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Heterometallic cluster-based organic frameworks as highly active electrocatalysts for oxygen reduction and oxygen evolution reaction: a density functional theory study

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Abstract

Recently, metal-organic frameworks are one of the potential catalytic materials for electrocatalytic applications. The oxygen reduction reaction and oxygen evolution reaction catalytic activities of heterometallic cluster-based organic frameworks are investigated using density functional theory. Firstly, the catalytic activities of heterometallic clusters are investigated. Among all heterometallic clusters, Fe2Mn-Mn has a minimum overpotential of 0.35 V for oxygen reduction reaction, and Fe2Co-Co possesses the smallest overpotential of 0.32 V for oxygen evolution reaction, respectively 100 and 50 mV lower than those of Pt(111) and RuO2(110) catalysts. The analysis of the potential gap of Fe2M clusters indicates that Fe2Mn, Fe2Co, and Fe2Ni clusters possess good bifunctional catalytic activity. Additionally, the catalytic activity of Fe2Mn and Fe2Co connected through 3,3′,5,5′-azobenzen-etetracarboxylate linker to form Fe2M-PCN-Fe2M is explored. Compared with Fe2Mn-PCN-Fe2Mn, Fe2Co-PCN-Fe2Co, and isolated Fe2M clusters, the mixed-metal Fe2Co-PCN-Fe2Mn possesses excellent bifunctional catalytic activity, and the values of potential gap on the Mn and Co sites of Fe2Co-PCN-Fe2Mn are 0.69 and 0.70 V, respectively. Furthermore, the analysis of the electron structure indicates that constructing a mixed-metal cluster can efficiently enhance the electronic properties of the catalyst. In conclusion, the mixed-metal cluster strategy provides a new approach to further design and synthesize high-efficiency bifunctional electrocatalysts.

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Acknowledgements

This work was supported by the Science and Technology Project of Sichuan Province (Grant No. 2022YFS0447), the Local Science and Technology Development Fund Projects Guided by the Central Government of China (Grant No. 2021ZYD0060), the Science and Technology Project of Southwest Petroleum University (Grant No. 2021JBGS03), the Special Project of Science and Technology Strategic Cooperation between Nanchong City and Southwest Petroleum University (Grant No. SXQHJH064), and the Postgraduate Research and Innovation Fund of Southwest Petroleum University (Grant No. 2021CXYB14). We acknowledge the National Supercomputing Center in Shenzhen for providing the computational resources and Materials Studio.

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Authors and Affiliations

  1. Center for Computational Chemistry and Molecular Simulation, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu, 610500, China

    Xin Chen, Liang Luo, Shihong Huang & Xingbo Ge

  2. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, 610500, China

    Xin Chen

  3. Oil & Gas Field Applied Chemistry Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu, 610500, China

    Xin Chen

  4. Department of Applied Physics, University of Eastern Finland, Kuopio, 70211, Finland

    Xiuyun Zhao

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  1. Xin Chen
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  2. Liang Luo
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Correspondence to Xin Chen.

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Heterometallic cluster-based organic frameworks as highly active electrocatalysts for oxygen reduction and oxygen evolution reaction: a density functional theory study

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Chen, X., Luo, L., Huang, S. et al. Heterometallic cluster-based organic frameworks as highly active electrocatalysts for oxygen reduction and oxygen evolution reaction: a density functional theory study. Front. Chem. Sci. Eng. 17, 570–580 (2023). https://doi.org/10.1007/s11705-022-2247-y

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