Exploring highly efficient heterostructured photocatalysts for converting CO2 to value-added chemicals has long been pursued, which is mainly limited by inefficient visible/near-infrared (NIR) photon capture, undesirable electron-hole recombination, and insufficient...

Construction of photocatalytic systems with spatially separated dual cocatalysts is considered as a promising route to modulate charge separation/transfer, promote surface redox reactivities, and prevent unwanted reverse reactions. However, past efforts on the loading of spatially separated double‐cocatalysts are limited to hollow structured semiconductors with inner/outer surface and monocrystalline semiconductors with different exposed facets. To overcome this limitation, herein, enabled by a unique stacked photocatalyst design, a facile and versatile strategy for spatial separation of redox cocatalysts on various semiconductors without structural and morphological restriction is demonstrated. The smart design begins with the deposition of light‐harvesting semiconductors on reduced graphene oxide (rGO) nanosheets, followed with the coverage of Ni(OH)2 outer layer. The ternary photocatalysts exhibit superior activities and stabilities of H2O oxidation and selective CO2‐to‐CO reduction, remarkably surpassing other counterparts. The origin of the enhanced performance is attributed to the synergistic interplay of rGO@Ni(OH)2 reduction cocatalysts surrounding the semiconductors and Ni(OH)2 oxidation cocatalysts directly supported by the semiconductors, which mitigates the charge recombination, supplies highly active and selective sites for overall reactions, and preserves the semiconductors from photocorrosion. This work presents a new approach to regulating the position of dual cocatalysts and ameliorating the net efficiency of photoredox catalysis.

Solar-driven photocatalytic conversion of CO2 to renewable fuels represents an appealing approach to remedy environmental damage and address energy crisis. Recently, photocatalytic conversion efficiencies have been improved with the implantation...

Rational phase engineering of reduction cocatalyst offers a promising route to modulate the photocatalytic activity and selectivity in the conversion of CO2 to chemical feedstocks. However, it remains a great challenge to choose a suitable phase given that high‐crystallinity phase is more conducive to the charge transfer and separation, while amorphous phase is more favorable for the adsorption and activation of CO2 molecules. To resolve this dilemma, herein, with Pd as a well‐defined model, a surface amorphization strategy has been developed to fabricate crystalline@amorphous semi‐core‐shell cocatalysts based on the transformation of outer layer atoms of crystalline cocatalysts to disorder phase. According to the theoretical and experimental analysis, in the heterostructured cocatalysts, crystalline core shuttles the photoexcited electrons from light‐harvesting semiconductor to amorphous shell due to its strong electronic coupling with both components. Meanwhile, amorphous shell provides efficient active sites for preferential activation and conversion of CO2 and suppression of undesirable proton reduction. Benefiting from the synergistic effects between crystalline core and amorphous shell, the optimized heterophase cocatalyst with suitable thickness of amorphous shell achieves superior CO (22.2 µmol gcat−1 h−1) and CH4 (38.1 µmol gcat−1 h−1) formation rates with considerable selectivity and high stability in comparison with crystalline and amorphous counterparts.

No abstract