CN111137927A - A kind of preparation method of nickel-copper cobaltate nanoparticles and its application in catalyzing ammonia borane hydrolysis to produce hydrogen - Google Patents
A kind of preparation method of nickel-copper cobaltate nanoparticles and its application in catalyzing ammonia borane hydrolysis to produce hydrogen Download PDFInfo
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- CN111137927A CN111137927A CN201911056504.4A CN201911056504A CN111137927A CN 111137927 A CN111137927 A CN 111137927A CN 201911056504 A CN201911056504 A CN 201911056504A CN 111137927 A CN111137927 A CN 111137927A
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000001257 hydrogen Substances 0.000 title claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 21
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims description 15
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims description 9
- 230000007062 hydrolysis Effects 0.000 title claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 title claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 39
- 239000012498 ultrapure water Substances 0.000 claims abstract description 39
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 239000012266 salt solution Substances 0.000 claims abstract description 34
- 239000001509 sodium citrate Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- 150000001879 copper Chemical class 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract 2
- 229940038773 trisodium citrate Drugs 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 29
- 229940044175 cobalt sulfate Drugs 0.000 claims description 29
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 29
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 29
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 29
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 122
- 239000010949 copper Substances 0.000 abstract description 86
- 239000000203 mixture Substances 0.000 abstract description 12
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- CKHXCOFTUKMQTA-UHFFFAOYSA-N [O].[Co].[Ni].[Cu] Chemical compound [O].[Co].[Ni].[Cu] CKHXCOFTUKMQTA-UHFFFAOYSA-N 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 abstract 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 64
- 229910052751 metal Inorganic materials 0.000 description 46
- 239000002184 metal Substances 0.000 description 46
- 238000010438 heat treatment Methods 0.000 description 32
- 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 29
- 229910000365 copper sulfate Inorganic materials 0.000 description 27
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- 229910052802 copper Inorganic materials 0.000 description 20
- 229910052759 nickel Inorganic materials 0.000 description 20
- 229910017052 cobalt Inorganic materials 0.000 description 17
- 239000010941 cobalt Substances 0.000 description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 16
- -1 Ni (OH))2 Chemical compound 0.000 description 16
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 16
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 16
- 238000000227 grinding Methods 0.000 description 16
- 239000004570 mortar (masonry) Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 5
- 229910003266 NiCo Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002070 nanowire Substances 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 241000257465 Echinoidea Species 0.000 description 2
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910003203 NH3BH3 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
- C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明公开了一种钴酸镍铜纳米颗粒的制备方法，属于纳米材料领域及催化剂制备技术领域。所述制备方法包括：（1）、将可溶性镍盐、钴盐、铜盐溶于超纯水中，配置成混合盐溶液A；（2）、将络合剂柠檬酸三钠溶于超纯水，配置成溶液B，所加入络合剂与金属离子的摩尔比为0.5~2.0；（3）、将沉淀剂溶于超纯水形成C溶液，所加入沉淀剂与金属离子的摩尔比为2~50；（4）、将B，C溶液按顺序缓慢加至A溶液混合，搅拌0~1 h；（5）、再转移至反应釜，80~180℃反应8~24 h，过滤洗涤，40~80℃下烘干，转移至马弗炉350~800℃煅烧1~8 h。本发明采用水热合成法，整个制备过程操作简单，环境友好，实验重现性非常好，成本低、易于工业化生产，可规模化生产CuxNi1‑ xCo2O4复合钴酸盐。
The invention discloses a method for preparing nickel-copper cobalt oxide nanoparticles, which belongs to the field of nanomaterials and the technical field of catalyst preparation. The preparation method includes: (1) dissolving soluble nickel salt, cobalt salt and copper salt in ultrapure water to prepare mixed salt solution A; (2) dissolving complexing agent trisodium citrate in ultrapure water Water, configured as solution B, the molar ratio of the added complexing agent to the metal ion is 0.5~2.0; (3), dissolve the precipitant in ultrapure water to form a solution C, and the molar ratio of the added precipitant to the metal ion is 2~50; (4), slowly add the B and C solutions to the A solution and mix in sequence, and stir for 0~1 h; (5), then transfer to the reaction kettle, react at 80~180 ℃ for 8~24 h, filter and wash , dried at 40~80℃, and transferred to a muffle furnace for calcination at 350~800℃ for 1~8 h. The invention adopts the hydrothermal synthesis method, the whole preparation process is simple to operate, environment friendly, the experiment reproducibility is very good, the cost is low, the industrial production is easy, and the Cu x Ni 1- x Co 2 O 4 composite cobaltate can be produced on a large scale.
