氧空位缺陷引入方法对Co3O4基电催化剂析氧性能影响

Effect of oxygen vacancy defect introduction method on oxygen evolution performance of Co3O4 based electrocatalyst

  • 摘要: 氧空位诱导尖晶石Co3O4上的析氧反应(OER)是一个备受关注的研究热点。探究不同引入氧空位方法、氧空位数量和空间分布与电催化活性的关系,对于设计高效的电催化剂具有重要的意义。本研究采用了空气煅烧法、NaBH4还原法、H2还原法、真空热处理法四种引入氧空位的方法,系统地研究了不同方法引入不同数量、不同空间分布的氧空位缺陷对Co3O4电催化活性的影响。研究结果表明,通过真空热处理法引入氧空位的Co3O4材料OER电催化活性表现最佳(η10=257 mV),优于NaBH4还原(η10=280 mV)、H2还原(η10=286 mV)和空气煅烧(η10=299 mV)。通过HRTEM观察到深层次的无序结构,并且XPS与ESR测试显示,表面氧空位含量减小,但Co3+的急剧减少,Co0的增多以及总体氧空位浓度升高,表明在材料中更深层的体相中产生了体相氧空位。本研究分析真空热处理产生的氧空位对Co具有更好的预氧化作用使Co(Ⅲ)更好的转换为Co(Ⅳ)活性物质,是OER性能提升最优的原因。这项工作加深了对氧缺陷型催化剂的认识,为氧缺陷型催化剂的开发提供了一种新的见解。

     

    Abstract: Oxygen evolution (OER) on spinel Co3O4 induced by oxygen vacancy has been a hot research topic. Exploring the relationship between different methods of introducing oxygen vacancies, the number and spatial distribution of oxygen vacancies and electrocatalytic activity is of great significance for the design of efficient electrocatalysts. In this study, four methods of introducing oxygen vacancies, namely, air calcination, NaBH4 reduction, H2 reduction, and vacuum heat treatment, were used to systematically investigate the effects of introducing different amounts and spatial distributions of oxygen vacancy defects by different methods on the electrocatalytic activity of Co3O4. The results show that the OER electrocatalytic activity of the Co3O4 material with oxygen vacancies introduced by vacuum thermal treatment showed the best performance (η10=257 mV), which was superior to that of NaBH4 reduction (η10=280 mV), H2 reduction (η10=286 mV) and air calcination (η10=299 mV). A deep disordered structure was observed by HRTEM and XPS and ESR tests showed a decrease in the surface oxygen vacancy content, but a sharp decrease in Co3+, an increase in Co0 and an increase in the overall oxygen vacancy concentration, suggesting the creation of bulk oxygen vacancies in the deeper bulk phase of the material. This study analyzed that the oxygen vacancy generated by vacuum heat treatment has a better pre-oxidation effect on Co, and the Co (Ⅲ) is better converted to Co (Ⅳ) active substance, which is the reason for the best improvement of OER performance. This work deepens the understanding of oxygen defect catalyst and provides a new insight for the development of oxygen defect catalyst.

     

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