CN111659416A - 一种含锶或其化合物的铂基催化剂 - Google Patents
一种含锶或其化合物的铂基催化剂 Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 34
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 15
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 150000003438 strontium compounds Chemical class 0.000 title description 2
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000013543 active substance Substances 0.000 claims abstract 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 50
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 4
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910002666 PdCl2 Inorganic materials 0.000 description 4
- 239000011865 Pt-based catalyst Substances 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910017398 Au—Ni Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- 229910018949 PtAu Inorganic materials 0.000 description 1
- 229910002837 PtCo Inorganic materials 0.000 description 1
- 229910002844 PtNi Inorganic materials 0.000 description 1
- -1 PtPd Inorganic materials 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- 229910002847 PtSn Inorganic materials 0.000 description 1
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
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- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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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- 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
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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
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
- H01M4/923—Compounds thereof with non-metallic elements
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- H—ELECTRICITY
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明属于催化剂技术领域，涉及一种含锶或其化合物的铂基催化剂。所述的铂基催化剂包含催化活性物质与催化辅助物质，所述的催化活性物质包含金属铂，所述的催化辅助物质包含助催化剂，所述的助催化剂包含Sr‑90的单质或化合物中的一种或几种。本发明的含锶或其化合物的铂基催化剂具有更好的催化性能与稳定性。
Description
技术领域
本发明属于催化剂技术领域，涉及一种含锶或其化合物的铂基催化剂。
背景技术
