CN110280240A - 一种碳纳米片负载贵金属纳米粒子催化剂及其制备方法和应用 - Google Patents
一种碳纳米片负载贵金属纳米粒子催化剂及其制备方法和应用 Download PDFInfo
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- CN110280240A CN110280240A CN201910617257.4A CN201910617257A CN110280240A CN 110280240 A CN110280240 A CN 110280240A CN 201910617257 A CN201910617257 A CN 201910617257A CN 110280240 A CN110280240 A CN 110280240A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 117
- 239000002135 nanosheet Substances 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 50
- 239000010970 precious metal Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 52
- 239000002243 precursor Substances 0.000 claims abstract description 45
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000006193 liquid solution Substances 0.000 claims abstract description 6
- 239000006194 liquid suspension Substances 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- -1 alkyl compound Chemical class 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- PVNIQBQSYATKKL-UHFFFAOYSA-N Glycerol trihexadecanoate Natural products CCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCC PVNIQBQSYATKKL-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000010948 rhodium Substances 0.000 description 16
- 235000002639 sodium chloride Nutrition 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229940045870 sodium palmitate Drugs 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 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
- B01J23/38—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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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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- 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
-
- 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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- Manufacturing & Machinery (AREA)
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Abstract
本发明公开了一种碳纳米片负载贵金属纳米粒子催化剂及其制备方法和应用,以无机盐为模板,提供商用碳源,并在所述商用碳前驱体上至少沉积至少具有多催化前景的贵金属而形成复合物,然后经过化学或物理方法得到所述碳纳米片负载贵金属纳米粒子催化剂,其特征在于包括:(1)、将商用贵金属前驱体溶解或分散于溶剂中,形成贵金属前驱体溶液或悬浮液;(2)、将商用碳前驱体与所述贵金属前驱体溶液或悬浮液混合均匀,后混入无机盐模板,经干燥后在惰性气氛中煅烧,从而获得碳纳米片负载贵金属纳米粒子催化剂。该催化剂能有效解决贵金属纳米粒子在商用化应用中不稳定性的问题,显著提升催化的性能,且其制备工艺可控、环境友好,适合大规模生产。
Description
技术领域
本发明涉及一种催化剂,尤其涉及一种碳负载贵金属纳米粒子催化剂及其制备方法和应用,属于能源、材料技术领域。
背景技术
贵金属由于其优异的化学稳定性而广泛应用于燃料电池、催化加氢、汽车尾气处理等能源环境相关领域,目前大量研究人员均致力于减少贵金属的用量而实现高效、高稳定催化性能。随和纳米技术的飞速发展,贵金属纳米粒子相比其块体原子利用率高、催化性能更加优越。但是其循环稳定性制约着其高性能的持续发挥。将贵金属纳米材料稳定在无机氧化物、金属氧化物或碳质载体上可以有效地抑制金属纳米粒子的团聚,并且也是研究人员的研究热点之一。
现有技术中,CN201410759362.9《嵌入式纳米金属负载型碳纳米片锂离子电池负极材料及其制备方法和应用》,以糖(壳聚糖、蔗糖、果糖和葡萄糖)为碳源,过渡金属(Fe,Co,Ni)的硝酸盐为金属源和催化剂,以惰性盐(硫酸钠、氯化钠、氯化钾和氯化铯)为模板和分散剂,采用热解法一步制备得到了均匀负载嵌入式镍(或铁或钴)纳米颗粒的二维碳纳米片。
CN201811281542.5《一种三维连续碳骨架负载的金属-氮-碳纳米片的制备方法及应用》,以三聚氰胺泡沫为模板,在含有金属盐的溶液中将苯胺原位聚合为片层状聚苯胺,并分立于三聚氰胺泡沫表面,再将其进行高温碳化,得到具有分级结构的多孔金属-氮-碳复合材料。与现有技术相比,三聚氰胺泡沫和其表面的聚苯胺纳米片形成三维立体结构,碳化后形成的金属-氮-碳复合材料形成三维立体多级孔结构,该结构有助于加速反应中物质传输速率,使暴露更多活性位,提高了活性位利用率。
CN201810843538.7《一种纳米银/碳复合光催化材料及其制备方法和应用》,包括如下步骤:将维生素C用水溶解后,以每分钟8~12℃的速率加热至180~220℃,并保持2~5h;离心、透析、分离,得到碳纳米点CDs;将硝酸银和碳纳米点CDs避光溶解在水中,在紫外光照射下反应,即可得到纳米银/碳复合光催化剂Ag/CDs。
其中,CN201410555642.8《一种碳纳米管复合材料及其制备方法和应用》,涉及一种嵌有贵金属纳米粒子的碳层包覆碳纳米管的复合材料的制备方法和应用。是一种嵌有贵金属纳米粒子的碳层包覆碳纳米管的复合材料,由碳纳米管和包覆在所述碳纳米管外的碳层组成,并且碳层嵌有贵金属纳米粒子。碳层为氮掺杂碳层。嵌入在碳层(如氮掺杂碳层)中的贵金属纳米粒子的粒径为0.1~20纳米,贵金属选自铂、钯、铑、钌和金中的一种或两种以上的组合。复合材料中贵金属的重量百分含量为1-30%,碳纳米管的长度可为0.1~30微米,直径可为1~80纳米,碳层(如氮掺杂碳层)的厚度可为0.1~3纳米,碳层(如氮掺杂碳层)的表面中氮原子的原子百分比为1~10wt%,碳层(如氮掺杂碳层)中的氮的种类有吡啶型氮、石墨型氮和吡咯型氮中的至少一种。制备的复合材料可作为燃料电池的阴极氧还原催化剂使用,其催化稳定性明显优于单纯的材料以及目前使用的商业化碳载铂催化剂。
