TY - JOUR
T1 - Evolution of bismuth-based metal-organic frameworks for efficient electroreduction of CO2
AU - Li, Lili
AU - Kang, Xinchen
AU - He, Meng
AU - Sheveleva, Alena
AU - Hu, Kui
AU - Xu, Shaojun
AU - Zhou, Yiqi
AU - Chen, Jin
AU - Sapchenko, Sergei
AU - Whitehead, George
AU - Lopez Odriozola, Laura
AU - Natrajan, Louise
AU - Mcinnes, Eric
AU - Schroder, Martin
AU - Yang, Sihai
AU - Tuna, Floriana
PY - 2022/8/3
Y1 - 2022/8/3
N2 - 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 Faradic 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.
AB - 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 Faradic 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.
M3 - Article
SN - 2050-7488
JO - Journal of Materials Chemistry A
JF - Journal of Materials Chemistry A
ER -