CN105536814B - 一种核壳结构催化剂的制备方法 - Google Patents
一种核壳结构催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 52
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000010941 cobalt Substances 0.000 claims abstract description 38
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 37
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 24
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 16
- -1 transition metal salt Chemical class 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 68
- 239000007864 aqueous solution Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 37
- 238000004140 cleaning Methods 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 28
- 239000001301 oxygen Substances 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 26
- 239000003381 stabilizer Substances 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 229910001868 water Inorganic materials 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 229920003081 Povidone K 30 Polymers 0.000 claims description 16
- 238000002604 ultrasonography Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229920003082 Povidone K 90 Polymers 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- NVEUWWMNWPNXOC-UHFFFAOYSA-N 2,2-dimethyltridecane Chemical compound CCCCCCCCCCCC(C)(C)C NVEUWWMNWPNXOC-UHFFFAOYSA-N 0.000 claims description 6
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000002045 lasting effect Effects 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 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
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910001260 Pt alloy Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910000923 precious metal alloy Inorganic materials 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 130
- 239000007789 gas Substances 0.000 description 68
- 229910052786 argon Inorganic materials 0.000 description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 235000019441 ethanol Nutrition 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 239000002105 nanoparticle Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000006227 byproduct Substances 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 206010013786 Dry skin Diseases 0.000 description 12
- 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 12
- 239000011734 sodium Substances 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 235000013339 cereals Nutrition 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 230000006641 stabilisation Effects 0.000 description 8
- 238000011105 stabilization Methods 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 238000006197 hydroboration reaction Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000002122 magnetic nanoparticle Substances 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 206010020880 Hypertrophy Diseases 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910002837 PtCo Inorganic materials 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- LXWRTCKMRTXLRZ-UHFFFAOYSA-L dichlorocobalt;ethanol Chemical compound CCO.Cl[Co]Cl LXWRTCKMRTXLRZ-UHFFFAOYSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- AQRRVVAHUPXEMW-UHFFFAOYSA-L ethanol;iron(2+);dichloride Chemical compound [Cl-].[Cl-].[Fe+2].CCO AQRRVVAHUPXEMW-UHFFFAOYSA-L 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- B01J23/8913—Cobalt and noble 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
- B01J23/70—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
- B01J23/8906—Iron and noble 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
- B01J23/70—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
- B01J23/892—Nickel and noble 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种核壳结构催化剂的制备方法,具体包括:1)惰性气体气氛下,在有机溶剂中,硼氢化钠将过渡金属盐还原得到过渡金属纳米颗粒;2)在惰性气体保护下,过渡金属纳米颗粒分散在分散溶液中,加入贵金属无机盐或贵金属酸的无机酸溶液进行反应,最后在惰性气体气氛下干燥即得核壳结构催化剂。本发明提高了硼氢化钠还原制备过渡金属纳米颗粒的反应速率,有效避免了水体系下金属硼化物的生成,通过控制置换反应溶液的pH值,直接在过渡金属纳米核表面包覆贵金属合金壳层。以铁、钴或镍纳米颗粒为核,铂合金为壳层的核壳结构催化剂,进一步提高催化剂的性能,增加铂的利用率,降低成本。本方法反应浓度高,操作简便,具有批量化生产的潜力。
