Cooperative catalysis coupling photo-/photothermal effect to drive Sabatier reaction with unprecedented conversion and selectivity

•We designed a catalyst coupling photo-/photothermal effect for Sabatier reaction •The 0.35%[email protected]2V2O7 catalyst achieved a record CH4 production rate •The conversion and selectivity approached the thermodynamic equilibrium limit The development of highly efficient catalysts to drive the Sabatier reactions under mild conditions remains a great challenge. Here, we report a 0.35%[email protected]2V2O7 catalyst exhibited an unprecedented solar-driven CO2 methanation rate of 114.9 mmol gcat−1h−1 (32.8 mol gRu−1 h−1 as normalized to the mass of the Ru catalyst), which was approximately 40 and 460 times larger than the rates obtained over the bare Ni2V2O7 and [email protected]2 catalysts, respectively. Moreover, the 0.35%[email protected]2V2O7 catalyst exhibited 93.5% CO2 conversion efficiency and 99% selectivity for CH4 production, approaching the thermodynamic equilibrium limit of thermocatalytic CO2 methanation. Further investigations revealed a cooperative mechanism coupling photocatalysis and photothermal catalysis between the Ru and Ni2V2O7. When illuminated, Ru clusters acted as a “nanoheater” and raised the local temperature to activate H2 and desorb H2O molecules. The spilled H adatoms reacted with adsorbed CO2 on the surface of O-vacancy-rich Ni2V2O7 to achieve cooperative catalysis for CO2 methanation. The development of highly efficient catalysts to drive the Sabatier reactions under mild conditions remains a great challenge. Here, we report a 0.35%[email protected]2V2O7 catalyst exhibited an unprecedented solar-driven CO2 methanation rate of 114.9 mmol gcat−1h−1 (32.8 mol gRu−1 h−1 as normalized to the mass of the Ru catalyst), which was approximately 40 and 460 times larger than the rates obtained over the bare Ni2V2O7 and [email protected]2 catalysts, respectively. Moreover, the 0.35%[email protected]2V2O7 catalyst exhibited 93.5% CO2 conversion efficiency and 99% selectivity for CH4 production, approaching the thermodynamic equilibrium limit of thermocatalytic CO2 methanation. Further investigations revealed a cooperative mechanism coupling photocatalysis and photothermal catalysis between the Ru and Ni2V2O7. When illuminated, Ru clusters acted as a “nanoheater” and raised the local temperature to activate H2 and desorb H2O molecules. The spilled H adatoms reacted with adsorbed CO2 on the surface of O-vacancy-rich Ni2V2O7 to achieve cooperative catalysis for CO2 methanation.