 2 /ZnO-rGO-10。
Performance test: ni-ZrO using electrode clamps 2 The ZnO-rGO-10 hydrogel film was immobilized as the anode working electrode. Graphite carbon rod as cathode counter electrode, saturated Calomel Electrode (SCE) as reference electrode, na with concentration of 0.5M in H-type double-chamber electrolytic cell 2 CO 3 In alkaline electrolyte. Methane was introduced at 30mL/min and evaluated by the potentiostatic method at a potential of 0.7V (vs. SCE) for 3 hours. The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 19.48 mug/mL and 9.93 mug/mL, respectively, CO 2 Reduced concentration of 2.69 μg/mL, methanol, isopropanol and CO 2 The selectivity of (2) was 52.20%,42.56% and 5.24%, respectively. Calculated: the methane conversion rate was 373.72. Mu.g/h.
Example 11
The embodiment provides a preparation method of a catalyst, which comprises the following steps:
(1) Uniformly mixing 100mL of GO dispersion liquid with the concentration of 0.2mg/mL with ammonia water and hydrazine hydrate, wherein the volume ratio of the ammonia water to the GO dispersion liquid is 8.4:1000, the volume ratio of the hydrazine hydrate to the GO dispersion liquid is 1:1000, and carrying out reflux heating at 80 ℃ for 3h to obtain rGO dispersion liquid.
(2) And slowly injecting the zinc acetate solution into the NaOH solution by using a syringe pump, wherein the concentration of zinc acetate in the mixed solution is 10mM, the mass concentration ratio of zinc acetate to NaOH is 1:5, uniformly stirring, heating at 70 ℃ for 3.5h to obtain a ZnO colloid solution, and adding deionized water to dilute to the target concentration of 0.2mg/mL.
(3) ZnO colloid solution and rGO dispersion (100 mL) are mixed according to the volume ratio of 1:5, and are subjected to vacuum filtration through a mixed cellulose ester microporous filter membrane to form a self-supporting ZnO-rGO hydrogel membrane. The membrane was peeled off the filter membrane, transferred to a petri dish, and immersed in deionized water to remove residual impurities.
(4) Placing the ZnO-rGO hydrogel film in H 2 In an O/NMP mixed solvent for 12H, wherein H 2 The O to NMP volume ratio was 7:3, and the membrane was then fixed using two coverslips and dried in vacuo at 60℃for 8h for capillary compression. And immersing the compressed ZnO-rGO film in deionized water for 0.5h to obtain the capillary compressed ZnO-rGO hydrogel film.
(5) According to Ni (NO) 3 ) 2 ·6H 2 The mass concentration of O is 1M, the concentration of nano zirconia powder is 10mg/mL, the concentration ratio of zirconia to SDS is 50:1, and the concentration ratio of zirconia to boric acid is 1:2. The capillary compressed ZnO-rGO hydrogel film is used as a cathode, a carbon rod is used as an anode and is connected to a direct current power supply, and the capillary compressed ZnO-rGO hydrogel film is immersed in the suspension to carry out direct current pulse electrophoresis deposition. Electrophoretic deposition conditions: average current density 8A/dm 2 The catalyst for preparing alcohol by electro-oxidation of methane is obtained by the steps of 80 percent of duty ratio, 100Hz of pulse frequency, 600rpm of stirring speed, 50 ℃ of electrophoretic deposition suspension and 20 minutes of deposition time and is named as Ni-ZrO 2 /ZnO-rGO-11。
Performance test: ni-ZrO using electrode clamps 2 The ZnO-rGO-11 hydrogel film was immobilized as the anode working electrode. Graphite carbon rod as cathode for electricityA Saturated Calomel Electrode (SCE) is used as a reference electrode and is placed in an H-type double-chamber electrolytic cell with Na concentration of 0.5M 2 CO 3 In alkaline electrolyte. Methane was introduced at 30mL/min and evaluated by the potentiostatic method at a potential of 0.9V (vs. SCE) for 3 hours. The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 3.11 mug/mL and 2.21 mug/mL, respectively, CO 2 Reduced concentration of 0.69. Mu.g/mL, methanol, isopropanol and CO 2 The selectivities of (a) are 43.51%,49.45% and 7.04%, respectively. Calculated: the methane conversion rate was 71.58. Mu.g/h.