Description
Technical Field
The invention belongs to the field of nano materials and the technical field of catalyst preparation. In particular to a preparation method of nickel copper cobaltate nano particles and application thereof in catalyzing ammonia borane hydrolysis to produce hydrogen.
Background
The depletion of fossil energy has forced the rise of new energy, and hydrogen energy is considered as one of the most promising energy sources in the future as a novel energy source with the advantages of safety, environmental protection, abundant sources, wide application range, zero emission and the like, and has a considerable status in the aspects of hydrogen fuel automobiles, batteries, illumination, urban life and the like. The key to the development of hydrogen energy is the search for suitable hydrogen storage materials. The hydrogen storage material mainly comprises chemical hydride, adsorption hydrogen storage material and metal hydride. Hydrogen in ammonia borane (NHBH, AB for short) has high energy density (142 MJ/kg), high hydrogen content (19.6 wt%), and is considered to be an extremely efficient hydrogen storage material. The catalyst hardly reacts at room temperature, but under the action of the catalyst, 1molAB can release 3mmol of hydrogen almost through hydrolysis, and the hydrogen release rate is greatly different along with the excellent performance of the catalyst, so that the research and development of a novel efficient catalyst for preparing hydrogen through ammonia borane hydrolysis are hot spots in the current novel energy research.
The nickel copper cobaltate is used as one of transition metal oxides, and has the characteristics of special lattice structure, high specific surface area, good conductivity and the like, so that the nickel copper cobaltate is widely applied to the fields of lithium ion battery materials, supercapacitors, photocatalysis, electrocatalysis and the like.
Chinese patent (CN 201810016038.6, 2018) proposes a preparation method of a foamed nickel-loaded echinoid copper cobaltate nano material: the copper cobaltate nano material with the sea urchin structure is prepared by taking cobalt nitrate hexahydrate, copper acetate monohydrate, ammonium fluoride and urea as raw materials and absolute ethyl alcohol and deionized water as solvents through hydrothermal growth and high-temperature calcination methods. The sea urchin-shaped copper cobaltate nano material loaded by the foamed nickel prepared by the method has uniform and ordered sea urchin shape, and shows excellent electrochemical performance and good rate performance, especially when the calcination temperature is about 550 ℃. But the method is directly obtained by growing on a foamed nickel current collector, which is not favorable for scale production.
Chinese patent (CN 201510204162.1, 2015) proposes a NiCo used as a supercapacitor electrode2O4@NiCo2O4The nanometer material and the preparation method thereof are as follows: preparing NiCo with a nuclear structure by a hydrothermal reaction method2O4Nano wire, on the nano wire the shell structure NiCo can be further made up by means of electrochemical deposition method2O4Nano wire to obtain NiCo with homogeneous core-shell structure2O4@NiCo2O4The nanowire can effectively improve the specific surface area and the space utilization rate of the electrode and the specific capacitance of the electrode material, but obviously has complex process and energy consumption.
Therefore, the invention aims to solve the problem of developing a method which has controllable appearance, lower cost and excellent product performance and can be used for industrially producing cobaltate compounds.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing nickel copper cobaltate nano particles with high specific surface area and uniform dispersionThe synthesis method is simple, the conditions are mild, and the Cu is synthesizedxNi1-xCo2O4The nano particles have the advantages of high specific surface area, uniform dispersion and the like.
