High‐Throughput Electron Transfer in Inorganic–Organic Interfacial Electric Field Enabling Selective CO₂ Photoreduction

The efficiency of photocatalytic CO 2 reduction has long been limited by the competing H 2 evolution reaction. In this study, we present an innovative strategy for boosting high‐throughput electron transfer to suppress H 2 evolution, thereby enhancing CO 2 reduction. By employing CdS and cobalt bipyridine as a model, we engineered the surface of CdS to create an electric field at the inorganic–organic interface. Through in situ and transient spectroscopy techniques, we discovered that CdS functionalized with ─COOH groups demonstrates remarkable noncovalent interactions and improved charge transfer capabilities compared to those functionalized with ─NH 2 groups. The fast delivery of electrons on cobalt bipyridine facilitates the adsorbed CO 2 to participate in the proton‐electron coupling reaction, rather than allowing adsorbed protons to accept electrons directly. Consequently, the established CdS‐COOH/Co(II)‐bpy system achieved a CO production rate of 2.523 mmol g −1 h −1 with a selectivity of 96.3%. This research presents an approach for creating efficient charge transport interfaces and provides a comprehensive strategy for designing high‐performance photocatalytic CO 2 reduction systems that effectively counteract the challenges posed by competing H 2 evolution reactions.