CN109158129A - 一种三维石墨烯负载CoCu-MOF复合电催化剂的制备 - Google Patents
一种三维石墨烯负载CoCu-MOF复合电催化剂的制备 Download PDFInfo
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Abstract
本发明属于新型能源技术领域，尤其是一种三维石墨烯负载CoCu‑MOF复合电催化剂的制备。本发明旨在设计出新型高效、廉价、原料丰富的非贵金属催化剂，以替代传统的贵金属催化剂，减少对贵金属催化剂的严重依赖。主要通过溶解热法来制备三维石墨烯负载双金属MOF基的复合电催化剂。其中，该复合材料优异的催化活性主要来源于以三维石墨烯为导电基底，三维石墨烯具有优良的导电、导热性能；以MOF材料为主催化剂，MOF材料本身具有的优良催化活性以及双金属中心的协同作用，从而实现两种材料之间的优势互补以达到在电解水过程中该催化剂具有明显的催化性能和稳定性的目标。
Description
技术领域
本发明属于新型能源技术领域，涉及了一种三维石墨烯负载CoCu-MOF复合电催化剂的制备。
背景技术
能源是现在世界上最重要的资源之一，不论是社会的发展与进步，还是人们的日常生活，都与能源息息相关。甚至绝大部分的战争都和能源问题有着千丝万缕的联系。而化石能源是我们日常生活中最常使用的能源之一。但这些化石能源的形成不仅需要及其苛刻的环境，还需要特别漫长的时间，凭借我们现有的技术根本无法人为的制造出化石能源，经过亿万年才能形成的化石能源在短短的一两百年间被过度使用，已经接近枯竭。同时出于对环境的保护，石油和煤炭等会产生污染的能源在将来一定会被清洁无污染的可再生能源所代替，其中无污染的能源如氢能凭借清洁、高效、原料来源广的特点被公认为特别有潜力的能量来源。氢能的制备方法也比较多，制备氢气的条件也不是很苛刻。但除了光解水制氢和生物制氢外，其余的都是将各种能源先转化为电能后再通过电解水制得氢气。
在电解水的过程中，阳极发生的是OER反应，阴极发生的是HER反应。阴极上的H2生成受到阳极析氧反应和阴极析氢反应的反应动力学的严重限制，这两个联合反应决定了总的水分解效率。因此，具有较高析氢反应和析氧反应活性的高效催化剂是降低能垒和提高整体水解能效的基础。虽然电解水的最终目的是为了制得氢气，但由于OER与HER相比反应更加缓慢且需要更高的过电势，因此提高OER的反应效率对于电解水过程有着更为重要的意义。而MOF材料(金属-有机框架材料)具有规整的孔道结构、大的孔径和高的比表面等优良的结构特征，使其在反应的催化、气体吸附和分离、传感器、药物输送及合成先进功能材料等方面有广阔的应用前景。在催化剂方面的应用是其中的一个较大的研究方向，也是近年来比较热门的研究领域。从MOF材料刚开始被发现具有催化性能开始，MOF材料在催化剂方面的应用出现迅速发展的趋势，到如今，基于MOF材料的催化剂主要分为三种不同的类型：(1)合成的MOF中的金属位点或金属簇起主要催化作用；(2)MOF中的有机配体发挥主要催化性能；(3)MOF仅仅作为载体，负载具有催化活性的分子起主要催化作用。基于MOF材料的上述特征，制备新型高效、廉价、简单易制备的MOF基催化剂作为非贵金属催化剂，以替代传统的贵金属催化剂，为减少对贵金属催化剂的严重依赖具有重要意义。
发明内容
本发明的目的制备一种新型高效、廉价、简单易制备的MOF基催化剂作为非贵金属催化剂，以替代传统的贵金属催化剂，减少对贵金属催化剂的依赖，从而提供了一种三维石墨烯负载CoCu-MOF复合电催化剂的制备。