催化剂材料与催化技术是当今化学工业发展的基础性、关键性的材料和技术之一。现代工业中，利用催化技术所产生的产值已占国民经济总产值的约30％。
贵金属Pt外层电子排布是5d86s2，其次外层共8个d电子，轨道未被填满。且由于能级中含有未成对电子，故Pt在物理性质中能够表现出较强的铁磁性或顺磁性；而在化学吸附的过程中，Pt的这些d电子能够与被吸附物中的p电子或s电子配对，发生化学吸附，生成中间产物，从而使被吸附的分子活化。
现代工业中，铂催化剂主要用于无机化工、石油精炼、有机化工、C1化工、精细化工、汽车尾气和工业气体的净化治理，以及燃料电池与传感器等领域，因而在工业催化、环境保护和绿色能源技术方面有着非常重要的地位，并显示了广阔的应用前景。
但纯Pt作为催化剂有3个主要的缺点，即利用率低、抗中毒能力低以及价格高昂。针对这些缺点，世界范围内大量的研究致力于开发高活性铂催化剂和降低铂催化剂用量，以提高Pt催化剂的催化活性、选择性，并延长其寿命。
关于Pt催化剂，目前主要的研究方向有：
1、一元Pt基催化剂
一元Pt基催化剂的研究方向集中在寻找具有优良性能的催化剂载体及改变Pt颗粒的大小、表面状态。例如Zhu等采用功能化多壁碳纳米管分散在聚苯胺中作为载体，合成了Pt/MWCNT/PAN分散性良好的催化剂。研究结果表明，与单纯聚苯胺为载体催化剂相比，该催化剂表现出较高的催化活性。又如Wu等制备了“壳核”结构的纳米碳材料，以炭黑颗粒为“核”负载，以型掺杂的石墨层为“壳”，这种催化剂具有较高的催化活性。又如Zhang等通过无模板电沉积法制备了形貌新颖的纳米花，其形貌具有多孔性，能够提供更大的活性中心。
2、二元Pt基催化剂
在纯Pt催化剂中加入第二种易吸附含氧物质的金属，制备合金型催化剂，将提高催化剂的抗中毒性，进而大大提高催化剂的性能。目前研究较多且催化效果较好的Pt基二元催化剂有PtRu、PtPd、PtSn、PtAu、PtNi、PtCo和金属氧化物(Pt+MOx，其中M＝Ti、W、Zr、Ce、Ta)等复合催化剂。
3、多元Pt基催化剂
研究者尝试通过添加第三种甚至第四种金属对Pt基合金改进，从而提高其催化活性。例如Park等研究了Pt/Ni、Pt/Ru/Ni纳米催化剂在甲醇氧化过程中的电子效应与化学效应。又如Jeon等人合成了PtCoCr三元催化剂，其实验结果表明Pt30Co30Cr40对甲醇电氧化性、稳定性及催化效果十分良好，是非常优异的甲醇电氧化催化剂。
综上所述，虽然在贵金属Pt催化领域科学家们已经开展了多项工作，但不同方法各有优劣。且这些Pt催化材料工业化的应用仍面临着很多挑战，比如大规模可控的合成方法、催化材料的稳定性、金属负载量的精确调控、催化剂抗中毒能力，以及如何更好地将金属材料先进的制备方法同碳负载材料有力的结合起来等等。因此，对贵金属Pt催化开发新的思路迫在眉睫。
发明内容
本发明的目的是提供一种含锶或其化合物的铂基催化剂，以能够具有更好的催化性能与稳定性。
为实现此目的，在基础的实施方案中，本发明提供一种含锶或其化合物的铂基催化剂，所述的铂基催化剂包含催化活性物质与催化辅助物质，所述的催化活性物质包含金属铂，所述的催化辅助物质包含助催化剂，所述的助催化剂包含Sr-90的单质或化合物中的一种或几种(该铂基催化剂可用于燃料电池)。
在一种优选的实施方案中，本发明提供一种含锶或其化合物的铂基催化剂，其中所述的催化活性物质与所述的催化辅助物质的质量比为1:0.01-10。
在一种优选的实施方案中，本发明提供一种含锶或其化合物的铂基催化剂，其中所述的催化活性物质与所述的助催化剂的质量比为1:0.0001-1。
在一种优选的实施方案中，本发明提供一种含锶或其化合物的铂基催化剂，其中所述的助催化剂还包含选自金、银、钴、镍、钯、钌、锡、铋、铜、铁、铱、锰、钼、铑、钨、锌的单质或氧化物中的一种或几种。
在一种优选的实施方案中，本发明提供一种含锶或其化合物的铂基催化剂，其中所述的催化辅助物质还包含催化剂载体，选自活性炭、碳化硅、三氧化二铝、石墨烯、二氧化硅、沸石中的一种或几种。
在一种优选的实施方案中，本发明提供一种含锶或其化合物的铂基催化剂，其中所述的化合物为无机化合物或有机化合物。
在一种优选的实施方案中，本发明提供一种含锶或其化合物的铂基催化剂，其中所述的化合物为氧化物。
本发明的有益效果在于，本发明的含锶或其化合物的铂基催化剂具有更好的催化性能与稳定性。
具体实施方式
以下通过实施例对本发明的具体实施方式作出进一步的说明。
实施例1：制备实施例
以同位素分离法的原理，通过中国原子能科学研究院核技术所CAE-1型磁分离装置分离天然同位素丰度的SrO，具体操作条件为：汽化温度2500度，磁场电压1000伏，磁分离参数Sr-90-100。在出料口收取分离后的SrO，通过ICP-MS检测，Sr-90丰度为100％，由此制得90SrO(以下实施例同理制备90SrO)。
