铂族金属高熵合金的设计、制备与应用研究进展

Research Progress on Design, Preparation, and Applications of Platinum-Group Metal High-Entropy Alloys

摘要:

高熵合金（high-entropy alloys，HEAs）由5种或更多主元素以等摩尔比或近等摩尔比组成，具有高熵效应、晶格畸变、缓慢扩散和多元协同效应等独特性质。铂族金属高熵合金（platinum-group metal high-entropy alloys，PGM-HEAs）兼具优异的催化活性与耐腐蚀性，同时在超导和磁制冷等领域也展现出独特优势，已成为高熵合金研究的重要分支。本文围绕成分设计、制备技术到功能应用这一主线，系统综述了PGM-HEAs的研究进展。成分设计方面，概述了基于相图计算、第一性原理计算及机器学习辅助筛选的多尺度设计方法，重点展示了机器学习在吸附能预测中的应用。针对块体材料，归纳了真空熔炼、粉末冶金及激光增材制造等主要制备技术，并评述了其力学性能、超导性、形状记忆效应及磁热效应的研究现状。针对纳米材料，梳理了“自上而下”与“自下而上”两类制备方法，讨论了其在燃料电池、电解水制氢等电催化反应中的应用与机理。最后，分析了高成本、规模化制备及成分均匀化等现存挑战，并对低贵金属化设计、绿色合成工艺及多尺度模拟等方向作了展望。

Abstract:

High-entropy alloys (HEAs) are composed of five or more principal elements in equimolar or near-equimolar ratios, and exhibit distinctive properties including high-entropy effects, lattice distortion, sluggish diffusion, and cocktail effects. Platinum-group metal high-entropy alloys (PGM-HEAs) combine outstanding catalytic activity with superior corrosion resistance, and also exhibit notable functional properties in superconductivity and magnetocaloric refrigeration, which have rendered them a significant branch of HEA research. This review surveys the state of the art in PGM-HEAs, proceeding from compositional design through fabrication techniques to functional applications. In terms of compositional design, the review outlines multi-scale design methods based on phase-diagram calculations, first-principles calculations, and machine learning-assisted screening, with emphasis on the application of machine learning in adsorption energy prediction. For bulk PGM-HEAs, major fabrication techniques including vacuum melting, powder metallurgy, and laser additive manufacturing are summarized, followed by an assessment of research progress concerning mechanical properties, superconductivity, shape memory effect, and magnetocaloric performance. For nanostructured PGM-HEAs, both “top-down” and “bottom-up” synthesis strategies are categorized, and their application and mechanisms in electrocatalytic reactions, including fuel cells and water electrolysis for hydrogen production are discussed in detail. Finally, persistent challenges related to high material cost, scalable production, and compositional homogenization are analyzed, while future research directions including low-PGM alloy design, green synthesis methodologies, and multi-scale computational modeling are discussed.