Example 12
The only difference from example 1 is that: h in step (4) 2 O and NMP are replaced with equal amounts of NMP, i.e. the mixed solvent contains no water.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ) Wherein the concentration of methanol and isopropanol is 3.73 mug/mL and 2.41 mug/mL, respectively, CO 2 The reduced concentration was 3.01. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (a) are 38.16%,39.44% and 22.40%, respectively. Calculated: the methane conversion rate was 97.88. Mu.g/h.
Example 13
The only difference from example 1 is that: h in step (4) 2 The volume ratio of O to NMP was 20:1.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 7.45 mug/mL and 8.03 mug/mL, respectively, CO 2 The reduced concentration was 2.27. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (a) are 33.95%,58.53% and 7.52%, respectively. Calculated: the methane conversion rate was 219.75. Mu.g/h.
Example 14
The only difference from example 1 is that: h in step (4) 2 The volume ratio of O to NMP was 2:1.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ) Wherein the concentration of methanol and isopropanol15.13 μg/mL and 11.74 μg/mL, respectively, CO 2 The reduced concentration was 0.43. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (a) are 44.21%,54.87% and 0.92%, respectively. Calculated: the methane conversion rate was 342.72. Mu.g/h.
Example 15
The only difference from example 1 is that: h in step (4) 2 The volume ratio of O to NMP was 3:1.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ) Wherein the concentration of methanol and isopropanol is 23.94 mug/mL and 12.04 mug/mL, respectively, CO 2 The reduced concentration was 2.12. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (a) are 53.51%,43.05% and 3.44%, respectively: the methane conversion rate was 448.01. Mu.g/h.
As can be seen in combination with example 1 and examples 12-15: within the preferred range H 2 Catalyst (H) of O/NMP volume ratio 2 O/nmp=2/1-3/1) has a higher methane conversion rate and can suppress the complete oxidation product CO 2 (CO within the preferred range in FIG. 4) 2 The selectivity is significantly reduced).
Example 16
The only difference from example 1 is that: in the step (3), the ZnO colloid solution and the rGO dispersion liquid (100 mL) are mixed according to a volume ratio of 2:1.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ) Wherein the concentration of methanol and isopropanol is 8.42 mug/mL and 7.17 mug/mL, respectively, CO 2 The reduced concentration was 1.55. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (a) are 40.07%,54.57% and 5.36%, respectively. Calculated: the methane conversion rate was 210.45. Mu.g/h.
Example 17
The only difference from example 1 is that: in the step (3), the ZnO colloid solution and the rGO dispersion liquid (100 mL) are mixed according to the volume ratio of 1:50.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ) Wherein the methanol and isopropanol concentrations were 6.89 μg/mL and 1, respectively.25μg/mL,CO 2 The reduced concentration was 2.72. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (a) are 63.40%,18.40% and 18.20%, respectively. Calculated: the methane conversion rate was 108.83. Mu.g/h.
Example 18
The only difference from example 1 is that: in the step (3), the ZnO colloid solution and the rGO dispersion liquid (100 mL) are mixed according to a volume ratio of 4:3.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ) Wherein the concentration of methanol and isopropanol is 10.25 mug/mL and 7.98 mug/mL, respectively, CO 2 The reduced concentration was 1.71. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (a) are 42.26%,52.62% and 5.12%, respectively. Calculated: the methane conversion rate was 242.90. Mu.g/h.
Example 19
The only difference from example 1 is that: in the step (3), the ZnO colloid solution and the rGO dispersion liquid (100 mL) are mixed according to a volume ratio of 3:4.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 12.41 mug/mL and 6.27 mug/mL, respectively, CO 2 Reduced concentration of 2.04. Mu.g/mL, methanol, isopropanol and CO 2 The selectivities of (a) are 51.88%,41.92% and 6.20%, respectively: the methane conversion rate was 239.56. Mu.g/h.
As can be seen in combination with example 1 and examples 16-19: catalysts with ZnO/rGO volume ratios in the preferred ranges (ZnO/rgo=4:3-3:4) have higher methane conversion rates, contributing to the production of high value added products, especially methanol (see fig. 5).
