Citation: Gao Zengqiang, Wang Congyong, Li Junjun, Zhu Yating, Zhang Zhicheng, Hu Wenping. Conductive Metal-Organic Frameworks for Electrocatalysis:Achievements, Challenges, and Opportunities[J]. Acta Physico-Chimica Sinica, ;2021, 37(7): 201002. doi: 10.3866/PKU.WHXB202010025 shu

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

Gao Zengqiang ^1,† ,
Wang Congyong ^2,3,† ,
Li Junjun ¹ ,
Zhu Yating ¹ ,
Zhang Zhicheng ^1,, ,
Hu Wenping ^1,2,,

1.
Tianjin 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.
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, China
3.
Department of Chemistry, Faculty of Science, National University of Singapore, Singapore 117543, Singapore

Author Bio:

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
Corresponding author: Zhang Zhicheng, zczhang19@tju.edu.cn Hu Wenping, huwp@tju.edu.cn

^†

Received Date: 13 October 2020
Revised Date: 25 November 2020
Accepted Date: 25 November 2020
Available Online: 30 November 2020
Fund Project: the National Natural Science Foundation of China 22071172This work was supported by the National Key R & D Program (2017YFA0204503), and the National Natural Science Foundation of China (22071172, 91833306, 21875158, 51633006, 51733004)the National Key R & D Program 2017YFA0204503the National Natural Science Foundation of China 51733004the National Natural Science Foundation of China 91833306the National Natural Science Foundation of China 21875158the National Natural Science Foundation of China 51633006

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.
- Conductive metal-organic frameworks,
- Electrocatalysis,
- CO2 reduction reaction,
- N2 reduction reaction,
- Oxygen evolution reaction,
- Hydrogen evolution reaction,
- Oxygen reduction reaction
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