物理化学学报 >> 2021, Vol. 37 >> Issue (7): 2010025.doi: 10.3866/PKU.WHXB202010025

所属专题: 电催化

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导电金属有机框架材料在电催化中的成就,挑战和机遇

高增强1, 王聪勇2,3, 李俊俊1, 朱亚廷1, 张志成1,*(), 胡文平1,2,*()   

  1. 1天津市分子光电科学重点实验室,天津大学理学院化学系,天津化学化工协同创新中心,天津 300072Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University & Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China
    2化学系,理学院,新加坡国立大学,新加坡 117543Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, China
    天津大学-新加坡国立大学福州联合学院,天津大学福州国际校区,滨海新城,福州3502073Department of Chemistry, Faculty of Science, National University of Singapore, Singapore 117543, Singapore
  • 收稿日期:2020-10-13 录用日期:2020-11-25 发布日期:2020-11-30
  • 通讯作者: 张志成,胡文平 E-mail:zczhang19@tju.edu.cn;huwp@tju.edu.cn
  • 作者简介:Zhicheng Zhang is a Professor in the Department of Chemistry, School of Science, Tianjin University. He received his Ph.D. degree from the College of Chemical Engineering, China University of Petroleum (Beijing) in 2012. Then, he worked as a Postdoctoral Researcher in the Department of Chemistry, Tsinghua University. Since 2014, he worked as a Research Fellow in the School of Materials Science and Engineering, Nanyang Technological University, Singapore. In 2019, he joined Tianjin University as a Full Professor. His research interests include the design and synthesis of functional nanomaterials and their applications in energy conversion, catalysis, and organic optoelectronics
    Wenping Hu is a Professor at Tianjin University and a Cheung Kong Professor of the Ministry of Education, China. He received his Ph.D. from ICCAS in 1999. Then, he joined Osaka University and Stuttgart University as a Research Fellow of the Japan Society for the Promotion of Sciences and an Alexander von Humboldt fellow, respectively. In 2003, he worked with Nippon Telephone and Telegraph and then joined ICCAS as a Full Professor. He worked for Tianjin University in 2013. His research focuses on organic optoelectronics第一联系人:

    These authors contributed equally to this work.

  • 基金资助:
    the National Key R & D Program(2017YFA0204503);the National Natural Science Foundation of China(22071172);the National Natural Science Foundation of China(91833306);the National Natural Science Foundation of China(21875158);the National Natural Science Foundation of China(51633006);the National Natural Science Foundation of China(51733004)

Conductive Metal-Organic Frameworks for Electrocatalysis:Achievements, Challenges, and Opportunities

Zengqiang Gao1, Congyong Wang2,3, Junjun Li1, Yating Zhu1, Zhicheng Zhang1,*(), Wenping Hu1,2,*()   

  • Received:2020-10-13 Accepted:2020-11-25 Published:2020-11-30
  • Contact: Zhicheng Zhang,Wenping Hu E-mail:zczhang19@tju.edu.cn;huwp@tju.edu.cn
  • About author:Email: huwp@tju.edu.cn (W.H.); Tel: +86-22-83613363 (Z.Z.)
    Email: zczhang19@tju.edu.cn (Z.Z.)
  • Supported by:
    国家重点研发计划(2017YFA0204503);国家自然科学基金(22071172);国家自然科学基金(91833306);国家自然科学基金(21875158);国家自然科学基金(51633006);国家自然科学基金(51733004)

摘要:

