CN109107609A - 一种葡萄糖酸增强催化活性的mof催化剂的制备方法和应用 - Google Patents
一种葡萄糖酸增强催化活性的mof催化剂的制备方法和应用 Download PDFInfo
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- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 title claims abstract description 60
- 239000000174 gluconic acid Substances 0.000 title claims abstract description 60
- 235000012208 gluconic acid Nutrition 0.000 title claims abstract description 60
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 36
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 28
- 239000012918 MOF catalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 90
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- 239000000243 solution Substances 0.000 claims abstract description 27
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- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 nickel -1,3,5-Benzenetricarboxylic acid nickel Chemical compound 0.000 claims abstract description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 229940075397 calomel Drugs 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 7
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
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- WQBNIORIDCTSRY-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid nickel Chemical compound [Ni].OC(=O)c1cc(cc(c1)C(O)=O)C(O)=O WQBNIORIDCTSRY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 4
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
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Abstract
本发明公开了一种葡萄糖酸增强催化活性的MOF催化剂的制备方法以及基于该催化剂电解水析氧的应用,属于纳米催化、纳米材料、金属有机框架物材料技术领域。其主要步骤是将间苯三甲酸溶液与硝酸镍溶液室温共混后,加入配制好的葡萄糖酸溶液,利用混合溶液作为电解液沉积到泡沫镍上,活化之后即得葡萄糖酸镍‑间苯三甲酸镍复合催化剂,即葡萄糖酸增强催化活性的MOF催化剂。该催化剂制备所用原料成本低,制备工艺简单,反应能耗低,具有工业应用前景。该催化剂用于高效催化电解水析氧,具有良好的析氧电催化活性与电化学稳定性。
