CN113813958B - Palladium-platinum supported metal oxide catalyst, preparation method and application thereof, working electrode and battery system - Google Patents
Palladium-platinum supported metal oxide catalyst, preparation method and application thereof, working electrode and battery system Download PDFInfo
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- CN113813958B CN113813958B CN202010566081.7A CN202010566081A CN113813958B CN 113813958 B CN113813958 B CN 113813958B CN 202010566081 A CN202010566081 A CN 202010566081A CN 113813958 B CN113813958 B CN 113813958B
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- palladium
- platinum
- oxide
- metal oxide
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- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 61
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 58
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 30
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 27
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 239000003921 oil Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000012018 catalyst precursor Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052755 nonmetal Inorganic materials 0.000 claims description 10
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 238000006722 reduction reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical class OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 229940090668 parachlorophenol Drugs 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006298 dechlorination reaction Methods 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 229910021126 PdPt Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- -1 chlorophenol compound Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 150000007529 inorganic bases Chemical class 0.000 description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 2
- 229910000413 arsenic oxide Inorganic materials 0.000 description 2
- 229960002594 arsenic trioxide Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LWCDLTXJKRTYCR-UHFFFAOYSA-M [Na+].C=1C=CNC=1.CCCCCCCCCCCCS([O-])(=O)=O Chemical compound [Na+].C=1C=CNC=1.CCCCCCCCCCCCS([O-])(=O)=O LWCDLTXJKRTYCR-UHFFFAOYSA-M 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ZBFQOIBWJITQRI-UHFFFAOYSA-H disodium;hexachloroplatinum(2-);hexahydrate Chemical compound O.O.O.O.O.O.[Na+].[Na+].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] ZBFQOIBWJITQRI-UHFFFAOYSA-H 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
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Abstract
The invention provides a palladium-platinum supported metal oxide catalyst, a preparation method and application thereof, a working electrode and a battery system, and belongs to the technical field of catalysts. The palladium-platinum supported metal oxide catalyst provided by the invention comprises an oxide and palladium-platinum alloy supported on the surface of the oxide. In the invention, the palladium-platinum alloy is an active component, the oxide is a carrier, the palladium-platinum alloy and the oxide have strong interaction, and the stability of the palladium-platinum supported metal oxide catalyst is high; pd metal in the palladium-platinum alloy has strong activity on chlorophenols, pt metal has strong hydrogenation effect on phenol, palladium and platinum act together to improve the deep hydrogenation performance of the catalyst, and the synergistic effect of the two metals hydrogenates the chlorophenols to generate KA oil, so that the selectivity and the yield of the KA oil are improved.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a palladium-platinum supported metal oxide catalyst, a preparation method and application thereof, a working electrode and a battery system.
Background
The chlorophenols are used as an important industrial raw material and are widely applied to the fields of medicine and health, paper industry, pesticide production, dye, chemical production and the like. Since chlorophenols are a typical class of persistent organic pollutants, they have strong toxicity, bioaccumulation, carcinogenicity, and resistance to natural degradation, and their use in large amounts causes serious environmental pollution.
At present, the treatment method of the chlorophenols mainly comprises an adsorption method, an extraction method, a high-temperature calcination method and catalytic hydrogenation dechlorination, wherein the catalytic hydrogenation dechlorination is a simple, safe and effective method and is widely focused. The catalyst commonly used for the catalytic hydrogenation dechlorination of chlorophenols is transition metal, for example, chinese patent CN101565356A discloses a method for the low-temperature catalytic dechlorination of chlorophenols, pd is used as a catalyst and hydrogen is used as a reducing agent; literature (cold. Surf. A414 (2012), 314-319) discloses modification of Pd catalysts by polymerizing sodium pyrrole-dodecyl sulfonate films; literature (Mater. Des.86 (2015), 664-669) discloses modification of Pd catalysts by Go; literature (ACS catalyst, 2013,3 (7), 1560-1563) discloses modification of Pd catalysts by Ag metal. However, the catalyst increases the conversion rate of chlorophenols to a certain extent, but the products of catalytic hydrogenation dechlorination are phenol which is also a toxic organic matter, so that secondary pollution is caused.
