CN114937782B - Supported metal-based catalyst and preparation method thereof - Google Patents
Supported metal-based catalyst and preparation method thereof Download PDFInfo
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- CN114937782B CN114937782B CN202210449344.5A CN202210449344A CN114937782B CN 114937782 B CN114937782 B CN 114937782B CN 202210449344 A CN202210449344 A CN 202210449344A CN 114937782 B CN114937782 B CN 114937782B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 149
- 239000002184 metal Substances 0.000 title claims abstract description 149
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 47
- 239000003463 adsorbent Substances 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 25
- 239000006227 byproduct Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 230000009471 action Effects 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 64
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052697 platinum Inorganic materials 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 150000004687 hexahydrates Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 150000001721 carbon Chemical class 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- -1 tungsten nitride Chemical class 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001567 cementite Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910001337 iron nitride Inorganic materials 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002923 metal particle Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 25
- 229910021607 Silver chloride Inorganic materials 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229960004643 cupric oxide Drugs 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UGNANEGDDBXEAS-UHFFFAOYSA-L nickel(2+);dichloride;dihydrate Chemical compound O.O.Cl[Ni]Cl UGNANEGDDBXEAS-UHFFFAOYSA-L 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- 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
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a supported metal-based catalyst and a preparation method thereof, and belongs to the technical field of catalysts. Solves the technical problems of high preparation cost, uncontrollable morphology and low metal utilization rate of the supported metal-based catalyst in the prior art. The preparation method of the metal-based catalyst comprises the following steps: firstly, taking all raw materials according to the proportion; then adsorbing the metal precursor and the auxiliary agent on a carrier to obtain powder for adsorbing the metal precursor; and finally, placing the powder for adsorbing the metal precursor and the adsorbent in a closed container in a separated manner, and performing heat treatment on the powder for adsorbing the metal precursor under the action of reducing gas, wherein the adsorbent removes gas byproducts to obtain the supported metal-based catalyst. The metal-based catalyst has smaller metal particle size, greatly improves the utilization rate of metal, and greatly improves the catalytic performance.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a supported metal-based catalyst and a preparation method thereof.
Background
As global climate deteriorates, fossil energy is depleted and sustainable clean energy such as solar, wind, nuclear and its associated energy storage devices are receiving widespread attention. In the fields of modern chemistry, energy and traffic, heterogeneous catalysis based on metals plays an irreplaceable role. In the past few decades, some metals such as palladium, platinum, ruthenium, rhodium, iridium, gold, silver, etc., have exhibited excellent catalytic activity and selectivity in a fairly broad catalytic reaction system due to their unique electronic structure. But these materials also exhibit very good corrosion resistance in long term stability tests. However, in important energy conversion processes such as electrolysis of water, fuel cells, etc., a high-loading metal-based catalyst occupies the major cost of the equipment, which is one of the important factors restricting the development of new energy technologies. Therefore, in order to alleviate the contradiction between the extremely low resource reserves of metals and the increasingly demanding use demands, the maximum utilization of metal resources without loss of catalytic performance is a critical issue to be addressed in the present stage.
In the prior art, commercial catalysts are prepared mainly by liquid phase reduction and thermal reduction. The former requires the consumption of large amounts of expensive chemical reagents, creating more chemical pollution, while the latter requires more energy consumption. In addition, the morphology of the catalyst is difficult to accurately regulate in a large range in both methods.
Disclosure of Invention
In view of the above, the invention provides a supported metal-based catalyst and a preparation method thereof, which are used for solving the technical problems of high preparation cost, uncontrollable morphology and low metal utilization rate of the supported metal-based catalyst in the prior art, wherein the supported metal-based catalyst has smaller particle size distribution and higher catalytic activity.
The invention solves the problems and adopts the following technical scheme:
the invention provides a preparation method of a supported metal-based catalyst, which comprises the following steps:
firstly, taking raw materials according to the mass ratio of metal precursors, auxiliary agents, carriers and adsorbents of 1 (0-30) (0.1-2) (0-300);
adsorbing the metal precursor and the auxiliary agent on a carrier to obtain powder for adsorbing the metal precursor;
and thirdly, placing the powder for adsorbing the metal precursor and the adsorbent in a closed container in a separated manner, and performing heat treatment on the powder for adsorbing the metal precursor under the action of reducing gas, wherein the adsorbent removes gas byproducts to obtain the supported metal-based catalyst.