Description
技术领域
本发明涉及一种葡萄糖酸增强催化活性的MOF催化剂的制备方法以及基于该催化剂电解水析氧的应用,属于纳米催化、纳米材料、金属有机框架物材料技术领域。
背景技术
现代社会的飞速发展引起了对环保可再生能源氢气的巨大需求,它作为一种理想能源,被提议变成未来世界的主要利用能源,属于二次能源。如今,氢气的产生主要通过天然气的蒸汽甲烷重整(即水和甲烷之间反应形成H2和CO2)。因此,现在生产氢气伴随着一系列的温室效应,这样既没做到再生也不能进行碳中和。相对于现在应用广泛的重整制氢,利用水的电解生产氢可再生又环保。电催化直接分解水制备氢气被认为实现该过程有效的方式。电催化分解水反应包括析氢(hydrogen evolution reaction,HER)和析氧(oxygenevolution reaction,OER)两个半反应,来自电阻、反应以及传输三个方面系统本征的能量损耗以及现有催化剂的价格、活性和稳定性方面的因素,都极大地限制了其推广和广泛应用。尽管析氧仅是一个副反应,但是为了驱动析氧反应给系统运行带来的功耗损失却最大,成为提高整体效率的瓶颈。寻找廉价易得且性能稳定的新型析氧电催化剂,对长远发展氢能、减小环境污染乃至缓解世界范围内的能源问题,具有广泛且重要的现实意义。
在众多的析氧催化剂中,对于MOF的研究越来越广泛和深入。金属-有机骨架材料(Metal-OrganicFrameworks)是指过渡金属离子与有机配体通过自组装形成的具有周期性网络结构的晶体多孔材料。它具有高孔隙率、低密度、大比表面积、孔道规则、孔径可调以及拓扑结构多样性和可裁剪性等优点,使得MOF在气体储存、分离、催化、识别和药物传输等领域获得了广泛的应用。
二氧化铱(IrO2)和二氧化钌(RuO2)是目前析氧催化剂中性能很好的组成部分,但是成本较高,因此开发高效、价廉且地球含量丰富的非贵金属析氧催化剂,降低析氧电消耗成为一个机遇和挑战。间苯三甲酸与硝酸镍形成的MOF已被许多实验及文献证实在电化学方面有着优异的性能,例如2018年孙旭平的团队用间苯三甲酸与硝酸镍合成了Ni3(BTC)2,并用来检测析氧性能,检测结果证明Ni3(BTC)2能够达到很好的析氧效果。提高析氧性能的途径一是使用更加稳定且性能更好的前驱体MOF以及基底如碳布、泡沫镍等,再者就是进行掺杂,常用的掺杂物质有石墨烯、含氮或含磷化合物、葡萄糖等等,早在1994年,ChebroluP. Rao就证实了糖类衍生物可以通过降低溶液pKa值来合成,并在文章中提及糖类衍生物的电化学使用价值[Chebrolu P. Rao等,Polyhedron, 1994, 13, 1895-1906],
目前,据我们所知,在此基础上掺杂葡萄糖酸进行析氧性能的研究未见报道。葡萄糖酸成本低,制备简易,价格低廉,本开发首先制备了间苯三甲酸-硝酸镍溶液,加入葡萄糖酸之后采用电化学沉积法,活化后制备了葡萄糖酸镍-间苯三甲酸镍复合催化剂,即一种葡萄糖酸增强催化活性的MOF催化剂。
发明内容
本发明的技术任务之一是为了弥补现有技术的不足,提供一种葡萄糖酸增强催化活性的MOF催化剂,即葡萄糖酸镍-间苯三甲酸镍复合催化剂的制备方法,该方法所用原料成本低,制备工艺简单,反应能耗低,具有工业应用前景。
本发明的技术任务之二是提供所述一种葡萄糖酸增强催化活性的MOF催化剂的用途,即将该葡萄糖酸镍-间苯三甲酸镍复合催化剂用于高效催化电解水析氧,该催化剂具有良好的析氧电催化活性与电化学稳定性。
为实现上述目的,本发明采用的技术方案如下:
1. 一种葡萄糖酸增强催化活性的MOF催化剂的制备方法,步骤如下:
将0.16-0.28 g葡萄糖酸钠与4.0-6.0 mL水共混,搅拌后在混合溶液中加入0.05-0.15mL硝酸,搅拌均匀后得葡萄糖酸溶液;
将0.20-0.22 g间苯三甲酸、0.35-0.37 g硝酸镍与4.0-6.0 mL N,N-二甲基甲酰胺共混,超声1min后,得绿色澄清溶液;