Disclosure of Invention
The invention aims to provide a palladium-platinum supported metal oxide catalyst, a preparation method and application thereof, a working electrode and a battery system. The palladium-platinum supported metal oxide catalyst provided by the invention can be used for deeply hydrogenating and catalyzing chlorophenols into KA oil, and the KA oil has high yield and high selectivity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a palladium-platinum supported metal oxide catalyst, which comprises an oxide and a palladium-platinum alloy supported on the surface of the oxide.
Preferably, the content of the palladium-platinum alloy in the palladium-platinum supported metal oxide catalyst is 0.2-6wt%;
the mass ratio of palladium to platinum in the palladium-platinum alloy is (0.1-4): (0.1-2).
Preferably, the oxide comprises a metal oxide or a non-metal oxide; the non-metal oxide comprises silicon dioxide or arsenic oxide; the metal oxide includes titanium dioxide, aluminum oxide, chromium oxide, or manganese oxide.
The invention provides a preparation method of the palladium-platinum supported metal oxide catalyst, which comprises the following steps:
mixing a water-soluble palladium source, a water-soluble platinum source and water to obtain a palladium-platinum mixed solution;
mixing the palladium-platinum mixed solution with an oxide, regulating the pH value to 8-14, and performing coprecipitation reaction to obtain a catalyst precursor;
and (3) calcining and reducing the catalyst precursor in sequence to obtain the palladium-platinum supported metal oxide catalyst.
Preferably, the calcination temperature is 200-600 ℃ and the time is 1-8 h.
Preferably, the reducing agent used in the reduction reaction comprises hydrogen or a hydrogen-protective atmosphere mixed gas; the temperature of the reduction reaction is 100-600 ℃ and the time is 1-5 h.
The invention provides an application of the palladium-platinum supported metal oxide catalyst prepared by the technical scheme or the palladium-platinum supported metal oxide catalyst prepared by the preparation method in preparing KA oil by hydrogenating chlorophenols.
The invention provides a working electrode, which comprises a substrate electrode and a modification layer coated on the working surface of the substrate electrode, wherein the modification layer is coated by a composition comprising the palladium-platinum supported metal oxide catalyst prepared by the technical scheme or the palladium-platinum supported metal oxide catalyst prepared by the preparation method, a perfluorinated sulfonic acid type polymer solution and an alcohol solvent.
Preferably, the load of the palladium-platinum loaded metal oxide catalyst on the substrate electrode is 2-8 mg/cm 2 。
The invention also provides a battery system, which uses the platinum sheet as an anode working electrode, uses the salt solution as anode liquid, uses the working electrode as a cathode working electrode according to the technical scheme, and uses the salt solution containing the chlorophenol compound as cathode liquid.
The invention provides a palladium-platinum supported metal oxide catalyst, which comprises an oxide and a palladium-platinum alloy supported on the surface of the oxide. In the invention, the palladium-platinum alloy is used as an active component, the oxide is used as a carrier, a strong chemical bond is formed between the palladium-platinum alloy and the oxide, agglomeration can not occur in the reaction process, and the stability of the palladium-platinum supported metal oxide catalyst is high; pd metal in the palladium-platinum alloy has strong activity on chlorophenols, pt metal has strong hydrogenation effect on phenol, palladium and platinum act together to improve the deep hydrogenation performance of the catalyst, and the synergistic effect of the two metals hydrogenates the chlorophenols to generate KA oil, so that the selectivity and the yield of the KA oil are improved. As shown by the results of the embodiment of the invention, the conversion rate of the palladium-platinum supported metal oxide catalyst to chlorophenols is up to 98.2%, and the KA oil selectivity is up to 95.3%.
The preparation method of the palladium-platinum supported metal oxide catalyst provided by the invention is simple to operate, low in raw material cost, free of secondary pollution and suitable for industrial production.
