Molecular tuning boosts asymmetric C-C coupling for CO conversion to acetate
Jie Ding, Fuhua Li, Xinyi Ren, Yuhang Liu, Yifan Li, Zheng Shen, Tian Wang, Weijue Wang, Yang‐Gang Wang, Yi Cui, Hongbin Yang, Tianyu Zhang, Bin Liu
Abstract
Abstract Electrochemical carbon dioxide/carbon monoxide reduction reaction offers a promising route to synthesize fuels and value-added chemicals, unfortunately their activities and selectivities remain unsatisfactory. Here, we present a general surface molecular tuning strategy by modifying Cu 2 O with a molecular pyridine-derivative. The surface modified Cu 2 O nanocubes by 4-mercaptopyridine display a high Faradaic efficiency of greater than 60% in electrochemical carbon monoxide reduction reaction to acetate with a current density as large as 380 mA/cm 2 in a liquid electrolyte flow cell. In-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy reveals stronger *CO signal with bridge configuration and stronger *OCCHO signal over modified Cu 2 O nanocubes by 4-mercaptopyridine than unmodified Cu 2 O nanocubes during electrochemical CO reduction. Density function theory calculations disclose that local molecular tuning can effectively regulate the electronic structure of copper catalyst, enhancing *CO and *CHO intermediates adsorption by the stabilization effect through hydrogen bonding, which can greatly promote asymmetric *CO-*CHO coupling in electrochemical carbon monoxide reduction reaction.