CN110835103B - 一种磷酸钴铜微球的制备方法及其在催化氨硼烷水解产氢上的应用 - Google Patents
一种磷酸钴铜微球的制备方法及其在催化氨硼烷水解产氢上的应用 Download PDFInfo
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- OFVABKPSLCGISO-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Co+2].[Cu+2] Chemical compound P(=O)([O-])([O-])[O-].[Co+2].[Cu+2] OFVABKPSLCGISO-UHFFFAOYSA-K 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004005 microsphere Substances 0.000 title claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 27
- 239000001257 hydrogen Substances 0.000 title claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 26
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims description 15
- 230000007062 hydrolysis Effects 0.000 title claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 title claims description 11
- 239000000243 solution Substances 0.000 claims abstract description 71
- 239000010949 copper Substances 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 20
- 239000012498 ultrapure water Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000013877 carbamide Nutrition 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
- 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 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 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
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-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
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229960004011 methenamine Drugs 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000003760 magnetic stirring Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 7
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 6
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 235000005811 Viola adunca Nutrition 0.000 description 2
- 240000009038 Viola odorata Species 0.000 description 2
- 235000013487 Viola odorata Nutrition 0.000 description 2
- 235000002254 Viola papilionacea Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000013507 mapping Methods 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
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal 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
