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

Lili Li; Xinchen Kang; Meng He; Alena Sheveleva; Kui Hu; Shaojun Xu; Yiqi Zhou; Jin Chen; Sergei Sapchenko; George Whitehead; Iñigo J. Vitorica-Yrezabal; Laura Lopez-Odriozola; Louise S. Natrajan; Eric J. L. McInnes; Martin Schröder; Sihai Yang; Floriana Tuna

doi:10.1039/D2TA04485D

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

Lili Li,^a Xinchen Kang,

^ab Meng He,

^a Alena Sheveleva,^ac Kui Hu,^a Shaojun Xu,

^de Yiqi Zhou,

^fg Jin Chen,^a Sergei Sapchenko,^a George Whitehead,

^a Iñigo J. Vitorica-Yrezabal,^a Laura Lopez-Odriozola,^a Louise S. Natrajan,

^a Eric J. L. McInnes,^ac Martin Schröder,

*^a Sihai Yang

*^a and Floriana Tuna

*^ac

Author affiliations

* Corresponding authors

^a Department of Chemistry, University of Manchester, Manchester, UK
E-mail: M.Schroder@manchester.ac.uk, Sihai.Yang@manchester.ac.uk, Floriana.Tuna@manchester.ac.uk

^b Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Science, Beijing, China

^c Photon Science Institute, University of Manchester, Manchester, UK

^d UK Catalysis Hub, Research Complex at Harwell, Didcot, UK

^e Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, UK

^f Department of Materials, University of Manchester, Manchester, UK

^g Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China

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.

Journal of Materials Chemistry A

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

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

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Journal of Materials Chemistry A