Modulating Electronic States of Cu in Metal‐Organic Frameworks for Emerging Controllable CH4/C2H4 Selectivity in CO2 Electroreduction

• Published in: Advanced science Vol. 11; no. 34; pp. e2404931 - n/a
• Main Authors: Sun, Mingxu, Cheng, Jiamin, Anzai, Akihiko, Kobayashi, Hirokazu, Yamauchi, Miho
• Format: Journal Article
• Language: English
• Published: Weinheim John Wiley & Sons, Inc 01-09-2024; John Wiley and Sons Inc; Wiley
• Subjects: CO2 reduction; controllable selectivity; Fourier transforms; in situ spectroscopy; Ligands; metal organic frameworks; Spectrum analysis; UiO‐66
• ISSN: 2198-3844; 2198-3844
• DOI: 10.1002/advs.202404931

The intensive study of electrochemical CO2 reduction reaction (CO2RR) has resulted in numerous highly selective catalysts, however, most of these still exhibit uncontrollable selectivity. Here, it is reported for the first time the controllable CH4/C2H4 selectivity by modulating the electronic states of Cu incorporated in metal‐organic frameworks with different functional ligands, achieving a Faradaic efficiency of 58% for CH4 on Cu‐incorporated UiO‐66‐H (Ce) composite catalysts, Cu/UiO‐66‐H (Ce) and that of 44% for C2H4 on Cu/UiO‐66‐F (Ce). In situ measurements of Raman and X‐ray absorption spectra revealed that the electron‐withdrawing ability of the ligand side group controls the product selectivity on MOFs through the modulation of the electronic states of Cu. This work opens new prospects for the development of MOFs as a platform for the tailored tuning of selectivity in CO2RR.
The electrocatalytic CO2 reduction reaction selectivity is controlled through modulating the electronic structure of Cu in metal‐organic frameworks. Ligand‐altered UiO‐66 led to a notable shift from CH4 to C2H4, achieving high Faradaic efficiencies of 58% for CH4 and 44% for C2H4.