Issue 25, 2023

A conductive catecholate-based framework coordinated with unsaturated bismuth boosts CO2 electroreduction to formate

Abstract

Bismuth-based metal–organic frameworks (Bi-MOFs) have received attention in electrochemical CO2-to-formate conversion. However, the low conductivity and saturated coordination of Bi-MOFs usually lead to poor performance, which severely limits their widespread application. Herein, a conductive catecholate-based framework with Bi-enriched sites (HHTP, 2,3,6,7,10,11-hexahydroxytriphenylene) is constructed and the zigzagging corrugated topology of Bi–HHTP is first unraveled via single-crystal X-ray diffraction. Bi–HHTP possesses excellent electrical conductivity (1.65 S m−1) and unsaturated coordination Bi sites are confirmed by electron paramagnetic resonance spectroscopy. Bi–HHTP exhibited an outstanding performance for selective formate production of 95% with a maximum turnover frequency of 576 h−1 in a flow cell, which surpassed most of the previously reported Bi-MOFs. Significantly, the structure of Bi–HHTP could be well maintained after catalysis. In situ attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirms that the key intermediate is *COOH species. Density functional theory (DFT) calculations reveal that the rate-determining step is *COOH species generation, which is consistent with the in situ ATR-FTIR results. DFT calculations confirmed that the unsaturated coordination Bi sites acted as active sites for electrochemical CO2-to-formate conversion. This work provides new insights into the rational design of conductive, stable, and active Bi-MOFs to improve their performance towards electrochemical CO2 reduction.

Graphical abstract: A conductive catecholate-based framework coordinated with unsaturated bismuth boosts CO2 electroreduction to formate

Supplementary files

Article information

Article type
Edge Article
Submitted
11 apr 2023
Accepted
22 may 2023
First published
31 may 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 6860-6866

A conductive catecholate-based framework coordinated with unsaturated bismuth boosts CO2 electroreduction to formate

Z. Gao, M. Hou, Y. Shi, L. Li, Q. Sun, S. Yang, Z. Jiang, W. Yang, Z. Zhang and W. Hu, Chem. Sci., 2023, 14, 6860 DOI: 10.1039/D3SC01876H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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