Drawings
FIG. 1 is a transmission electron microscopic image of the palladium-platinum supported metal oxide catalyst prepared in example 1.
Detailed Description
The invention provides a palladium-platinum supported metal oxide catalyst, which comprises an oxide and a palladium-platinum alloy supported on the surface of the oxide.
In the present invention, the oxide preferably includes a metal oxide or a nonmetal oxide; the metal oxide preferably comprises titanium dioxide, aluminum oxide, chromium oxide or manganese oxide; the non-metal oxide preferably comprises silicon dioxide or arsenic oxide.
In the present invention, the content of the palladium-platinum alloy in the palladium-platinum supported metal oxide catalyst is preferably 0.2 to 6wt%, more preferably 0.5 to 5wt%, and most preferably 0.8 to 3%. In the present invention, the mass ratio of palladium to platinum in the palladium-platinum alloy is preferably (0.1 to 4): (0.1 to 2), more preferably (0.2 to 2): (0.2 to 1), most preferably (0.4 to 0.8): (0.4-0.6). In the invention, pd metal in the palladium-platinum alloy has strong activity on chlorophenols, pt metal has strong hydrogenation effect on phenol, palladium and platinum act together to improve the deep hydrogenation performance of the catalyst, and the two metals act together to hydrogenate the chlorophenols to generate KA oil, so that the selectivity and yield of the KA oil are improved.
The invention provides a preparation method of the palladium-platinum supported metal oxide catalyst, which comprises the following steps:
mixing a water-soluble palladium source, a water-soluble platinum source and water to obtain a palladium-platinum mixed solution;
mixing the palladium-platinum mixed solution with an oxide, regulating the pH value to 8-14, and performing coprecipitation reaction to obtain a catalyst precursor;
and (3) calcining and reducing the catalyst precursor in sequence to obtain the palladium-platinum supported metal oxide catalyst.
The invention mixes a water-soluble palladium source, a water-soluble platinum source and water to obtain a palladium-platinum mixed solution.
In the present invention, the water-soluble palladium source preferably includes palladium nitrate, palladium acetate, sodium chloropalladate, palladium acetylacetonate, ammonium tetrachloropalladate or palladium chloride, more preferably palladium nitrate.
In the present invention, the water-soluble platinum source preferably includes chloroplatinic acid, platinum nitrate, potassium chloroplatinate, potassium chloroplatinic acid, sodium hexachloroplatinate hexahydrate, or platinum (II) chloride, more preferably chloroplatinic acid.
In the present invention, the water-soluble palladium source and the water-soluble platinum source are preferably in terms of palladium and platinum, respectively, in a mass ratio of (0.1 to 4): (0.1 to 2), more preferably (0.2 to 2): (0.2 to 1), most preferably (0.4 to 0.8): (0.4-0.6).
In the present invention, the water is preferably deionized water. In the present invention, the ratio of the mass of the water-soluble palladium source to the volume of water is preferably 1mg: (1-10) mL, more preferably 1mg: (2-5) mL.
In the present invention, the mixing method is preferably stirring mixing, and the speed of the stirring mixing is not particularly limited, and the raw materials can be uniformly mixed; the mixing time is preferably 20 to 60 minutes, more preferably 30 to 50 minutes; the temperature of the mixing is preferably room temperature.
After the palladium-platinum mixed solution is obtained, the invention mixes the palladium-platinum mixed solution and the oxide, adjusts the pH value to 8-14, and carries out coprecipitation reaction to obtain the catalyst precursor.
In the present invention, the ratio of the mass of the oxide to the volume of the palladium-platinum mixed solution is preferably 1g: (10-50) mL, more preferably 1g: (20-40) mL, most preferably 1g: (30-40) mL.
In the present invention, the mixing method is preferably stirring mixing, and the speed of the stirring mixing is not particularly limited, and the raw materials can be uniformly mixed; the mixing time is preferably 6 to 24 hours, more preferably 7 to 15 hours, most preferably 8 to 12 hours; the temperature of the mixing is preferably room temperature. In the invention, in the mixing process, metal ions are uniformly distributed and adsorbed on the surface of the carrier.
