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Understanding the role of central metal and coordination environment of single atom catalysts embedded in graphene flakes on CO2RR performance

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Abstract

Single atom catalysts are promising for enhancing performance of electrocatalytic CO2 reduction reaction (CO2RR). Herein, first-principle calculations were conducted to investigate the mechanism of two electron/proton transfers during CO2RR on two types of structures of single metal atom with four coordinated nitrogen atoms (M‒N4, M = Fe, Co, Ni, and Cu), namely metal phthalocyanine (MPc) and metal anchored nitrogen-containing carbon (M‒NC). Our results demonstrate that nitrogen-containing carbon plane effectively immobilizes and activates metal centers. The physical adsorption of CO2 suggests that the initial activation of CO2 proceeds through a concerted proton-electron transfer step. M‒NC surfaces exhibit higher favorability toward reactions of CO2 → *COOH and CO2 → *HCOO compared to MPc with the same metal center. Noteworthily, MPc structures featuring pyrrolic N coordination environment exhibit greater stability, whereas M‒NC with pyridinic N coordination environment demonstrate higher activity in the initial reduction of CO2. CoPc and Fe‒NC are the optical catalysts for achieving high CO2RR performance in the formation of CO and HCOOH, respectively. The strong binding of *COOH/*HCOO on catalyst can effectively reduce the reaction energy required for its subsequent reduction. The results of this study provide profound insights into the intricate coordination environment and the distinct role by various metal centers in M‒Nx materials.

Graphical abstract

Both central metals and coordination environment of single atom catalysts have great influence on CO2RR. Metal anchored nitrogen-containing carbon catalysts are more favorable for activation of CO2 while metal phthalocyanine catalysts exhibit higher stability. CoPc and Fe‒NC are the optical catalysts for achieving high CO2RR performance in the formation of CO and HCOOH, respectively.

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Acknowledgements

This work was supported by The National Natural Science Foundation of China (22101300), Shandong Natural Science Foundation, China (ZR2020ME053 and ZR2020QB027), State Key Laboratory of Enhanced Oil Recovery of Open Fund Funded Project (2022-KFKT-28), Major Special Projects of CNPC (2021ZZ01-05), and the Fundamental Research Funds for the Central Universities (20CX05010A and 22CX03010A). The funds and project numbers are The National Natural Science Foundation of China (22101300), Shandong Natural Science Foundation (ZR2023ME004, ZR2022ME105), Qingdao Natural Science Foundation (23-2-1-232-zyyd-jch), and the Fundamental Research Funds for the Central Universities (22CX01002A-1).

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Authors and Affiliations

  1. School of Materials Science and Engineering, China University of Petroleum, Qingdao, 266580, Shandong, People’s Republic of China

    Shoufu Cao, Jiao Li, Chunyu Yang, Shuxian Wei, Siyuan Liu, Zhaojie Wang & Xiaoqing Lu

  2. College of Science, China University of Petroleum, Qingdao, 266580, Shandong, People’s Republic of China

    Hongyu Chen, Zengxuan Chen, Shuxian Wei & Siyuan Liu

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  1. Shoufu Cao
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Contributions

SC Writing—review and editing, Writing—original draft, Data curation, Formal analysis. Investigation, Visualization. HC Resources, Software. JL, CY Writing—review and editing, Methodology. SW, SL, ZW Funding acquisition, Supervision. XL Writing—review and editing, Conceptualization, Formal analysis.

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Correspondence to Siyuan Liu or Xiaoqing Lu.

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Cao, S., Chen, H., Li, J. et al. Understanding the role of central metal and coordination environment of single atom catalysts embedded in graphene flakes on CO2RR performance. J Mater Sci 58, 15714–15726 (2023). https://doi.org/10.1007/s10853-023-09012-2

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