CN110124687A - 一种钌掺杂的LDH/rGO复合材料的制备方法及其在析氢反应上的应用 - Google Patents
一种钌掺杂的LDH/rGO复合材料的制备方法及其在析氢反应上的应用 Download PDFInfo
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Abstract
本发明公开了一种钌掺杂的LDH/rGO复合材料的制备方法及其在析氢反应上的应用。本发明利用水滑石与氧化石墨烯具有静电相互作用，通过一步回流法制备钌掺杂的LDH/rGO复合材料。本发明将水滑石负载在大表面积的石墨烯上除了增强其导电性外，其锚定作用还有利于避免水滑石团聚，增大活性比表面积，暴露更多活性位点。本发明制备的复合材料具有钴、钌两个电催化活性位点，二者协同作用，降低了电催化反应的能量壁垒，从而显著降低了电催化过电势。由于Ru的掺杂改变了复合材料表面的电子状态，氧缺陷增多，助力于反应活性位点对中间体的吸附，加快水电解，提高析氢性能。
Description
技术领域
本发明属于电催化材料制备技术领域，特别涉及一种钌掺杂的LDH/rGO复合材料的制备方法及其在析氢反应上的应用。
背景技术
能源短缺和环境污染是人类社会实现不断续发展面临的现实难题。电解水技术能够分解水制氢，将电能转换为氢能。产生的氢能作为燃料和能量载体，不但具有高的燃烧热值，高能量密度，而且全程对环境无污染。因此，电催化材料与技术是当前世界上公认的能够“同时解决环境和能源问题”的领域中最具有应用前景的新技术之一。全水解由析氢反应(Hydrogen evolution reaction)和析氧反应 (Oxygen evolution reaction)两个半反应构成，其中阴极发生的析氢反应由于存在较高过电位导致能耗较大，选择恰当的电催化剂有利于降低反应过电位，从而提高能量利用率。因为具有优异电催化性能的铂基贵金属催化剂存在价格较昂贵，资源稀缺的缺点，所以探索替代铂基贵金属析氢催化剂和具有高效、稳定，价格低廉的析氢催化剂引起科学家的广泛关注。研究表明，增加催化材料的固有活性和提高活性位点数目，通过负载导电基底提高材料的电子导电率，降低物质传输阻力，以上措施都有利于提高催化材料电催化性能。
过渡金属钴地壳含量较为丰富，成本较有优势，且作为电催化反应的活性中心具有丰富的电子态，因此成为制氢催化剂的研究热点。水滑石具有二维层状纳米片结构，超大比表面积，因此可以通过调节其形态，组成，嵌入离子和剥离等策略来提升其电催化性能。正是由于其二维纳米片结构赋予的这些独特的优势，让LDH及其衍生物(如氧化物，硫化物，金属氢氧化物和羟基氧化物等)在电化学储能和转化应用中显示出巨大的潜力。然而水滑石本身团聚现象严重，导电性较差，严重影响制氢催化剂的催化转换率并引起大的过电势。而氧化石墨烯作为一种石墨烯材料的衍生物，由于其片层的表面和边缘存在大量的含氧官能团具有锚定作用，在水中分散性良好，组装能力和功能化强，导电性强，因此已被广泛用于制备电化学储能、催化材料的导电基底。
发明内容
本发明的目的是提供一种钌掺杂的水滑石和还原氧化石墨烯复合材料的制备方法及其在析氢反应上的应用。本发明利用水滑石与氧化石墨烯具有静电相互作用，通过一步回流法制备钌掺杂的LDH/rGO复合材料。通过调变复合材料中层板上金属元素Ru的含量，并控制复合材料的形貌，拓展了提升双金属氢氧化物电催化活性的新方法。