In the present invention, the pH value to be adjusted to a pH value of 8 to 14 is more preferably 9 to 12, still more preferably 9 to 10. In the present invention, the pH adjustment is preferably performed using an inorganic base, which preferably includes sodium hydroxide or potassium hydroxide; the inorganic base is preferably used in the form of an inorganic base solid or an inorganic base solution; the invention is not particularly limited to the amount of the inorganic alkali and the concentration of the inorganic alkali solution, and the pH value can be adjusted to 8-14; in the embodiment of the invention, the concentration of the inorganic alkali solution is preferably 0.5 to 1mol/L. In the present invention, the pH is preferably adjusted to 8 to 14 under stirring, and the stirring speed is not particularly limited, and the inorganic base may be uniformly dispersed in the palladium-platinum mixed solution.
In the present invention, the temperature of the coprecipitation reaction is preferably room temperature, and the time of the coprecipitation reaction is preferably 1 to 3 hours, more preferably 1 to 2 hours. In the invention, palladium ions and platinum ions in the palladium-platinum mixed solution are subjected to coprecipitation on the surface of an oxide under an alkaline condition in the coprecipitation reaction process to obtain palladium-platinum hydroxide.
After the coprecipitation reaction, the invention preferably further comprises solid-liquid separation of the obtained system, and drying of the obtained solid product to obtain the catalyst precursor. The mode of the solid-liquid separation is not particularly limited, and a solid-liquid separation mode known to those skilled in the art, specifically, filtration may be employed. In the present invention, the drying temperature is preferably 20 to 200 ℃, more preferably 50 to 150 ℃, and most preferably 60 to 100 ℃; the time is preferably 1 to 12 hours, more preferably 3 to 10 hours, most preferably 5 to 7 hours.
After the catalyst precursor is obtained, the catalyst precursor is subjected to calcination and reduction reaction in sequence to obtain the palladium-platinum supported metal oxide catalyst.
In the present invention, the temperature of the calcination is preferably 200 to 600 ℃, more preferably 300 to 500 ℃, and most preferably 350 to 450 ℃; the time is preferably 1 to 8 hours, more preferably 2 to 6 hours, most preferably 3 to 4 hours; the calcination is preferably carried out in air. In the invention, during the calcination process, the palladium-platinum hydroxide in the catalyst precursor is decomposed to generate palladium oxide and platinum oxide.
In the invention, the reducing agent utilized in the reduction reaction comprises hydrogen or a hydrogen-protective atmosphere mixed gas; the protective atmosphere preferably comprises nitrogen or argon; the volume percentage of hydrogen in the hydrogen-protective atmosphere mixed gas is preferably 4-6%, more preferably 5%. In the present invention, the temperature of the reduction reaction is preferably 100 to 600 ℃, more preferably 200 to 500 ℃, and most preferably 300 to 400 ℃; the time is preferably 1 to 5 hours, more preferably 2 to 4 hours, and most preferably 3 to 4 hours. In the invention, in the reduction reaction process, palladium oxide is reduced to metal palladium, platinum oxide is reduced to metal platinum, palladium and platinum are combined together through metal bonds, and the stability of the catalyst is high.
The invention provides an application of the palladium-platinum supported metal oxide catalyst prepared by the technical scheme or the palladium-platinum supported metal oxide catalyst prepared by the preparation method in preparing KA oil by hydrogenating chlorophenols.
In the present invention, the KA oil is preferably cyclohexanone and cyclohexanol.
In the present invention, the chlorophenols preferably include one or more of o-chlorophenol, m-chlorophenol, p-chlorophenol, 2, 4-dichlorophenol, 2,3,4, 6-tetrachlorophenol and pentachlorophenol. In the invention, the source of the chlorophenols is preferably commercial wastewater, more preferably wastewater discharged from pharmaceutical factories, has low cost, changes waste into valuable and reduces environmental pollution.