本发明的思路：通过将三维石墨烯与双金属-MOF材料复合的方式制备出性能优异的电催化剂。在复合材料中，以三维石墨烯为基底，MOF材料为催化主体，利用三维石墨烯优良的导电、导热性能、MOF材料本身优良的催化活性和柔韧性能以及双金属中心的协同作用，从而使电解水过程中该催化剂拥有显著的催化性能和稳定性。
具体按以下步骤进行：
(1)首先根据改良Hummers法制备氧化石墨，取120mg氧化石墨溶于40mL水中制成3mg/mL的溶液，超声1h后用氨水调节pH至10，将上述3mg/mL的溶液放入水热釜中180℃反应20h，自然冷却后反复多次洗涤，将所得产品置于玻璃皿中放入冰箱冷冻直至完全凝固，再放入冷冻干燥机中冷冻干燥48h得到三维石墨烯，样品标记为3D Gr；
(2)按照一定摩尔比称取对苯二甲酸(H2BDC)、CuCl2·2H2O、C4H6CoO4·4H2O于玻璃制烧杯中，随后加入32mL DMF和20mL乙二醇，密封并常温下磁力搅拌53min。再称取适量的三维石墨烯加入到浆液中再超声10min使三维石墨烯均匀分散在浆液中。将上述分散液置于水热反应釜中以某一温度反应一定时间，然后自然冷却至室温后，将反应液取出离心处理，用乙醇和水分别洗涤3～4次，60℃烘干、研磨均匀，标记为3D Gr/CoCu-MOF。
本发明所取得的积极进步效果在于：(1)三维石墨烯具有良好的相互重叠堆积结构，同时又保持着有序的网络孔状结构，具有很高的比表面积和很高的导电性能，因此将其作为导电基底，应用在柔性的催化材料中改善材料的催化活性。(2)双金属之间具有协同作用起到促进电荷转移并且优化电子结构的作用，两种或多种物质结合在一起可以显著增强该材料的电催化性能。(3)经过测试，3D Gr/CoCu-MOF复合催化剂具有明显的OER活性，表明所制备的复合材料是一种新型、廉价、简单易制备的非贵金属催化剂，是一种具有可替代传统贵金属催化剂潜能的候选者。
附图说明
图1为CoCu-MOF的扫描电镜图。
图2为3D Gr/CoCu-MOF的扫描电镜图。
具体实施方式
具体实施方式一：本实施方式的一种三维石墨烯负载CoCu-MOF复合电催化剂的制备是按以下步骤进行：
(1)首先根据改良Hummers法制备氧化石墨，取120mg氧化石墨溶于40mL水中制成3mg/mL的溶液，超声1h后用氨水调节pH至10，将上述3mg/mL的溶液放入水热釜中180℃反应20h，自然冷却后反复多次洗涤，将所得产品置于玻璃皿中放入冰箱冷冻直至完全凝固，再放入冷冻干燥机中冷冻干燥48h得到三维石墨烯，样品标记为3D Gr；
(2)按照一定摩尔比称取对苯二甲酸(H2BDC)、CuCl2·2H2O、C4H6CoO4·4H2O于玻璃制烧杯中，随后加入32mL DMF和20mL乙二醇，密封并常温下磁力搅拌53min。再称取适量的三维石墨烯加入到浆液中再超声10min使三维石墨烯均匀分散在浆液中。将上述分散液置于水热反应釜中以某一温度反应一定时间，然后自然冷却至室温后，将反应液取出离心处理，用乙醇和水分别洗涤3～4次，60℃烘干、研磨均匀，标记为3D Gr/CoCu-MOF。
具体实施方式二：本实施方式与具体实施方式一不同的是步骤(2)中摩尔比为2:1:3，三维石墨烯的加入量为1.3mg，以160℃水热反应9h。其他与具体实施方式一相同。
通过以下实施例和比较例具体说明一种三维石墨烯负载CoCu-MOF复合电催化剂的成功制备。
实施例一：
(1)首先根据改良Hummers法制备氧化石墨，取120mg氧化石墨溶于40mL水中制成3mg/mL的溶液，超声1h后用氨水调节pH至10，将上述3mg/mL的溶液放入水热釜中180℃反应20h，自然冷却后反复多次洗涤，将所得产品置于玻璃皿中放入冰箱冷冻直至完全凝固，再放入冷冻干燥机中冷冻干燥48h得到三维石墨烯，样品标记为3D Gr；
