Issue 34, 2022

Evolution of bismuth-based metal–organic frameworks for efficient electroreduction of CO2

Abstract

Understanding the structural and chemical changes that reactive metal–organic frameworks (MOFs) undergo is crucial for the development of new efficient catalysts for electrochemical reduction of CO2. Here, we describe three Bi(III) materials, MFM-220, MFM-221 and MFM-222, which are constructed from the same ligand (biphenyl-3,3′,5,5′-tetracarboxylic acid) but which show distinct porosity with solvent-accessible voids of 49.6%, 33.6% and 0%, respectively. We report the first study of the impact of porosity of MOFs on their evolution as electrocatalysts. A Faradaic efficiency of 90.4% at −1.1 V vs. RHE (reversible hydrogen electrode) is observed for formate production over an electrode decorated with MFM-220-p, formed from MFM-220 on application of an external potential in the presence of 0.1 M KHCO3 electrolyte. In situ electron paramagnetic resonance spectroscopy confirms the presence of ·COOH radicals as a reaction intermediate, with an observed stable and consistent Faradaic efficiency and current density for production of formate by electrolysis over 5 h. This study emphasises the significant role of porosity of MOFs as they react and evolve during electroreduction of CO2 to generate value-added chemicals.

Graphical abstract: Evolution of bismuth-based metal–organic frameworks for efficient electroreduction of CO2

Supplementary files

Article information

Article type
Paper
Submitted
05 iyn 2022
Accepted
03 avq 2022
First published
18 avq 2022
This article is Open Access
Creative Commons BY license

J. Mater. Chem. A, 2022,10, 17801-17807

Evolution of bismuth-based metal–organic frameworks for efficient electroreduction of CO2

L. Li, X. Kang, M. He, A. Sheveleva, K. Hu, S. Xu, Y. Zhou, J. Chen, S. Sapchenko, G. Whitehead, I. J. Vitorica-Yrezabal, L. Lopez-Odriozola, L. S. Natrajan, E. J. L. McInnes, M. Schröder, S. Yang and F. Tuna, J. Mater. Chem. A, 2022, 10, 17801 DOI: 10.1039/D2TA04485D

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