CN110304657A - 基于硫链聚合物的过渡金属硫化物电极材料及其制备方法和应用 - Google Patents
基于硫链聚合物的过渡金属硫化物电极材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种基于硫链聚合物的过渡金属硫化物电极材料及其制备方法和在电解水催化析氢中的应用。首先以1,3‑二(1‑甲基乙烯基)苯和硫磺为原料通过熔融聚合法制得了硫链聚合物，然后以硫链聚合物和过渡金属盐为原料通过溶剂热反应制得了片状结构的过渡金属硫化物。硫链聚合物的引入一方面增加了活性位点的数量，另一方面增加了活性位点的活性，此外还改变了金属硫化物的微观结构，使其在酸性条件下性能较为稳定，保持了较高的电解水催化析氢效率，具有较好的工业化应用前景。
Description
技术领域
本发明涉及电极材料技术领域，具体涉及一种基于硫链聚合物的过渡金属硫化物电极材料及其制备方法和在电解水催化析氢中的应用。
背景技术
能源短缺和环境污染问题是21世纪以来人类社会发展所面临的两大难题，寻找洁净可再生能源及开发高效的能量储存和转换技术是当务之急。目前电解水产氢最好的催化剂仍然是Pt系贵金属，但这些贵金属成本较高且稳定性不好，不利于大规模生产。在寻找低廉、高效催化剂的过程中，具有多层次结构的非贵金属硫化物受到了大量的关注和研究，其特殊的二维超薄结构既可以提供大量的表面原子作为催化活性位点，又有利于通过引入缺陷、掺杂或者化学修饰等手段调控其电子结构和催化活性。目前，非贵金属硫化物材料已被广泛用于电解水制氢领域。
传统方法制备硫化物电极材料所使用的原料一般为小分子物质，常见的硫源主要有硫磺、硫脲、硫代乙酰胺等(参见CN108823602A)，由此制备得到的纳米级材料存在易团聚、活性位点无法得以充分暴露、催化活性提高有限等问题。在制备硫化物电极材料的过程中，涉及到的大分子物质往往以软模板、硬模板、表面活性剂等辅助剂的形式存在，还有学者以石墨烯、聚苯胺、聚吡咯等聚合物以及硫化物为原料(参见CN104190443A)，制得了复合材料。这些研究虽然使用了大分子物质，但这些大分子物质本身并未直接参与或影响金属-S分子键的形成，并没有增加每个活性位点的本征活性，对制造缺陷以及片层间的剥离作用不大，因此对电催化活性的提高影响不大。
有鉴于此，本发明从增加活性位点的数量和活性位点的活性两个方面出发，创造性的采用大分子硫链聚合物作为前驱体，制得了一种具有较好催化析氢性能的过渡金属硫化物复合材料。
发明内容
本发明的目的在于提供一种基于硫链聚合物的过渡金属硫化物电极材料制备方法，该方法包括以下步骤：(a)以1,3-二(1-甲基乙烯基)苯和硫磺为原料，制备硫链聚合物；(b)将硫链聚合物溶于有机溶剂中，再加入过渡金属盐进行溶剂热反应，分离得到目标产物。
进一步的，硫链聚合物的制备过程具体如下：将硫磺加热熔融，再加入1,3-二(1-甲基乙烯基)苯，在180-200℃下充分反应即可。
进一步的，1,3-二(1-甲基乙烯基)苯与硫磺的质量用量比为1:1-9。
进一步的，所述过渡金属盐具体为钼、钴、铜等金属的硝酸盐、醋酸盐、氯化盐或其水合物。
进一步的，溶剂热反应温度为160-200℃，反应时间为10-24h。在高温高压条件下，硫链聚合物中的硫与过渡金属盐中的金属形成金属-S键，从而得到相应的过渡金属硫化物。
进一步的，硫链聚合物中的硫原子与过渡金属盐中金属离子的摩尔比为4-20:1。
进一步的，分离所得粗产物用有机溶剂、水反复洗涤多次，然后冷冻干燥。
进一步的，所述有机溶剂选自N,N-二甲基甲酰胺、四氢呋喃、氯仿中的任意一种。
本发明的另一目的在于提供一种按照上述方法制得的基于硫链聚合物的过渡金属硫化物。该过渡金属硫化物为粉末状，其分子中含有大量的晶型缺陷，整体具有纳米级片状结构。