本发明所述的钌掺杂的LDH/rGO复合材料的组成包含钌掺杂的钴基水滑石和还原氧化石墨烯，该复合材料为纳米片阵列结构，纳米片尺寸为100nm；该复合材料具有钴、钌两个电催化活性位点。
本发明所述的钌掺杂的LDH/rGO复合材料的制备方法为：将氧化石墨烯超声分散在硝酸钴水溶液中，然后加入RuCl3水溶液，超声分散后加入持续通入纯氧气的氨水溶液中，在30-60℃下搅拌反应12-36小时，洗涤干燥得到钌掺杂的LDH/rGO 复合材料。
所述的氧化石墨烯的制备方法为：将石墨粉加入到浓H2SO4与浓H3PO4的混合溶液中，再加入KMnO4，升温至40-60℃并搅拌反应6-20h；加入冰冷却至室温后加入双氧水，离心过滤，再依次用水、盐酸和乙醇洗涤，最后用去离子水洗涤至中性，冷冻干燥，即得氧化石墨烯。
将上述制备得到的钌掺杂的LDH/rGO复合材料作为催化剂应用于电解水析氢反应中。该反应具体条件为：
(1)将钌掺杂的LDH/rGO复合材料与导电剂炔黑以质量比0.2-20的比例混合均匀，加入乙醇后超声，再加入Nafion溶液，混合均匀后涂覆于导电碳纸集流体上，室温下干燥得到析氢反应电极；
(2)将制备好的析氢反应电极置于碱溶液中，采用三电极体系进行反应，所用三电极体系的参比电极为银/氯化银电极，辅助电极为石墨电极。
本发明的优点如下：
1)本发明制备得到的钌掺杂的LDH/rGO复合材料的析氢催化剂具有钴、钌两个电催化活性位点，二者协同作用，降低了电催化反应的能量壁垒，从而显著降低了电催化过电势。
2)本发明制备得到的钌掺杂的LDH/rGO复合材料的析氢催化剂具有纳米片阵列结构，使其具有较大的活性比表面积，充分暴露电催化活性位点，构成的丰富的网状结构也有利于电解液与活性位充分接触，加快反应速率。
3)本发明制备得到的钌掺杂的LDH/rGO复合材料的析氢催化剂将水滑石负载在大表面积的石墨烯上除了增强其导电性外，其锚定作用还有利于避免水滑石团聚，增大活性比表面积，暴露更多活性位点。
4)本发明制备得到的钌掺杂的LDH/rGO复合材料的析氢催化剂由于Ru的掺杂改变了复合材料表面的电子状态，氧缺陷增多，助力于反应活性位点对中间体的吸附，加快水电解能力增强，提高析氢性能。
5)，本发明制备得到的钌掺杂的LDH/rGO复合材料，其中水滑石中钌和钴的原子比为0.0943的复合材料作为析氢催化剂，在10mA/cm2的电流密度下，其过电位能够低至60mv，塔菲尔斜率为74mv/dec。
附图说明
图1是本发明实施例得到的不同钌含量的钌掺杂的LDH/rGO复合材料和对比例得到的LDH/rGO复合材料的析氢反应线扫图。
图2是本发明实施例得到的不同钌含量的钌掺杂的LDH/rGO复合材料的 XRD图。
具体实施方式
实施例1
1、3.0g石墨粉加入到浓H2SO4与浓H3PO4按9：1体积比的混合溶液中，再将18.0gKMnO4缓慢加入到上述混合溶液中，升温至50℃并搅拌12h；加入400mL 冰冷却至室温，然后加入3mL 30％H2O2，过滤，将滤液离心(4000rpm，10分钟)，去除上清液后，依次用水(200mL)，30％HCl水溶液(200mL)和乙醇(200mL) 洗涤，最后用去离子水将产物洗涤至中性，冷冻干燥，即得氧化石墨烯。
