Nickel and Frustrated Lewis Pairs on Ceria as Dual-Active Sites for Enhanced CO₂ Reduction at Low Temperatures

The simultaneous and efficient activation of CO2 and H2 is critical for enabling rapid CO2 methanation at low temperatures, which is essential for practical integration with intermittent renewable H2 sources and significant process energy savings. In this study, we have successfully developed an innovative dual-active site catalyst that consists of Ni nanoparticles and surface-anchored heterologous frustrated Lewis pairs (FLPs) supported on CeO2–Ov. This catalyst exhibits a remarkable enhancement in the efficiency of low-temperature CO2 methanation. The FLP-rich Ni/CeO2–Ov catalyst demonstrates exceptional performance at 350 °C, achieving 91.3% CO2 conversion and ∼99% CH4 selectivity. These results not only approach thermodynamic equilibrium limits but also far exceed those of conventional Ni/CeO2 catalysts. Combined experimental and computational analyses reveal that the superior catalytic activity arises from the FLP structure, where adjacent Ce3+···O2– and OH groups synergistically activate and convert the slurry to CO2. Moreover, compared to Ni/CeO2, the Ni nanoparticles in Ni/CeO2–Ov exhibit enhanced H2 activation and dissociation, along with a significantly lower energy barrier for hydrogen spillover to CeO2. The synergistic interaction between FLP sites and Ni active centers dramatically boosts the reaction kinetics. This work provides novel insights into the rational design of highly efficient multisite CO2 methanation catalysts.