物理化学学报 >> 2021, Vol. 37 >> Issue (7): 2009099.doi: 10.3866/PKU.WHXB202009099

所属专题: 电催化

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过渡金属氮化物的活性起源、合成方法及电催化应用

秦睿1,2, 王鹏彦1, 林灿1, 曹菲1, 张金咏1, 陈磊1,*(), 木士春1,2,*()   

  1. 1 武汉理工大学,材料复合新技术国家重点实验室,武汉 430070
    2 佛山仙湖实验室,先进能源科学与技术广东省实验室佛山分中心, 广东 佛山 528200
  • 收稿日期:2020-09-29 录用日期:2020-10-31 发布日期:2020-11-09
  • 通讯作者: 陈磊,木士春 E-mail:CHL0588@163.com;msc@whut.edu.cn
  • 作者简介:陈磊,1968年生。2006年于武汉理工大学获计算机科学与技术学士学位。现工作于武汉理工大学材料复合新技术国家重点实验室,为高级实验师。主要从事燃料电池及电化学产氢技术等研发工作
    木士春,1973年生。2001年于中国科学院中国科学院广州地球化学研究所获理学博士学位。现为武汉理工大学学科首席教授。目前主要从事质子交换膜燃料电池、电化学产氢催化剂及器件等研究工作
  • 基金资助:
    国家自然科学基金(51672204);国家自然科学基金(22075223)

Transition Metal Nitrides: Activity Origin, Synthesis and Electrocatalytic Applications

Rui Qin1,2, Pengyan Wang1, Can Lin1, Fei Cao1, Jinyong Zhang1, Lei Chen1,*(), Shichun Mu1,2,*()   

  1. 1 State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
    2 Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Xianhu Hydrogen Valley, Foshan 528200, Guangdong Province, China
  • Received:2020-09-29 Accepted:2020-10-31 Published:2020-11-09
  • Contact: Lei Chen,Shichun Mu E-mail:CHL0588@163.com;msc@whut.edu.cn
  • About author:Email: msc@whut.edu.cn (S.M.), Tel.: +86-13720130760 (S.M.)
    Email: CHL0588@163.com (L.C.), Tel.:+86-13507117678 (L.C.)
  • Supported by:
    the National Natural Science Foundation of China(51672204);the National Natural Science Foundation of China(22075223)

摘要:

过渡金属电催化剂因其优良的电催化性能、低廉的成本,以及在电解水、燃料电池、锌空电池等领域展现出极大的应用潜力,逐渐成为人们的研究热点。其中,过渡金属氮化物(Transition Metal Nitrides,TMNs)因氮化过程能使金属的d带收缩变窄,填充态发生改变,从而调节金属-氢的键能,达到提高导电性及催化活性的目的,近来备受学者们的关注。因此,本文综述了TMNs纳米电催化剂的最新研究进展,包括借助d带理论讨论了氮元素对其结构及活性的影响;评述了TMNs的物理、化学等合成方法及掺杂、复合等改性方法;列举了其在析氢反应、析氧反应、氧还原反应等电催化领域中的重要应用;最后,指出了TMNs在现阶段所面临的挑战和问题,并对其今后发展作出展望。

关键词: 过渡金属氮化物, 催化剂, 纳米结构, 电催化

Abstract:

Currently, because of the worldwide over-exploitation and consumption of fossil fuels, energy crisis and environmental pollution are becoming more prominent. Hence, the production and utilization of clean energy such as hydrogen are crucial. As significant electrochemical reactions in energy conversion devices, the oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR) have garnered considerable attention. However, the sluggish kinetics of these reactions, especially of the OER and ORR because of the multiple electron transfer steps, and the inevitable usage of noble metal catalysts (such as those based on Pt for HER/ORR and Ru/Ir for HER/OER) are the bottlenecks to realizing energy conversion devices, including overall water-splitting electrolyzers, fuel cells, and metal-air batteries. Therefore, the development of efficient non-precious metal catalysts is imperative. Transition metal nitrides (TMNs) have been recently studied and shown to exhibit high catalytic activity because of their ability to alter the electronic structure of host metals, specifically the downshift of the d-band center, the contraction of the filled state, and the broadening of the unfilled state. This high activity is attributed to the optimization of the adsorption energy between metals and adsorbates. In addition, metallic bonding in TMNs increases the conductivity of the catalysts. Thus, in this review, we focus on the latest developments in TMNs and their application as high-activity and high-stability electrocatalysts for water splitting and in fuel cells and zinc-air batteries. First, the origin of the high activity of TMNs is explained with the help of the d-band theory. The effect of nitrogen on TMNs, such as in terms of the location in the crystal structure, is briefly discussed. The preparation strategies for TMNs, including physical and chemical methods as well as the modification techniques such as doping, changing carrier properties, and defect construction, are outlined. Next, we summarize the applications of TMNs as an electrocatalyst for the HER, OER, and ORR. At the same time, to explain the bifunctional catalytic activity of TMNs, we discuss the modification strategies for single-metal-based nitrides, such as doping with other highly active atoms to adjust the electronic structure and increase the catalytic activities as well as using coupling materials with different catalytic selectivities to construct heterostructures. Finally, we discuss the challenges and development approaches for realizing the electrocatalytic applications of TMNs, such as through further improvement in catalytic activity, and for facilitating in-depth understanding of electrocatalytic processes through in situ characterization to reveal the electrocatalytic mechanism of TMNs. Undoubtedly, this review will promote the application of TMNs in the field of electrocatalysis.

Key words: Transition metal nitrides (TMNs), Catalyst, Nano structure, Electrocatalysis

MSC2000: 

  • O643