Example 20
The only difference from example 1 is that: ni (NO) in step (5) 3 ) 2 ·6H 2 The mass concentration of O is 0.5M, and the concentration of nano zirconia powder is 20mg/mL.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 2.72 mug/mL and 3.16 mug/mL, respectively, CO 2 Folding concentrationThe degree of refraction was 0.01. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (a) are 34.96%,64.96% and 0.08%, respectively. Calculated: the methane conversion rate was 77.92. Mu.g/h.
Example 21
The only difference from example 1 is that: ni (NO) in step (5) 3 ) 2 ·6H 2 The mass concentration of O is 3M, and the concentration of nano zirconia powder is 15mg/mL.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 1.68 mug/mL and 0.39 mug/mL, respectively, CO 2 The reduced concentration was 4.32. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivity of (2) was 30.86%,11.46% and 57.68%, respectively. Calculated: the methane conversion rate was 54.52. Mu.g/h.
Example 22
The only difference from example 1 is that: ni (NO) in step (5) 3 ) 2 ·6H 2 The mass concentration of O is 5M, and the concentration of nano zirconia powder is 1mg/mL.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 18.31 mug/mL and 23.29 mug/mL, respectively, CO 2 The reduced concentration was 0.99. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (2) are 32.53%,66.19% and 1.28%, respectively. Calculated: the methane conversion rate was 563.63. Mu.g/h.
As can be seen in combination with example 1 and examples 20-22: zrO (ZrO) 2 Helps to inhibit the complete oxidation of product CO 2 Excessive ZrO generation 2 The methane conversion rate is reduced. While Ni has higher oxidation activity, excessive Ni can lead to CO 2 The selectivity was significantly increased (see fig. 6). Therefore, only suitable Ni and ZrO 2 The ratio can only give consideration to the catalytic activity and the selectivity.
Comparative example 1
The only difference from example 1 is that: ni (NO) 3 ) 2 ·6H 2 O is replaced by equivalent Cu (NO) 3 ) 2 ·3H 2 O.
The results show that: methane is oxidized to methanol, isopropanol and a small amount of carbon dioxide (CO), a complete oxidation product 2 ). Wherein the concentrations of methanol and isopropanol are 4.79 mug/mL and 0.41 mug/mL, respectively, CO 2 The reduced concentration was 1.80. Mu.g/mL. Methanol, isopropanol and CO 2 The selectivities of (a) are 70.89%,9.71% and 19.40%, respectively. Calculated: the methane conversion rate was 67.66. Mu.g/h.
Comparative example 2
The only difference from example 1 is that: no zirconia is introduced, i.e. the feedstock in step (5) is free of nano zirconia powder.
The results show that: methane is oxidized to the complete oxidation product carbon dioxide (CO 2 )，CO 2 Reduced concentration of 6.70. Mu.g/mL, CO 2 The selectivity was about 100.00%. Calculated: the methane conversion rate was 48.73. Mu.g/h.
Comparative example 3
The only difference from example 1 is that: without introduction of nickel, i.e. the starting material in step (5) is free of Ni (NO) 3 ) 2 ·6H 2 O。
The results show that: methane is oxidized to fully oxidize product carbon dioxide (CO) 2 )，CO 2 Reduced concentration of 0.41. Mu.g/mL, CO 2 The selectivity was about 100.00%. Calculated: the methane conversion rate was 2.98. Mu.g/h.
Comparative example 4
The only difference from example 1 is that: step (5) is not performed, i.e. no nickel and no zirconia are introduced.
The results show that: the catalyst is inactive, and can not detect the methanol and the isopropanol which are liquid products and the CO which is a complete oxidation product 2 . In FIG. 7 methane (CH) 4 ) The cyclic voltammograms are substantially coincident under the atmosphere and helium (He) atmosphere, proving that the catalyst is catalytically inactive under methane atmosphere.