Preferably, the reducing gas is volatilized in the process of carrying out heat treatment on powder for adsorbing the metal precursor by using a liquid reducing agent at normal temperature, and the reducing agent is one or more of water, methanol, ethanol, propanol, oleylamine and octadecene which are mixed according to any proportion; more preferably, the ratio of the volume of the reducing agent to the volume of the closed vessel is 0 or more and 0.6 or less.
Preferably, the method for adsorbing the metal precursor and the auxiliary agent on the carrier comprises the following steps: uniformly mixing a carrier, a metal precursor and an auxiliary agent in a dispersion liquid to obtain a suspension liquid, and then carrying out solid-liquid separation on the suspension liquid to obtain powder for adsorbing the metal precursor; more preferably, the uniform mixing is by ultrasonic stirring.
Preferably, the closed container is a reaction kettle, a sample stage is arranged in the reaction kettle, the powder for adsorbing the metal precursor is placed in the sample stage, and the adsorbent is placed around the sample stage.
Preferably, the solid powder obtained after the heat treatment is washed and dried to obtain the supported metal-based catalyst.
Preferably, the metal precursor is one or a mixture of a plurality of platinum-containing compounds, gold-containing compounds, silver-containing compounds, iridium-containing compounds, ruthenium-containing compounds, palladium-containing compounds, rhodium-containing compounds, copper-containing compounds, iron-containing compounds, cobalt-containing compounds and nickel-containing compounds in any proportion; more preferably, the platinum-containing compound is one or a mixture of a plurality of platinum chloride, chloroplatinic acid hexahydrate and platinum acetylacetonate according to any proportion, and particularly preferably chloroplatinic acid hexahydrate; more preferably, the gold-containing compound is one or two of gold chloride and chloroauric acid hexahydrate, and particularly preferably, the gold chloride hexahydrate is mixed according to any proportion; more preferably, the silver-containing compound is silver nitrate; more preferably, the iridium-containing compound is chloroiridic acid; more preferably, the ruthenium-containing compound is ruthenium chloride; more preferably, the palladium-containing compound is one or two of palladium chloride and palladium acetylacetonate, and particularly preferably palladium chloride; more preferably, the rhodium-containing compound is rhodium chloride; more preferably, the copper-containing compound is one or a mixture of a plurality of copper sulfate, copper chloride and copper nitrate according to any proportion, and particularly preferably copper chloride; preferably, the iron-containing compound is one or more of ferric chloride, ferric nitrate and ferric sulfate, and particularly preferably ferric chloride; preferably, the nickel-containing compound is one or a mixture of several of nickel chloride, nickel nitrate and nickel sulfate according to any proportion, and particularly preferably nickel chloride.
Preferably, the carrier is one or more of carbon, modified carbon, metal oxide, metal carbide and metal nitride mixed according to any proportion; more preferably, the carbon is activated carbon; more preferably, the modified carbon is one or two of heteroatom-doped carbon and surface-treated carbon, and the carbon in the modified carbon refers to activated carbon, graphene or carbon nano tube; more preferably, the metal oxide is one or more of cerium oxide, copper oxide, iron oxide and titanium dioxide mixed according to any proportion; more preferably, the metal carbide is one or two of iron carbide and tungsten carbide mixed according to any proportion; more preferably, the metal nitride is one or more of iron nitride, tungsten nitride and titanium nitride mixed according to any proportion.
Preferably, the auxiliary agent is one or a mixture of more of potassium chloride, potassium sulfate, sodium chloride and sodium sulfate according to any proportion.
Preferably, the dispersion liquid is one or a mixture of two of water and an organic solvent according to any proportion; more preferably, the organic solvent is one or more of methanol, ethanol and isopropanol mixed according to any proportion.
Preferably, the adsorbent is one or a mixture of two of metal and metal oxide according to any proportion; more preferably, the metal is one or a mixture of several of iron, nickel and copper according to any proportion; more preferably, the metal oxide is one or a mixture of two of ferric oxide and cupric oxide in any proportion.