开发用于各种能量转化过程的新型催化剂对于满足绿色和可持续能源的需求至关重要。由于其具有可调节的晶体结构,显著的化学和物理性质以及稳定性,金属有机骨架(MOFs)已经广泛应用于电化学能量转换领域,比如CO2还原反应、N2还原反应、析氧反应、析氢反应和氧还原反应。更重要的是,MOFs具有可调节的化学环境、孔径和孔隙率,这些性质将促进反应物在多孔网络中的扩散,从而改善其电催化性能。但是,由于高的电荷转移能垒和受限的自由载流子,大多数MOFs展示了差的导电性,阻碍了其多样化应用。在先前的报道中,MOFs常被用作多孔基质来限制纳米颗粒生长或经退火处理作为共掺杂电催化剂。而导电MOFs不仅结合了传统MOFs的优点,还具有电子导电性和高电催化活性,使其无需退火处理就可以通过电子或离子途径实现导电,从而极大提高了电催化性能,这有助于拓宽其在电化学能源领域或其他方面的潜在应用。在一些催化反应中,导电MOFs的催化活性甚至超过了商业化的RuO2催化剂或Pt基催化剂。本文主要总结了构建导电MOFs的机制,并概述了其合成方法,如水/溶剂热合成和界面辅助合成。此外,本文阐述了导电MOFs在电催化应用中的最新研究进展。值得一提的是,导电MOFs的形态和结构可改变底物与MOFs之间的界面接触,从而影响其催化性能,需要进一步深入研究。基于系统的合成策略,在未来可以根据各种电催化反应的需求设计合成更多的导电MOFs。高性能的导电MOF基催化剂将有望获得突破。

关键词: 导电金属有机框架, 电催化, 二氧化碳还原反应, 氮还原反应, 析氧反应, 析氢反应, 氧还原反应

Abstract:

To fulfill the demands of green and sustainable energy, the production of novel catalysts for different energy conversion processes is critical. Owing to the intriguing advantages of the intrinsic active species, tunable crystal structure, remarkable chemical and physical properties, and good stability, metal-organic frameworks (MOFs) have been extensively investigated in various electrochemical energy conversions, such as the CO2 reduction reaction, N2 reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, and oxygen reduction reaction. More importantly, it is feasible to change the chemical environments, pore sizes, and porosity of MOFs, which will theoretically facilitate the diffusion of reactants across the open porous networks, thereby improving the electrocatalytic performance. However, owing to the high energy barriers of charge transfer and limited free charge carriers, most MOFs show poor electrical conductivity, thus limiting their diverse applications. As reported previously, MOFs were used as a porous substrate to confine the growth of nanoparticles or co-doped electrocatalysts after annealing. The conductive MOFs can combine the advantages of conventional MOFs with electronic conductivity, which significantly enhance the electrocatalytic performance. In addition, conductive MOFs can achieve conductivity via electronic or ionic routes without post-annealing treatment, thereby extending their potential applications. Different synthesis strategies have recently been developed to endow MOFs with electrical conductivity, such as post-synthesis modification, guest molecule introduction, and composite formatting. The performance of conductive MOFs can even outperform those of commercial RuO2 catalysts or Pt-group catalysts. However, it is difficult to endow most MOFs with high conductivity. This review summarizes the mechanisms of constructing conductive MOFs, such as redox hopping, through-bond pathways, through-space pathways, extended conjugation, and guest-promoted transport. Synthetic methods, including hydro/solvothermal synthesis and interface-assisted synthesis, are introduced. Recent advances in the use of conductive MOFs as heterogeneous catalysts in electrocatalysis have been comprehensively elucidated. It has been reported that conductive MOFs can demonstrate considerable catalytic activity, selectivity, and stability in different electrochemical reactions, revealing the immense potential for future displacement of Pt-group catalysts. Finally, the challenges and opportunities of conductive MOFs in electrocatalysis are discussed. Based on systematic synthesis strategies, more conductive MOFs can be constructed for electrocatalytic reactions. In addition, the morphology and structure of conductive MOFs, which can change the electrochemical accessibility between substrates and MOFs, are also crucial for catalysis, and thus, they should be extensively studied in the future. It is believed that a breakthrough for high-performance conductive MOF-based electrocatalysts could be achieved.

Key words: Conductive metal-organic frameworks, Electrocatalysis, CO2 reduction reaction, N2 reduction reaction, Oxygen evolution reaction, Hydrogen evolution reaction, Oxygen reduction reaction

MSC2000: 

  • O643