The test data for examples 1-22 and comparative examples 1-4 are summarized as shown in Table 1:
table 1 summary of methane electrooxidation properties for examples and comparative examples
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The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (33)
1. The catalyst for preparing alcohol by electro-oxidation of methane is characterized by comprising a hydrogel film formed by reducing graphene oxide and zinc oxide, wherein the zinc oxide is dispersed in a film layer of the hydrogel film, and zirconium oxide and nickel are loaded on the surface of the hydrogel film;
the preparation method of the catalyst comprises the following steps: preparing a zinc oxide-reduced graphene oxide hydrogel film by taking reduced graphene oxide dispersion liquid and zinc oxide colloid solution as raw materials; depositing zirconia and nickel on the zinc oxide-reduced graphene oxide hydrogel film;
the preparation process of the zinc oxide-reduced graphene oxide hydrogel film comprises the following steps: mixing the reduced graphene oxide dispersion liquid and the zinc oxide colloidal solution, and performing vacuum suction filtration to form a hydrogel film;
capillary compression of the zinc oxide-reduced graphene oxide hydrogel film prior to depositing zirconium oxide and nickel thereon;
and depositing zirconium oxide and nickel on the zinc oxide-reduced graphene oxide hydrogel film by adopting an electrophoretic deposition method.
2. The catalyst according to claim 1, wherein the reduced graphene oxide and the zinc oxide are present in the catalyst in a total mass ratio of 60% to 95% and the zirconium oxide and the nickel are present in a total mass ratio of 5% to 40% in terms of mass fraction.
3. The catalyst of claim 2, wherein the reduced graphene oxide and the zinc oxide are present in a combined mass ratio of 75% to 85%, and the zirconium oxide and the nickel are present in a combined mass ratio of 15% to 25%.
4. The catalyst according to claim 2, wherein the mass ratio of the zinc oxide to the reduced graphene oxide is 1 (0.5-50).
5. The catalyst of claim 4, wherein the mass ratio of the zinc oxide to the reduced graphene oxide is 4:3 to 3:4.
6. The catalyst according to claim 2, wherein the mass ratio of the zirconia to the nickel is 1 (4-20).
7. The catalyst of claim 6, wherein the mass ratio of zirconia to nickel is 1 (4-6).
8. A method for preparing the catalyst according to any one of claims 1 to 7, comprising:
preparing a zinc oxide-reduced graphene oxide hydrogel film by taking reduced graphene oxide dispersion liquid and zinc oxide colloid solution as raw materials;
depositing zirconia and nickel on the zinc oxide-reduced graphene oxide hydrogel film;
the preparation process of the zinc oxide-reduced graphene oxide hydrogel film comprises the following steps: mixing the reduced graphene oxide dispersion liquid and the zinc oxide colloidal solution, and performing vacuum suction filtration to form a hydrogel film;
Capillary compression of the zinc oxide-reduced graphene oxide hydrogel film prior to depositing zirconium oxide and nickel thereon;
and depositing zirconium oxide and nickel on the zinc oxide-reduced graphene oxide hydrogel film by adopting an electrophoretic deposition method.
9. The method of claim 8, wherein the vacuum filtration is performed using a mixed cellulose ester microporous filter.
10. The method of claim 8, wherein the hydrogel film formed is peeled from the filter membrane and introduced into water to remove residual impurities.
11. The method of claim 8, wherein the preparation of the reduced graphene oxide dispersion comprises: uniformly mixing the graphene oxide dispersion liquid, ammonia water and hydrazine hydrate, and reacting for 0.5-4 h at the temperature of 70-100 ℃.
12. The preparation method according to claim 11, wherein the concentration of the graphene oxide dispersion liquid is 0.05mg/mL to 0.5mg/mL, the ammonia water is an aqueous solution with an ammonia content of 25 to 28wt%, the hydrazine hydrate is an aqueous solution with a hydrazine hydrate content of 80 to 90wt%, the volume ratio of the ammonia water to the graphene oxide dispersion liquid is 1 (100 to 1000), and the volume ratio of the hydrazine hydrate to the graphene oxide dispersion liquid is 1 (1000 to 10000).
13. The method of claim 11, wherein the preparing of the graphene oxide dispersion comprises: and diluting the graphene oxide with water, performing ultrasonic stripping, and centrifuging to remove the non-stripped part, thereby obtaining the graphene oxide dispersion liquid meeting the concentration requirement.
14. The method of claim 8, wherein the preparation of the zinc oxide colloid solution comprises: and (3) dropwise adding the zinc salt aqueous solution into the alkaline precipitant aqueous solution, reacting for 0.5-5 h at 50-90 ℃, cooling and diluting to 0.05-0.5 mg/mL.