Preferably, the temperature of the heat treatment is 100-250 ℃ and the time is 4-24 hours.
The invention also provides the supported metal-based catalyst prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
in the supported metal-based catalyst provided by the invention, the distribution particle size of the metal on the carrier is small (the optimal distribution particle size is 5-10 nanometers) and quite uniform (the average particle size is 6.3 nanometers), so that the utilization rate of the metal is improved, and the catalytic activity of the catalyst is improved. Through the regulation and control of the metal precursor, the carrier and the auxiliary agent, the size and the morphology of the metal particles can be accurately regulated and controlled, which has important significance for the development of the catalytic technology.
The preparation method of the supported metal-based catalyst provided by the invention has the advantages of simple process, low requirements on production and experimental equipment, good reproducibility, and certain universality, and can select different metals and carriers according to requirements.
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, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an image of a supported metal-based catalyst prepared in example 1 of the present invention under a transmission electron microscope.
FIG. 2 is a linear sweep voltammogram of the metal-based catalysts of comparative example 1, example 1 and example 2 of the present invention.
FIG. 3 is a linear sweep voltammogram of the metal-based catalysts of comparative example 2, example 3 and example 4 of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below, but it is to be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The preparation method of the supported metal-based catalyst comprises the following steps:
firstly, taking raw materials according to the mass ratio of metal precursors, auxiliary agents, carriers and adsorbents of 1 (0-30) (0.1-2) (0-300);
adsorbing the metal precursor and the auxiliary agent on a carrier to obtain powder for adsorbing the metal precursor;
and thirdly, placing the powder for adsorbing the metal precursor and the adsorbent in a closed container in a separated manner, and performing heat treatment on the powder for adsorbing the metal precursor under the action of reducing gas, wherein the adsorbent removes byproducts to obtain the supported metal-based catalyst.
In the above-described embodiments, the metal precursor is a substance that can be reduced by a reducing gas to obtain a metal, and the metal precursor is preferably one or a mixture of several of a platinum-containing compound, a gold-containing compound, a silver-containing compound, an iridium-containing compound, a ruthenium-containing compound, a palladium-containing compound, a rhodium-containing compound, a copper-containing compound, an iron-containing compound, a cobalt-containing compound, and a nickel-containing compound in an arbitrary ratio. Wherein the compound containing platinum can be one or more of platinum chloride, chloroplatinic acid hexahydrate and platinum acetylacetonate, and the mixture of the platinum chloride, the chloroplatinic acid hexahydrate and the platinum acetylacetonate is particularly preferred. The gold-containing compound may be one or a mixture of two of gold chloride and chloroauric acid hexahydrate in an arbitrary ratio, and particularly preferred is gold chloride hexahydrate. The silver-containing compound may be silver nitrate. The iridium-containing compound may be chloroiridic acid. The ruthenium-containing compound may be ruthenium chloride. The palladium-containing compound may be one or a mixture of two of palladium chloride and palladium acetylacetonate in an arbitrary ratio, and palladium chloride is particularly preferable. The rhodium-containing compound may be rhodium chloride. The copper-containing compound may be one or more of copper sulfate, copper chloride and copper nitrate, and copper chloride is particularly preferred. The iron-containing compound is one or more of ferric chloride, ferric nitrate and ferric sulfate, and particularly preferably ferric chloride. The nickel-containing compound may be one or more of nickel chloride, nickel nitrate and nickel sulfate, and nickel chloride is particularly preferred.
In the technical scheme, the adsorbent can react with the gas by-product to remove the gas by-product, and the gas by-product is chloride, nitrogen oxide and other gases generated after the metal precursor is reduced, so that the gas by-product is corrosive to the product, and is timely converted into a solid compound, thereby being beneficial to improving the quality of the product; if the amount of the adsorbent is 0, in the third step, the powder to which the metal precursor is adsorbed is placed in a closed container, and the powder to which the metal precursor is adsorbed is subjected to heat treatment under the action of a reducing gas, so as to obtain the supported metal-based catalyst, preferably, the content of the adsorbent is greater than 0, and the adsorbent is excessive, so that the gas by-product can be completely removed. The adsorbent is one or a mixture of more than one of active metals and metal oxides with larger surface areas according to any proportion; the metal is preferably one or a mixture of more of iron, nickel and copper according to any proportion; the metal oxide is preferably one or a mixture of several of ferric oxide powder and cupric oxide powder according to any proportion.
