Efficient Photothermal CO Hydrogenation into C2+ Hydrocarbons on in situ Generated Fe0 in Fe5C2 Active Sites via Cu‐Promoted Hydrogen Dissociation and Spillover†

Comprehensive Summary Photothermal hydrogenation of carbon monoxide (CO) holds the potential to generate valuable C 2+ chemicals using renewable solar energy. However, its activity and selectivity towards C 2 —C 3 alkanes are limited compared to conventional thermal catalysis. In this study, we developed a robust catalyst consisting of Cu/Fe 3 O 4 nanoparticles on Mo 2 C T x MXene, showing enhanced photothermal C 2 —C 3 production. The Cu component plays a crucial role in H 2 dissociation and subsequent H spillover, facilitating the in situ generation of Fe 0 in Fe 5 C 2 active sites and thus efficiently promoting photothermal CO hydrogenation. As a result, we achieved a 51.3% C 2+ selectivity and 78.5% CO conversion at a high gas hourly space velocity (GHSV) of 12000 mL·g cat −1 ·h −1 and 2.5 MPa in a flow reactor at 320 °C. The overall C 2 —C 3 yield reached 23.6% with Cu/Fe 3 O 4 /Mo 2 C T x catalysts, marking a 2.8‐fold increase compared to the performance of the bare Fe 3 O 4 /Mo 2 C T x catalyst.