15. The preparation method according to claim 14, wherein the concentration of the zinc salt aqueous solution is 1mM-10mM, and the mass ratio of the zinc salt to the alkaline precipitant used in the reaction is 1 (2-5).
16. The method of preparing according to claim 14, wherein the zinc salt is selected from at least one of zinc acetate dihydrate, zinc nitrate hexahydrate, zinc chloride, zinc acetylacetonate hydrate, and zinc sulfate heptahydrate.
17. The method according to claim 15, wherein the alkaline precipitant is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and aqueous ammonia.
18. The method of claim 8, wherein the capillary compression process comprises: immersing the zinc oxide-reduced graphene oxide hydrogel film in a mixed solution formed by water and N-methylpyrrolidone for 8-15 h, taking out, vacuum drying at 40-90 ℃ for 4-20 h to compress the film, and immersing the compressed zinc oxide-reduced graphene oxide hydrogel film in water again.
19. The process according to claim 18, wherein the volume ratio of water to N-methylpyrrolidone is (0-19): 1.
20. The process according to claim 19, wherein the volume ratio of water to N-methylpyrrolidone is (2-3): 1.
21. The method of claim 18, wherein the vacuum drying temperature is 50 ℃ to 70 ℃ and the vacuum drying time is 6h to 10h.
22. The method of claim 8, wherein the electrophoretic deposition process comprises: dispersing nickel salt, zirconia powder, surfactant and buffer agent in water to form suspension, taking the zinc oxide-reduced graphene oxide hydrogel film as a cathode, and immersing the cathode and the anode in the suspension for electrophoretic deposition.
23. The method of claim 22, wherein the concentration of the nickel salt in the suspension is 0.5M-5M and the concentration of zirconium oxide is 1mg/mL-20mg/mL.
24. The method according to claim 22, wherein the surfactant is sodium dodecyl sulfate, the buffer is boric acid, the mass ratio of zirconia to sodium dodecyl sulfate is (5-50): 1, and the mass ratio of zirconia to boric acid is (0.5-5).
25. The method of producing according to claim 22, wherein the nickel salt is at least one selected from the group consisting of nickel chloride hexahydrate, nickel nitrate hexahydrate, nickel acetate tetrahydrate and nickel acetylacetonate dihydrate.
26. The method of claim 22, wherein the zirconia powder has an average particle size of 5nm to 20nm.
27. The method of claim 22, wherein the anode is a carbon rod.
28. The method according to claim 8, wherein the average current density is controlled to be 1A/dm by using a DC pulse power source deposition method during the electrophoretic deposition 2 -10 A/dm 2 The duty ratio is 5% -95%, the pulse frequency is 50Hz-2000 Hz, the stirring speed is 200rpm-1000rpm, the suspension temperature is 20-90 ℃, and the deposition time is 0.5-40 min.
29. The method of claim 28, wherein the average current density is controlled to be 3A/dm 2 -8 A/dm 2 The duty ratio is 40-80%, the pulse frequency is 100-1200 Hz, the stirring speed is 400-600 rpm, the suspension temperature is 50-7%The deposition time is 10min-30min at 0 ℃.
30. A method for preparing alcohol by electro-oxidation of methane, which is characterized in that the catalyst of any one of claims 1-7 or the catalyst prepared by the preparation method of any one of claims 8-29 is used as an electrocatalytic anode working electrode.
31. The method of claim 30, wherein graphite carbon rod is used as a cathode counter electrode, saturated Calomel Electrode (SCE) is used as a reference electrode, each electrode is placed in an alkaline electrolyte of an H-type double-chamber electrolytic cell, methane is introduced into the alkaline electrolyte for electrocatalytic oxidation, and constant potential reaction is carried out for 2H-4H under the condition of potential interval of 0.5V-1.0V.
32. The method of claim 31, wherein the alkaline electrolyte is selected from Na 2 CO 3 、K 2 CO 3 And NaOH and KOH, wherein the mass concentration of the alkaline electrolyte is 0.3M-1.0M.
33. The method of claim 31, wherein the reaction pressure is normal pressure, the reaction temperature is room temperature, and the methane gas flow rate is 25mL/min-35mL/min.
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