The invention provides a preparation method of copper nickel cobaltate nanoparticles, which comprises the following steps:
(1) dissolving soluble nickel salt, cobalt salt and copper salt in ultrapure water to prepare a mixed salt solution A;
(2) dissolving sodium citrate serving as a complexing agent into ultrapure water to prepare solution B, wherein the molar ratio of the added complexing agent to metal ions is 0.5-2.0;
(3) dissolving a precipitator in ultrapure water to form a solution C, wherein the molar ratio of the added precipitator to metal ions is 2-50;
(4) slowly adding the solution B and the solution C to the solution A in sequence, mixing, and stirring for 0-1 h;
(5) and transferring to a reaction kettle, reacting for 8-24 h at 80-180 ℃, filtering, washing, drying at 40-80 ℃, transferring to a muffle furnace for calcining for 1-8 h at 350-800 ℃.
Preferably, the step (1) is configured to contain Co2+/(Ni2+、Cu2+) Mixed salt solution a in a molar ratio of 2: 1.
Preferably, the soluble nickel salt in step (1) is selected from one or more of nickel chloride hexahydrate, nickel sulfate heptahydrate, nickel nitrate hexahydrate, nickel chloride, nickel sulfate, nickel nitrate and nickel acetate.
Preferably, the soluble cobalt salt in step (1) is selected from one or more of cobalt acetate tetrahydrate, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate, cobalt nitrate hexahydrate and cobalt acetate.
Preferably, the soluble copper salt in step (1) is selected from one or more of copper chloride dihydrate, copper sulfate pentahydrate, copper nitrate and copper acetate.
Preferably, the precipitant in step (1) is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, ammonia water, hexamethylenetetramine and urea.
The invention also discloses application of the nickel copper cobaltate nanoparticles prepared by the method as a catalyst in catalyzing ammonia borane hydrolysis to produce hydrogen.
In conclusion, the preparation method disclosed by the invention has the following beneficial effects:
1. the invention adopts a hydrothermal synthesis method, firstly raw materials are mixed according to a certain proportion, a precipitator is added to generate multi-element metal hydroxide, and cobaltate is synthesized by calcination, the process effectively realizes the setting of the proportion of nickel, cobalt and copper in the raw materials, the whole preparation process is simple to operate, environment-friendly, very good in experimental reproducibility, low in cost, easy for industrial production, and capable of producing Cu in a large scalexNi1- xCo2O4A complex cobaltate.
2. Nano-particle Cu prepared by the inventionxNi1-xCo2O4The composite cobaltate material shows excellent performance in catalyzing ammonia borane hydrolysis to produce hydrogen, and particularly Cu0.5Ni0.5Co2O4Shows stronger catalytic activity.
Drawings
FIG. 1 shows Cu prepared by the present invention0.5Ni0.5Co2O4SEM image of (d).
FIG. 2 shows Cu prepared by the present invention0.5Ni0.5Co2O4A TEM image of (a).
FIG. 3 shows Cu prepared by the present invention0.5Ni0.5Co2O4XRD test curve of (a).
FIG. 4 shows Cu prepared by the present invention0.5Ni0.5Co2O4And (5) a catalytic hydrogen production performance diagram.
Detailed Description
The foregoing summary of the invention is described in further detail below with reference to specific embodiments. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples. Various substitutions, alterations, modifications and the like are included in the scope of the present invention according to the common technical knowledge and the conventional means in the field without departing from the technical idea of the present invention.
Example 1
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 2mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 100mmol of sodium hydroxide in 20 mL of ultrapure water, slowly dropwise adding the sodium hydroxide into the metal salt solution, magnetically stirring for 30 min, moving the mixture to a reaction kettle, reacting for 8 h at 120 ℃, filtering, washing, drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 2
Preparing a precursor: dissolving cobalt chloride (2 mmol), nickel chloride (0.5 mmol) and copper chloride (0.5 mmol) in 40 mL of water, magnetically stirring until the cobalt chloride, the nickel chloride and the copper chloride are dissolved, adding 20 mL of 2mmol sodium citrate solution and 20 mL of 50mmol sodium carbonate solution, magnetically stirring for 30 min, transferring to a reaction kettle, reacting at 120 ℃ for 8 h, filtering, washing, drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate CuxNi1-xCo2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 2 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a targetProduct CuxNi1-xCo2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The morphology is still a nanoparticle structure.
