CN109174192B - 一种Cu-MOF/碳点纳米片阵列催化剂的制备方法和应用 - Google Patents
一种Cu-MOF/碳点纳米片阵列催化剂的制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种Cu‑MOF/碳点纳米片阵列催化剂的制备方法以及该材料电解水析氧的应用,属于催化技术、复合材料技术领域。其主要步骤是将硝酸铜溶液与H6L配体及山梨醇共混,制得电沉积溶液;在三电极体系中,采用恒电位电沉积工艺,将得到的材料微波活化后,制得Cu‑MOF/碳点纳米片阵列催化剂。该催化剂制备所用原料成本低,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
本发明公开了一种Cu-MOF/碳点纳米片阵列催化剂的制备方法以及该材料电解水析氧的应用,属于催化技术、复合材料技术领域。
背景技术
氢能源是一种理想的绿色能源,电催化分解水制氢具有重要的发展前景。水分解过程中的析氧半反应(OER),比析氢半反应过程更为困难,需经历一个复杂的电质耦合(proton-coulped electron transfer, PCET)过程, 过电位更高, 消耗能量更多,为电解水制氢的瓶颈,为此, 寻找一种能够有效降低析氧过电位的析氧催化剂至关重要。在已开发的氧电催化剂中,Ir和Ru氧化物用于OER是当前被认为活性最高的催化剂,但其价格高、储量资源低、稳定性差是其难以逾越的缺陷。金属有机框架物(MOF)具有组成、孔尺寸、功能可调可设计的重要特征,这为设计和制备高效氧电催化剂提供了重要途径。2010年Marker团队开始使用纯MOF开发OER电催化(Journal of Membrane Science, 2009, 328(1):165-173)。后来, Co-ZIF-9(Co2+-苯并咪唑)也作为OER电催化剂(富氮金属—有机骨架的合成与功能性研究[D]. 吉林: 吉林大学, 2014),研究表明它在很宽的pH范围内具有OER活性。除了直接作为电催化剂外,多孔MOF,也可涂覆其他活性物质物种进一步提高其电催化性能。
碳点是一类以碳为主要元素且含多功能官能团的新型纳米材料,其粒径通常小于10 nm,它不仅继承了碳基材料的低毒和生物相容性好等特性,还兼具高度优异的水溶性、抗光漂白能力强、合成工艺简单并表面易于功能化等诸多优势,在生物成像,药物运载光电器件以及分析检测等方面已显示出广阔的发展前景。当前,科学家相继开展了针对其制备方法、性能分析、机理探讨和拓展型应用等发面的研究,并取得了突破性进展。碳点因含有羧基等极性官能团,预计可以与金属离子配位镶嵌在MOF结构的空隙中,因碳点比表面积大,且MOF结构以及碳点均可暴露更多且不同的活性位点,具有MOF晶体和碳点的协同作用,易于电子的传递和离子的扩散,活性位点多,从而使该材料的催化性能大大提高。
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Cu-MOF/碳点纳米片阵列催化剂的制备方法,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催化剂的用途,即将该催化剂用于高效催化电解水析氧,具有良好的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Cu-MOF/碳点纳米片阵列催化剂的制备方法
将0.160-0.170 g的Cu (NO3)2·3 H2O溶于由2-3 mL DMA、2-3 mL DMSO、80-120 μL H2O组成的混合溶剂中,得到澄清的硝酸铜溶液;
将0.025-0.035 g H6L配体、0.26-0.35 g的山梨醇与硝酸铜溶液共混,加入0.8-1.0 mL HBF4,超声1-3min,得到澄清的电沉积溶液;
使用1.0 cm × 1.0 cm的活化铜网CuF作为工作电极、铂片为辅助电极、甘汞电极为参比电极,在三电极体系中,采用恒电位电沉积工艺,制得Cu-MOF/山梨醇纳米片阵列负载在铜网上的复合材料;将其水洗后,采用250 W微波炉活化3 min,制得活化Cu-MOF/碳点/CuF纳米片阵列复合材料,即Cu-MOF/碳点纳米片阵列催化剂。
所述的Cu-MOF/碳点纳米片阵列催化剂的制备方法,其特征在于,所述H6L配体,其构造式如下:
H6L制备步骤如下:
