物理化学学报 >> 2020, Vol. 36 >> Issue (1): 1906063.doi: 10.3866/PKU.WHXB201906063

所属专题: 庆祝唐有祺院士百岁华诞特刊

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多酸在电催化析氢反应中的应用研究进展

葛靖暄1,胡钧1,朱盈婷1,泽妮诗1,臧德进1,秦召贤2,黄毅超1,*(),张江威2,*(),魏永革1,*()   

  1. 1 有机光电子与分子工程教育部重点实验室,清华大学化学系,北京 100084
    2 催化基础国家重点实验室,中国科学院大连化学物理研究所,辽宁 大连 116023
  • 收稿日期:2019-06-24 录用日期:2019-09-23 发布日期:2019-09-29
  • 通讯作者: 黄毅超,张江威,魏永革 E-mail:yichao_huang@tsinghua.edu.cn;jwzhang@dicp.ac.cn;yonggewei@tsinghua.edu.cn
  • 作者简介:黄毅超,1992年3月出生。本科就读于北京化工大学;2014年9月保送至清华大学化学系直博,师从魏永革教授;2019年1月至今在组里做博士后。研究方向是多酸合成和电催化析氢、电催化产氧、电催化氧还原和燃料电池等|张江威,1987年11月出生,本科就读于北京化工大学;2016获得清华大学化学系博士学位,师从魏永革教授。2016年加入中国科学院大连化学物理研究所任助理研究员,主要研究方向是金属原子簇精准制备及光电性能研究和同步辐射光源精准结构探测|魏永革,清华大学教授,国家杰出青年基金获得者。1967年6月出生。1995年在北京大学获得博士学位,之后留校任教。2005年加入清华大学化学系。主要从事多酸合成结构、化学修饰、组装、有机催化反应和电催化能源转化研究
  • 基金资助:
    中国博士后科学基金(2019M650027);中国博士后科学基金(2019TQ0169);国家自然科学基金(21901136);国家自然科学基金(21225103);国家自然科学基金(21471087);国家自然科学基金(21631007)

Recent Advances in Polyoxometalates for Applications in Electrocatalytic Hydrogen Evolution Reaction

Jingxuan Ge1,Jun Hu1,Yingting Zhu1,Zonish Zeb1,Dejin Zang1,Zhaoxian Qin2,Yichao Huang1,*(),Jiangwei Zhang2,*(),Yongge Wei1,*()   

  1. 1 Key Lab of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China
    2 State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, P. R. China
  • Received:2019-06-24 Accepted:2019-09-23 Published:2019-09-29
  • Contact: Yichao Huang,Jiangwei Zhang,Yongge Wei E-mail:yichao_huang@tsinghua.edu.cn;jwzhang@dicp.ac.cn;yonggewei@tsinghua.edu.cn
  • Supported by:
    the China Postdoctoral Science Foundation(2019M650027);the China Postdoctoral Science Foundation(2019TQ0169);the National Natural Science Foundation of China(21901136);the National Natural Science Foundation of China(21225103);the National Natural Science Foundation of China(21471087);the National Natural Science Foundation of China(21631007)

摘要:

电催化水裂解是一种可持续用于生产可再生氢能源的技术。然而,开发高效稳定、低成本的析氢电催化剂仍是一项具有挑战性的任务。多金属氧酸盐(多酸)是一种离散的金属氧簇合物,通常由氧配体和高价的钒(Ⅴ)、钼(Ⅵ)、钨(Ⅵ)金属构成。由于多酸含有丰富的氧化还原活性金属中心,因此,近几年来,多酸在水裂解应用研究方面备受关注。本综述将聚焦于多酸在电催化水裂解析氢的应用研究进展。本文还突出强调了电催化析氢目前面临的主要问题,以及对多酸基催化剂及作为催化剂前体在电催化析氢方面的应用及发展前景做了展望。

关键词: 多酸, 氧化还原活性位点, 电催化, 水裂解, 析氢反应

Abstract:

Hydrogen (H2), a clean and sustainable energy carrier, is regarded as one of the most promising alternatives to carbon-based fuels. Hydrogen can be generated in a more sustainable way from renewable energy sources via electrocatalytic water splitting. However, the high cost and low abundance of the benchmarking platinum-based hydrogen evolution reaction (HER) catalysts hinder their widespread applications. Thus, developing highly efficient, stable, and low-cost electrocatalysts to replace platinum for HER is imperative, but remains a challenging task. Recently, efforts have been devoted to developing non-noble HER electrocatalysts, including transition metal carbides, oxides, phosphides, and sulfides. However, traditional synthetic strategies cannot effectively control active sites and the catalysts tend to aggregate under high temperature. Recently, polyoxometalates (POMs) have been applied as precursors for the preparation of non-noble HER electrocatalysts as they contain discrete metal-oxygen clusters with well-defined structures. POMs are typically composed of oxygen ligands and high-valent metal ions such as Ⅴ(Ⅴ), Mo(Ⅵ), and W(Ⅵ), which can serve as Ⅴ, Mo, and W sources to produce the corresponding metal carbides, oxides, phosphides, and sulfides by pyrolysis at high temperature. Some POMs may also contain a series of redox-active heteroatoms, which are usually named hetero-polyoxometalates. These can serve as precursors to electrocatalysts with uniform heteroatom doping. Moreover, direct applications of POMs as molecular catalysts in HER have, in recent years, received rapidly growing attention. This is because POMs not only serve as mediators or molecular catalysts to facilitate the HER, but can also be deposited on the electrode surface to catalyze the HER. However, the interpretation that HER catalytic activity enhancement is due to the intrinsic catalytic properties of the electrodeposited polyoxometalate or the deposition of small amounts of platinum has been highly debated. Reviewing these studies may help us understand the intrinsic active sites as well the intrinsic HER mechanism of POMs and POMs-derived catalysts, and thus design more efficient HER catalysts. This review, therefore, focuses on recent progress in the applications of POMs and their derivatives in electrocatalytic HER. Firstly, basic HER mechanisms for common metal catalysts and POMs molecular catalysts are discussed along with challenges in the field of HER. Next, applications of POMs molecular catalysts and POMs-derived catalysts in HER are summarized. Finally, some perspectives of POMs-based catalysts/pre-catalysts for electrocatalytic HER are proposed.

Key words: Polyoxometalate, Redox-active site, Electrocatalysis, Water-splitting, Hydrogen evolution reaction

MSC2000: 

  • O646