2、称取步骤1所得到的300mg GO分散于20.0ml的0.25M Co(NO3)2澄清溶液中超声12h，分别加入1.5，3，5，7，9，11mL浓度为12.238mg/mL的RuCl3水溶液，超声12h，然后快速加入至持续通入纯氧气的100ml的0.125M氨水溶液中，在40℃下搅拌24小时，洗涤干燥得到钌掺杂的LDH/rGO复合材料，分别记为S-1，S-2，S-3，S-4，S-5，S-6。
对比例1
将实施例1制备的GO 300mg分散于20.0ml的0.25M Co(NO3)2澄清溶液中超声12h，然后快速加入至持续通入纯氧气的100ml的0.125M氨水溶液中，在 40℃下搅拌24小时，洗涤干燥得到LDH/rGO复合材料，记为S-0。
应用实施例
1.取实施例1制备的钌掺杂的LDH/rGO复合材料9mg与0.1mg导电剂炔黑混合均匀，加入1mL乙醇后超声，再加入50μL的5wt％Nafion溶液，涂覆于1×1 cm2的导电碳纸上，室温下干燥24h，得到析氢反应电极；
2.将制备好的析氢反应电极置于1mol/L的KOH溶液中，采用三电极体系进行测试，参比电极为银/氯化银电极电极，辅助电极为石墨电极，其线扫曲线见附图1。
对照实施例
1.取对比例1制备的LDH/rGO复合材料9mg与0.1mg导电剂炔黑混合均匀，加入1mL乙醇后超声，再加入50μL的5wt％Nafion溶液，涂覆于1×1cm2的导电碳纸上，室温下干燥24h，得到析氢反应电极；
2.将制备好的析氢反应电极置于1mol/L的KOH溶液中，采用三电极体系进行测试，参比电极为银/氯化银电极电极，辅助电极为石墨电极，其线扫曲线见附图1。
可以理解的是，以上实施方式仅仅是为了说明本发明的原理而采用的示例性实施方式，然而本发明并不局限于此。对于本领域内的普通技术人员而言，在不脱离本发明的精神和实质的情况下，可以做出各种变型和改进，这些变型和改进也为本发明的保护范围。
Claims (5)
1.一种钌掺杂的LDH/rGO复合材料，其特征在于，该复合材料的组成包含钌掺杂的钴基水滑石和还原氧化石墨烯，该复合材料为纳米片阵列结构，纳米片尺寸为100nm；该复合材料具有钴、钌两个电催化活性位点。
2.一种钌掺杂的LDH/rGO复合材料的制备方法，其特征在于，该制备方法为：将氧化石墨烯超声分散在硝酸钴水溶液中，然后加入RuCl3水溶液，超声分散后加入持续通入纯氧气的氨水溶液中，在30-60℃下搅拌反应12-36小时，洗涤干燥得到钌掺杂的LDH/rGO复合材料。
3.根据权利要求2所述的制备方法，其特征在于，所述的氧化石墨烯的制备方法为：将石墨粉加入到浓H2SO4与浓H3PO4的混合溶液中，再加入KMnO4，升温至40-60℃并搅拌反应6-20h；加入冰冷却至室温后加入双氧水，离心过滤，再依次用水、盐酸和乙醇洗涤，最后用去离子水洗涤至中性，冷冻干燥，即得氧化石墨烯。
4.根据权利要求1-3任一所述的方法制备得到的钌掺杂的LDH/rGO复合材料作为催化剂在电解水析氢反应中的应用。
5.根据权利要求4所述的应用，其特征在于，所述的电解水析氢反应的具体操作条件为：
(1)将钌掺杂的LDH/rGO复合材料与导电剂炔黑以质量比0.2-20的比例混合均匀，加入乙醇后超声，再加入Nafion溶液，混合均匀后涂覆于导电碳纸集流体上，室温下干燥得到析氢反应电极；
(2)将制备好的析氢反应电极置于碱溶液中，采用三电极体系进行反应，所用三电极体系的参比电极为银/氯化银电极，辅助电极为石墨电极。
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