Description
技术领域
本发明属于催化剂制备技术领域,特别涉及一种核壳结构催化剂的制备方法,尤其涉及一种具有过渡金属@贵金属合金的核壳结构催化剂的制备方法。
背景技术
铁、钴、镍是非常好的磁性材料,磁性纳米颗粒有着广泛的用处,尤其在催化及磁记录材料应用方面,磁性纳米颗粒的磁性与颗粒尺寸相关(张立德,牟季美.纳米材料和纳米结构.北京:科学出版社,2002:74-79;Diandra L,Leslie P.Chem.Mater.1996,8(8):l770-1783;陈敬中主编.纳米材料科学导论.北京:高等教育出版社,2006:98-100),制备单分散、颗粒尺寸小的纳米磁性颗粒是应用的关键。
铁、钴和镍纳米核的合成方法主要是采用溶剂热法或多元醇还原法(Y.M.Chen,F.Yang,et.al.J.Phys.Chem.C 2008,112,1645-1649;M.K.Carpenter,T.E.Moylan,et.al.J.Am.Chem.Soc.2012,134,8535-8542),在较高温度和压力下,还原出铁、钴、镍纳米颗粒,以及采用乙酰丙酮铁(钴、镍)、羰基铁(钴、镍)等有机金属盐高温还原制备相应的纳米磁性颗粒(C.Wang,M.F.Chi,G.F.Wang,etal.Adv.Funct.Mater.2011,21,147-152)。上述方法制备出的过渡金属纳米颗粒纯度高,并且可以通过控制温度、浓度、稳定剂种类和浓度等条件控制过渡金属纳米颗粒的形貌(晶面、过渡生长方向等)、尺寸,已普遍应用在实验室制备过渡金属纳米颗粒,但是其对反应环境要求高(高温、一定压力、特定溶剂和稳定剂),需要对浓度、温度等条件精确控制,操作复杂;同时,反应底物浓度低,产率低,难以批量化生产,稳定剂一般为难挥发、难溶于水的有机物,后处理困难。
还有人采用化学还原法制备铁、钴、镍纳米核。化学还原法的优点是对反应体系要求低,同种还原剂能同时在几种体系中反应;反应温度低,室温下就能发生反应;可以在较高浓度下制备出纳米颗粒,具有实现批量生产的潜力。目前化学还原采用的还原剂大多是硼氢化钠和水合肼:
水合肼:水合肼相对于酰胺类还原剂还原能力更强,能在室温还原制备铂、金、银和铜等金属离子,是比较常用的还原剂。但是,水合肼很难还原制备出纳米铁、钴和镍颗粒,主要原因有:1.水合肼还原能力较弱,直接还原制备铁、钴和镍纳米颗粒困难;2.水合肼和铁、钴和镍金属配位性强,并且具有弱碱性,在较高浓度时会有氢氧化物生成,难以除去氢氧化物,反应产物纯度不高。另外,水合肼毒性大,挥发性强,具有一定危险性。
硼氢化钠:硼氢化钠具有比水合肼更强的还原性,能在常温下还原铁钴、镍金属离子,反应速度快,反应温度低。虽然硼氢化钠还原制备铁、钴和镍的优势很明显,但是,由于硼氢化钠稳定性差,易分解,同时易与铁、钴和镍离子反应生成硼化物,所以副产物多,产物纯度低(G.N.Glavee,K.J.Klabunde,C.M.Sorensen,G.C.Hadjipanayis.Langmuir 1993,9,162-169)。硼氢化钠作为还原剂制备铁、钴或镍纳米颗粒,首先得解决产物纯度和如何除去副产物的问题。
具有贵金属壳层的核壳结构磁性纳米颗粒具有高的矫顽力和高的截止温度,并且贵金属壳层为磁性纳米颗粒核提供很好的保护,这更加扩展了核壳结构的磁性纳米颗粒在生物及信息方面的应用,例如信息储存、磁性传感器、生物分离及药物释放等(J.P.Liu,E.Fullerton,O.Gutfleisch.Eds.,Nanoscale Magnetic Materials andApplications.Springer Science,2009,35-65.)。另一方面,铂合金催化剂,尤其是铂与铁、钴、镍三种过渡金属的合金催化剂,具有优异的氧化还原催化性能,在燃料电池领域有很好的应用。
发明内容
针对现有技术不足,本发明提供了一种核壳结构催化剂的制备方法。
一种核壳结构催化剂的制备方法,所述核壳结构催化剂以过渡金属为核层,以贵金属与过渡金属的合金为壳层,该方法包括如下步骤:
1)将过渡金属盐溶解于有机溶剂中,加入稳定剂,搅拌均匀后,通惰性气体0.5~2h;然后在惰性气体气氛保护下,持续搅拌,并逐滴滴加硼氢化钠水溶液,滴加完毕后继续反应0.5~2h至反应完全;将产物用乙醇清洗数次,再用去离子水清洗数次,得到过渡金属纳米颗粒;