The invention provides a working electrode, which comprises a substrate electrode and a modification layer coated on the working surface of the substrate electrode, wherein the modification layer is coated by the palladium-platinum supported metal oxide catalyst prepared by the technical scheme or the composition of the palladium-platinum supported metal oxide catalyst prepared by the preparation method, a perfluorinated sulfonic acid type polymer solution and an alcohol solvent.
In the present invention, the base electrode preferably includes carbon cloth; the size of the matrix electrode is preferably (0.5 to 4) cm, more preferably (1 to 3) cm, and most preferably 2cm×2m. In the invention, the loading capacity of the palladium-platinum loaded metal oxide catalyst on the substrate electrode is preferably 2-8 mg/cm 2 More preferably 3 to 6mg/cm 2 Most preferably 3 to 5mg/cm 2 。
In the present invention, the method for preparing the working electrode preferably includes the steps of: and mixing the palladium-platinum supported metal oxide catalyst, the perfluorinated sulfonic acid polymer solution and the alcohol solvent, and coating the mixture on the surface of the substrate electrode to obtain the working electrode.
In the present invention, the concentration of the perfluorosulfonic acid polymer (Nafion) solution is preferably 4 to 10% by mass, more preferably 5%. In the present invention, the alcohol solvent preferably includes methanol or ethanol. In the invention, the ratio of the mass of the bimetallic composite catalyst to the volume of Nafion solution and the volume of alcohol solvent is preferably 1mg: (5-20) μl: (100 to 130). Mu.L, more preferably 1mg: (10-15) μl: (110-115) mu L, most preferably 1mg:12.5 μl:112.5 μl. In the invention, the mixing is preferably ultrasonic mixing, the ultrasonic power is not particularly limited, and the bimetallic composite catalyst can be uniformly dispersed in Nafion solution and alcohol solvent; the time of the ultrasonic mixing is preferably 20 to 40 minutes, more preferably 25 to 35 minutes, and most preferably 30 minutes. In the present invention, the coating means is preferably a drop coating. The present invention is not particularly limited, and the dripping operation well known to those skilled in the art may be employed. The working electrode provided by the invention is applied to the preparation of KA oil by dechlorination and hydrogenation of chlorophenols, the conversion rate of the chlorophenols is high, and the KA oil selectivity is high.
The invention also provides a battery system, which uses the platinum sheet as an anode working electrode, uses the salt solution as anode liquid, uses the working electrode as a cathode working electrode according to the technical scheme, and uses the salt solution containing the chlorophenol compound as cathode liquid.
In the present invention, the container of the battery system is preferably an electrolytic cell, more preferably an H-type electrolytic cell. In the present invention, the cathode and anode compartments of the electrolyzer are preferably separated by a bipolar membrane, which preferably comprises a Nafion membrane. In the present invention, the anodic working electrode and anolyte are preferably located in the anodic compartment and the cathodic working electrode and catholyte are preferably located in the cathodic compartment. In the present invention, the volume of the cathode chamber and the anode chamber is independently preferably 5 to 50mL, more preferably 10 to 40mL, and most preferably 20 to 30mL.
In the invention, the anolyte is a salt solution, and the catholyte is a salt solution containing chlorinated phenol compounds. In the present invention, the salts in the salt solutions of the anolyte and the catholyte independently preferably include sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, sodium carbonate, sodium phosphate, or potassium phosphate; the concentration of the salt solution of the anolyte and the catholyte is independently preferably 0.1 to 4mol/L, more preferably 0.2 to 2mol/L, and still more preferably 0.2 to 1mol/L. In the present invention, the concentration of the chlorophenol compound in the catholyte is preferably 5 to 40mmol/L, more preferably 10 to 30mmol/L. The salt solution utilized by the invention has the advantages of low toxicity, no generation of harmful gas and harmful waste liquid, low cost and repeated use.
In the invention, the specific operation for preparing KA oil by hydrogenating the chlorophenols preferably comprises the following steps: and carrying out electrocatalytic hydrogenation reaction on the chlorophenols by adopting the battery system to obtain KA oil.