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- 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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Abstract
本发明公开了一种磷酸钴铜微球的制备方法,所述制备方法包括:(1)、将pH调节剂、表面活性剂、溶于超纯水形成A溶液;(2)、将可溶性钴盐、铜盐溶液溶于超纯水中,配置成混合盐溶液B;(3)、将B溶液缓慢加至A溶液混合形成C溶液,搅拌0~1h;(4)、缓慢向C溶液滴加30%的H3PO4溶液;(5)、再转移至反应釜,80~180℃反应2~24h,过滤洗涤,收集产品,在真空烘箱40~80℃下烘干。本发明采用水热合成法,通过对反应条件的选择和优化可控合成制备出一系列磷酸钴铜微球催化剂。此过程有效实现了原料中设定钴铜配比,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Cu3‑3xCo3x(PO4)2磷酸盐。
Description
技术领域
本发明属于催化领域及储氢材料领域。尤其涉及一种磷酸钴铜微球的制备方法及其在催化氨硼烷水解产氢上的应用。
背景技术
随着世界经济的快速发展,煤炭和石油等不可再生能源过度消耗,环境污染的日趋恶化,因此寻找一种可再生的清洁能源已经成为科学研究的热点。氢气因为其燃烧热值高、产物无污染等特点而备受关注。高效储氢及运输氢气是目前制约氢能开发利用的重要因素。为了解决储氢及运输氢气的难题,利用氢化物制氢成为了当下研究热点。在众多的储氢材料中,氨硼烷(NH3BH3,简称AB)含氢量高并且释氢速率快,有较好的稳定性,环境友好,被认为是很有潜力的储氢材料之一。但由于氨硼烷水解制氢在常温没有催化剂催化的情况下,反应速率异常缓慢,而在以往催化剂的研究中,贵金属催化剂表现出优异的催化产氢性能,但由于贵金属价格昂贵,限制了其工业化应用。因此寻找一种存量丰富,价格低廉的非贵金属催化剂用于氨硼烷水解快速释氢成为了当下研究热点。文献报道,引入杂原子(P、B、N等)可以引起催化剂在反应过程中电子结构的变化,进而降低氨硼烷B-N键断键所需要的能量,从而提升催化剂性能。
过渡金属磷酸盐(Co3(PO4)2、Cu3(PO4)2等)纳米材料由于其具有特殊的晶格结构、高比表面积、良好的导电性、复杂的电子结构等特点,在超级电容器、锂离子电池、电催化、光催化等领域有着广泛的应用。
中国专利(CN107096555A)提出了一种碳酸钴复合磷酸钴光催化剂的制备方法,以硝酸钴、碳酸钠、去离子水配制得到前驱体溶液;将以上两种溶液搅拌混合,形成胶状物质,在搅拌过程中碳酸钠和硝酸钴反应,生成碳酸钴胶体;将碳酸钴胶体置于半透膜袋内,用蒸馏水洗涤,去除掉游离离子,再将该碳酸钴胶体加入到浓度一定的磷酸钠溶液中,浸泡至碳酸钴颗粒表面形成磷酸钴纳米颗粒,固液分离,去离子水洗涤固体,烘干,制得一种碳酸钴复合磷酸钴光催化剂。但是制备周期太长且能耗较高,不利于工业化应用。
中国专利(CN104269528A)公开了一种磷酸钴粉体材料的制备方法,通过简单的将可溶性钴盐和可溶性磷酸盐反应得到磷酸钴,接着用氨水调节反应体系pH值中性,进而通过洗涤、烘干后研磨、筛分,可以制备出磷酸钴粉体材料,但是该方法制备出的磷酸钴粉体材料形貌分布并不均匀。
因此,研发一种形貌可控、成本较低、产品性能优良的能够应用于工业化生产磷酸盐复合物的方法是本发明的所解决的问题。
发明内容
本发明所要解决的技术问题是提供一种形貌规整的磷酸盐催化剂的制备方法,本发明合成方法简单、条件温和,合成出的Cu3-3xCo3x(PO4)2为球形,具有分散均匀、形貌规整等优点。
本发明提供一种磷酸钴铜微球的制备方法,包括以下步骤:
(1)、将pH调节剂、表面活性剂、溶于超纯水形成A溶液;
(2)、将可溶性钴盐或可溶性铜盐或两者一起溶于超纯水中,配置成混合盐溶液B;
(3)、将B溶液缓慢加至A溶液混合形成C溶液,搅拌0~1h;
(4)、缓慢向C溶液滴加30%的H3PO4溶液;
(5)、再转移至反应釜,80~180℃反应2~24h,过滤洗涤,收集产品,在真空烘箱40~80℃下烘干。
优选的,步骤(1)中所述表面活性剂为包括十二烷基硫酸钠、聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、聚乙二醇中的一种或多种。
优选的,步骤(1)中所述pH调节剂为尿素、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、氨水、六次甲基四胺中的一种或多种。
优选的,步骤(2)中所述可溶性钴盐选自四水乙酸钴、氯化钴、硫酸钴、硝酸钴、六水氯化钴、七水硫酸钴、六水硝酸钴中的一种或多种。
优选的,步骤(2)中所述可溶性铜盐选自二水氯化铜、五水硫酸铜、硝酸铜中的一种或多种。
