How local electric field regulates C–C coupling at a single nanocavity in electrocatalytic CO2 reduction

C–C coupling is of utmost importance in the electrocatalytic reduction of CO 2 , as it governs the selectivity of diverse product formation. Nevertheless, the difficulties to directly observe C–C coupling pathways at a specific nanocavity hinder the advances in catalysts and electrolyzer design for efficient high-value hydrocarbon production. Here we develop a nano-confined Raman technology to elucidate the influence of the local electric field on the evolution of C–C coupling intermediates. Through precise adjustments to the Debye length in nanocavities of a copper catalyst, the overlapping of electrical double layers drives a transition in the C–C coupling pathway at a specific nanocavity from *CHO–*CO coupling to the direct dimerization of *CO species. Experimental evidence and simulations validate that a reduced potential drop across the compact layer promotes a higher yield of CO and promotes the direct dimerization of *CO species. Our findings provide insights for the development of highly selective catalyst materials tailored to promote specific products. Precisely tunning the C–C coupling pathway through local microenvironments remains somewhat unclear. Here, the authors developed a nano-confined Raman spectroscopic strategy to uncover how the local electric field regulates the evolution of C–C coupling intermediates at a specific nanocavity.