2)去离子水中加入分散剂,通惰性气体除去氧气后,在惰性气体气氛保护下,将过渡金属纳米颗粒分散在分散剂水溶液中,分散溶液中继续通惰性气体0.5~2h;然后在惰性气体气氛保护下,搅拌均匀,再超声0.5~3h后,加入贵金属无机盐与无机酸的混合水溶液,或贵金属酸与无机酸的混合水溶液,持续搅拌下反应0.5~3h至反应完全后,将产物用去离子水清洗数次,再用乙醇清洗数次,最后在惰性气体气氛下干燥,即得所述核壳结构催化剂。
所述过渡金属为铁、钴或镍,所述贵金属为铂、金、银或钯。
所述过渡金属盐为过渡金属的硝酸盐、氯化物或硫酸盐;所述稳定剂为含铵基的表面活性剂,包括三甲基十二烷基溴化铵、三甲基十六烷基溴化铵、四丁基溴化铵或四丁基氯化铵;所述有机溶剂为四氢呋喃、二甲基甲酰胺或醇;所述分散剂为PVP K5、PVP K15、PVPK30或PVP K90。
所述硼氢化钠水溶液的浓度为0.5~5mol/L,pH值大于8。
步骤1)中所述有机溶剂中,过渡金属盐的浓度为0.001~1.0mol/L,稳定剂浓度为0.005~0.05mol/L。
步骤1)中反应所加入硼氢化钠的量与过渡金属盐的摩尔比为(1~10):1。
步骤2)中,分散剂在分散溶液中的质量分数为0.1%~5%。
步骤2)中,贵金属与过渡金属的摩尔比为1:(20~1)。
步骤2)中,所述无机酸为盐酸、硫酸或硝酸,以调节混合水溶液的pH值小于6。
步骤2)中所述干燥温度为室温~100℃。
本发明的有益效果为:本发明提供了一种有机溶剂与水相结合的反应体系,提高了硼氢化钠在有机溶剂中还原制备铁、钴或镍的金属纳米颗粒的反应速率,并有效的避免水体系下金属硼化物的生成,在室温下即可获得铁、钴或镍的金属纳米颗粒,水和乙醇清洗去除部分杂质后,通过控制置换反应溶液的pH值,可直接在过渡金属纳米核表面包覆相应的贵金属合金壳层。以铁、钴或镍纳米颗粒为核,铂合金为壳层的核壳结构催化剂,可进一步提高催化剂的性能,增加铂的利用率,降低成本。本发明的方法反应浓度高,操作简便,具有实现批量化生产的潜力。
附图说明
图1为实施例1合成的催化剂的高角环形暗场扫描透射电镜图(HAADF);
图2为实施例1合成的催化剂的XRD图谱;
图3是实施例2合成的催化剂的高角环形暗场扫描透射电镜图(HAADF);
图4是实施例2合成的催化剂的XRD图谱;
图5为实施例1和实施例2中催化剂与商用铂碳催化剂的氧还原性能的对比。
具体实施方式
下面结合附图和具体实施方式对本发明做进一步说明。应该强调的是,下述说明仅仅是示例性的,而不是为了限制本发明的范围及其应用。
实施例1
配置0.025mol/L氯化钴四氢呋喃溶液,然后加入三甲基十六烷基溴化铵作为稳定剂,稳定剂浓度为0.01mol/L,搅拌均匀后移入反应釜中,通氩气半小时以除去氧气。以硼氢化钠与氯化钴的摩尔比为4:1的比例称取硼氢化钠固体溶解于pH值为12的氢氧化钠水溶液中,硼氢化钠的浓度为3mol/L,然后在氩气保护下,强烈搅拌下向反应釜中逐滴加入硼氢化钠水溶液,反应1h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到钴纳米颗粒。质量分数为1%的PVP K30水溶液中通氩气除去氧气后,在氩气保护下,将钴纳米颗粒分散在PVP K30水溶液中,继续通氩气半小时,然后在氩气保护下,搅拌均匀,再超声1h,根据钴与铂的摩尔比为15:1,将氯铂酸与盐酸混合溶液(pH值为1)滴加至上述分散溶液中,反应2h至反应完全后,将产物分别用水和乙醇离心清洗数次,最后在氩气气氛下,70℃干燥。所得核壳结构催化剂的高角环形暗场扫描透射电镜图(HAADF)如图1所示,清晰显示出了核壳结构,并且纳米颗粒的尺寸为10~15nm。其XRD谱图如图2所示,结果显示合金壳层为PtCo合金。其在酸性条件下对氧还原的催化活性与商用铂碳催化剂的比较如图5中所示。
实施例2