In the technical scheme, the auxiliary agent is a substance capable of improving the catalytic effect of the metal-based catalyst; if the dosage of the auxiliary agent is 0, in the second step, the metal precursor is adsorbed on the carrier to obtain powder for adsorbing the metal precursor; preferably the content of auxiliary agent is greater than 0. The auxiliary agent is preferably one or a mixture of more of potassium chloride, potassium sulfate, sodium chloride and sodium sulfate according to any proportion.
In the above technical scheme, the carrier is not particularly limited, and can realize the loading function. The carrier is preferably one or more of carbon, modified carbon, metal oxide, metal carbide and metal nitride mixed according to any proportion; the carbon may be activated carbon; the modified carbon can be one or two of heteroatom-doped carbon and surface-treated carbon, wherein the carbon in the modified carbon refers to activated carbon, graphene or carbon nano tube; the metal oxide can be one or a mixture of several of cerium oxide, copper oxide, iron oxide and titanium dioxide according to any proportion; the metal carbide can be one or two of iron carbide and tungsten carbide mixed according to any proportion; the metal nitride can be one or a mixture of several of iron nitride, tungsten nitride and titanium nitride according to any proportion.
In the above technical solution, the reducing gas is a gas capable of reducing the metal precursor to metal; the reducing gas is preferably volatilized by a reducing agent which is liquid at normal temperature in the process of heat-treating the powder to which the metal precursor is adsorbed, and a gas-solid reaction occurs on the surface of the powder to which the metal precursor is adsorbed. The reducing agent is preferably one or more of water, methanol, ethanol, propanol, oleylamine and octadecene in any proportion; the ratio of the volume of the reducing agent to the volume of the closed vessel is preferably 0 or more and 0.6 or less.
In the technical scheme, the dispersion liquid is one or a mixture of two of water and an organic solvent according to any proportion. The organic solvent can be one or more of methanol, ethanol and isopropanol.
In the technical scheme, the method for adsorbing the metal precursor and the auxiliary agent on the carrier comprises the following steps: and (3) uniformly stirring and mixing the carrier, the metal precursor and the auxiliary agent in the dispersion liquid by ultrasonic to obtain a suspension liquid, and then carrying out solid-liquid separation on the suspension liquid to obtain powder for adsorbing the metal precursor.
In the technical scheme, the closed container is preferably a reaction kettle, a sample stage is arranged in the reaction kettle, powder for adsorbing the metal precursor is placed in the sample stage, and the adsorbent is placed around the sample stage.
In the technical scheme, the solid powder obtained after heat treatment is washed and dried to obtain the supported metal-based catalyst.
In the technical scheme, the temperature of the heat treatment is 100-250 ℃ and the time is 4-24 hours.
The invention also provides the supported metal-based catalyst prepared by the preparation method, the distribution particle size of the metal catalyst on the carrier is smaller, the optimal distribution particle size is 5-10 nanometers, the metal catalyst is quite uniform, and the average particle size is 6.3 nanometers.
