CN114797900A - 一种金属有机骨架衍生的炭载硫化钴电催化剂及其制备方法和应用 - Google Patents
一种金属有机骨架衍生的炭载硫化钴电催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种金属有机骨架衍生的炭载硫化钴电催化剂及其制备方法和应用，以沸石咪唑酯金属有机骨架材料（ZIF‑67）为前驱体，经高温硫化后制备得到。本发明采用的方法简单可行，材料价格低廉，制备得到的炭载硫化钴（Co9S8/C）电催化剂材料能高效催化氧析出反应，在电解水催化剂领域具有广阔的应用前景。
Description
技术领域
本发明属于电催化材料领域，具体涉及一种金属有机骨架衍生的炭载硫化钴电催化剂及其制备方法和应用。
背景技术
氢能作为清洁、可再生、高能量密度的能源替代品，是解决能源危机和环境污染问题的有效手段。当前，制氢方式主要包括化石燃料制氢、工业副产物制氢以及电解水制氢。其中，电解水制氢通过电能将可再生资源转化为高价值燃料氢气，具有绿色环保、生产灵活、纯度高的优点，可克服传统的工业制氢技术易产生温室气体的缺陷。电解水制取氢气过程包括阴极析氢反应（HER）和阳极析氧反应 （OER），其中，OER反应过程涉及多步质子耦合、电子转移和多相反应，动力学过程缓慢。目前，OER仍依赖贵金属材料，如IrO2、RuO2基商业化催化剂等，成本高、储量低，限制了电解水的商业化应用。因此，开发一种低成本且高性能的非贵金属OER催化剂对于推动电解水技术发展具有重要意义。
中国发明专利申请CN201811057741.8公开了一种硫化钴-碳原位电极的制备方法，将钴盐、Tx-100和苯胺等含碳有机物溶于挥发非水溶剂，并加入硫脲作为硫源，获得Co-C-S前躯液；上述前躯液涂布到基底上，干燥后放在Ar气氛中或N气氛中，退火硫化。所得到的产品可用于HER、OER和ORR的多功能电催化剂。
中国发明专利申请CN201910311837.0公开了一种球形二硫化钴/碳复合高效氧析出催化剂的制备方法，通过简单的水热法首先以葡萄糖为原料合成了一种形貌均一、尺寸均匀的碳基体，在此基础上，将钴前驱体负载到碳基体上，该前驱体材料与硫粉以1:2的质量比均匀混合后置于管式炉中进行硫化，得到最终产物：纳米球形二硫化钴/碳复合催化剂材料，以其作为氧析出电催化剂表现出优异性能。
目前，已研发的OER催化剂包括过渡金属氧化物、磷化物、硫化物和纳米炭材料。近年来，过渡金属硫属化合物Transition metal chalcogenides（TMCs），尤其是钴硫属元素化合物（如CoSe2、CoS2和Co9S8）被认为是具有前景的OER电催化剂。然而，金属硫化物仍存在金属纳米颗粒分散性、导电性差以及比表面积小等缺点，限制了其在电催化领域的应用。
发明内容
为了解决现有技术中存在的电解水制氢贵金属材料的高成本、储量低的问题，本发明提供一种金属有机骨架衍生的炭载硫化钴电催化剂及其制备方法和应用。本发明所涉及的制备方法简单可行，材料来源广泛，价格低廉，制备得到的金属有机骨架衍生的炭载硫化钴催化剂具有高效的氧析出催化活性，在电解水催化剂方面具有广泛的应用前景。本发明针对金属硫化物存在的导电性差、比表面积低的问题，提出采用碳作为基底锚定金属硫化物，并构建炭载金属硫化物复合结构的策略，所述的金属有机骨架衍生的炭载硫化钴电催化剂是以具有周期性排列的有序金属-氮（TM-N4）配位结构的沸石型咪唑酯金属有机骨架材料（ZIF-67）为前驱体，利用ZIFs材料的大表面积、高孔隙率以及金属离子在原子水平上的均匀分布，经高温硫化后得到了炭载高度均匀分散且小粒径的金属硫化物催化剂。
