红毛丹状磷化钴@钼钴氧空心微米小球用于碱性电催化析氢

doi:10.1016/S1872-2067(20)63530-6

摘要/Abstract

摘要： 氢气因其能量密度高、零排放和可再生的特点被广泛认为是最有前景的能源.电解水是一种产生高纯氢气的有效途径.目前，高性能的促进水电解的催化剂主要是贵金属材料，例如贵金属铂.然而，高成本大大阻碍了贵金属材料在电催化水分解中的广泛应用.因此，我们致力于研究具有高活性的非贵金属催化剂.
因为电催化水分解析氢反应更容易发生在质子浓度高的条件下，所以研究碱性条件下催化析氢比研究酸性条件下催化析氢更具挑战性.在工业应用中，酸性电解质溶液对仪器设备的腐蚀性比碱性溶液更大，因此研究应用在碱性溶液中的析氢催化剂更有发展前景.过渡金属磷化物被广泛地研究作为高性能析氢电催化剂，然而过渡金属磷化物作为析氢催化剂的稳定性通常不是很好.我们通过钼元素的引入，提高过渡金属磷化物作为析氢催化剂的稳定性.电化学催化效率同样受到材料形貌和导电性的影响.大的比表面积有利于暴露更多的活性位点，使活性位点与电解质溶液的接触更加充分，有利于催化剂和溶液之间的传质.据报道，金属磷化物具有良好的导电性是由于磷化物中存在金属-金属键.所以合成具有大比表面积形貌的过渡金属磷化物材料能够满足析氢电催化剂对比表面积和导电性的两个需求.
界面效应是调节催化剂性能的一个有效方法.析氢催化剂常常存在吸附质子能力过强或过弱、稳定性不好等问题.这些问题可以通过界面效应来解决.本文通过形成磷化估和钼钴氧的界面来调节改善磷化钴表面原来的电子密度，以达到理想的氢吸附自由能；同时此界面效应还能起到稳定催化剂性能的作用.
本文首先采用水热法合成了红毛丹状钼钴氧空心微米小球前驱体.在钼酸根离子的引导下，利用奥斯特瓦尔德熟化原理一步实现了红毛丹状空心结构.前驱体再以次亚磷酸钠为磷源进行气相磷化，得到产物红毛丹状磷化钴@钼钴氧空心微米小球.通过扫描电镜和透射电镜对其红毛丹状空心结构进行了表征.利用X射线衍射和X射线光电子能谱等手段表征了材料的物相组成和价态分布.电化学测试均使用电化学工作站完成.该材料在碱性电解质溶液中展现了极好的电化学催化析氢性能，在电流密度为10mA cm^-2时对应的析氢过电位仅为62mV.在1 MKOH溶液中10mA cm^-2电流密度下测试55h，过电位仅增大约17mV，显示了非常强的碱性析氢稳定性.得益于磷化钴和钼钴氧之间的界面效应，以及特殊的三维空心结构，红毛丹状磷化钴@钼钴氧空心微米小球表现出优异的析氢催化性能和稳定性.

关键词: 磷化钴@钼钴氧, 红毛丹状, 空心微米小球, 界面效应, 析氢反应

Abstract: Water electrolysis has attracted a lot of attention in recent years for hydrogen production. CoP has been widely investigated as a traditional electrocatalyst for hydrogen evolution reaction (HER). However, the strong bond strength of P-H bond and weak chemical stability are still the key problems in affecting catalytic performance of CoP. In this work, we synthesized rambutan-like CoP@Mo-Co-O hollow microspheres as HER electrocatalyst, solving the two problems of CoP as electrocatalyst. Benefiting from the unique three-dimensional space structure and interface effect between CoP and Mo-Co-O, the synthesized CoP@Mo-Co-O shows a small overpotential of 62 mV at the current density of 10 mA cm^-2 for HER, which is much lower than the corresponding overpotential of pure CoP microspheres (117 mV). Rambutan-like CoP@Mo-Co-O hollow microspheres also show robust long-term stability and excellent cycling stability. This work provides a new method for the design and improvement of non-precious HER electrocatalysts.

Key words: CoP@Mo-Co-O, Rambutan-like hollow microspheres, Interfacial effect, Hydrogen evolution reaction

中图分类号:

周文, 吴明娒, 李高仁. 红毛丹状磷化钴@钼钴氧空心微米小球用于碱性电催化析氢[J]. 催化学报, 2020, 41(4): 691-697.

Wen Zhou, Mingmei Wu, Gaoren Li. Rambutan-like CoP@Mo-Co-O hollow microspheres for efficient hydrogen evolution reaction in alkaline solution[J]. Chinese Journal of Catalysis, 2020, 41(4): 691-697.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63530-6

https://www.cjcatal.com/CN/Y2020/V41/I4/691

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