According to the preparation method of the supported metal-based catalyst, the metal precursor and the reducing gas react, if the reaction of the metal precursor and the reducing gas generates a gas byproduct, and if the adsorbent exists in the container, the reaction of the adsorbent and the gas byproduct exists, so that the corresponding supported metal-based catalyst can be prepared as long as the reducing gas is ensured to fully reduce the metal precursor, and the adsorbent (preferably excessive) can remove the gas byproduct, thereby improving the quality of the supported metal-based catalyst. The auxiliary agent is used for improving the catalytic performance of the metal-based catalyst, and is loaded on a carrier without reaction. The carrier is mainly used for loading the metal-based catalyst and the auxiliary agent (if contained) and preventing agglomeration of the metal-based catalyst powder. Therefore, after the type of the metal-based catalyst is selected, a person skilled in the art can determine the corresponding metal precursor and the reducing gas, the types of the carrier and the auxiliary agent can be flexibly changed according to the reaction system, and the adsorbent is a substance which can be rapidly reacted with the byproducts according to the types of the byproducts. The finally obtained supported metal-based catalyst material, the loading capacity of the metal-based catalyst and the like can be regulated and controlled according to specific requirements. For example, after determining to prepare a platinum-based catalyst, one skilled in the art may use chloroplatinic acid hexahydrate as a metal precursor, activated carbon as a carrier, potassium chloride as an auxiliary agent, and ethanol as a reducing gas. For example, after determining the preparation of the platinum-based and nickel-based composite catalysts, one skilled in the art may use chloroplatinic acid hexahydrate and nickel chloride dihydrate as metal precursors, tungsten carbide as a carrier, potassium chloride as an aid, and ethanol as a reducing gas. For example, after determining the preparation of the platinum-based and copper-based composite catalyst, one skilled in the art may use chloroplatinic acid hexahydrate and copper chloride dihydrate as metal precursors, activated carbon as a carrier, potassium chloride as an auxiliary agent, and ethanol as a reducing gas. But is not limited thereto.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated. In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be described in further detail with reference to examples.
In the following examples, various processes and methods, which are not described in detail, are conventional methods well known in the art. Materials, reagents, devices, instruments, equipment and the like used in the examples described below are commercially available unless otherwise specified.
The invention is further illustrated below with reference to examples.
Comparative example 1
To a mixture of 50. Mu.L of Nafion at a mass concentration of 5% and 950. Mu.L of isopropanol was added 5mg of a commercial carbon-supported platinum catalyst (commercially available from Johnson Matthey, brand) with a platinum loading of 20%, and the mixture was sonicated for 30min to give a uniform ink to be tested. And (3) taking 10 mu l of the ink to be tested, dripping the ink to be tested on the rotary disc electrode, and naturally airing at room temperature to obtain the modified electrode (namely the working electrode). Silver/silver chloride is used as a reference electrode, and a platinum net is used as a counter electrode and a working electrode to form a three-electrode system. 0.1mol/L HClO saturated with oxygen 4 The linear voltammetric test was performed in the electrolyte at a sweep rate of 10mV/s, and the results are shown in curve 21 in FIG. 2, which shows that the oxygen reduction half-wave potential of the carbon-supported platinum catalyst is 0.56V.
Comparative example 2
To a mixture of 50. Mu.L of Nafion at a mass concentration of 5% and 950. Mu.L of isopropanol was added 5mg of a commercial carbon-supported platinum catalyst (commercially available from Johnson Matthey, brand) with a platinum loading of 20%, and the mixture was sonicated for 30min to give a uniform ink to be tested. And (3) taking 10 mu l of the ink to be tested, dripping the ink to be tested on the rotary disc electrode, and naturally airing at room temperature to obtain the modified electrode (namely the working electrode). Silver/silver chloride is used as a reference electrode, and a platinum net is used as a counter electrode and a working electrode to form a three-electrode system. Saturated with nitrogen containing 0.1mol/L HClO 4 And 1mol/L of methanol in an electrolyteThe voltammetric test shows that the sweep rate is 50mV/s, and the result is shown as curve 31 in FIG. 3, and the front sweep current of the electrocatalytic methanol oxidation of the carbon-supported platinum catalyst is 0.7A/mg Pt 。
Example 1
160mg of activated carbon and 106mg of chloroplatinic acid hexahydrate were placed in a beaker containing 200mL of water and stirred ultrasonically to give a uniform suspension.
The suspension was transferred to a 250mL round bottom flask and dried by rotary evaporation at 60 ℃ using a rotary evaporator to give a powder that adsorbed the metal precursor.
Taking a reaction kettle with the volume of 200mL, adding 10mL of ethanol at the bottom, placing a sample table made of polytetrafluoroethylene at the upper part of the reaction kettle, placing powder for adsorbing a metal precursor on the sample table, placing 1g of foam nickel around the sample as an adsorbent of a byproduct, and sealing the reaction kettle.
The reaction kettle is put into an oven to be heated to 160 ℃ and kept for 12 hours.
