物理化学学报 >> 2021, Vol. 37 >> Issue (7): 2009077.doi: 10.3866/PKU.WHXB202009077

所属专题: 电催化

综述 上一篇    下一篇

高熵纳米合金在电化学催化中的应用

赵康宁, 李潇, 苏东()   

  • 收稿日期:2020-09-25 录用日期:2020-10-31 发布日期:2020-11-10
  • 通讯作者: 苏东 E-mail:dongsu@iphy.ac.cn
  • 作者简介:第一联系人:

    Contribute equally to this work.

  • 基金资助:
    中国科学院先导(B)(XDB07030200)

High-Entropy Alloy Nanocatalysts for Electrocatalysis

Kangning Zhao, Xiao Li, Dong Su()   

  • Received:2020-09-25 Accepted:2020-10-31 Published:2020-11-10
  • Contact: Dong Su E-mail:dongsu@iphy.ac.cn
  • About author:Dong Su, Email: dongsu@iphy.ac.cn; Tel: +86-10-82649555
  • Supported by:
    the Strategic Priority Research Program (B)(XDB07030200)

摘要:

高熵合金具有广泛的成分调制范围和固有的复杂表面,使其有望成为理想的电催化材料。最近的研究表明,高熵纳米合金在电催化反应中表现出优异性能。本文总结了近年来高熵纳米合金催化剂的研究进展。第一部分介绍了高熵合金的概念、结构及四个“核心效应”;第二部分总结了包含碳热冲击法、纳米液滴介导电沉积法、快速移动床热解法、多元醇法和脱合金法等制备方法;第三部分探讨了高熵纳米合金电催化剂对于各个不同电化学反应的研究进展;在最后,本文展望了高熵纳米合金在电催化领域的未来发展趋势。

关键词: 高熵合金纳米, 电催化, 单相固溶体, 吸附能, 活性位点

Abstract:

The implementation of clean energy techniques, including clean hydrogen generation, use of solar-driven photovoltaic hybrid systems, photochemical heat generation as well as thermoelectric conversion, is crucial for the sustainable development of our society. Among these promising techniques, electrocatalysis has received significant attention for its ability to facilitate clean energy conversion because it promotes a higher rate of reaction and efficiency for the associated chemical transformations. Noble-metal-based electrocatalysts typically show high activity for electrochemical conversion processes. However, their scarcity and high cost limit their applications in electrocatalytic devices. To overcome this limitation, binary catalysts prepared by alloying with transition metals can be used. However, optimization of the activity of the binary catalysts is considerably limited because of the presence of the miscibility gap in the phase diagram of binary alloys. The activity of binary electrocatalysts can be attributed to the adsorption energy of molecules and intermediates on the surface. High-entropy alloys (HEAs), which consist of diverse elements in a single NP, typically exhibit better physical and/or chemical properties than their single-element counterparts, because of their tunable composition and inherent surface complexity. Further, HEAs can improve the performance of binary electrocatalysts because they exhibit a near-continuous distribution of adsorption energy. Recently, HEAs have gained considerable attention for their application in electrocatalytic reactions. This review summarizes recent research advances in HEA nanostructures and their application in the field of electrocatalysis. First, we introduce the concept, structure, and four core effects of HEAs. We believe that this part will provide the basic information about HEAs. Next, we discuss the reported top-down and bottom-up synthesis strategies, emphasizing on the carbothermal shock method, nanodroplet-mediated electrodeposition, fast moving bed pyrolysis, polyol process, and dealloying. Other methods such as combinatorial co-sputtering, ultrashort-pulsed laser ablation, ultrasonication-assisted wet chemistry, and scanning-probe block copolymer lithography are also highlighted. Among these methods, wet chemistry has been reported to be effective for the formation of nano-scale HEAs because it facilitates the concurrent reduction of all metal precursors to form solid-solution alloys. Next, we present the theoretical investigation of HEA nanocatalysts, including their thermodynamics, kinetic stability, and adsorption energy tuning for optimizing their catalytic activity and selectivity. To elucidate the structure–property relationship in HEAs, we summarize the research progress related to electrocatalytic reactions promoted by HEA nanocatalysts, including the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, methanol oxidation reaction, and CO2 reduction reaction. Finally, we discuss the challenges and various strategies toward the development of HEAs.

Key words: High-entropy alloy nanostructures, Electrocatalysis, Single-phase solid solution, Adsorption energy, Active site

MSC2000: 

  • O643