Example 3
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.1 mmol) and copper sulfate (0.9 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 2mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 100mmol of sodium hydroxide in 20 mL of ultrapure water, slowly dropwise adding the sodium hydroxide into the metal salt solution, magnetically stirring for 30 min, moving the mixture to a reaction kettle, reacting for 8 h at 120 ℃, filtering, washing, drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.9Ni0.1Co2O4。
Through determination, the Cu obtained by the invention0.9Ni0.1Co2O4The appearance is a nanoparticle structure.
Example 4
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.7 mmol) and copper sulfate (0.3 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 2mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 100mmol of sodium hydroxide in 20 mL of ultrapure water, slowly dropwise adding the sodium hydroxide into the metal salt solution, magnetically stirring for 30 min, moving the mixture to a reaction kettle, reacting for 8 h at 120 ℃, filtering, washing, drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.3Ni0.7Co2O4。
Through determination, the Cu obtained by the invention0.3Ni0.7Co2O4The appearance is a nanoparticle structure.
Example 5
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 4mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 100mmol of sodium hydroxide in 20 mL of ultrapure water, slowly dropwise adding the sodium hydroxide into the metal salt solution, magnetically stirring for 30 min, moving the mixture to a reaction kettle, reacting for 8 h at 120 ℃, filtering, washing, drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 6
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until dissolving, dissolving 1mmol sodium citrate in 20 mL of ultrapure water, slowly dropping into metal salt solution, dissolving 100mmol sodium hydroxide in 20 mL of ultrapure water, slowly dropping into metal salt solution, magnetically stirring for 30 min, transferring to a reaction kettle, and reacting at 120 deg.CFiltering and washing for 8 h, and drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 7
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 2mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 50mmol of sodium hydroxide in 20 mL of ultrapure water, slowly dropwise adding the sodium hydroxide into the metal salt solution, magnetically stirring for 30 min, moving the mixture to a reaction kettle, reacting for 8 h at 120 ℃, filtering, washing, drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 8
Preparing a precursor: cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) are dissolved in 40 mL of water,magnetically stirring until dissolving, dissolving 2mmol sodium citrate in 20 mL ultrapure water, slowly dripping into metal salt solution, dissolving 100mmol urea in 20 mL ultrapure water, slowly dripping into metal salt solution, magnetically stirring for 30 min, transferring to a reaction kettle, reacting at 120 deg.C for 8 h, suction filtering, washing, and drying in a vacuum oven at 40 deg.C to obtain precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 9
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 2mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 100mmol of sodium carbonate in 20 mL of ultrapure water, slowly dropwise adding the sodium carbonate into the metal salt solution, magnetically stirring for 30 min, moving the mixture to a reaction kettle, reacting for 8 h at 120 ℃, filtering, washing, drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 10
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 2mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 100mmol of hexamethylenetetramine in 20 mL of ultrapure water, slowly dropwise adding the hexamethylenetetramine into the metal salt solution, magnetically stirring for 30 min, moving the mixture to a reaction kettle, reacting for 8 h at 120 ℃, carrying out suction filtration and washing, and drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 11
