Construction of Dual-Active Sites by Interfacing with Polyhydroxy Fullerene on Nickel Hydroxide Surfaces to Promote CO 2 Deep Photoreduction to CH 4 .

Due to the complex series of elementary steps involved, achieving deep photoreduction of CO 2 to multielectron products such as CH 4 remains a challenging task. Therefore, it is crucial to strategically design catalysts that facilitate the controlled formation of the crucial intermediates and provide precise control over the reaction pathway. Herein, we present a pioneering approach by employing polyhydroxy fullerene (PHF) molecules to modify the surface of Ni(OH) 2 , creating stable and effective synergistic sites to enhance the formation of CH 4 from CO 2 under light irradiation. As a result, the optimized PHF-modified Ni(OH) 2 cocatalyst achieves a CH 4 production rate of 455 μmol g -1 h -1 , with an electron-based selectivity of approximately 60%. The combination of in situ characterizations and theoretical calculations reveals that the hydroxyl species on the surface of PHF can participate in stabilizing crucial intermediates and facilitating water activation, thereby altering the reaction pathway to form CH 4 instead of CO. This study provides a novel approach to regulating the selectivity of photocatalytic CO 2 reduction by exploring molecular surface modification through interfacing with functionalized carbon clusters.