为了实现发明目的，本发明采用如下技术方案：一种金属有机骨架衍生的炭载硫化钴电催化剂，所述的炭载硫化钴电催化剂呈规则的正十二面体形貌，粒径范围为400-1000 nm，Co9S8纳米颗粒均匀分散在炭骨架表面，其粒径大小为15-25 nm。
在本发明的优选的实施方式中，所述的电催化剂的平均粒径约为600 nm。
本发明还保护所述的金属有机骨架衍生的炭载硫化钴（Co9S8/C）电催化剂的制备方法，以沸石咪唑酯金属有机骨架材料（ZIF-67）为前驱体，采用硫粉作为硫源，在惰性气氛下高温硫化制备得到。
更为具体的，所述的制备方法包括如下步骤：
（1）将钴源溶于溶剂中得到溶液A，同时将2-甲基咪唑溶于溶剂中得到溶液B，然后将溶液A倒入溶液B，搅拌均匀后静置，经抽滤、洗涤后置于烘箱中干燥8-12 h，得到ZIF-67前驱体；
（2）将步骤（1）中所得的ZIF-67与硫源在溶剂中充分研磨混合均匀后，置于烘箱中干燥；
（3）将步骤（2）中所得的ZIF-67与硫源的混合物在惰性气氛下高温硫化， 经保温一定时间后，得到所述的金属有机骨架衍生的炭载硫化钴（Co9S8/C）电催化剂。
在本发明的优选的实施方式中，步骤（1）中，所述的钴源优选为六水合硝酸钴，所述的溶剂优选为无水甲醇。
在本发明的优选的实施方式中，步骤（1）中，2-甲基咪唑和六水合硝酸钴的质量比为5-30，静置温度为30-60 oC，静置时间为5-20 h。
在本发明的优选的实施方式中，步骤（2）中，所述硫源为升华硫，所述溶剂为乙醇，ZIF-67与硫源的质量比为2-20；所述干燥温度为60-80 oC，干燥时间为20-60 min。
在本发明的优选的实施方式中，步骤（3）中，所述的高温硫化的温度为500-1000℃，升温速率为3-10 ℃ min-1，保温时间为1-3 h；所述的惰性气氛为200-300 sccm的氮气或氩气。
本发明还保护所述的金属有机骨架衍生的炭载硫化钴电催化剂在电解水制氢、金属-空气电池领域中的应用。
与现有技术相比，本发明具有以下优点：
（1）本发明制备的电解水氧析出电催化剂，采用具有周期性排列的有序TM-N4配位结构的ZIF-67为前驱体，充分利用ZIFs中金属离子在原子水平上的均匀分布以确保嵌入炭基质中的硫化钴纳米颗粒的良好分散，获得了纳米颗粒均匀分散且小粒径的Co9S8纳米颗粒。
（2）本发明制备电解水氧析出电催化剂，最大程度上保有了ZIF-67前驱体的十二面体形貌，继承了ZIF-67高比表面积和微孔孔道结构的特点，并同时具有丰富的介孔，有利于加快氧析出反应物传质。
（3）本发明制备的电解水氧析出电催化剂，以ZIF-67为前驱体，一步硫化构造了炭载硫化钴复合结构，炭的引入可提高硫化物的导电性，有利于促进氧析出反应过程中的电子传输。
（4）本发明所提供的金属有机骨架衍生的炭载硫化钴作为一种高效耐用的氧析出电催化剂，制备方法简单，材料来源广泛，价格低廉，制备得到的金属有机骨架衍生的炭载硫化钴（Co9S8/C）电催化剂具有高效的氧析出性能。
附图说明
下面结合附图作进一步的说明。
图1是实施例1中的金属有机骨架衍生的炭载硫化钴电催化剂的扫描电子显微镜照片。
图2是实施例1中金属有机骨架衍生的炭载硫化钴电催化剂和商业RuO2的氧析出反应的极化曲线。
具体实施方式
为了使本发明的目的、技术方案及有益效果更加清楚，本发明用以下具体实施例进行说明，但本发明绝非限于这些例子。
实施例1：
