Photothermal synergistic empowerment of Ni/Ce1-xZrxO2 catalyst for DRM: Photothermal coupling regulation and product generation mechanism

The dry reforming of methane (DRM) reaction enables the resourceful utilization of two greenhouse gases, holding significant implications for mitigating the climate crisis and preserving ecological balance. Based on our previous systematic research on the optical and electronic properties of Ce 1-x Zr x O 2 catalysts, this study constructs a model of Ni13 clusters supported on the (111) surface of Ce 1-x Zr x O 2 (x = 0, 1/4, 1) catalysts using density functional theory (DFT). Simulate the activation of CH 4 molecules and the formation of product CO and H 2 during the thermocatalytic DRM reaction. The results indicate that Ce-Zr doping optimizes the charge distribution on the catalyst surface, thereby accelerating the reaction process. The CH species react through an oxygen-assisted dehydrogenation pathway, effectively suppressing carbon deposition. By introducing an additional electric field to simulate the photogenerated carrier effect induced by light excitation, the electron transfer from the support to the active metal is enhanced. The separation and migration of photogenerated electron - hole pairs alter the adsorption configurations and transition state energies of reaction intermediates, reducing the reaction potential energy curve. This study provides a solid theoretical foundation for the development of highly efficient photothermal-coupled DRM catalysts. • Ni/Ce 1-x Zr x O 2 catalyst reduces surface carbon generation through oxygen assisted dehydrogenation pathway. • The Ni/Ce 1/4 Zr 3/4 O 2 catalyst contributes to promoting the generation of CO and H 2 . • An increase in light intensity enables DRM reaction to occur under relatively mild conditions.