CN107970944A - 一种复合钼酸盐空心微球的制备方法及其应用 - Google Patents
一种复合钼酸盐空心微球的制备方法及其应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- -1 compound molybdate Chemical class 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 6
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910018965 MCl2 Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 239000010949 copper Substances 0.000 description 15
- 229910015667 MoO4 Inorganic materials 0.000 description 13
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910018864 CoMoO4 Inorganic materials 0.000 description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910003203 NH3BH3 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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Abstract
本发明公开了一种复合钼酸盐空心微球的制备方法，包括以下步骤：(1)、取MCl2 1～4mmol溶于20mL水，得溶液A；再取钼酸1～4mmol溶于20mL水，得溶液B；将二者混合；其中M表示Co、Ni、Cu；(2)、取10～40mmol尿素溶于40mL水，加入上述溶液；搅拌均匀；(3)、将上述混合液移至反应釜，120～160℃反应6～12h；(4)、抽滤水洗，真空烘箱40～60℃烘干；(5)马弗炉350～500℃煅烧2～4h。本发明制备的复合钼酸盐空心微球，具有较高的有效接触面积及孔隙率；且工艺简单，原料价廉易得；且制备过程并未使用表面活性剂等作为结构导向剂来控制形貌；合成的多元钼酸盐空心微球因微观结构特点有望作为高活性催化剂，如在催化氨硼烷水解产氢方面表现出优越的催化活性。
Description
技术领域
本发明涉及化合物制备技术领域，尤其涉及一种复合钼酸盐空心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
钼酸盐化合物通过(MoO4)2-与一种或一种以上阳离子组合成具有不同性质的钼酸盐，例如，与La、Eu等可以组成荧光粉体材料；与Co、Ni、Cu可以组成具有优越催化性能的催化剂。通过不同组合的钼酸盐能在光学领域，电学领域，催化领域，医疗领域都有不俗的表现，因此钼酸盐是无机功能材料中的重要成员。
近年来，钼酸盐纳米材料的制备方法一直是研究热点，传统的高温固相法需要较高温度，而且不能保证得到形貌较好的晶体，因此，一些低温合成方法，如水热合成法、模板法、微乳液法、沉淀法应运而生。如L.Zhen等人(L.Zhen et al.High photocatalyticactivity and photoluminescence property of hollow CdMoO4microspheres.ScriptaMaterialia,2008,58,461–464)用沉淀法在室温水溶液中合成了中空的CdMoO4微球。在反应过程中加入的可溶性的无机盐NaCl虽然没有参加反应，但作为配合助剂而影响CdMoO4的沉淀速度；但此制备方法需要将悬浮液静置5天，周期较长，不利于工业化生产；LiangjunWang等人(Liangjun Wang et al.Synthesis of porous CoMoO4nanorods as abifunctional cathode catalyst for a Li–O2battery and superior anode for a Li-ion battery.Nanoscale,2017,9,3898–3904)采用溶剂热合成法合成CoMoO4纳米棒，在反应过程中用超纯水、乙醇、乙二醇的混合液为溶剂制备前驱体，经氩气氛围煅烧得到CoMoO4纳米棒，该方法制备工艺简单，但有机溶剂与稀有气体的使用，成本较高；Xiaoqin Yan等人(Xiaoqin Yan et al.3D architecture of a graphene/CoMoO4composite forasymmetric supercapacitors usable at various temperatures.J.Colloid InterfaceSci.,2017,493,42–50)以石墨烯作为模板，两步水热法合成了CoMoO4纳米片，而且煅烧阶段以氩气作为保护气体，仍然使得制备成本不菲；钼酸钴及钼酸铜合成产物形貌多为纳米片、纳米颗粒，微米空心球未见报道，空心球具有较高的有效接触面积及孔隙率，因此对于催化剂的活性而言是一种促进。
发明内容
本发明所要解决的技术问题是，针对上述制备过程中存在的制备成本高、形貌不可控等关键问题，而提供一种多元钼酸盐空心微球的制备方法，其以尿素为沉淀剂，应用水热合成法成功合成了多元钼酸盐空心微球结构；该合成方法为系统研究多元钼酸盐纳米材料微观结构与性能之间的构效关系提供了技术支持，同时也为推动材料的低成本规模化生产迈出了重要一步。
为解决以上技术问题，本发明采用的技术方案是：一种复合钼酸盐空心微球的制备方法，包括以下步骤：
(1)、取MCl2 1～4mmol溶于20mL水，得溶液A；再取钼酸1～4mmol溶于20mL水，得溶液B；将二者混合；其中M表示Co、Ni、Cu；