称取873.2 mg的六水合硝酸钴溶于160 mL无水甲醇中得到溶液A，称取3.9408 g的2-甲基咪唑溶于160 mL无水甲醇中得到溶液B，将溶液A倒入溶液B后搅拌一段时间，充分搅拌均匀后放入水浴锅中，在30 oC下静置12 h，经抽滤、洗涤后置于烘箱中干燥8 h得到ZIF-67前驱体。 然后，称取12.5 mg的硫粉加入无水乙醇，研磨5 min后，加入100 mg ZIF-67再研磨3 min，置于烘箱中干燥30 min。将所得到的ZIF-67前驱体和硫粉置于瓷舟中，在200 sccm的气流量下通入氮气进行高温硫化，以5 oC min-1的升温速率加热升温至900 oC保温2 h，最终得到金属有机骨架衍生的炭载硫化钴（Co9S8/C）电催化剂。
将金属有机骨架衍生的炭载硫化钴（Co9S8/C）电催化剂进行物理化学表征。由图1可见，制备的金属有机骨架衍生的炭载硫化钴（Co9S8/C）电催化剂为正十二面体形貌，表面粗糙。由图2的氧析出反应的极化曲线可见，在10 mA cm-2的电流密度下，催化剂的过电势为336 mV，接近商业RuO2。
实施例2
操作条件如同实施例1，保证其他条件一致，改变ZIF-67与升华硫的质量比为12/1。由图2可见，催化剂仍表现出较好的氧析出性能，在10 mA cm-2的电流密度下，过电势为341 mV，接近商业RuO2。
以上已对本发明的较佳实施例进行了具体说明，但本发明并不限于所述实施例，熟悉本领域的技术人员在不违背本发明精神的前提下还可作出种种的等同的变型或替换，这些等同的变型或替换均包含在本申请权利要求所限定的范围。
Claims (9)
1.一种金属有机骨架衍生的炭载硫化钴电催化剂，其特征在于，所述的炭载硫化钴电催化剂呈规则的正十二面体形貌，粒径范围为400-1000 nm，Co9S8纳米颗粒均匀分散在炭骨架表面，其粒径大小为15-25 nm。
2.根据权利要求1所述的电催化剂，其特征在于，所述的电催化剂的平均粒径约为600nm。
3.根据权利要求1或2所述的电催化剂的制备方法，其特征在于，以沸石咪唑酯金属有机骨架材料（ZIF-67）为前驱体，采用硫粉作为硫源，在惰性气氛下高温硫化制备得到。
4.根据权利要求3所述的制备方法，其特征在于，包括如下步骤：
（1）将钴源溶于溶剂中得到溶液A，同时将2-甲基咪唑溶于溶剂中得到溶液B，然后将溶液A倒入溶液B，搅拌均匀后静置，经抽滤、洗涤后置于烘箱中干燥8-12 h，得到ZIF-67前驱体；
（2）将步骤（1）中所得的ZIF-67与硫源在溶剂中充分研磨混合均匀后，置于烘箱中干燥；
（3）将步骤（2）中所得的ZIF-67与硫源的混合物在惰性气氛下高温硫化， 经保温一定时间后，得到所述的金属有机骨架衍生的炭载硫化钴（Co9S8/C）电催化剂。
5.根据权利要求4所述的制备方法，其特征在于，步骤（1）中，所述的钴源优选为六水合硝酸钴，所述的溶剂优选为无水甲醇。
6.根据权利要求5所述的制备方法，其特征在于，步骤（1）中，2-甲基咪唑和六水合硝酸钴的质量比为5-30，静置温度为30-60 oC，静置时间为5-20 h。
7.根据权利要求4所述的制备方法，其特征在于，步骤（2）中，所述硫源为升华硫，所述溶剂为乙醇，ZIF-67与硫源的质量比为2-20；所述干燥温度为60-80 oC，干燥时间为20-60min。
8.根据权利要求4所述的制备方法，其特征在于，步骤（3）中，所述的高温硫化的温度为500-1000 oC，升温速率为3-10 oC min-1，保温时间为1-3 h；所述的惰性气氛为200-300sccm的氮气或氩气。
9.根据权利要求1或2所述的电催化剂、或是权利要求3-8中任一项所述的制备方法制备得到的电催化剂在电解水制氢、金属-空气电池领域中的应用。
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