发明内容
本发明的主要目的在于提供一种碳纳米片负载贵金属纳米粒子催化剂及其制备方法和应用,以提升贵金属纳米粒子催化性能,克服现有技术中的不足。
为了达到上述发明目的,本发明采用的技术方案之一:
一种碳纳米片负载贵金属纳米粒子催化剂的制备方法,以无机盐为模板,提供商用碳源,并在所述商用碳前驱体上至少沉积至少具有多催化前景的贵金属而形成复合物,然后经过化学或物理方法得到所述碳纳米片负载贵金属纳米粒子催化剂,包括:
(1)、将商用贵金属前驱体溶解或分散于溶剂中,形成贵金属前驱体溶液或悬浮液;
(2)、将商用碳前驱体与所述贵金属前驱体溶液或悬浮液混合均匀,后混入无机盐模板,经干燥后在惰性气氛中煅烧,所得产物经水洗而获得碳纳米片负载贵金属纳米粒子催化剂;
其中,贵金属负载量质量百分数根据催化剂应用所需要求而定,贵金属负载量与碳的负载量合计为100%。
进一步,溶剂为易挥发或者加热易挥发;商用贵金属前驱体为含多种贵金属元素的化合物粉体,在溶剂加热挥发过程中,商用贵金属前驱体不分解。
进一步,碳纳米片负载贵金属纳米粒子催化剂中贵金属负载量质量百分数为1%~60%。
进一步,为了改善所得碳纳米片的孔隙率,商用贵金属前驱体和商用碳前驱体的质量比为1:1~100;无机盐加入的量比商用贵金属前驱体和商用碳前驱体质量之和比为10~50:1。
进一步,所述无机盐模板包括硫酸盐、碳酸盐、磷酸盐或卤化物;
所述商用碳前驱体为长链烷基化合物,包括油酸钠、十二烷基硫酸钠、硬脂酸钠或软脂酸钠,碳纳米片由商用碳前驱体提供;
所述商用贵金属前驱体为化学惰性金属,其贵金属元素包括Au、Ag、Ru、Rh、Pd、Os、Ir、Pt中的一种或多种元素。
进一步,所属商用贵金属前驱体还包括卤化物和/或配合物等。
进一步,所述碳纳米片载体的微观形态为片形,粒径在200nm-20μm,厚度在4nm~100nm,贵金属纳米粒子的大小在2nm-50nm,贵金属的含量在0.5wt%~10wt%。
进一步,贵金属纳米粒子前驱体与商用碳前驱体通过包括匀浆搅拌、旋涂、浸渍或喷雾方法混合复合均匀。
优选的,所述无机盐为NaCl、KCl、Na2SO4。
优选的,所述商用碳前驱体可仅为油酸钠。
碳纳米片载体粒径优选为200nm-1μm,尤其优选为200nm-500nm,厚度优选为4nm~100nm,尤其优选为4nm~50nm。
考虑到碳纳米片载体的质量对催化性能的影响,优选为2wt%~10wt%,尤其优选为2wt%~5wt%。
本发明采用的技术方案之二:上述制备方法制备的碳纳米片负载贵金属纳米粒子催化剂。
本发明采用的技术方案之三:上述述制备方法制备的碳纳米片负载贵金属纳米粒子催化剂在燃料电池氧还原反应中的应用。
与现有技术相比,本发明的优点包括:
(1)通过采用商用的含碳前躯体及商用贵金属前驱体等作为原料,通过简单工艺形成了碳纳米片负载贵金属纳米粒子催化剂,其工艺简单可控,原料来源广泛,成本低廉,利于大规模实施;
(2)在获得的碳纳米片负载贵金属纳米粒子催化剂中,商用含碳前躯体可作为基本骨架形成碳,然后贵金属纳米粒子在碳上均匀沉积的,催化过程中贵金属得到极大的利用;
(3)该碳纳米片负载贵金属纳米粒子催化剂在应用催化时,如燃料电池氧还原反应,能显著改善和提升催化效率和循环稳定性。
以CN201410555642.8为例对比分析,本发明直接用廉价的商用碳源大规模制备超薄碳纳米片,无需高昂的碳纳米管,且无机盐模板热稳定性高,可高温煅烧获得石墨化程度高的碳片,且无机盐模板可缓解碳片和贵金属纳米颗粒在煅烧过程中的烧结作用,无机盐模板加入量可科学合理地控制,且易处理,可循环使用。碳源的可选择性广,易产生杂原子掺杂的碳,且贵金属前驱体与商用碳前驱体之间的相互作用使得贵金属纳米粒子负载在碳纳米片上,稳定贵金属纳米粒子,最终协同提升复合材料的性能。