将0.084 mol氨基间苯二甲酸、0.134 mol NaOH与0.104 mol NaHCO3加入到140ml蒸馏水中,混合后在0 ℃下搅拌30 min;同时逐滴滴加三聚氰氯的1,4-二氧六环溶液;该混合液在100 ℃下加热24 h, 用HCl调节混合物溶液的pH=2,过滤,用蒸馏水洗涤几次,室温下干燥后得到H6L配体,其产率为95%。
活化铜网CuF,是将1.0 cm × 1.0 cm的铜网CuF,于质量分数为1.5%的稀盐酸中超声2-4 min去除表面杂物,然后分别用蒸馏水、乙醇清洗后制得。
所述恒电位电沉积,是在-0.8~-1.5V的电压下沉积10-15 min,制得Cu-MOF/碳点/CuF纳米片阵列复合材料。
所述Cu-MOF,其结构单元为[Cu3L(H2O)3]·10H2O·5DMA,是由3个Cu2+、1个L6-、3个主体水分子、10个客体水分子和5个客体DMA分子构成,DMA为N,N-二甲基乙酰胺。
2. 如上所述的Cu-MOF/碳点纳米片阵列催化剂用于电解水析氧催化的应用。
将面积为1.0 cm×1cm的Cu-MOF/碳点纳米片阵列催化剂作为工作电极;使用三电极电化学工作站, Pt 片 (5 mm×5 mm×0.1 mm)为对电极,饱和甘汞电极电极为参比电极,在电解液为 1.0 M KOH水溶液中测试电催化分解水析氧性能。
上述Cu-MOF/碳点纳米片阵列催化剂电解水催化析氧,当电流密度J=10 mA/cm2时,过电位小于0.23 Vvs Hg/HgO;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Cu-MOF/碳点纳米片阵列催化剂的制备方法,采用恒电位电沉积工艺、一步法电沉积,制备出山梨醇掺杂Cu-MOF纳米片阵列负载在铜网上的复合材料,即Cu-MOF/山梨醇/CuF复合材料,再通过方便的微波热解山梨醇成为碳点并且活化Cu-MOF,快速制得Cu-MOF/碳点纳米片阵列催化剂,制备工艺简单,易操作,易工业化。
(2)本发明制得的催化剂,其结构为碳点掺杂的金属有机框架物MOF阵列,比表面积大,且纳米片状MOF阵列以及碳点均暴露了更多且不同的活性位点,发挥了MOF晶体和碳点的协同作用,易于电子的传递和离子的扩散,活性位点多。
(3)催化析氧效率高且稳定性好
本发明提供了一种Cu-MOF/碳点纳米片阵列催化剂,直接作为工作电极催化水分解析氧,免除了传统工作电极采用全氟化树脂或其它胶黏剂黏结催化剂粉末,使得该复合材料的催化析氧,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Cu-MOF/碳点纳米片阵列催化剂的制备方法
将0.160 g的Cu (NO3)2·3 H2O溶于由2 mL DMA、2 mL DMSO、80 μL H2O组成的混合溶剂中,得到澄清的硝酸铜溶液;
将0.025 g H6L配体、0.26g山梨醇与硝酸铜溶液共混,加入0.8 mL HBF4,超声1min,得到澄清的电沉积溶液;
使用1.0 cm × 1.0 cm的活化铜网CuF作为工作电极、铂片为辅助电极、甘汞电极为参比电极,在三电极体系中,采用恒电位电沉积工艺,制得Cu-MOF/山梨醇纳米片阵列负载在铜网上的复合材料;将其水洗后,采用250 W微波炉活化3 min,制得活化Cu-MOF/碳点/CuF纳米片阵列复合材料,即Cu-MOF/碳点纳米片阵列催化剂。
实施例2 一种Cu-MOF/碳点纳米片阵列催化剂的制备方法
将0.165 g的Cu (NO3)2·3 H2O溶于由2.5 mL DMA、2.5 mL DMSO、100 μL H2O组成的混合溶剂中,得到澄清的硝酸铜溶液;
将0.030 g H6L配体、0.35 g山梨醇与硝酸铜溶液共混,加入0.9 mL HBF4,超声2min,得到澄清的电沉积溶液;
使用1.0 cm × 1.0 cm的活化铜网CuF作为工作电极、铂片为辅助电极、甘汞电极为参比电极,在三电极体系中,采用恒电位电沉积工艺,制得Cu-MOF/山梨醇纳米片阵列负载在铜网上的复合材料;将其水洗后,采用250 W微波炉活化3 min,制得活化Cu-MOF/碳点/CuF纳米片阵列复合材料,即Cu-MOF/碳点纳米片阵列催化剂。
实施例3 一种Cu-MOF/碳点纳米片阵列催化剂的制备方法
将0.170 g的Cu (NO3)2·3 H2O溶于由3 mL DMA、3 mL DMSO、120 μL H2O组成的混合溶剂中,得到澄清的硝酸铜溶液;
