Abstract
Exploring effective ways to detect intermediates during the electrochemical CO(2) reduction reaction (CO(2)RR) process is pivotal for understanding reaction pathways and underlying mechanisms. Recently, two-dimensional FeN(4)-embedded graphene has received increasing attention as a promising catalyst for CO(2)RR. Here, by means of density functional theory computations combined with the non-equilibrium Green's function (NEGF) method, we proposed a detection device to evaluate the performance of FeN(4)-embedded graphene in intermediates detection during the CO(2)RR process. Our results reveal that the four key intermediates, including *COOH, *OCHO, *CHO, and *COH, can be chemisorbed on FeN(4)-embedded graphene with high adsorption energies and appropriate charge transfer. The computed current-voltage (I-V) characteristics and transmission spectra suggest that the adsorption of these intermediates induces significant type-dependent changes in currents and transmission coefficients of FeN(4)-embedded graphene. Remarkably, the FeN(4)-embedded graphene is more sensitive to *COOH and *COH than to *OCHO and *CHO within the entire bias window. Consequently, our theoretical study indicates that the FeN(4)-embedded graphene can effectively detect the key intermediates during the CO(2)RR process, providing a practical scheme for identifying catalytic reaction pathways and elucidating underlying reaction mechanisms.