取0.6g Vulcan XC-72碳粉，0.1g 90SrO粉末，10.25mL的H2PtCl6(0.1mol/L)溶液和17.04mL的NiSO4(0.1mol/L)溶液混合加入到80mL去离子水中，超声30min使其分散均匀，然后在搅拌下，用1mol/L的NaOH溶液调节pH值至8-9后，缓慢加入过量2.0mg/mL的NaBH4溶液，继续搅拌3h。用超纯水洗涤至无Cl-后，于60℃下真空干燥4h，得到Pt-Ni-90SrO/C催化剂。
实施例2：对照制备实施例
取0.6g Vulcan XC-72碳粉，10.25mL的H2PtCl6(0.1mol/L)溶液和17.04mL的NiSO4(0.1mol/L)溶液混合加入到80mL去离子水中，超声30min使其分散均匀，然后在搅拌下，用1mol/L的NaOH溶液调节pH值至8-9后，缓慢加入过量2.0mg/mL的NaBH4溶液，继续搅拌3h。用超纯水洗涤至无Cl-后，于60℃下真空干燥4h，得到Pt-Ni/C催化剂。
实施例3：制备实施例
取0.6g Vulcan XC-72碳粉，0.1g 90SrO粉末，与80mL乙二醇加入250mL烧杯中，超声振荡2h，滴加10.25mL的H2PtCl6(0.1mol/L)溶液和16.97mL的CoCl2(0.1mol/L)溶液，再加入21mL甲酸，室温搅拌30min，放入微波炉中加热20s停10s反复5次，然后加热10s停10s反复5次，冷却抽滤，真空烘干，得到Pt-Co-90SrO/C催化剂。
实施例4：对照制备实施例
取0.6g Vulcan XC-72碳粉，与80mL乙二醇加入250mL烧杯中，超声振荡2h，滴加10.25mL的H2PtCl6(0.1mol/L)溶液和16.97mL的CoCl2(0.1mol/L)溶液，再加入21mL甲酸，室温搅拌30min，放入微波炉中加热20s停10s反复5次，然后加热10s停10s反复5次，冷却抽滤，真空烘干，得到Pt-Co/C催化剂。
实施例5：制备实施例
取0.6g Vulcan XC-72碳粉与0.1g 90SrO粉末加入到HCOOH含量为0.7mol的水溶液中，超声30min后，将所得的悬浊液加热至80℃，在不断搅拌下，将10.25mL的H2PtCl6(0.1mol/L)溶液和9.4mL的PdCl2(0.1mol/L)溶液滴加到悬浊液中。继续在80℃搅拌2h，以保证Pd和Pt完全被还原。冷却后，用超纯水抽滤洗涤多次，直至无Cl-为止。最后，将所得催化剂放在60℃烘箱中真空干燥，得到Pt-Pd-90SrO/C催化剂。
实施例6：对照制备实施例
取0.6g Vulcan XC-72碳粉加入到HCOOH含量为0.7mol的水溶液中，超声30min后，将所得的悬浊液加热至80℃，在不断搅拌下，将10.25mL的H2PtCl6(0.1mol/L)溶液和9.4mL的PdCl2(0.1mol/L)溶液滴加到悬浊液中。继续在80℃搅拌2h，以保证Pd和Pt完全被还原。冷却后，用超纯水抽滤洗涤多次，直至无Cl-为止。最后，将所得催化剂放在60℃烘箱中真空干燥，得到Pt-Pd/C催化剂。
实施例7：制备实施例
取0.6g Vulcan XC-72活性炭，0.1g 90SrO粉末，10.25mL的H2PtCl6(0.1mol/L)溶液、5.08mL的HAuCl4(0.1mol/L)溶液和17.04mL的NiSO4(0.1mol/L)溶液混合加入到80mL超纯水中，将所得的悬浊液超声1h。再加入200mL乙二醇(EG)溶液，超声1h后，将所得溶液在水浴加热到90℃，并不断搅拌4h。冷却至室温过滤后，将所得催化剂用蒸馏水和乙醇混合溶液清洗几次，60℃真空干燥，得到Pt-Au-Ni-90SrO/C催化剂。
实施例8：对照制备实施例
取0.6g Vulcan XC-72活性炭，10.25mL的H2PtCl6(0.1mol/L)溶液、5.08mL的HAuCl4(0.1mol/L)溶液和17.04mL的NiSO4(0.1mol/L)溶液混合加入到80mL超纯水中，将所得的悬浊液超声1h。再加入200mL乙二醇(EG)溶液，超声1h后，将所得溶液在水浴加热到90℃，并不断搅拌4h。冷却至室温过滤后，将所得催化剂用蒸馏水和乙醇混合溶液清洗几次，60℃真空干燥，得到Pt-Au-Ni/C催化剂。
实施例9：制备实施例
