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Designing CdS Mesoporous Networks on Co-C@Co9 S8 Double-Shelled Nanocages as Redox-Mediator-Free Z-Scheme Photocatalyst.

Designing porous nanostructures with unprecedented functionalities and an effective ability to harvest the maximum energy region of the solar spectrum and suppress the charge-carrier recombination rate offers promising potential for sustainable energy production. Although several functional porous nanostructures have been developed, high-efficiency materials are still needed. Herein, we report a new, highly active, noble-metal-free, and redox-mediator-free Z-scheme photocatalyst, CdS/Co-C@Co9 S8 , for H2 production through water splitting under solar irradiation. The designed photocatalytic system contains open 3 D CdS mesopores as a light absorber for wider solar-light harvesting. Metal-organicframework-derived cobalt nanocrystal-embedded few-layered carbon@Co9 S8 double-shelled nanocages were used as a co-semiconductor to hamper the photo charge-carrier recombination by accelerating the photogenerated electrons and holes from the other semiconductor. The optimized catalyst shows a H2 evolution rate of 26.69 mmol g-1  h-1 under simulated solar irradiation, which is 46 times higher than that of the as-synthesized CdS mesoporous nanostructures. The apparent quantum yield reached 7.82 % at λ=425 nm in 5 h. The outstanding photocatalytic activity of CdS/Co-C@Co9S8 reflects the favorable suppression of the charge-carrier recombination rate, as determined by photoluminescence, photocurrent, and impedance analyses. We believe that the findings reported here may inspire the design of new noble-metal-free porous nanohybrids for sustainable H2 production.