将两溶液混合,超声2-3 min;在该溶液中,以面积为1 cm×1 cm的活化泡沫镍NiF为工作电极,铂片为对电极,甘汞电极为参比电极,采用恒电位沉积法,合成葡萄糖酸镍-间苯三甲酸镍/NiF复合材料;将获得的复合材料,85℃活化4h,制得了活化的葡萄糖酸镍-间苯三甲酸镍/NiF复合材料,即葡萄糖酸增强催化活性的MOF催化剂。
所述活化泡沫镍,是将泡沫镍依次在丙酮、无水乙醇及蒸馏水下超声2-4 min,洗涤除去表面杂物,再将泡沫镍浸渍在质量分数为10 %的盐酸中超声1 min制得。
所述恒电位沉积法,电位为-1.6~-2.0V,沉积时间为5-15 min。
所述葡萄糖酸镍-间苯三甲酸镍/NiF复合材料,是掺杂了葡萄糖酸镍的间苯三甲酸镍Ni3(BTC)2负载在泡沫镍上的纳米复合材料;
所述负载在泡沫镍上的纳米复合材料,由宽小于100 nm、长为4-5 μm的纳米棒阵列构成。
2. 如上所述的制备方法制备的一种葡萄糖酸增强催化活性的MOF催化剂作为电解水析氧催化剂的应用,步骤如下:
将活化的葡萄糖酸镍-间苯三甲酸镍/NiF复合材料作为工作电极,Pt 片 (5 mm×5 mm×0.1 mm)为对电极,甘汞电极为参比电极,使用三电极电化学工作站,在电解液为 1.0 MKOH的水溶液中测试电催化分解水性能;
上述葡萄糖酸增强催化活性的MOF催化剂电解水析氧,当电流密度J=5 mA/cm2时,电位小于1.25 V vs RHE;当电流密度J=10 mA/cm2时,电位小于1.38V vs RHE,均说明该材料高效的析氧催化活性;循环 1000 次前后,该类材料极化曲线没有发现明显的变化,表明催化剂具有良好的稳定性。
本发明的有益的技术效果:
1.本发明制得的一种葡萄糖酸增强催化活性的MOF催化剂是由金属有机框架物Ni3(BTC)2与葡萄糖酸镍配合物复合生成,制备过程工艺简单,简单易控,产物制备效率高,易于工业化。
2. 本发明制得的一种葡萄糖酸增强催化活性的MOF催化剂,即葡萄糖酸镍-间苯三甲酸镍/NiF催化剂,是掺杂了葡萄糖酸镍的Ni3(BTC)2 负载在泡沫镍上的纳米复合材料。由于该材料由负载在泡沫镍上的纳米棒阵列构成,比表面积大,MOF特有的微孔以及纳米棒阵列构成的介孔和大孔,有利于电荷的传递;葡萄糖酸镍掺杂在间苯三甲酸镍的复合材料中,协同增强了导电及析氧催化性能,催化效率高且稳定性好。
具体实施方式
下面结合实施例对本发明作进一步描述,但本发明的保护范围不仅局限于实施例,该领域专业人员对本发明技术方案所作的改变,均应属于本发明的保护范围内。
实施例1 一种葡萄糖酸增强催化活性的MOF催化剂制备方法
将0.16 g葡萄糖酸钠与4.0 mL水共混,搅拌后在混合溶液中加入0.05 mL硝酸,搅拌均匀后得葡萄糖酸溶液;
将0.20 g间苯三甲酸、0.35 g硝酸镍与4.0 mL N,N-二甲基甲酰胺共混,超声1min后,得绿色澄清溶液;
将两溶液混合,超声2 min;在该溶液中,以面积为1 cm×1 cm的活化泡沫镍NiF为工作电极,铂片为对电极,甘汞电极为参比电极,采用恒电位沉积法,合成葡萄糖酸镍-间苯三甲酸镍/NiF复合材料;将获得的复合材料,85℃活化4h,制得了葡萄糖酸增强催化活性的MOF催化剂;
所述活化泡沫镍,是将泡沫镍依次在丙酮、无水乙醇及蒸馏水下超声2 min,洗涤除去表面杂物,再将泡沫镍浸渍在质量分数为10 %的盐酸中超声1 min制得。
所述恒电位沉积法,电位为-1.6V,沉积时间为5 min;
所述葡萄糖酸镍-间苯三甲酸镍/NiF复合材料,是掺杂了葡萄糖酸镍的Ni3(BTC)2 负载在泡沫镍上的纳米复合材料。
实施例2 一种葡萄糖酸增强催化活性的MOF催化剂制备方法
将0.22 g葡萄糖酸钠与5.0 mL水共混,搅拌后在混合溶液中加入0.10 mL硝酸,搅拌均匀后得葡萄糖酸溶液;
将0.21 g间苯三甲酸、0.36 g硝酸镍与5.0 mL N,N-二甲基甲酰胺共混,超声1min后,得绿色澄清溶液;
将两溶液混合,超声2.5 min;在该溶液中,以面积为1 cm×1 cm的活化泡沫镍NiF为工作电极,铂片为对电极,甘汞电极为参比电极,采用恒电位沉积法,合成葡萄糖酸镍-间苯三甲酸镍/NiF复合材料;将获得的复合材料,85℃活化4h,制得了葡萄糖酸增强催化活性的MOF催化剂;