优选的,步骤(4)中所加入磷酸的量与金属盐Co2+或Cu2+或两者的摩尔比为2/3~3。
本发明还公开了利用上述方法制得的磷酸钴铜催化剂在催化氨硼烷水解产氢上的应用。综上所述,本发明的制备方法具有以下有益效果:
1.制备方法简单,合成产品为微球状,且分散均匀。
2.可对钴铜比例进行灵活调配,合成出具有化学通式为Cu3-3xCo3x(PO4)2的磷酸钴铜催化剂。
3.本发明制备的Cu3-3xCo3x(PO4)2微球,在催化氨硼烷水解产氢方面。表现出优异的性能,尤其是Cu0.6Co2.4(PO4)2表现出强劲的催化性能。
附图说明
图1为本发明制备的Cu0.6Co2.4(PO4)2的SEM图;
图2为本发明制备的Cu0.6Co2.4(PO4)2的TEM图;
图3为本发明制备的Cu0.6Co2.4(PO4)2的Mapping图;
图4为本发明制备的Cu0.6Co2.4(PO4)2的XRD图;
图5为本发明制备的Cu0.6Co2.4(PO4)2的FT-IR图;
图6为本发明制备的钴铜不同配比的Cu3-3xCo3x(PO4)2催化剂催化产氢性能图。
具体实施方式
下面结合具体实施方式对本发明的上述发明内容做进一步的详细描述。但不应将此理解为本发明上述主题的范围仅局限于下述实施例。在不脱离本发明上述技术思想情况下,根据本领域普通技术知识和惯用手段,做出各种替换、变更和改进等均应包括在本发明的范围内。
实施例1
前驱体的制备:称取6.0g尿素和0.5g十二烷基硫酸钠(SDS)溶于61.3mL超纯水,磁力搅拌溶解,得到溶液A溶液,称取0.281gCoSO4·7H2O溶于2.7mL超纯水,磁力搅拌溶解,得到溶液B。将B溶液缓慢滴加至A中,得到C溶液,继续搅拌30min。向C溶液中缓慢滴加0.326gH3PO4(30wt%),将所得到的溶液转移至反应釜中,拧紧90℃下水热反应4h。反应结束后,冷却至室温,抽滤洗涤,收集产品,水洗2-3遍,乙醇洗2-3遍,在真空烘箱60℃下烘干后,待其冷却至室温后,取出样品得到目标产物Co3(PO4)2。
经测定,本发明所得Co3(PO4)2形貌为球形,颜色为深紫色。
实施例2
前驱体的制备:称取6.0g尿素和0.5g十二烷基硫酸钠(SDS)溶于61.3mL超纯水,磁力搅拌溶解,得到溶液A溶液,称取0.225gCoSO4·7H2O和0.050gCuSO4·5H2O溶于2.7mL超纯水,磁力搅拌溶解,得到溶液B。将B溶液缓慢滴加至A中,得到C溶液,继续搅拌30min。向C溶液中缓慢滴加0.326gH3PO4(30wt%),将所得到的溶液转移至反应釜中,拧紧90℃下水热反应4h。反应结束后,冷却至室温,抽滤洗涤,收集产品,水洗2-3遍,乙醇洗2-3遍,在真空烘箱60℃下烘干后,待其冷却至室温后,取出样品得到目标产物Cu0.6Co2.4(PO4)2。
经测定,本发明所得Cu0.6Co2.4(PO4)2形貌为球形,颜色为深紫色。
实施例3
前驱体的制备:称取6.0g尿素和0.5g十二烷基硫酸钠(SDS)溶于61.3mL超纯水,磁力搅拌溶解,得到溶液A溶液,称取0.169gCoSO4·7H2O和0.100gCuSO4·5H2O溶于2.7mL超纯水,磁力搅拌溶解,得到溶液B。将B溶液缓慢滴加至A中,得到C溶液,继续搅拌30min。向C溶液中缓慢滴加0.326gH3PO4(30wt%),将所得到的溶液转移至反应釜中,拧紧90℃下水热反应4h。反应结束后,冷却至室温,抽滤洗涤,收集产品,水洗2-3遍,乙醇洗2-3遍,在真空烘箱60℃下烘干后,待其冷却至室温后,取出样品得到目标产物Cu1.2Co1.8(PO4)2。
经测定,本发明所得Cu1.2Co1.8(PO4)2形貌为球形,颜色为蓝紫色。
实施例4
前驱体的制备:称取6.0g尿素和0.5g十二烷基硫酸钠(SDS)溶于61.3mL超纯水,磁力搅拌溶解,得到溶液A溶液,称取0.141gCoSO4·7H2O和0.125gCuSO4·5H2O溶于2.7mL超纯水,磁力搅拌溶解,得到溶液B。将B溶液缓慢滴加至A中,得到C溶液,继续搅拌30min。向C溶液中缓慢滴加0.326gH3PO4(30wt%),将所得到的溶液转移至反应釜中,拧紧90℃下水热反应4h。反应结束后,冷却至室温,抽滤洗涤,收集产品,水洗2-3遍,乙醇洗2-3遍,在真空烘箱60℃下烘干后,待其冷却至室温后,取出样品得到目标产物Cu1.5Co1.5(PO4)2。
经测定,本发明所得Cu1.5Co1.5(PO4)2形貌为球形,颜色为蓝紫色。
实施例5
前驱体的制备:称取6.0g尿素和0.5g十二烷基硫酸钠(SDS)溶于61.3mL超纯水,磁力搅拌溶解,得到溶液A溶液,称取0.225gCoSO4·7H2O和0.050gCuSO4·5H2O溶于2.7mL超纯水,磁力搅拌溶解,得到溶液B。将B溶液缓慢滴加至A中,得到C溶液,继续搅拌30min。向C溶液中缓慢滴加0.625gH3PO4(30wt%),将所得到的溶液转移至反应釜中,拧紧90℃下水热反应4h。反应结束后,冷却至室温,抽滤洗涤,收集产品,水洗2-3遍,乙醇洗2-3遍,在真空烘箱60℃下烘干后,待其冷却至室温后,取出样品得到目标产物Cu0.6Co2.4(PO4)2。