In the present invention, the temperature of the electrocatalytic hydrogenation reaction is preferably 20 to 80 ℃, more preferably 30 to 60 ℃, and most preferably 40 to 50 ℃; the time of the electrocatalytic hydrogenation reaction is preferably 0.5-3 h, more preferably 1-2 h; the electric current of the electrocatalytic hydrogenation reaction is preferably 10-100 mA, more preferably 20-30 mA; the voltage of the electrocatalytic hydrogenation reaction is preferably 1-4V, more preferably 2-3V; the magnitude of the current and voltage is preferably controlled by a constant current meter. The invention utilizes the electrocatalytic process to catalyze the chlorophenols to prepare KA oil in the cathode chamber, has mild and safe reaction conditions, and has high conversion rate and high selectivity of catalyzing the chlorophenols.
After the electrocatalytic hydrogenation reaction, the invention preferably further comprises the steps of cooling a cathode reaction product system of the electrocatalytic hydrogenation reaction to room temperature, extracting, and rectifying the obtained organic phase at normal pressure. The cooling mode is not particularly limited, and a cooling mode well known to those skilled in the art, such as natural cooling, may be adopted. In the present invention, the extractant for extraction preferably includes ethyl acetate, diethyl ether, chloroform or toluene, more preferably ethyl acetate; the amount of the extractant used in the present invention is not particularly limited, and may be any amount known to those skilled in the art. The conditions for the atmospheric distillation are not particularly limited, and the atmospheric distillation conditions well known to those skilled in the art may be employed. The method provided by the invention can obtain the target product KA oil through simple extraction and normal pressure rectification, has the advantages of small environmental pollution, easily available raw materials, simple and convenient operation, simple process flow and higher yield, and is suitable for industrial production.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Palladium nitrate (10.85 mg), chloroplatinic acid (10.51 mg) and 30mL deionized water are stirred and mixed for 30min to obtain a palladium-platinum mixed solution;
(2) Mixing 1g of titanium dioxide with the palladium-platinum mixed solution obtained in the step (1) for 10 hours at room temperature under stirring, adding 0.2mol/L sodium hydroxide solution to adjust the pH value to 10, coprecipitating for 1 hour under stirring, filtering, and drying the obtained solid product at 80 ℃ for 6 hours to obtain a catalyst precursor;
(3) Calcining the catalyst precursor in air at 500 ℃ for 4 hours, and then carrying out reduction reaction for 2 hours in a hydrogen atmosphere at 300 ℃ to obtain a palladium-platinum supported metal oxide catalyst (abbreviated as PdPt/TiO) 2 The palladium content was 0.5wt% and the platinum content was 0.4 wt%).
PdPt/TiO prepared in this example 2 As shown in FIG. 1, the Pd and Pt metal particles are relatively uniformly distributed, and the Pd and Pt metal particles have a particle size of about 4nm and a smaller particle size, as can be seen from FIG. 1.
Example 2
A palladium-platinum supported metal oxide catalyst was prepared in accordance with the method of example 1, which differs from example 1 in that the amount of palladium nitrate used was 6.55mg, and PdPt/TiO was obtained 2 The content of palladium in the catalyst was 0.3wt% and the content of platinum was 0.4wt%.
Example 3
A palladium-platinum supported metal oxide catalyst was prepared as in example 1, differing from example 1 in chloroplatinic acidThe amount of (C) was 6.31mg, and PdPt/TiO was obtained 2 The content of palladium in the catalyst was 0.5wt% and the content of platinum was 0.2wt%.
Example 4
A palladium-platinum supported metal oxide catalyst was prepared in accordance with the method of example 1, which differs from example 1 in that titanium dioxide was replaced with silicon dioxide, to obtain a palladium-platinum supported metal oxide catalyst (abbreviated as PdPt/SiO 2 The palladium content was 0.5wt% and the platinum content was 0.4 wt%).
Comparative example 1
A palladium-platinum supported metal oxide catalyst was prepared in accordance with the method of example 1, which differs from example 1 in that chloroplatinic acid was not added to give a palladium-supported metal oxide catalyst (Pd/TiO 2 The palladium content was 0.5 wt%).