配置0.1mol/L氯化钴四氢呋喃溶液,然后加入三甲基十六烷基溴化铵作为稳定剂,稳定剂浓度为0.05mol/L,搅拌均匀后移入反应釜中,通氩气半小时除去氧气。以硼氢化钠与氯化钴的摩尔比为4:1的比例称取硼氢化钠固体溶解于pH为12的氢氧化钠水溶液中,硼氢化钠的浓度为5mol/L,然后在氩气保护下,强烈搅拌下向反应釜中逐滴加入硼氢化钠水溶液,反应0.5h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到钴纳米颗粒。质量分数为5%的PVP K30水溶液中通氩气除去氧气后,在氩气保护下,将钴纳米颗粒分散在PVP K30水溶液中,继续通氩气半小时,然后在氩气保护下,搅拌均匀,再超声1h,根据钴与铂的摩尔比为12:1,将氯铂酸与盐酸混合溶液(pH值为1)滴加至上述分散溶液中,反应2h至反应完全后,将产物分别用水和乙醇离心清洗数次后,在氩气气氛下,70℃干燥。所得核壳结构催化剂的高角环形暗场扫描透射电镜图(HAADF)如图3所示,清晰显示出核壳结构,且纳米颗粒的尺寸约为5nm。其XRD谱图如图4所示,结果显示合金壳层为Pt3Co合金。其在酸性条件下对氧还原的催化活性与商用铂碳催化剂的比较如图5所示。实施例3
配置0.05mol/L硫酸钴四氢呋喃溶液,然后加入三甲基十二烷基溴化铵作为稳定剂,稳定剂浓度为0.025mol/L,搅拌均匀后移入反应釜中,通氮气半小时除去氧气。以硼氢化钠与硫酸钴的摩尔比为4:1的比例称取硼氢化钠固体溶解于pH为11的氢氧化钾水溶液中,硼氢化钠的浓度为1mol/L,然后在氮气保护下,强烈搅拌下向反应釜中逐滴加入硼氢化钠水溶液,反应2h至反应完全后,将产物移出反应釜。将产物分别用乙醇和去离子水离心清洗数次后,得到钴纳米颗粒。质量分数为2.5%的PVP K15水溶液中通氮气除去氧气后,在氮气保护下,将钴纳米颗粒分散在PVP K15水溶液中,继续通氮气半小时,然后在氮气保护下,搅拌均匀,再超声1h,根据钴与铂的摩尔比为5:1,将氯铂酸与盐酸混合溶液(pH值为3)滴加至上述分散溶液中,反应3h至反应完全后,将产物分别用水和乙醇离心清洗数次后,最后在氩气气氛下,70℃干燥。
实施例4
配置0.001mol/L硝酸钴的二甲基甲酰胺溶液,然后加入四丁基溴化铵作为稳定剂,稳定剂浓度为0.01mol/L,搅拌均匀后移入反应釜中,通氩气半小时以除去氧气。以硼氢化钠与硝酸钴的摩尔比为10:1的比例称取硼氢化钠固体溶解于pH为10的氢氧化钠水溶液中,硼氢化钠浓度为0.5mol/L,然后在氩气保护下,强烈搅拌下向反应釜中逐滴加入硼氢化钠水溶液,反应3h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到钴纳米颗粒。质量分数为0.1%的PVP K90水溶液中通氩气除去氧气后,在氩气保护下,将钴纳米颗粒分散在PVP K90水溶液中,继续通氩气半小时,然后在氩气保护下,搅拌均匀,再超声1h,根据钴与金的摩尔比为20:1,将氯金酸与盐酸混合溶液(pH值为3)滴加至上述分散溶液中,反应2h至反应完全后,将产物用水和乙醇离心清洗数次,最后在氩气气氛下,70℃干燥。
实施例5
配置0.005mol/L氯化钴乙醇溶液,然后加入三甲基十二烷基溴化铵作为稳定剂,稳定剂浓度为0.01mol/L,搅拌均匀后移入反应釜中,通氩气半小时以除去氧气。以硼氢化钠与氯化钴的摩尔比为4:1的比例称取硼氢化钠固体溶解于pH为10的氢氧化钠水溶液中,硼氢化钠浓度为1mol/L,然后在氩气保护下,强烈搅拌下向反应釜中逐滴加入硼氢化钠水溶液,反应1h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到钴纳米颗粒。质量分数为1%的PVP K5水溶液中通氩气除去氧气后,在氩气保护下,将钴纳米颗粒分散在PVP K5水溶液中,继续通氩气半小时,然后在氩气保护下,搅拌均匀,再超声1h,根据钴与银的摩尔比为10:1,将硝酸银与硝酸混合溶液(pH值为5)滴加至上述分散溶液中,反应2h至反应完全后,将产物用水和乙醇离心清洗数次,最后在氩气气氛下,70℃干燥。
实施例6
配置0.05mol/L氯化钴四氢呋喃溶液,然后加入三甲基十六烷基溴化铵作为稳定剂,稳定剂浓度为0.025mol/L,搅拌均匀后移入反应釜中,通氮气半小时除去氧气。以硼氢化钠与氯化钴的摩尔比为8:1的比例称取硼氢化钠固体溶解于pH为12的氢氧化钠水溶液中,硼氢化钠浓度为5mol/L,然后在氮气保护下,强烈搅拌下向反应釜中逐滴加入硼氢化钠水溶液,反应0.5h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到钴纳米颗粒。质量分数为2.5%的PVP K30水溶液中通氮气除去氧气后,在氮气保护下,将钴纳米颗粒分散在PVP K30水溶液中,继续通氮气半小时,然后在氮气保护下,搅拌均匀,再超声1h,根据钴与钯的摩尔比为2:1,将氯化钯与盐酸混合溶液(pH值为1)滴加至上述分散溶液中,反应1h至反应完全后,将产物用水和乙醇离心清洗数次,最后在氮气气氛下,70℃干燥。