经测定,本发明所得Cu0.6Co2.4(PO4)2形貌为球形,颜色为深紫色。
实施例6
前驱体的制备:称取6.0g尿素和0.5g十六烷基三甲基溴化铵(CTAB)溶于61.3mL超纯水,磁力搅拌溶解,得到溶液A溶液,称取0.225gCoSO4·7H2O和0.050gCuSO4·5H2O溶于2.7mL超纯水,磁力搅拌溶解,得到溶液B。将B溶液缓慢滴加至A中,得到C溶液,继续搅拌30min。向C溶液中缓慢滴加0.326gH3PO4(30wt%),将所得到的溶液转移至反应釜中,拧紧90℃下水热反应4h。反应结束后,冷却至室温,抽滤洗涤收集产品,水洗2-3遍,乙醇洗2-3遍,在真空烘箱60℃下烘干后,待其冷却至室温后,取出样品得到目标产物Cu0.6Co2.4(PO4)2。
经测定,本发明所得Cu0.6Co2.4(PO4)2形貌为球形,颜色为深紫色。
实施例7
前驱体的制备:称取6.0g六次甲基四胺和0.5g十二烷基硫酸钠(SDS)溶于61.3mL超纯水,磁力搅拌溶解,得到溶液A溶液,称取0.225gCoSO4·7H2O和0.050gCuSO4·5H2O溶于2.7mL超纯水,磁力搅拌溶解,得到溶液B。将B溶液缓慢滴加至A中,得到C溶液,继续搅拌30min。向C溶液中缓慢滴加0.326gH3PO4(30wt%),将所得到的溶液转移至反应釜中,拧紧90℃下水热反应4h。反应结束后,冷却至室温,抽滤洗涤,收集产品,水洗2-3遍,乙醇洗2-3遍,在真空烘箱60℃下烘干后,待其冷却至室温后,取出样品得到目标产物Cu0.6Co2.4(PO4)2。
经测定,本发明所得Cu0.6Co2.4(PO4)2形貌为球形,颜色为深紫色。
下面以Cu0.6Co2.4(PO4)2为例,对本发明制备的复合磷酸盐的结构和性能进行分析和测试。
1、SEM分析
图1为本发明制备的Cu0.6Co2.4(PO4)2的SEM图。从扫描电镜图中可以看出,所合成的Cu0.6Co2.4(PO4)2形貌为球状,粒径约为500nm。
2、TEM分析
图2为本发明制备的Cu0.6Co2.4(PO4)2的TEM图。从透射电镜扫描图中可以看出,所合成的Cu0.6Co2.4(PO4)2形貌为球状,粒径约为500nm,内部是实心结构。
3、元素分布测试
图2为本发明制备的Cu0.6Co2.4(PO4)2的Mapping图,从图中可以看出,Cu、Co、P和O元素均匀分布。
4、XRD分析
图4为本发明制备的Cu0.6Co2.4(PO4)2的XRD测试。
5、红外分析
图5为本发明制备的Cu0.6Co2.4(PO4)2的FT-IR测试。
6、催化产氢性能的测试
图6为本发明制备不同钴铜配比的Cu3-3xCo3x(PO4)2,作为催化剂催化氨硼烷水解产氢的性能测试,NH3BH3用量为3mmol,NaOH用量为20mmol,催化剂5mg。测得25℃下Cu3-3xCo3x(PO4)2产氢速率曲线。
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本发明的保护范围。
Claims (4)
1.磷酸钴铜作为催化剂在催化氨硼烷水解产氢上的应用,其特征在于,磷酸钴铜微球的制备方法包括以下步骤:
(1)、将pH调节剂、表面活性剂、溶于超纯水形成A溶液;
(2)、将可溶性钴盐和可溶性铜盐一起溶于超纯水中,配置成混合盐溶液B;
(3)、将B溶液缓慢加至A溶液混合形成C溶液,搅拌0~1 h;
(4)、缓慢向C溶液滴加30%的H3PO4溶液;
(5)、再转移至反应釜,80~180℃反应2~24 h,过滤洗涤,收集产品,在真空烘箱40~80℃下烘干;
步骤(1)中所述表面活性剂为包括十六烷基三甲基溴化铵、十二烷基硫酸钠、聚乙二醇中的一种或多种;
步骤(4)中所加入磷酸的量与金属盐Co2+和Cu2+的摩尔比为2/3~3。
2.根据权利要求1所述磷酸钴铜作为催化剂在催化氨硼烷水解产氢上的应用,其特征在于:步骤(1)中所述pH调节剂为尿素、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、氨水、六次甲基四胺中的一种或多种。
3.根据权利要求1所述磷酸钴铜作为催化剂在催化氨硼烷水解产氢上的应用,其特征在于:步骤(2)中所述可溶性钴盐选自四水乙酸钴、硫酸钴、硝酸钴、六水氯化钴、七水硫酸钴、六水硝酸钴中的一种或多种。
4.根据权利要求1所述磷酸钴铜作为催化剂在催化氨硼烷水解产氢上的应用,其特征在于:步骤(2)中所述可溶性铜盐选自二水氯化铜、五水硫酸铜、硝酸铜中的一种或多种。
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CN108328593A (zh) * | 2018-02-11 | 2018-07-27 | 济南大学 | 一种棉花团状磷酸钴球及其制备方法 |
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