posted on 2021-12-09, 18:38authored byQiaowan Chang, Ji Hoon Lee, Yumeng Liu, Zhenhua Xie, Sooyeon Hwang, Nebojsa S. Marinkovic, Ah-Hyung Alissa Park, Shyam Kattel, Jingguang G. Chen
The electrochemical
carbon dioxide reduction reaction (CO2RR) using copper
(Cu)-based catalysts has received significant attention
mainly because Cu is an element capable of producing hydrocarbons
and oxygenates. One possible way to control the CO2RR performance
at the electrode interface is by modifying catalysts with specific
functional groups of different polymeric binders, which are necessary
components in the process of electrode fabrication. However, the modification
effect of the key functional groups on the CO2RR activity
and selectivity is poorly understood over Cu-based catalysts. In this
work, the role of functional groups (e.g., −COOH
and −CF2 groups) in hydrophilic and hydrophobic
polymeric binders on the CO2RR of Cu-based catalysts is
investigated using a combination of electrochemical measurements, in situ characterization, and density functional theory
(DFT) calculations. DFT results reveal that functional groups influence
the binding energies of key intermediates involved in both CO2RR and the competing hydrogen evolution reaction, consistent
with experimental observation of binder-dependent product distributions
among formic acid, CO, CH4, and H2. This study
provides a fundamental understanding that the selection of desired
polymeric binders is a useful strategy for tuning the CO2RR activity and selectivity.