实施例7
配置0.1mol/L氯化铁乙醇溶液,然后加入四丁基溴化铵作为稳定剂,稳定剂浓度为0.005mol/L,搅拌均匀后移入反应釜中,通氩气半小时以除去氧气。以硼氢化钠与氯化铁的摩尔比为10:1的比例称取硼氢化钠固体溶解于pH为12的氢氧化钠水溶液中,硼氢化钠浓度为5mol/L,然后在氩气保护下,强烈搅拌下向反应釜中逐滴加入硼氢化钠水溶液,反应1h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到铁纳米颗粒。质量分数为5%的PVP K90水溶液中通氩气除去氧气后,在氩气保护下,将铁纳米颗粒分散在PVP K90水溶液中,继续通氩气半小时,然后在氩气保护下,搅拌均匀,再超声1h,根据铁与铂的摩尔比为5:1,将氯铂酸与盐酸混合溶液(pH值为3)滴加至上述分散溶液中,反应1h至反应完全后,将产物用水和乙醇离心清洗数次,最后在氩气气氛下,70℃干燥。
实施例8
配置0.01mol/L硝酸铁四氢呋喃溶液,然后加入三甲基十六烷基溴化铵作为稳定剂,稳定剂浓度为0.01mol/L,搅拌均匀后移入反应釜中,通氩气半小时以除去氧气。以硼氢化钠与硝酸铁的摩尔比为4:1的比例称取硼氢化钠固体溶解于pH为11的氢氧化钠水溶液中,硼氢化钠浓度为1mol/L,然后在氩气保护下,强烈搅拌下向反应釜中逐滴加入硼氢化钠水溶液,反应0.5h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到铁纳米颗粒。质量分数为2%的PVP K15水溶液中通氩气除去氧气后,在氩气保护下,将铁纳米颗粒分散在PVP K15水溶液中,继续通氩气半小时,然后在氩气保护下,搅拌均匀,再超声1h,根据铁与铂的摩尔比为5:1,将氯铂酸与盐酸混合溶液(pH值为3)滴加至上述分散溶液中,反应0.5h至反应完全后,将产物用水和乙醇离心清洗数次,最后在氩气气氛下,70℃干燥。
实施例9
配置0.01mol/L氯化镍二甲基甲酰胺溶液,然后加入三甲基十二烷基溴化铵作为稳定剂,稳定剂浓度为0.01mol/L,搅拌均匀后移入反应釜中,通氮气半小时除去氧气。以硼氢化钠与氯化镍的摩尔比为4:1的比例称取硼氢化钠固体溶解于pH为11的氢氧化钠水溶液中,硼氢化钠浓度为2mol/L,然后在氮气保护下,强烈搅拌下逐滴加入硼氢化钠水溶液,反应2h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到镍纳米颗粒。质量分数为2%的PVP K30水溶液中通氮气除去氧气后,在氮气保护下,将镍纳米颗粒分散在PVP K30水溶液中,继续通氮气半小时,然后在氮气保护下,搅拌均匀,再超声1h,根据镍与铂的摩尔比为5:1,将氯铂酸与盐酸混合溶液(pH值为3)滴加至上述分散溶液中,反应1h至反应完全后,将产物用水和乙醇离心清洗数次,最后在氮气气氛下,70℃干燥。
实施例10
配置0.1mol/L硫酸镍四氢呋喃溶液,然后加入三甲基十六烷基溴化铵作为稳定剂,稳定剂浓度为0.05mol/L,搅拌均匀后移入反应釜中,通氩气半小时除去氧气。以硼氢化钠与硫酸镍的摩尔比为10:1的比例称取硼氢化钠固体溶解于pH为12的氢氧化钾水溶液中,硼氢化钠浓度为3mol/L,然后在氩气保护下,强烈搅拌下逐滴加入硼氢化钠水溶液,反应1h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到镍纳米颗粒。质量分数为5%的PVP K90水溶液中通氩气除去氧气后,在氩气保护下,将镍纳米颗粒分散在PVP K90水溶液中,继续通氩气半小时,然后在氩气保护下,搅拌均匀,再超声1h,根据镍与铂的摩尔比为10:1,将氯铂酸与盐酸混合溶液(pH值为3)滴加至上述分散溶液中,反应1h至反应完全后,将产物用水和乙醇离心清洗数次,最后在氩气气氛下,70℃干燥。
实施例11
配置0.05mol/L硫酸亚铁四氢呋喃溶液,然后加入三甲基十二烷基溴化铵作为稳定剂,稳定剂浓度为0.025mol/L,搅拌均匀后移入反应釜中,通氩气半小时除去氧气。以硼氢化钠与硫酸亚铁的摩尔比为6:1的比例称取硼氢化钠固体溶解于PH为11的氢氧化钠水溶液中,硼氢化钠浓度为5mol/L,然后在氩气保护下,强烈搅拌下逐滴加入硼氢化钠水溶液,反应0.5h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到铁纳米颗粒。质量分数为2%的PVP K30水溶液中通氩气除去氧气后,在氩气保护下,将铁纳米颗粒分散在PVP K30水溶液中,继续通氩气半小时,然后在氩气保护下,搅拌均匀,再超声1h,根据铁与铂的摩尔比为5:1,将氯铂酸与盐酸混合溶液(pH值为3)滴加至上述分散溶液中,反应0.5h至反应完全后,将产物用水离心清洗数次后,再用氯化铵溶液搅拌超声离心清洗数次后,再分别用水和乙醇离心清洗数次,最后在氩气气氛下,70℃干燥。