附图说明
图1是本发明一典型实施方案之中一种碳纳米片负载贵金属纳米粒子催化剂的结构示意图;
图2是本发明实施例1中碳纳米片负载Ru纳米粒子的SEM电镜照片;
图3是本发明实施例2中碳纳米片负载Rh纳米粒子的TEM电镜照片对比图;
图4是本发明实施例3中碳纳米片负载Rh纳米粒子的SEM电镜照片
图5是本发明实施例1中碳纳米片负载Ru纳米粒子的XRD图片;
图6是本发明实施例2中碳纳米片负载Rh纳米粒子的XRD图片;
图7是本发明实施例3中碳纳米片负载Rh纳米粒子的XRD图片;
图8是本发明实施例2中碳纳米片负载Rh纳米粒子的在0.1MKOH溶液中的氧还原LSV性能比较图;
图9是本发明实施例2中碳纳米片负载Rh纳米粒子催化剂在0.1M KOH溶液中的氧还原循环稳定性比较图。
具体实施方式
本发明的一个方面提供了一种碳纳米片负载贵金属纳米粒子催化剂,其主要由两部分组成,请参阅图1,其中一部分为碳纳米片载体;另一部分为主要由沉积在碳载体上的贵金属纳米粒子。
本发明的另一个方面提供了一种制备所述碳纳米片负载贵金属纳米粒子催化剂的方法,其主要包括:以无机盐为模板,将商用碳前驱体上至少沉积至少具有多催化前景的贵金属形成复合物,然后经过化学或物理方法得到所述碳纳米片负载贵金属纳米粒子催化剂。
本发明的再一个方面提供所述碳纳米片负载贵金属纳米粒子催化剂于催化(如催化加氢,燃料电池等)中的应用。
以下通过若干实施例及附图更为直观地说明本发明的技术方案,以便本领域技术人员更容易理解本发明的创新实质。
实施例1,将207.4mgRuCl3溶于2mL去离子水中,搅拌下加入1.22g油酸钠,为了使其混合均匀,90℃下搅拌两小时后加入10gNa2SO4,烘干放入管式炉中惰性气氛下500℃下煅烧3h,煅烧完后水洗烘干所得碳纳米片负载的Ru纳米粒子催化剂。
实施例2,将263.3mgRhCl3溶于2mL去离子水中,搅拌下加入1.22g油酸钠,为了使其混合均匀,90℃下搅拌两小时后加入10gNa2SO4,烘干放入管式炉中惰性气氛下500℃下煅烧3h,煅烧完后水洗烘干所得碳纳米片负载的Rh纳米粒子催化剂。图3是碳纳米片负载Rh纳米粒子的TEM电镜照片;a是放大后的低分辨透射电镜照片,b正常低分辨透射电镜照片,c为高分辨透射电镜照片。
实施例3,将293.2mgNa4Rh2(CO3)4·2.5H2O溶于2mL去离子水中,搅拌下加入1.22g油酸钠,为了使其混合均匀,90℃下搅拌两小时后加入10gNa2SO4,烘干放入管式炉中惰性气氛下500℃下煅烧3h,煅烧完后水洗烘干所得碳纳米片负载的Rh纳米粒子催化剂。
实施例4,取5mg实施实例2的碳纳米片负载的Rh纳米粒子催化剂超声分散于0.95mL无水乙醇中,然后加入0.5mL的商用的5wt%的Nafion溶液,制成均匀的催化剂墨水。去20μL上述碳纳米片负载的Rh纳米粒子催化剂滴在直径为5mm的旋转圆盘玻碳电极上,60℃下烘干。然后以饱和的Ag/AgCl为参比电极,Pt丝为对电极,滴有纳米片负载的Rh纳米粒子催化剂的玻碳电极为工作电极,在0.1MKOH电解液中通入高纯氧气进行相应的电化学测试。商用的Rh/C(国产或进口试剂5wt%Rh)和商用的Pt/C(10wt%Pt)催化剂均采用相同的条件进行制样和测试。
尤其需要说明的是,本发明首次盐作为模板,采用长链的烷基化合物作为碳源与贵金属前驱体混合后经过相应的化学处理得到碳纳米片负载的贵金属纳米粒子催化剂,其催化效果优于其相应的商用的碳载的贵金属催化剂,这主要是由于碳纳米片优异的二维结构有利于电子和离子的快速输运,另外其稳定性也大大地提升。
本发明碳纳米片负载贵金属纳米粒子催化剂的制备工艺简单,安全,成本低,并可扩展到碳载的金属或金属氧化物材料中,对于制备高效、高稳定性的催化剂具有极大价值。
应当理解,上述实例仅为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种碳纳米片负载贵金属纳米粒子催化剂的制备方法,以无机盐为模板,提供商用碳源,并在所述商用碳前驱体上至少沉积至少具有多催化前景的贵金属而形成复合物,然后经过化学或物理方法得到所述碳纳米片负载贵金属纳米粒子催化剂,其特征在于包括:
