高熵合金作为一种优异电催化剂的理解、合理设计和应用:综述

The understanding,rational design,and application of high-entropy alloys as excellent electrocatalysts:A review

高熵合金近年来在电催化领域广受关注.由于其四大“核心效应”,即高熵效应、晶格畸变效应、迟滞扩散效应和鸡尾酒效应,高熵合金在诸多电催化反应中展现出了优异的活性和选择性.然而在已报道的文献综述中,有关其优异性能的理解以及合理设计的系统性总结仍然具有局限性.本文不仅综述了高熵合金电催化剂的特点和设计准则,还对其应用的最新进展进行了系统性的归纳整理,对高熵合金未来的发展具有指导意义.首先我们从多个角度阐明了高熵合金作为一种优异电催化剂的原因,包括其出色的机械性能、可优化的结构和组成、大量具有高本征活性的活性位点,以及出色的稳定性.为了进一步深入对高熵合金电催化剂的理解,我们还从设计准则、元素选择,以及理论计算预测材料性质等角度,详细介绍了高熵合金的合理设计.随后,我们介绍了高熵合金电催化剂在电解水、有机小分子氧化、燃料电池和碳/氮基转化反应的最新研究进展,其中还包括了一系列理论计算和原位表征在理解催化反应机理方面的应用.最后,我们展望了高熵合金电催化剂在未来发展中面临的挑战和机遇.

High-entropy alloys(HEAs)are attracting considerable attention in the field of electrocatalysis.In many cases,HEAs exhibit excellent activity and selectivity toward several catalytic reactions,which is often attributed to their four“core effects”:the high entropy effect,the lattice distortion effect,the sluggish diffusion effect and the cocktail effect.However,the understanding and rational design of HEA electrocatalysts lack a systematic summarization.In this review,a systematic summary of HEA electrocatalysts’characteristics and applications,as well as a clarification of their design principles,is provided,which has guiding importance for HEA development.First,the reason why HEAs could be excellent electrocatalysts is illustrated from several aspects,including their outstanding mechanical properties,optimized structure and composition,abundant active sites with high intrinsic activity,and ultrahigh stability.To deepen the understanding of HEA electrocatalysts,the rational design of HEAs is carefully demonstrated in terms of design principles,element selection,and the use of computation methods for property prediction.Second,the latest advances in HEA electrocatalysts in the fields of water electrolysis,fuel cells,small organic molecule electrochemical oxidation,and carbon-and nitrogen-based conversion are discussed in detail.Importantly,theoretical calculations and in situ characterizations for an understanding of HEAs’mechanism are carefully illustrated.Finally,we propose the challenges and perspectives in the future design and application of HEA electrocatalysts.