本发明的第三重目的在于提供一种将制得的基于硫链聚合物的过渡金属硫化物作为电极材料用于电解水催化析氢的应用。
与现有技术相比，本发明具有如下有益效果：(1)采用硫链聚合物作为前驱体，在提供硫源的同时也会因聚合物大分子含有的刚性苯环，影响无机硫化物的结晶过程，由此得到晶型发生改变、缺陷较多、尺寸和层数较少、更为分散的过渡金属硫化物；(2)制得的金属硫化物作为析氢材料，活性位点主要集中在片层的边缘，此外其纳米片层结构具有较大的表面积和晶型缺陷，极大的增加了片层边缘的暴露几率，因而能提供更多活性位点，相应的催化性能更好；(3)本发明方法适用范围广，可用于大多数过渡金属硫化物的制备，包括双金属和多金属硫化物的制备；(4)制得的电极材料在酸性条件下稳定性好，pH适用范围广；(5)工艺简单，能耗低，便于工业化大规模生产。
附图说明
图1为实施例1制得的MoS2材料的SEM、TEM照片；
图2为实施例1制得的MoS2材料作为工作电极在酸性条件下的析氢极化曲线图；
图3为本发明实施例2制得的CoS材料作为工作电极在酸性条件下的析氢极化曲线图；
图4为本发明实施例3制得的CuS材料作为工作电极在酸性条件下的析氢极化曲线图。
具体实施方式
为使本领域普通技术人员充分理解本发明的技术方案和有益效果，以下结合具体实施例进行进一步说明。
实施例1
将3.2g硫磺粉和小号磁性搅拌棒置于玻璃瓶中，将玻璃瓶放入185℃恒温油浴锅内，快速磁力搅拌使得硫磺粉完全熔融成液体。用注射器向玻璃瓶内快速注入3.2g 1,3-二(1-甲基乙烯基)苯，在185℃恒温油浴下继续搅拌反应十分钟左右，待黄色液体转变成红色液体时取出玻璃瓶，玻璃瓶内的固体即为硫链聚合物。以上过程涉及的反应如下：
将0.64g硫链聚合物与28mL N,N-二甲基甲酰胺混合，水浴加热并磁力搅拌使其完全溶解，得到硫链聚合物溶液。将0.2732g MoCl5与2mL N,N-二甲基甲酰胺混合均匀，得到浓度为0.5mol/L的MoCl5溶液。
将配制好的硫链聚合物溶液与MoCl5溶液混合均匀，接着将反应液转移50mL高温高压釜中，升温至180℃保温反应12h。溶剂热反应完成后离心分离，依次用30mL N,N-二甲基甲酰胺和水反复洗涤粗产物，最后冷冻干燥得到黑色粉末，即为MoS2电极材料。
实施例2
将3.2g硫磺粉和小号磁性搅拌棒置于玻璃瓶中，将玻璃瓶放入185℃恒温油浴锅内，快速磁力搅拌使得硫磺粉完全熔融成液体。用注射器向玻璃瓶内快速注入3.2g 1,3-二(1-甲基乙烯基)苯，在185℃恒温油浴下继续搅拌反应十分钟左右，待黄色液体转变成红色液体时取出玻璃瓶，玻璃瓶内的固体即为硫链聚合物。
将0.512g硫链聚合物与60mL N,N-二甲基甲酰胺混合，水浴加热并磁力搅拌使其完全溶解，得到硫链聚合物溶液。将硫链聚合物溶液转移至100mL高温高压釜中，再加入0.1993g Co(CH3COO)2·4H2O粉末并搅拌使其完全溶解，升温至180℃保温反应12h。溶剂热反应完成后离心分离，依次用30mL N,N-二甲基甲酰胺和水反复洗涤粗产物，最后冷冻干燥得到黑色粉末，即为CoS电极材料。
实施例3
将3.2g硫磺粉和小号磁性搅拌棒置于玻璃瓶中，将玻璃瓶放入185℃恒温油浴锅内，快速磁力搅拌使得硫磺粉完全熔融成液体。用注射器向玻璃瓶内快速注入3.2g 1,3-二(1-甲基乙烯基)苯，在185℃恒温油浴下继续搅拌反应十分钟左右，待黄色液体转变成红色液体时取出玻璃瓶，玻璃瓶内的固体即为硫链聚合物。