实施例12
配置0.002mol/L硫酸铁乙醇溶液,然后加入三甲基十六烷基溴化铵作为稳定剂,稳定剂浓度为0.01mol/L,搅拌均匀后移入反应釜中,通氩气半小时除去氧气。以硼氢化钠与硫酸铁的摩尔比为4:1的比例称取硼氢化钠固体溶解于pH为10的氢氧化钠水溶液中,硼氢化钠浓度为1mol/L,然后在氩气保护下,强烈搅拌下逐滴加入硼氢化钠水溶液,反应1h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到铁的纳米颗粒。质量分数为0.25%的PVP K30水溶液中通氩气除去氧气后,在氩气保护下,将铁纳米颗粒分散在PVP K30水溶液中,继续通氩气半小时,然后在氩气保护下,搅拌均匀,再超声1h,根据铁与铂的摩尔比为15:1,将氯铂酸与盐酸混合溶液(pH值为1)滴加至上述分散溶液中,反应0.5h至反应完全后,将产物用水和乙醇离心清洗数次,最后在氩气气氛下,70℃干燥。
实施例13
配置0.002mol/L硝酸镍四氢呋喃溶液,然后加入三甲基十六烷基溴化铵作为稳定剂,稳定剂浓度为0.01mol/L,搅拌均匀后移入反应釜中,通氩气半小时除去氧气。以硼氢化钠与硝酸镍的摩尔比为4:1的比例称取硼氢化钠固体溶解于pH为10的氢氧化钠水溶液中,硼氢化钠浓度为1mol/L,然后在氩气保护下,强烈搅拌下逐滴加入硼氢化钠水溶液,反应1h至反应完全后,将产物移出反应釜,分别用乙醇和去离子水离心清洗数次后,得到镍纳米颗粒。质量分数为0.25%的PVP K30水溶液中通氩气除去氧气后,在氩气保护下,将镍纳米颗粒分散在PVP K30水溶液中,继续通氩气半小时,然后在氩气保护下,搅拌均匀,再超声1h,根据镍与铂的摩尔比为5:1,将氯铂酸与盐酸混合溶液(pH值为3)滴加至上述分散溶液中,反应1h至反应完全后,将产物用水和乙醇离心清洗数次,最后在氩气气氛下,70℃干燥。
Claims (3)
1.一种核壳结构催化剂的制备方法,其特征在于,该方法包括如下步骤:
1)将过渡金属盐溶解于有机溶剂中,加入稳定剂,搅拌均匀后,通惰性气体0.5~2 h;然后在惰性气体气氛保护下,持续搅拌,并逐滴滴加硼氢化钠水溶液,形成有机溶剂和水的混合体系,滴加完毕后继续反应0.5~2 h至反应完全,将产物用乙醇清洗数次,再用去离子水清洗数次,得到过渡金属纳米颗粒;
所述硼氢化钠水溶液的浓度为0.5~5 mol/L,pH值大于8;
所加入硼氢化钠的量与过渡金属盐的摩尔比为(1~10): 1;
所述有机溶剂中,加入过渡金属盐的浓度为0.001~1.0 mol/L,稳定剂浓度为0.005~0.05 mol/L;
所述过渡金属盐为过渡金属的硝酸盐、氯化物或硫酸盐;所述稳定剂为含铵基的表面活性剂,包括三甲基十二烷基溴化铵、三甲基十六烷基溴化铵、四丁基溴化铵或四丁基氯化铵;所述有机溶剂为四氢呋喃、二甲基甲酰胺或醇;
2)去离子水中加入分散剂,通惰性气体除去氧气后,在惰性气体气氛保护下,将过渡金属纳米颗粒分散在分散溶液中,分散溶液中继续通惰性气体0.5~2 h;然后在惰性气体气氛保护下,搅拌均匀,再超声0.5~3 h后,加入贵金属无机盐与无机酸的混合水溶液,或贵金属酸与无机酸的混合水溶液,持续搅拌下反应0.5~3 h至反应完全后,将产物用去离子水清洗数次,再用乙醇清洗数次,最后在惰性气体气氛下干燥,即得核壳结构催化剂;
所述分散剂为PVP K5、PVP K15、PVP K30或PVP K90;
分散剂在分散溶液中的质量分数为0.1 %~5 %;
贵金属与过渡金属的摩尔比为1 :(20~1);
所述核壳结构催化剂以过渡金属为核层,以贵金属与过渡金属的合金为壳层;其中所述过渡金属为铁、钴或镍,所述贵金属为铂、金、银或钯。
2.根据权利要求1所述一种核壳结构催化剂的制备方法,其特征在于,步骤2)中,所述无机酸为盐酸、硫酸或硝酸,以调节混合水溶液的pH值小于6。
3.根据权利要求1所述一种核壳结构催化剂的制备方法,其特征在于,步骤2)中所述干燥温度为室温~100℃。
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