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Booming of photocatalytic water splitting technology (PWST) opens a new avenue for the sustainable synthesis of high-value-added hydrogenated and oxidized fine chemicals, in which the design of efficient semiconductors for the in-situ and synergistic utilization of photogenerated redox centers are key roles. Herein, a porous polymeric carbon nitride (PPCN) with a crystalline backbone was constructed for visible light-induced photocatalytic hydrogen generation by photoexcited electrons, followed by in-situ utilization for olefin hydrogenation. Simultaneously, various alcohols were selectively transformed to valuable aldehydes or ketones by photoexcited holes. The porosity of PPCN provided it with a large surface area and a short transfer path for photogenerated carriers from the bulk to the surface, and the crystalline structure facilitated photogenerated charge transfer and separation, thus enhancing the overall photocatalytic performance. High reactivity and selectivity, good functionality tolerance, and broad reaction scope were achieved by this concerted photocatalysis system. The results contribute to the development of highly efficient semiconductor photocatalysts and synergistic redox reaction systems based on PWST for high-value-added fine chemical production.

Photocatalytic water splitting technology (PWST) enables the direct use of water as appealing "liquid hydrogen source" for transfer hydrogenation reactions. Currently, the development of PWST-based transfer hydrogenations is still in an embryonic stage. Previous reports generally centered on the rational utilization of the in situ generated H-source (electrons) for hydrogenations, in which photogenerated holes were quenched by sacrificial reagents. Herein, the fully-utilization of the liquid H-source and holes during water splitting is presented for photo-reductive N -alkylation of nitro-aromatic compounds. In this integrate system, H-species in situ generated from water splitting were designed for nitroarenes reduction to produce amines, while alkanols were oxidized by holes for cascade alkylating of anilines as well as the generated secondary amines. More than 50 examples achieved with a broad range scope validate the universal applicability of this mild and sustainable coupling approach. The synthetic utility of this protocol was further demonstrated by the synthesis of existing pharmaceuticals via selective N -alkylation of amines. This strategy based on the sustainable water splitting technology highlights a significant and promising route for selective synthesis of valuable N -alkylated fine chemicals and pharmaceuticals from nitroarenes and amines with water and alkanols.

Solar-driven H2 evolution is an essential process for sustainable energy development. Currently, the greatest challenge is the development of efficient photocatalysts to drive this reaction, especially in pure water systems (without the use of a sacrificial agent). In this study, structural defects in Zn-Cd-S nanorod photocatalysts are found to increase charge separation efficiency significantly by sevenfold. Efficient H2 evolution (352.7 μmol h-1 g-1 , 100 mg of catalyst) is achieved by using this defective Zn-Cd-S nanorod photocatalyst in the absence of sacrificial agents and precious metal cocatalysts under visible-light irradiation. Thus, this cocatalyst- and sacrificial-agent-free, visible-light-responsive system shows remarkable potential as a new artificial photosynthesis route for green H2 production.