(1)、将商用贵金属前驱体溶解或分散于溶剂中,形成贵金属前驱体溶液或悬浮液;
(2)、将商用碳前驱体与所述贵金属前驱体溶液或悬浮液混合均匀,后混入无机盐模板,经干燥后在惰性气氛中煅烧,所得产物经水洗而获得碳纳米片负载贵金属纳米粒子催化剂;
其中,贵金属负载量质量百分数根据催化剂应用所需要求而定,贵金属负载量与碳的负载量合计为100%。
2.根据权利要求1所述的一种碳纳米片负载贵金属纳米粒子催化剂的制备方法,其特征在于,溶剂为易挥发或者加热易挥发;商用贵金属前驱体为含多种贵金属元素的化合物粉体,在溶剂加热挥发过程中,商用贵金属前驱体不分解。
3.根据权利要求1所述的一种碳纳米片负载贵金属纳米粒子催化剂的制备方法,其特征在于,碳纳米片负载贵金属纳米粒子催化剂中贵金属负载量质量百分数为1%~60%。
4.根据权利要求1所述的一种碳纳米片负载贵金属纳米粒子催化剂的制备方法,其特征在于,为了改善所得碳纳米片的孔隙率,商用贵金属前驱体和商用碳前驱体的质量比为1: 1~100;无机盐加入的量比商用贵金属前驱体和商用碳前驱体质量之和比为10~50:1。
5.根据权利要求1所述的一种碳纳米片负载贵金属纳米粒子催化剂的制备方法,其特征在于,所述无机盐模板包括硫酸盐、碳酸盐、磷酸盐或卤化物;
所述商用碳前驱体为长链烷基化合物,包括油酸钠、十二烷基硫酸钠、硬脂酸钠或软脂酸钠,碳纳米片由商用碳前驱体提供;
所述商用贵金属前驱体为化学惰性金属,其贵金属元素包括Au、Ag、Ru、Rh、Pd、Os、Ir、Pt中的一种或多种元素。
6.根据权利要求5所述的一种碳纳米片负载贵金属纳米粒子催化剂的制备方法,其特征在于,所属商用贵金属前驱体还包括卤化物和/或配合物。
7.根据权利要求1所述的一种碳纳米片负载贵金属纳米粒子催化剂的制备方法,其特征在于,所述碳纳米片载体的微观形态为片形,粒径在200nm-20μm,厚度在4nm~100nm,贵金属纳米粒子的大小在2nm-50nm,贵金属的含量在0.5wt%~10wt%。
8.根据权利要求1所述的一种碳纳米片负载贵金属纳米粒子催化剂的制备方法,其特征在于,贵金属纳米粒子前驱体与商用碳前驱体通过包括匀浆搅拌、旋涂、浸渍或喷雾方法,混合复合均匀。
9.权利要求1-8中任一项所述制备方法制备的碳纳米片负载贵金属纳米粒子催化剂。
10.权利要求1-8中任一项所述制备方法制备的碳纳米片负载贵金属纳米粒子催化剂在燃料电池氧还原反应中的应用。
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CN112973688B (zh) * | 2019-12-13 | 2022-07-26 | 中国科学院大连化学物理研究所 | 一种离子交换树脂基负载金属炭小球及制备方法 |
CN111482169A (zh) * | 2020-04-14 | 2020-08-04 | 中北大学 | 负载贵金属的纳米光催化剂及其制备方法和应用 |
CN111482169B (zh) * | 2020-04-14 | 2023-04-18 | 中北大学 | 负载贵金属的纳米光催化剂及其制备方法和应用 |
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CN112973759A (zh) * | 2021-03-10 | 2021-06-18 | 中国石油大学(华东) | 金属单原子催化剂的制备方法、金属单原子催化剂和应用 |
CN113140741A (zh) * | 2021-04-01 | 2021-07-20 | 邵阳学院 | 一种碳包覆的PtPdIr/C氧还原电催化剂及其制备方法和应用 |
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