(2)按照2:1:3摩尔比称取对苯二甲酸(H2BDC)、CuCl2·2H2O、C4H6CoO4·4H2O于玻璃制烧杯中，随后加入32mL DMF和20mL乙二醇，密封并常温下磁力搅拌53min。再称取1.3mg三维石墨烯加入到浆液中再超声10min使三维石墨烯均匀分散在浆液中。将上述分散液置于水热反应釜中以160℃水热反应9h，然后自然冷却至室温后，将反应液取出离心处理，用乙醇和水分别洗涤3～4次，60℃烘干、研磨均匀，标记为3D Gr/CoCu-MOF。
图1为CoCu-MOF的扫描电镜图，可以看出该CoCu-MOF材料由大小约为1～3μm，厚度约为20nm的片层堆叠而成，在堆叠的过程中产生了大量的大小不一的孔道结构，拥有着较大的比表面。
图2为3D Gr/CoCu-MOF的扫描电镜图，从图中可以看出来，在加入三维石墨烯后，MOF材料的结构发生了显著的变化，首先是大量片状结构的MOF材料负载在三维石墨烯的表面，形成了以三维石墨烯为载体，以MOF材料为催化主体的理想的电催化材料；并且还可以看出在加入三维石墨烯后，片状结构的MOF材料在形貌方面变得更加一致，变成了竹叶状的形貌。并且MOF片相互之间不仅规则地堆叠了起来，而且在片与片之间还存在着一定的缝隙，形成了一种生长在三维石墨烯基底上的花瓣状结构，拥有着较大的比表面。这种结构的材料在电解水的过程中非常有利于电解质溶液的渗透及扩散，会在电解水的反应过程中增加反应的接触面积，有利于电解反应的进行。
比较例一:
按照2:1:3摩尔比称取对苯二甲酸(H2BDC)、CuCl2·2H2O、C4H6CoO4·4H2O于玻璃制烧杯中，随后加入32mL DMF和20mL乙二醇，密封并常温下磁力搅拌53min。将上述分散液置于水热反应釜中以160℃水热反应9h，然后自然冷却至室温后，将反应液取出离心处理，用乙醇和水分别洗涤3～4次，60℃烘干、研磨均匀，标记为CoCu-MOF。
经过测试，3D Gr/CoCu-MOF复合催化剂相比于CoCu-MOF具有明显的OER活性，表明所制备的复合材料是一种新型、廉价、简单易制备的非贵金属催化剂，是一种具有可替代传统贵金属催化剂潜能的候选者。
Claims (4)
1.一种三维石墨烯负载CoCu-MOF复合电催化剂的制备，其特征在于该催化剂是按以下步骤进行：
(1)首先根据改良Hummers法制备氧化石墨，取120mg氧化石墨溶于40mL水中制成3mg/mL的溶液，超声1h后用氨水调节pH至10，将上述3mg/mL的溶液放入水热釜中180℃反应20h，自然冷却后反复多次洗涤，将所得产品置于玻璃皿中放入冰箱冷冻直至完全凝固，再放入冷冻干燥机中冷冻干燥48h得到三维石墨烯，样品标记为3D Gr；
(2)按照一定摩尔比称取对苯二甲酸(H2BDC)、CuCl2·2H2O、C4H6CoO4·4H2O于玻璃制烧杯中，随后加入32mL DMF和20mL乙二醇，密封并常温下磁力搅拌53min。再称取适量的三维石墨烯加入到浆液中再超声10min使三维石墨烯均匀分散在浆液中。将上述分散液置于水热反应釜中以某一温度反应一定时间，然后自然冷却至室温后，将反应液取出离心处理，用乙醇和水分别洗涤3～4次，60℃烘干、研磨均匀，标记为3D Gr/CoCu-MOF。
2.根据权利要求1所述的一种三维石墨烯负载CoCu-MOF复合电催化剂的制备，其特征在于步骤(2)中摩尔比为2:1:3。
3.根据权利要求1所述的一种三维石墨烯负载CoCu-MOF复合电催化剂的制备，其特征在于步骤(2)中三维石墨烯的加入量为1.3mg。
4.根据权利要求1所述的一种三维石墨烯负载CoCu-MOF复合电催化剂的制备，其特征在于步骤(2)中以160℃水热反应9h。
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