And opening the reaction kettle, taking out the powder solid, dispersing the powder solid into water again, carrying out suction filtration, washing and drying to obtain the supported metal-based catalyst.
The supported metal-based catalyst was observed under a transmission electron microscope and the image is shown in fig. 1. As can be seen from fig. 1, in the supported metal-based catalyst of example 1, the metal precursor was reduced to metal nanoparticles, which were uniformly dispersed on the surface of the support, and the particle size of the metal nanoparticles was mainly distributed in the range of 5 to 10 nm, and the average particle size was about 6.3 nm.
5mg of the supported metal-based catalyst prepared above was added to a mixture containing 50. Mu.L of Nafion having a mass concentration of 5% and 950. Mu.L of isopropyl alcohol, and the mixture was subjected to ultrasonic dispersion for 30 minutes to obtain a uniform ink to be tested. And (3) taking 10 mu l of the ink to be tested, dripping the ink to be tested on the rotary disc electrode, and naturally airing at room temperature to obtain the modified electrode (namely the working electrode). Silver/silver chloride is used as a reference electrode, and a platinum net is used as a counter electrode and a working electrode to form a three-electrode system. 0.1mol/L HClO saturated with oxygen 4 As a result of conducting a linear voltammetric test in an electrolyte solution at a sweep rate of 10mV/s and a result of the test, see curve 22 in FIG. 2, it was found that the oxygen reduction half-wave potential of the supported metal-based catalyst of example 1 was 0.62V,greatly exceeding the oxygen reduction performance of commercial catalysts.
Example 2
120mg of activated carbon, 213mg of chloroplatinic acid hexahydrate and 800mg of potassium chloride were placed in a beaker containing 200mL of water and stirred ultrasonically to obtain a uniform suspension.
The suspension was transferred to a 250mL round bottom flask and dried by rotary evaporation at 60 ℃ using a rotary evaporator to give a powder that adsorbed the metal precursor.
Taking a reaction kettle with the volume of 200mL, adding 15mL of ethanol at the bottom, placing a sample table made of polytetrafluoroethylene at the upper part of the reaction kettle, placing powder for adsorbing a metal precursor on the sample table, placing 2g of foam nickel around the sample as an adsorbent of a byproduct, and sealing the reaction kettle.
The reaction kettle is put into an oven to be heated to 180 ℃ and kept for 8 hours.
And opening the reaction kettle, taking out the powder solid, dispersing the powder solid into water again, carrying out suction filtration, washing and drying to obtain the supported metal-based catalyst.
5mg of the supported metal-based catalyst prepared above was added to a solution containing 50. Mu.L of Nafion having a mass concentration of 5% and 950. Mu.L of isopropyl alcohol, and the mixture was subjected to ultrasonic dispersion for 30 minutes to obtain a uniform ink to be tested. And (3) taking 10 mu l of the ink to be tested, dripping the ink to be tested on the rotary disc electrode, and naturally airing at room temperature to obtain the modified electrode (namely the working electrode). Silver/silver chloride is used as a reference electrode, and a platinum net is used as a counter electrode and a working electrode to form a three-electrode system. 0.1mol/L HClO saturated with oxygen 4 The linear voltammetry test was performed in the electrolyte solution at a sweep rate of 10mV/s, and the results are shown in curve 22 in FIG. 2, which shows that the oxygen reduction half-wave potential of the supported metal-based catalyst of example 2 is 0.65V, and the oxygen reduction performance is further improved as compared with the catalysts of comparative example 1 and example 1.
Example 3
190mg of tungsten carbide powder, 27mg of chloroplatinic acid hexahydrate, 120mg of nickel chloride dihydrate and 200mg of potassium chloride were placed in a beaker containing 200mL of water and stirred ultrasonically to obtain a uniform suspension.
The suspension was transferred to a 250mL round bottom flask and dried by rotary evaporation at 60 ℃ using a rotary evaporator to give a powder that adsorbed the metal precursor.
Taking a reaction kettle with the volume of 200mL, adding 15mL of ethanol at the bottom, placing a sample table made of polytetrafluoroethylene at the upper part of the reaction kettle, placing powder for adsorbing a metal precursor on the sample table, placing 2g of foam iron around the sample as an adsorbent of a byproduct, and sealing the reaction kettle.
