2D Metal Covalent Organic Frameworks Towards Electrochemical Catalysis
Authors: Huang Hao , Wang Kaiying 
Published: February 2024

In the past century, innovative electrochemical reactions with low-consumption and environmental-friend have been a key substance for worldwide chemical industry.[1] Nowadays, the majority of the electrochemical reactions rely on low-cost and high-efficient catalysts, and there is an ever-growing need for the development of advanced catalysts to secure a sustainable future for our society.[2] The pursuit for sustainable energy stimulates the innovative concepts of advanced catalytic materials for electrochemical reactions, such as metal-air battery, nitrogen fixation and carbon neutrality etc.[3] The electrocatalysts play a vital role to promote the renewable energy conversion efficiencies and system performance.[4]

However, the electrocatalytic activities of most inorganic catalysts arises from the unsaturated metal sites exposed on the surfaces or edges, and the internal metal atoms in bulk phase are totally inert, resulting in the low utilization and efficiency of metal atoms for electrocatalysis.[5] Exploring novel electrocatalysts with high metal utilization is essential for electrochemical reactions. Recently, single-atom catalysts (SACs) strategy has been proposed to promote the efficiency and utilization of metal atoms in electrocatalysts. In particular, SACs could provide an ideal approach to maximize the efficiency of active metal atom utilization (in principle, up to 100%) and lower the cost of the electrochemical reactions.[6]

Inspired by SACs strategy, metal covalent-organic-frameworks (MCOFs) can be emerged as efficient catalysts, due to the numerous single-atom sites, ordered in-plane porous structure and outstanding stable framework. We propose a novel two-dimensional MCOFs, constructed by porphyrin subgroup (Figure 1), for achieving high efficiency of electrochemical reactions. Porphyrinsubgroup is a type of heterocyclic molecules with conjugated structure, which has strong ability to coordinate almost all transition metal ions to form high active single-metal sites. Thus, MCOFs with porphyrin could be a promising next-generation electrocatalyst, and an ideal catalytic model to reveal the mechanism of electrochemical reactions.

Acknowledgments: The authors gratefully acknowledge the financial support from H2020 Marie Skłodowska-Curie Actions (101024758) and National Natural Science Foundation of China (22002083).

References

[1] X. X. Zou, and Y. Zhang, Chem. Soc.
Rev.,
44, 5148-5180 (2015).
[2] S. L. Foster, S. I. Perez Bakovic, R. D. Duda, S. Maheshwari, R. D. Milton, S. D. Minteer, M. J. Janik, J. N. Renner, L. F. Greenlee,Nat. Catal.,
1, 490-500 (2018).
[3] C. Zhang, X. Liang, R. Xu, C. Dai, B. Wu, G. Yu, B. Chen, X. Wang, N. Liu, Adv. Funct. Mater, 31, 2008298 (2021).
[4] Y. Wang, H. Su, Y. He, L. Li, S. Zhu, H. Shen, P. Xie, X. Fu, G. Zhou, C. Feng, D. Zhao, F. Xiao, X. Zhu, Y. Zeng, M. Shao, h. Chen, G. Wu, J. Zeng, C. Wang, Chem. Rev., 120, 12217-12314 (2020).
[5] M. D. Hossain, Z. Liu, M. Zhuang, X. Yan, G.-L. Xu, C. A. Gadre, A. Tyagi, I. H. Abidi, C.-J. Sun, H. Wong, A. Guda, Yufeng Hao, X. Pan, K. Amine, Z. Luo, Adv. Energy Mater., 9, 1803689 (2019).
[6] J. Yang, W. Li, D. Wang, Y. Li, Adv. Mater., 32, 2003300 (2020).

Figure 1