将0.512g硫链聚合物与60mL N,N-二甲基甲酰胺混合，水浴加热并磁力搅拌使其完全溶解，得到硫链聚合物溶液。将硫链聚合物溶液转移至100mL高温高压釜中，再加入0.1597g Cu(CH3COO)2·H2O并搅拌使其完全溶解，升温至180℃保温反应12h。溶剂热反应完成后离心分离，依次用30mL N,N-二甲基甲酰胺和水反复洗涤粗产物，最后冷冻干燥得到黑色粉末，即为CuS电极材料。
为充分了解制得的电极材料的微观结构，以实施例1产物为例进行了SEM和TEM分析，结果如图1所示，其中A为SEM图，B为TEM图。从图1中可以看出，该MoS2电极材料为纳米片状结构，纳米片尺寸约几十纳米。分析可知，这种纳米片状结构可以有效增加硫化钼活性位点的暴露程度，提高其催化性能。
分别以实施例1-3制得的纳米片材料作为电解水装置中阴极析氢反应电极材料，进行电化学析氢实验，具体过程如下：称取4mg制得的纳米片材料(MoS2、CoS、CuS)，依次加入1mL体积分数为50％的乙醇水溶液、10μL质量分数为5wt％的Nafion溶液，超声30min得到催化剂溶液。取5mL催化剂溶液，分两次滴在玻碳电极头上，烤灯烘干后得到三种工作电极。以饱和甘汞电极(SCE)作为参比电极，碳棒电极作为对电极，与工作电极组装成三电极体系后放入电解槽中。以0.5mol/L的H2SO4水溶液作为电解液，持续向电解液中通入N2以便除尽氧气，然后开始测试，得到如图2-4所示的极化曲线。期间工作电极在0至-0.6V vs RHE电压区间内，曲线扫描速度为2mV/s。
由图2可知，纳米片状MoS2作为催化剂在析氢实验中达到10mA/cm3的电流密度所需要的过电位为168mV，而对比设置的块状MoS2在相同测试条件下基本上没有析氢性能。图3也表明，纳米片状CoS作为催化剂，在析氢实验中达到10mA/cm3的电流密度所需要的过电位为135mV；图4中纳米片状CuS作为催化剂，在析氢实验中达到10mA/cm3的电流密度所需要的过电位为372mV。这些结果说明，按照本发明方法制得的纳米片状金属硫化物材料的确具有良好的析氢催化性能，在工业上有较强的应用潜力。
Claims (10)
1.一种基于硫链聚合物的过渡金属硫化物制备方法，其特征在于包括以下步骤：
(a)以1,3-二(1-甲基乙烯基)苯和硫磺为原料，制备硫链聚合物；
(b)将硫链聚合物溶于有机溶剂中，再加入过渡金属盐进行溶剂热反应，分离即可。
2.如权利要求1所述的制备方法，其特征在于步骤(a)具体过程如下：将硫磺加热熔融，再加入1,3-二(1-甲基乙烯基)苯，在180-200℃下充分反应。
3.如权利要求1所述的制备方法，其特征在于：步骤(a)中1,3-二(1-甲基乙烯基)苯与硫磺的质量用量比为1:1-9，步骤(b)硫链聚合物中的硫原子与过渡金属盐中金属离子的摩尔比为4-20:1。
4.如权利要求1所述的制备方法，其特征在于：步骤(b)所述过渡金属盐具体为钼、钴、铜或其他过渡金属的硝酸盐、醋酸盐、氯化盐或其水合物。
5.如权利要求1所述的制备方法，其特征在于：步骤(b)中溶剂热反应温度为160-200℃，反应时间为10-24h。
6.如权利要求1所述的制备方法，其特征在于：步骤(b)分离所得粗产物用有机溶剂、水反复洗涤多次，然后冷冻干燥。
7.如权利要求1或6所述的制备方法，其特征在于：所述有机溶剂选自N,N-二甲基甲酰胺、四氢呋喃、氯仿中的任意一种。
8.一种基于硫链聚合物的过渡金属硫化物，其特征在于：该过渡金属硫化物按照权利要求1-6中任一种方法制备得到。
9.如权利要求8所述的一种基于硫链聚合物的过渡金属硫化物，其特征在于：该过渡金属硫化物为粉末状，其分子中含有大量晶型缺陷，整体具有纳米级片状结构。
10.权利要求8-9任一项所述的一种基于硫链聚合物的过渡金属硫化物作为电极材料用于电解水催化析氢的应用。
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