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An electrochromic coordination nanosheet for robust CO2 photoreduction via ligand-based electron transfer

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Abstract

A coordination nanosheet composed of [Fe(tpy)2]2+ (tpy = 2,2′:6′,2″-terpyridine) units, showing reversible electrochromism at the ligand-based cathodic potential, has been prepared through a liquid/liquid interfacial synthesis. The noble metal-free nanosheet exhibited a CO evolution rate of 114.3 mmol·g−1·h−1 with the selectivity up to 99.3% under visible light irradiation in the presence of water, which is in the front rank of heterogeneous catalysis for CO2 photoreduction. Such robust photocatalytic performance is due to efficient ligand-based electron transfer through long-lived π radical anion tpy− with a lifetime more than 25 min, as evidenced by in situ electron paramagnetic resonance (EPR) and ultraviolet—visible—near infrared (UV—vis—NIR) spectroscopy studies. Fe(II) cation in [Fe(tpy)2]2+ mainly contributes to enhancing reduction potentials of ligand and stabilizing π radical anion tpy−. This ligand-based electron transfer with the aid of metal cation represents a promising strategy for selective CO2 photoreduction, especially towards gaining CO from CO2.

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Acknowledgements

This work was supported by the Natural Science Foundation of Ningbo (No. 202003N4077) and the Scientific Research Fund of Zhejiang Provincial Education Department (No. Y202146152).

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  1. School of Materials Science and Chemical Engineering, Ningbo University, Ningbo, 315211, China

    Longxin Chen, Ting Liu & Duobin Chao

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  1. Longxin Chen
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Chen, L., Liu, T. & Chao, D. An electrochromic coordination nanosheet for robust CO2 photoreduction via ligand-based electron transfer. Nano Res. 15, 5902–5911 (2022). https://doi.org/10.1007/s12274-022-4245-2

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