将0.035 g H6L配体、0.30g山梨醇与硝酸铜溶液共混,加入1.0 mL HBF4,超声3min,得到澄清的电沉积溶液;
使用1.0 cm × 1.0 cm的活化铜网CuF作为工作电极、铂片为辅助电极、甘汞电极为参比电极,在三电极体系中,采用恒电位电沉积工艺,制得Cu-MOF/山梨醇纳米片阵列负载在铜网上的复合材料;将其水洗后,采用250 W微波炉活化3 min,制得活化Cu-MOF/碳点/CuF纳米片阵列复合材料,即Cu-MOF/碳点纳米片阵列催化剂。
实施例4
实施例1-3所述的H6L配体,其构造式如下:
H6L制备步骤如下:
将0.084 mol氨基间苯二甲酸、0.134 mol NaOH与0.104 mol NaHCO3加入到140ml蒸馏水中,混合后在0 ℃下搅拌30 min;同时逐滴滴加三聚氰氯的1,4-二氧六环溶液;该混合液在100 ℃下加热24 h, 用HCl调节混合物溶液的pH=2,过滤,用蒸馏水洗涤几次,室温下干燥后得到H6L配体,其产率为95%。
实施例5
实施例1-3所述活化铜网CuF,是将1.0 cm × 1.0 cm的铜网CuF在质量分数为1.5%的稀盐酸中超声2-4 min去除表面杂物,然后分别用蒸馏水、乙醇清洗后制得。
实施例6
实施例1-3所述Cu-MOF,其基本结构单元为[Cu3L(H2O)3]·10H2O·5DMA,是由3个Cu2+、1个配体L6-、3个主体水分子和10个客体水分子以及5个客体DMA分子构成,DMA为N,N-二甲基乙酰胺。
实施例7
将实施例1、实施例2、实施例3的面积为1.0 cm×1cm的Cu-MOF/碳点纳米片阵列催化剂作为工作电极;使用三电极电化学工作站, Pt 片 (5 mm×5 mm×0.1 mm)为对电极,饱和甘汞电极电极为参比电极,在电解液为 1.0 M KOH水溶液中测试电催化分解水析氧性能。当电流密度J=10 mA/cm2时,过电位为0.23、0.21、0.20 Vvs Hg/HgO;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 (5)
1.一种Cu-MOF/碳点纳米片阵列催化剂的制备方法,其特征在于,步骤如下:
(1)配制电沉积溶液
将0.160-0.170 g的Cu (NO3)2·3 H2O溶于由2-3 mL DMA、2-3 mL DMSO、80-120 μL H2O组成的混合溶剂中,得到澄清的硝酸铜溶液;
将0.025-0.035 g H6L配体、0.25-0.35 g的山梨醇与硝酸铜溶液共混,加入0.8-1.0 mLHBF4,超声1-3min,得到澄清的电沉积溶液;
(2)制备Cu-MOF/碳点纳米片阵列催化剂
使用1.0 cm × 1.0 cm的活化铜网CuF作为工作电极、铂片为辅助电极、甘汞电极为参比电极,在三电极体系中,采用恒电位电沉积工艺,制得Cu-MOF/山梨醇纳米片阵列负载在铜网上的复合材料;将其水洗后,采用250 W微波炉活化3 min,制得活化Cu-MOF/碳点/CuF纳米片阵列复合材料,即Cu-MOF/碳点纳米片阵列催化剂;
步骤(1)中所述H6L配体,其构造式如下:
2.根据权利要求1所述的Cu-MOF/碳点纳米片阵列催化剂的制备方法,其特征在于,步骤(2)中所述的活化铜网CuF,是将1.0 cm × 1.0 cm的铜网CuF,于质量分数为1.5%的稀盐酸中超声2-4 min去除表面杂物,然后分别用蒸馏水、乙醇清洗后制得。
3.根据权利要求1所述的Cu-MOF/碳点纳米片阵列催化剂的制备方法,其特征在于,步骤(2)中所述恒电位电沉积,是在-0.8~-1.5V的电压下沉积10-15 min,制得Cu-MOF/碳点/CuF纳米片阵列复合材料。
4.根据权利要求1所述的Cu-MOF/碳点纳米片阵列催化剂的制备方法,其特征在于,步骤(2)中所述Cu-MOF,其结构单元为[Cu3L(H2O)3]·10H2O·5DMA,是由3个Cu2+、1个L6-、3个主体水分子、10个客体水分子和5个客体DMA分子构成,DMA为N,N-二甲基乙酰胺。
5.根据权利要求1所述的制备方法制备的一种Cu-MOF/碳点纳米片阵列催化剂用于电解水析氧催化的应用。
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