An Exceptionally Efficient Co−Co2P@N, P‐Codoped Carbon Hybrid Catalyst for Visible Light‐Driven CO2‐to‐CO Conversion

Abstract Artificial photosynthesis has attracted wide attention, particularly the development of efficient solar light‐driven methods to reduce CO 2 to form energy‐rich carbon‐based products. Because CO 2 reduction is an uphill process with a large energy barrier, suitable catalysts are necessary to achieve this transformation. In addition, CO 2 adsorption on a catalyst and proton transfer to CO 2 are two important factors for the conversion reaction, and catalysts with high surface area and more active sites are required to improve the efficiency of CO 2 reduction. Here, a visible light‐driven system for CO 2 ‐to‐CO conversion is reported, which consists of a heterogeneous hybrid catalyst of Co and Co 2 P nanoparticles embedded in carbon nanolayers codoped with N and P (Co‐Co 2 P@NPC) and a homogeneous Ru II ‐based complex photosensitizer. The average generation rate of CO of the system was up to 35 000 μmol h −1 g −1 with selectivity of 79.1 % in 3 h. Linear CO production at an exceptionally high rate of 63 000 μmol h −1 g −1 was observed in the first hour of reaction. Inspired by this highly active catalyst, Co@NC and Co 2 P@NPC materials were also synthesized and their structure, morphology, and catalytic properties for CO 2 photoreduction were explored. The results showed that the nanoparticle size, partially adsorbed H 2 O molecules on the catalyst surface, and the hybrid nature of the systems influenced their photocatalytic CO 2 reduction performance.