Comparative example 2
A palladium-platinum supported metal oxide catalyst was prepared in accordance with the method of example 1, which differs from example 1 in that palladium nitrate was not added to obtain a platinum-supported metal oxide catalyst (Pt/TiO 2 The platinum content was 0.4 wt%).
Application example
(1) 4mg of the platinum-supported metal oxide catalysts prepared in examples 1 to 4 and comparative examples 1 to 2, 100. Mu.L of LNafion solution (mass percent: 5%) and 900. Mu.L of ethanol were ultrasonically mixed for 30 minutes, respectively, to obtain catalyst slurries; coating the obtained catalyst slurry on the surface of carbon cloth with the length of 2cm multiplied by 2cm to obtain a working electrode;
(2) The current and voltage are controlled by a constant current instrument, an H-shaped electrolytic tank is adopted, and a cathode chamber and an anode chamber are separated by a Nafion film; in an anode chamber with a volume of 10mL, a platinum sheet was used as an anode working electrode, and Na was used at a concentration of 0.2mol/L 2 SO 4 The solution was an anolyte, and p-chlorophenol was dissolved in 0.2mol/L Na in a cathode chamber having a volume of 10mL using the working electrode obtained in (1) as a cathode working electrode, respectively 2 SO 4 The solution was used as a catholyte (p-chlorophenol concentration 10mmol/L, na 2 SO 4 Concentration of 0.5 mol/L), the electrocatalytic hydrogenation reaction is carried out for 1h under the conditions of 60 ℃ temperature, 20mA current and 1.5V voltage, and the reaction is finishedAnd (3) cooling to obtain a KA oil crude product, extracting the KA oil crude product by using methylene dichloride, and rectifying the obtained organic phase at normal pressure to obtain the KA oil. Analysis of KA oil by gas chromatography the results of catalysts prepared in examples 1-4 and comparative examples 1-2 for parachlorophenol conversion and KA oil selectivity are shown in Table 1.
The detection condition of the gas chromatography is that the initial column temperature is 60 ℃, the temperature is kept for 2min, the temperature is raised to 260 ℃ at the speed of 20 ℃/min, the gasification temperature is 260 ℃, the detection temperature is 260 ℃, the pre-column pressure is 0.1MPa, the split ratio is 20:1, and the sample injection amount is 2 mu L.
TABLE 1 catalytic Effect of the catalysts prepared in examples 1 to 4 and comparative examples 1 to 2
| Catalyst source | Conversion of parachlorophenol (%) | KA oil Selectivity (%) |
| Example 1 | 98.2％ | 95.3％ |
| Example 2 | 75.8％ | 90.1％ |
| Example 3 | 91.4％ | 72.9％ |
| Example 4 | 90.5％ | 85.6％ |
| Comparative example 1 | 88.5％ | 10.5％ |
| Comparative example 2 | 18.6％ | 87.5％ |
As can be seen from Table 1, the palladium-platinum supported metal oxide catalyst prepared by the invention is applied to the hydrogenation of parachlorophenol to prepare KA oil, the conversion rate of parachlorophenol is 75.8-98.2%, and the selectivity of KA oil is 72.9-95.3%; as can be seen from comparison of example 1, comparative example 1 and comparative example 2, the conversion of parachlorophenol and KA oil selection were significantly reduced by loading only one of palladium and platinum. The palladium-platinum supported metal oxide catalyst provided by the invention is used for preparing KA oil by hydrogenating parachlorophenol, and has high conversion rate of parachlorophenol and high KA oil selectivity.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The application of an oxide-supported palladium-platinum catalyst in preparing KA oil by hydrogenating chlorophenols compounds is disclosed, wherein the oxide-supported palladium-platinum catalyst comprises an oxide and a palladium-platinum alloy supported on the surface of the oxide; the oxide comprises a metal oxide or a nonmetal oxide; the non-metal oxide comprises silicon dioxide; the metal oxide comprises titanium dioxide;
the content of the palladium-platinum alloy in the oxide-supported palladium-platinum catalyst is 0.2-6wt%;
the mass ratio of palladium to platinum in the palladium-platinum alloy is (0.1-4): (0.1-2).