取0.6g的棕黄色氧化石墨烯，0.1g 90SrO粉末加入到50mL去离子水中，超声分散30min，用移液枪移取10.25mL的H2PtCl6(0.1mol/L)溶液、17.04mL的NiSO4(0.1mol/L)溶液和15.74mL的CuCl2(0.1mol/L)溶液混合加入到氧化石墨烯溶液中，搅拌10min后移入双口烧瓶中，加入9.5mL去离子水，在0℃，N2气气氛下混合均匀后，用注射器快速注入5mL7.72mmol/L的KBH4溶液，溶液颜色由棕黄色变为黑色，继续在0℃，N2气气氛下搅拌30min使其充分反应，最后抽滤洗涤，烘干研磨，得到Pt-Ni-Cu-90SrO/C催化剂。
实施例10：对照制备实施例
取0.6g的棕黄色氧化石墨烯加入到50mL去离子水中，超声分散30min，用移液枪移取10.25mL的H2PtCl6(0.1mol/L)溶液、17.04mL的NiSO4(0.1mol/L)溶液和15.74mL的CuCl2(0.1mol/L)溶液混合加入到氧化石墨烯溶液中，搅拌10min后移入双口烧瓶中，加入9.5mL去离子水，在0℃，N2气气氛下混合均匀后，用注射器快速注入5mL 7.72mmol/L的KBH4溶液，溶液颜色由棕黄色变为黑色，继续在0℃，N2气气氛下搅拌30min使其充分反应，最后抽滤洗涤，烘干研磨，得到Pt-Ni-Cu/C催化剂。
实施例11：制备实施例
取0.6g Vulcan XC-72活性炭，0.1g 90SrO粉末，加入超纯水与异丙醇(体积比2:1)的混合溶液中，超声分散0.5h。再依次滴加10.25mL的H2PtCl6(0.1mol/L)溶液、9.4mL的PdCl2(0.1mol/L)溶液和15.74mL的CuCl2(0.1mol/L)溶液和20mg柠檬酸钠，搅拌1h。调节溶液PH>12，升温至80℃，缓慢滴加0.2mol/L过量的硼氢化钠溶液，保持2h。随后室温下继续搅拌3h，抽滤洗涤，60℃鼓风烘干，得到Pt-Pd-Cu-90SrO/C催化剂。
实施例12：对照制备实施例
取0.6g Vulcan XC-72活性炭，加入超纯水与异丙醇(体积比2:1)的混合溶液中，超声分散0.5h。再依次滴加10.25mL的H2PtCl6(0.1mol/L)溶液、9.4mL的PdCl2(0.1mol/L)溶液和15.74mL的CuCl2(0.1mol/L)溶液和20mg柠檬酸钠，搅拌1h。调节溶液PH>12，升温至80℃，缓慢滴加0.2mol/L过量的硼氢化钠溶液，保持2h。随后室温下继续搅拌3h，抽滤洗涤，60℃鼓风烘干，得到Pt-Pd-Cu/C催化剂。
实施例13：稳定性测试实施例
分别测定实施例1-12获得的催化剂的稳定性，具体方法为：使用电化学工作站三电极体系测试催化剂的I-t曲线，并依此判断催化剂稳定性，其中滴涂催化剂的玻碳电极做工作电极，饱和甘汞电极做参比电极，铂丝电极做对电极。待测溶液为0.5mol/L C2H5OH+0.5mol/L H2SO4，测试之前向溶液中通15分钟高纯氮气，以排除氧气干扰。所有催化剂的测试电位统一为0.6V，测试时间为1000s。结果如下表1所示。
表1催化剂稳定性测试结果
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若对本发明的这些修改和变型属于本发明权利要求及其同等技术的范围之内，则本发明也意图包含这些改动和变型在内。上述实施例或实施方式只是对本发明的举例说明，本发明也可以以其它的特定方式或其它的特定形式实施，而不偏离本发明的要旨或本质特征。因此，描述的实施方式从任何方面来看均应视为说明性而非限定性的。本发明的范围应由附加的权利要求说明，任何与权利要求的意图和范围等效的变化也应包含在本发明的范围内。
Claims (7)
1.一种含锶或其化合物的铂基催化剂，其特征在于：所述的铂基催化剂包含催化活性物质与催化辅助物质，所述的催化活性物质包含金属铂，所述的催化辅助物质包含助催化剂，所述的助催化剂包含Sr-90的单质或化合物中的一种或几种。
2.根据权利要求1所述的铂基催化剂，其特征在于：所述的催化活性物质与所述的催化辅助物质的质量比为1:0.01-10。
3.根据权利要求1所述的铂基催化剂，其特征在于：所述的催化活性物质与所述的助催化剂的质量比为1:0.0001-1。
4.根据权利要求1所述的铂基催化剂，其特征在于：所述的助催化剂还包含选自金、银、钴、镍、钯、钌、锡、铋、铜、铁、铱、锰、钼、铑、钨、锌的单质或氧化物中的一种或几种。
5.根据权利要求1所述的铂基催化剂，其特征在于：所述的催化辅助物质还包含催化剂载体，选自活性炭、碳化硅、三氧化二铝、石墨烯、二氧化硅、沸石中的一种或几种。
6.根据权利要求1所述的铂基催化剂，其特征在于：所述的化合物为无机化合物或有机化合物。
7.根据权利要求1所述的铂基催化剂，其特征在于：所述的化合物为氧化物。
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Application publication date: 20200915 |