(2)、取10～40mmol尿素溶于40mL水，加入上述溶液；搅拌均匀；
(3)、将上述混合液移至反应釜，120～160℃反应6～12h；
(4)、抽滤水洗，真空烘箱40～60℃烘干；
(5)马弗炉350～500℃煅烧2～4h。
优选的，步骤(1)中可溶性镍盐、钴盐、铜盐总物质量与钼酸的物质量比值1:1。
优选的，步骤(2)中，搅拌时间为0.5-1h。
优选的，步骤(3)中，真空烘箱温度为40～60℃。
综上所述，运用本发明的技术方案，具有如下有益效果：
1.本发明制备的独特纳米空心球，具有较高的有效接触面积及孔隙率；
2.工艺简单，原料价廉易得；
3.制备过程并未使用表面活性剂等作为结构导向剂来控制形貌；
4.合成的多元钼酸盐空心微球因微观结构特点有望作为高活性催化剂，如在催化氨硼烷水解产氢方面表现出优越的催化活性。
附图说明
图1为本发明制备的Co0.8Cu0.2MoO4的SEM图；
图2为本发明制备的Co0.8Cu0.2MoO4的TEM图；
图3为本发明制备的Co0.8Cu0.2MoO4的BET测试曲线；
图4为本发明制备的Co0.8Cu0.2MoO4的XRD测试曲线；
图5为本发明制备的Co0.8Cu0.2MoO4的催化产氢测试曲线。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，但不构成对本发明保护范围的限制。
实施例1
1、取CuCl2 1mmol溶于20mL水，得溶液A；再取钼酸1mmol溶于20mL水，得溶液B；将二者混合；
2、取10mmol尿素溶于40mL水，加入上述溶液；搅拌30min后移至反应釜，160℃反应8h；抽滤水洗，真空烘箱40℃烘干；马弗炉500℃煅烧2h；该样品组成为CuMoO4；
实施例2
1、取CuCl2x mmol、NiCl2y mmol、CoCl2(1-x-y)mmol溶于20mL水，得溶液A；再取钼酸2mmol溶于20mL水，得溶液B；将二者混合；
2、取20mmol尿素溶于40mL水，加入上述溶液；搅拌30min后移至反应釜，120℃反应12h；抽滤水洗，真空烘箱60℃烘干；马弗炉500℃煅烧2h；该样品组成为CuxCoyNi1-x-yMoO4；
实施例3
1、取CuCl2x mmol、NiCl2y mmol、CoCl2(1-x-y)mmol溶于20mL水，得溶液A；再取钼酸2mmol溶于20mL水，得溶液B；将二者混合；
2、取30mmol尿素溶于40mL水，加入上述溶液；搅拌30min后移至反应釜，160℃反应8h；抽滤水洗，真空烘箱40℃烘干；马弗炉350℃煅烧2h；该样品组成为CuxCoyNi1-x-yMoO4；
实施例4
1、取CuCl2x mmol、NiCl2y mmol、CoCl2(1-x-y)mmol溶于20mL水，得溶液A；再取钼酸2mmol溶于20mL水，得溶液B；将二者混合；
2、取40mmol尿素溶于40mL水，加入上述溶液；搅拌30min后移至反应釜，160℃反应12h；抽滤水洗，真空烘箱40℃烘干；马弗炉500℃煅烧4h；该样品组成为CuxCoyNi1-x-yMoO4；
实施例5
1、取CuCl2x mmol、NiCl2y mmol、CoCl2(1-x-y)mmol溶于20mL水，得溶液A；再取钼酸4mmol溶于20mL水，得溶液B；将二者混合；
2、取40mmol尿素溶于40mL水，加入上述溶液；搅拌1h后移至反应釜，160℃反应12h；抽滤水洗，真空烘箱60℃烘干；马弗炉500℃煅烧4h；该样品组成为CuxCoyNi1-x-yMoO4；
1、SEM分析
图1为本发明制备的Co0.8Cu0.2MoO4的SEM图。从扫描图中可以看出，通过水热合成的Co0.8Cu0.2MoO4形貌呈直径约为0.5～0.8um的纳米空心微球。
2、TEM测试
为本发明制备的Co0.8Cu0.2MoO4的TEM图，从投射图中可以进一步证实空心微球的催化剂性能。
3、BET测试
图2为本发明制备的Co0.8Cu0.2MoO4的氮气吸附脱附等温曲线，比表面积为30.01m2/g。
4、XRD
图3为本发明制备的Co0.8Cu0.2MoO4的XRD测试。图中所标示出的为CuMoO4与CoMoO4对应晶面的特征峰。
5、催化产氢性能的测试
图4为本发明制备的Co0.8Cu0.2MoO4作为催化剂催化氨硼烷水解产氢的性能测试，NH3BH3用量3mmol，NaOH 20mmol，催化剂10mg。测得25℃下Co0.8Cu0.2MoO4作为催化剂每分钟产氢56mL。
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 (5)
1.一种复合钼酸盐空心微球的制备方法，其特征在于，包括以下步骤：
(1)、取MCl2 1～4mmol溶于20mL水，得溶液A；再取钼酸1～4mmol溶于20mL水，得溶液B；将二者混合；其中M表示Co、Ni、Cu；
(2)、取10～40mmol尿素溶于40mL水，加入上述溶液；搅拌均匀；
(3)、将上述混合液移至反应釜，120～160℃反应6～12h；
(4)、抽滤水洗，真空烘箱40～60℃烘干；
(5)马弗炉350～500℃煅烧2～4h。
2.根据权利要求1所述的一种复合钼酸盐空心微球的制备方法，其特征在于：步骤(1)中可溶性镍盐、钴盐、铜盐总物质量与钼酸的物质量比值1:1。
3.根据权利要求1所述的一种复合钼酸盐空心微球的制备方法，其特征在于：步骤(2)中，搅拌时间为0.5-1h。
4.根据权利要求1所述的一种复合钼酸盐空心微球的制备方法，其特征在于：步骤(3)中，真空烘箱温度为40～60℃。
5.如权利要求1～4任一项所述的制备方法所制备的复合钼酸盐空心微球作为催化剂在催化氨硼烷水解产氢上的应用。
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