The reaction kettle is put into an oven to be heated to 160 ℃ and kept for 12 hours.
And (3) starting the reaction kettle, taking out the powder solid, dispersing the powder solid into water again, carrying out suction filtration, washing and drying to obtain the supported platinum-nickel alloy catalyst.
5mg of the supported platinum copper alloy catalyst prepared above was added to 50. Mu.L of Nafion having a mass concentration of 5% and 950. Mu.L of isopropyl alcohol, and the mixture was subjected to ultrasonic dispersion for 30 minutes to obtain a uniform ink to be tested. And (3) taking 10 mu l of the ink to be tested, dripping the ink to be tested on the rotary disc electrode, and naturally airing at room temperature to obtain the modified electrode. Silver/silver chloride is used as a reference electrode, and a platinum net is used as a counter electrode and a working electrode to form a three-electrode system. Saturated with nitrogen containing 0.1mol/L HClO 4 And 1mol/L of methanol, the sweep rate is 50mV/s, and the result is shown as curve 32 in FIG. 3, and the front sweep current of the electrocatalytic methanol oxidation of the carbon-supported platinum catalyst is 2.3A/mg Pt Exceeding the performance of commercial catalysts for electrocatalytic methanol oxidation.
Example 4
190mg of activated carbon, 27mg of chloroplatinic acid hexahydrate, 120mg of cupric chloride dihydrate and 200mg of potassium chloride were placed in a beaker containing 200mL of water and stirred ultrasonically to obtain a uniform suspension.
The suspension was transferred to a 250mL round bottom flask and dried by rotary evaporation at 60 ℃ using a rotary evaporator to give a powder that adsorbed the metal precursor.
Taking a reaction kettle with the volume of 200mL, adding 15mL of ethanol at the bottom, placing a sample table made of polytetrafluoroethylene at the upper part of the reaction kettle, placing powder for adsorbing a metal precursor on the sample table, placing 2g of foam iron around the sample as an adsorbent of a byproduct, and sealing the reaction kettle.
The reaction kettle is put into an oven to be heated to 160 ℃ and kept for 12 hours.
And (3) starting the reaction kettle, taking out the powder solid, dispersing the powder solid into water again, carrying out suction filtration, washing and drying to obtain the supported platinum-copper alloy catalyst.
5mg of the supported platinum copper alloy catalyst prepared above was added to 50. Mu.L of Nafion having a mass concentration of 5% and 950. Mu.L of isopropyl alcohol, and the mixture was subjected to ultrasonic dispersion for 30 minutes to obtain a uniform ink to be tested. And (3) taking 10 mu l of the ink to be tested, dripping the ink to be tested on the rotary disc electrode, and naturally airing at room temperature to obtain the modified electrode (namely the working electrode). Silver/silver chloride is used as a reference electrode, and a platinum net is used as a counter electrode and a working electrode to form a three-electrode system. Saturated with nitrogen containing 0.1mol/L HClO 4 And 1mol/L of methanol, the sweep rate is 50mV/s, and the result is shown as curve 33 in figure 3, and the front sweep current of the electrocatalytic methanol oxidation of the carbon-supported platinum catalyst is 4.1A/mgPt, which is far superior to the electrocatalytic methanol oxidation performance of the commercial catalyst.
It is apparent that the above embodiments are merely examples for clarity of illustration and are not limiting examples. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (9)
1. The preparation method of the supported metal-based catalyst is characterized by comprising the following steps:
firstly, taking raw materials according to the mass ratio of metal precursors, auxiliary agents, carriers and adsorbents of 1 (0-30) (0.1-2) (0-300);
adsorbing the metal precursor and the auxiliary agent on a carrier to obtain powder for adsorbing the metal precursor;
thirdly, placing the powder for adsorbing the metal precursor and the adsorbent in a closed container in a separated manner, performing heat treatment on the powder for adsorbing the metal precursor under the action of reducing gas, removing gas byproducts by the adsorbent, washing, and drying to obtain the supported metal-based catalyst;
the closed container is a reaction kettle, a sample stage is arranged in the reaction kettle, powder for adsorbing the metal precursor is placed in the sample stage, and the adsorbent is placed around the sample stage;
the temperature of the heat treatment is 100-250 ℃ and the time is 4-24 hours.