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 2mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 100mmol of sodium hydroxide in 20 mL of ultrapure water, slowly dropwise adding the sodium hydroxide into the metal salt solution, magnetically stirring for 30 min, moving the mixture to a reaction kettle, reacting for 24 h at 120 ℃, filtering, washing, drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min,keeping for 2 h; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 12
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 2mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 100mmol of sodium hydroxide in 20 mL of ultrapure water, slowly dropwise adding the sodium hydroxide into the metal salt solution, magnetically stirring for 30 min, moving the mixture to a reaction kettle, reacting for 16 h at 120 ℃, filtering, washing, drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 13
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 2mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 100mmol of sodium hydroxide in 20 mL of ultrapure water, slowly dropwise adding the sodium hydroxide into the metal salt solution, magnetically stirring for 30 min, moving the mixture to a reaction kettle, reacting for 8 h at 160 ℃, filtering, washing, drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 14
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 2mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 100mmol of sodium hydroxide in 20 mL of ultrapure water, slowly dropwise adding the sodium hydroxide into the metal salt solution, magnetically stirring for 30 min, moving to a reaction kettle, reacting at 180 ℃ for 8 h, performing suction filtration and washing, and drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 15
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until dissolving, dissolving 2mmol sodium citrate in 20 mL of ultrapure water, slowly dropping into metal salt solution, dissolving 100mmol sodium hydroxide in 20 mL of ultrapure water, slowly dropping into metal salt solutionIn the solution, magnetically stirring for 30 min, transferring to a reaction kettle, reacting at 120 ℃ for 8 h, filtering, washing, and drying in a vacuum oven at 40 ℃ to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Example 16
Preparing a precursor: dissolving cobalt sulfate (2 mmol), nickel sulfate (0.5 mmol) and copper sulfate (0.5 mmol) in 40 mL of water, magnetically stirring until the cobalt sulfate, the nickel sulfate and the copper sulfate are dissolved, dissolving 2mmol of sodium citrate in 20 mL of ultrapure water, slowly dropwise adding the sodium citrate into a metal salt solution, dissolving 100mmol of sodium hydroxide in 20 mL of ultrapure water, slowly dropwise adding the sodium hydroxide into the metal salt solution, magnetically stirring for 30 min, moving the mixture to a reaction kettle, reacting for 8 h at 120 ℃, filtering, washing, drying at 40 ℃ in a vacuum oven to obtain a precursor M (OH)2M is metal nickel, copper, cobalt (i.e. Ni (OH))2、Cu(OH)2、Co(OH)2）。
Nanoparticulate Cu0.5Ni0.5Co2O4The preparation of (1): putting the dried precursor into a mortar for even grinding, putting the ground precursor into a muffle furnace, heating to 350 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours; after the sample is cooled to room temperature, taking out the sample to obtain a target product Cu0.5Ni0.5Co2O4。
Through determination, the Cu obtained by the invention0.5Ni0.5Co2O4The appearance is a nanoparticle structure.
Below with nanoparticles of Cu0.6Ni0.4Co2O4For example, to the present inventionThe structure and performance of the prepared composite cobaltate are analyzed and tested.
1. SEM analysis
FIG. 1 shows Cu prepared by the present invention0.5Ni0.5Co2O4SEM image of (d). From the scanned image, Cu synthesized by hydrothermal synthesis0.5Ni0.5Co2O4The morphology is particles with a particle size of about 50 nm.
2. TEM test
FIG. 2 shows Cu prepared by the present invention0.5Ni0.5Co2O4From the transmission image, the synthesized Cu can be further confirmed0.5Ni0.5Co2O4Is uniform nano-particles.
3、XRD
FIG. 3 shows Cu prepared by the present invention0.5Ni0.5Co2O4XRD test of (1). Marked in the figure as Cu0.5Ni0.5Co2O4Characteristic peaks of different crystal planes.
