Intercepting Elusive Intermediates in Cu-Mediated CO Electrochemical Reduction with Alkyl Species

Understanding of the reaction network of Cu-catalyzed CO₂/CO electroreduction reaction [CO₍₂₎RR] remains incomplete despite intense research efforts. This is in part because the rate-determining step occurs early in the reaction network, leading to short lifetimes of subsequent surface-bound intermediates, the knowledge of which is key to selectivity control. In this work, we demonstrate that alkyl groups can effectively couple with surface intermediates in the Cu-catalyzed CORR and, for the first time, intercept elusive C₁ and C₂ intermediates. Combined reactivity data and in situ spectroscopic results demonstrated that surface-bound alkyl groups derived from the corresponding alkyl iodides are able to couple with adsorbed CO to form carboxylates and ketones via one and two successive nucleophilic attacks, respectively. Leveraging this new chemistry, CH (x ≤ 3) and C₂H (x ≤ 4) are intercepted and identified as precursors for methane and n-propanol in the CORR, respectively. Importantly, reaction pathways leading to methane and C₂₊ products are not intrinsically orthogonal, but their connection is mainly impeded by low coverages of energetic intermediates. This study shows that perturbing the reaction of interest by introducing a slightly interacting probe reaction network could be an effective and general strategy in mechanistic studies of catalytic reactions.