2. The method for preparing a supported metal-based catalyst according to claim 1, wherein the reducing gas is volatilized during the heat treatment of the powder adsorbing the metal precursor by a reducing agent in a liquid state at normal temperature, and the reducing agent is one or a mixture of water, methanol, ethanol, propanol, oleylamine and octadecene in any ratio.
3. The method for producing a supported metal-based catalyst according to claim 2, wherein the ratio of the volume of the reducing agent to the volume of the closed vessel is 0 or more and 0.6 or less.
4. The method for preparing the supported metal-based catalyst according to claim 1, wherein the method for adsorbing the metal precursor and the auxiliary agent on the carrier is as follows: and uniformly mixing the carrier, the metal precursor and the auxiliary agent in the dispersion liquid to obtain suspension liquid, and then carrying out solid-liquid separation on the suspension liquid to obtain powder for adsorbing the metal precursor.
5. The method for preparing a supported metal-based catalyst according to claim 4, wherein the dispersion is one or a mixture of two of water and an organic solvent in an arbitrary ratio.
6. The method for preparing a supported metal-based catalyst according to claim 5, wherein the organic solvent is one or more of methanol, ethanol and isopropanol mixed according to an arbitrary ratio.
7. The method for producing a supported metal-based catalyst according to claim 1, wherein the metal precursor is one or a mixture of several of a platinum-containing compound, a gold-containing compound, a silver-containing compound, an iridium-containing compound, a ruthenium-containing compound, a palladium-containing compound, a rhodium-containing compound, a copper-containing compound, an iron-containing compound, a cobalt-containing compound, and a nickel-containing compound in an arbitrary ratio;
the carrier is one or a mixture of more of carbon, modified carbon, metal oxide, metal carbide and metal nitride according to any proportion;
the auxiliary agent is one or a mixture of more of potassium chloride, potassium sulfate, sodium chloride and sodium sulfate according to any proportion;
the adsorbent is one or a mixture of two of metal and metal oxide according to any proportion.
8. The method for preparing a supported metal-based catalyst according to claim 7, wherein,
the compound containing platinum is one or a mixture of more of platinum chloride, chloroplatinic acid hexahydrate and platinum acetylacetonate according to any proportion; the gold-containing compound is one or two of gold chloride and chloroauric acid hexahydrate mixed according to any proportion; the silver-containing compound is silver nitrate; the iridium-containing compound is chloroiridic acid; the ruthenium-containing compound is ruthenium chloride; the palladium-containing compound is one or two of palladium chloride and palladium acetylacetonate, which are mixed according to any proportion; the rhodium-containing compound is rhodium chloride; the copper-containing compound is one or a mixture of a plurality of copper sulfate, copper chloride and copper nitrate according to any proportion; the iron-containing compound is one or a mixture of more of ferric chloride, ferric nitrate and ferric sulfate according to any proportion; the nickel-containing compound is one or a mixture of a plurality of nickel chloride, nickel nitrate and nickel sulfate according to any proportion;
the carbon is one or a mixture of more of active carbon, graphene and carbon nano tubes according to any proportion; the modified carbon is carbon doped with hetero atoms and/or carbon subjected to surface treatment, wherein the carbon in the modified carbon refers to activated carbon, graphene or carbon nano tube; the carrier is metal oxide, wherein the metal oxide is one or a mixture of a plurality of cerium oxide, copper oxide, iron oxide and titanium dioxide according to any proportion; the metal carbide is one or two of iron carbide and tungsten carbide mixed according to any proportion; the metal nitride is one or a mixture of more of iron nitride, tungsten nitride and titanium nitride according to any proportion;
the metal is one or a mixture of more of iron, nickel and copper according to any proportion, and the adsorbent is one or a mixture of two of iron oxide and copper oxide according to any proportion.
9. A supported metal-based catalyst prepared by the method for preparing a supported metal-based catalyst according to any one of claims 1 to 8.
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