所述活化泡沫镍,制备同实施例1;
所述恒电位沉积法,电位为-1.8V,沉积时间为10 min;
所述葡萄糖酸镍-间苯三甲酸镍/NiF复合材料,是掺杂了葡萄糖酸镍的Ni3(BTC)2 负载在泡沫镍上的纳米复合材料。
实施例3 一种葡萄糖酸增强催化活性的MOF催化剂制备方法
将0.28 g葡萄糖酸钠与6.0 mL水共混,搅拌后在混合溶液中加入0.15 mL硝酸,搅拌均匀后得葡萄糖酸溶液;
将0.22 g间苯三甲酸、0.37 g硝酸镍与6.0 mL N,N-二甲基甲酰胺共混,超声1min后,得绿色澄清溶液;
将两溶液混合,超声3 min;在该溶液中,以面积为1 cm×1 cm的活化泡沫镍NiF为工作电极,铂片为对电极,甘汞电极为参比电极,采用恒电位沉积法,合成葡萄糖酸镍-间苯三甲酸镍/NiF复合材料;将获得的复合材料,85℃活化4h,制得了葡萄糖酸增强催化活性的MOF催化剂。
所述活化泡沫镍,制备同实施例1;
所述恒电位沉积法,电位为-1.8V,沉积时间为15 min。
所述葡萄糖酸镍-间苯三甲酸镍/NiF复合材料,是掺杂了葡萄糖酸镍的Ni3(BTC)2负载在泡沫镍上的纳米复合材料。
实施例4 实施例1-3所述的一种葡萄糖酸增强催化活性的MOF催化剂制备方法,所述间苯三甲酸镍,化学式为Ni3(BTC)2 。
实施例5 葡萄糖酸增强催化活性的MOF催化剂作为电解水析氧催化剂的应用
将实施例1、实施例2和实施例3制得的活化葡萄糖酸镍-间苯三甲酸镍/NiF复合材料分别作为工作电极,Pt 片 (5 mm×5 mm×0.1 mm)为对电极,甘汞电极为参比电极,使用三电极电化学工作站,在电解液为 1.0 M KOH的水溶液中,采用线性扫描伏安法,测试电催化水分解析氧极化曲线;
三种活化葡萄糖酸镍-间苯三甲酸镍/NiF复合材料,当电流密度J=5 mA/cm2时,电位均小于1.25 V(vs RHE);当电流密度J=10 mA/cm2时,电位小于1.38V(vs RHE),均说明该材料高效的析氧催化活性;循环1000 次前后,该类材料极化曲线没有发现明显的变化,表明催化剂具有良好的稳定性。
Claims (6)
1.一种葡萄糖酸增强催化活性的MOF催化剂的制备方法,其特征在于,步骤如下:
将0.16-0.28 g葡萄糖酸钠与4.0-6.0 mL水共混,搅拌后在混合溶液中加入0.05-0.15mL质量分数为97 %的硝酸,搅拌均匀后得葡萄糖酸溶液;
将0.20-0.22 g间苯三甲酸、0.35-0.37 g硝酸镍与4.0-6.0 mL N,N-二甲基甲酰胺共混,超声1min后,得绿色澄清溶液;
将两溶液混合,超声2-3 min;在该溶液中,以面积为1 cm×1 cm的活化泡沫镍NiF为工作电极,铂片为对电极,甘汞电极为参比电极,采用恒电位沉积法,合成葡萄糖酸镍-间苯三甲酸镍/NiF复合材料;将获得的复合材料,85℃活化4h,制得了活化的葡萄糖酸镍-间苯三甲酸镍/NiF复合材料,即葡萄糖酸增强催化活性的MOF催化剂。
2.如权利要求1所述的一种葡萄糖酸增强催化活性的MOF催化剂的制备方法,其特征在于,所述活化泡沫镍,是将泡沫镍依次在丙酮、无水乙醇及蒸馏水下超声2-4 min,洗涤除去表面杂物,再将泡沫镍浸渍在质量分数为10%的盐酸中超声1 min制得。
3.如权利要求1所述的一种葡萄糖酸增强催化活性的MOF催化剂的制备方法,其特征在于,所述恒电位沉积法,电位为-1.6~-2.0V,沉积时间为5-15 min。
4.如权利要求1所述的一种葡萄糖酸增强催化活性的MOF催化剂的制备方法,其特征在于,所述间苯三甲酸镍,化学式为Ni3(BTC)2。
5.如权利要求1所述的一种葡萄糖酸增强催化活性的MOF催化剂的制备方法,其特征在于,所述葡萄糖酸镍-间苯三甲酸镍/NiF复合材料,是掺杂了葡萄糖酸镍的间苯三甲酸镍Ni3(BTC)2负载在泡沫镍上的纳米复合材料。
6.如权利要求1所述的制备方法制备的一种葡萄糖酸增强催化活性的MOF催化剂作为电解水析氧催化剂的应用。
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