2. The use according to claim 1, wherein the preparation method of the oxide supported palladium platinum catalyst comprises the following steps:
mixing a water-soluble palladium source, a water-soluble platinum source and water to obtain a palladium-platinum mixed solution;
mixing the palladium-platinum mixed solution with an oxide, adjusting the pH value to 8-14, and performing coprecipitation reaction to obtain a catalyst precursor;
and (3) calcining and reducing the catalyst precursor in sequence to obtain the oxide supported palladium-platinum catalyst.
3. The use according to claim 2, wherein the calcination is carried out at a temperature of 200-600 ℃ for a time of 1-8 hours.
4. The use according to claim 2, wherein the reducing agent utilized in the reduction reaction comprises hydrogen or a hydrogen-protective atmosphere gas mixture; the temperature of the reduction reaction is 100-600 ℃ and the time is 1-5 h.
5. The application of the working electrode in preparing KA oil by hydrogenating chlorophenols is characterized in that the working electrode comprises a matrix electrode and a modification layer coated on the working surface of the matrix electrode, wherein the modification layer is coated by a composition of an oxide-supported palladium-platinum catalyst, a perfluorinated sulfonic acid type polymer solution and an alcohol solvent;
the oxide-supported palladium-platinum catalyst comprises an oxide and a palladium-platinum alloy supported on the surface of the oxide; the oxide comprises a metal oxide or a nonmetal oxide; the non-metal oxide comprises silicon dioxide; the metal oxide comprises titanium dioxide; the content of the palladium-platinum alloy in the oxide-supported palladium-platinum catalyst is 0.2-6wt%; the mass ratio of palladium to platinum in the palladium-platinum alloy is (0.1-4): (0.1-2).
6. Root of Chinese characterThe use according to claim 5, wherein the oxide-supported palladium-platinum catalyst has a loading of 2-8 mg/cm on the substrate electrode 2 。
7. A battery system is characterized in that a platinum sheet is used as an anode working electrode, a salt solution is used as an anode liquid, the working electrode is used as a cathode working electrode, and the salt solution containing chlorinated phenol compounds is used as a cathode liquid;
the working electrode comprises a matrix electrode and a modification layer coated on the working surface of the matrix electrode, wherein the modification layer is obtained by coating a composition of an oxide-supported palladium-platinum catalyst, a perfluorinated sulfonic acid type polymer solution and an alcohol solvent;
the oxide-supported palladium-platinum catalyst comprises an oxide and a palladium-platinum alloy supported on the surface of the oxide; the oxide comprises a metal oxide or a nonmetal oxide; the non-metal oxide comprises silicon dioxide; the metal oxide comprises titanium dioxide; the content of the palladium-platinum alloy in the oxide-supported palladium-platinum catalyst is 0.2-6wt%; the mass ratio of palladium to platinum in the palladium-platinum alloy is (0.1-4): (0.1-2).
8. The use of the battery system of claim 7 in the preparation of KA oil by hydrogenation of chlorophenols.
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| CN108660479A (en) * | 2018-04-29 | 2018-10-16 | 浙江工业大学 | A kind of method that lignin-base phenolic compound electrocatalytic hydrogenation produces KA oil and its derivative |
| CN109939674A (en) * | 2019-04-25 | 2019-06-28 | 重庆工商大学 | A kind of Pd/TiO with Schottky hetero-junctions2Elctro-catalyst and its preparation and application |
| CN110280292A (en) * | 2019-07-09 | 2019-09-27 | 浙江工业大学 | A kind of compound Pt nanoparticle and metal nitride materials catalyst and its preparation method and application |
| CN110280239A (en) * | 2019-07-23 | 2019-09-27 | 西安凯立新材料股份有限公司 | A kind of synthesis 2,3- dichloropyridine catalyst and its preparation method and application |
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