4. Testing of catalytic Hydrogen production Performance
FIG. 4 shows Cu prepared by the present invention0.5Ni0.5Co2O4Performance testing of ammonia borane as a catalyst for Hydrogen production by hydrolysis, NH3BH3The dosage is 3mmol, NaOH is 20 mmol and the catalyst is 5 mg. Measured Cu at 25 ℃0.5Ni0.5Co2O4The catalyst is used for producing 21 mL of hydrogen in the first minute.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (7)
1. A preparation method of nickel copper cobaltate nanoparticles is characterized by comprising the following steps:
(1) dissolving soluble nickel salt, cobalt salt and copper salt in ultrapure water to prepare a mixed salt solution A;
(2) dissolving trisodium citrate serving as a complexing agent into ultrapure water to prepare solution B, wherein the molar ratio of the added complexing agent to metal ions is 0.5-2.0;
(3) dissolving a precipitator in ultrapure water to form a solution C, wherein the molar ratio of the added precipitator to metal ions is 2-50;
(4) slowly adding the solution B and the solution C to the solution A in sequence, mixing, and stirring for 0-1 h;
(5) and transferring to a reaction kettle, reacting for 8-24 h at 80-180 ℃, filtering, washing, drying at 40-80 ℃, transferring to a muffle furnace for calcining for 1-8 h at 350-800 ℃.
2. The method for preparing nickel copper cobaltate nanoparticles according to claim 1, wherein the method comprises the following steps: co-containing preparation in step (1)2+/(Ni2+、Cu2+) Mixed salt solution a in a molar ratio of 2: 1.
3. The method for preparing nickel copper cobaltate nanoparticles according to claim 1, wherein the method comprises the following steps: the soluble nickel salt in the step (1) is selected from one or more of nickel chloride hexahydrate, nickel sulfate heptahydrate, nickel nitrate hexahydrate, nickel chloride, nickel sulfate, nickel nitrate and nickel acetate.
4. The method for preparing nickel copper cobaltate nanoparticles according to claim 1, wherein the method comprises the following steps: in the step (1), the soluble cobalt salt is selected from one or more of cobalt acetate tetrahydrate, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate, cobalt nitrate hexahydrate and cobalt acetate.
5. The method for preparing nickel copper cobaltate nanoparticles according to claim 1, wherein the method comprises the following steps: in the step (1), the soluble copper salt is selected from one or more of copper chloride dihydrate, copper sulfate pentahydrate, copper nitrate and copper acetate.
6. The method for preparing nickel copper cobaltate nanoparticles according to claim 1, wherein the method comprises the following steps: the precipitant is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, ammonia water, hexamethylenetetramine and urea.
7. Use of the nanoparticles of cupronickel cobaltate prepared by the preparation method according to any one of claims 1 to 6 as a catalyst for catalyzing the hydrolysis of ammonia borane to produce hydrogen.
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Cited By (4)
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| CN113181916A (en) * | 2021-03-24 | 2021-07-30 | 常州大学 | Preparation method and application method of flaky copper-cobalt nano composite material |
| CN113913859A (en) * | 2021-11-22 | 2022-01-11 | 四川启睿克科技有限公司 | Electrolyzed water catalyst applicable to full pH range and preparation method thereof |
| CN114210337A (en) * | 2021-10-28 | 2022-03-22 | 惠州学院 | Nickel copper tungstate nano heterojunction particles, preparation method thereof and application of nickel copper tungstate nano heterojunction particles in catalytic hydrogen production |
| CN119838600A (en) * | 2025-03-07 | 2025-04-18 | 福州大学 | Preparation method and application of hollow sea urchin-shaped 1D/3D NiCuCo heterostructure nanomaterial |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113181916A (en) * | 2021-03-24 | 2021-07-30 | 常州大学 | Preparation method and application method of flaky copper-cobalt nano composite material |
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| CN114210337B (en) * | 2021-10-28 | 2024-02-13 | 惠州学院 | Nickel-copper tungstate nanoheterojunction particles and their preparation methods and applications in catalytic hydrogen production |
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| CN113913859B (en) * | 2021-11-22 | 2023-11-03 | 四川启睿克科技有限公司 | Electrolytic water catalyst applicable to full pH range and preparation method thereof |
| CN119838600A (en) * | 2025-03-07 | 2025-04-18 | 福州大学 | Preparation method and application of hollow sea urchin-shaped 1D/3D NiCuCo heterostructure nanomaterial |
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Application publication date: 20200512 |