Merging hydrogen (H 2 ) evolution with oxidative organic synthesis in a semiconductor-mediated photoredox reaction is extremely attractive because the clean H 2 fuel and high-value chemicals can be coproduced under mild conditions using light as the sole energy input. Following this dual-functional photocatalytic strategy, a dreamlike reaction pathway for constructing C−C/C−X (X = C, N, O, S) bonds from abundant and readily available X−H bond-containing compounds with concomitant release of H 2 can be readily fulfilled without the need of external chemical reagents, thus offering a green and fascinating organic synthetic strategy. In this review, we begin by presenting a concise overview on the general background of traditional photocatalytic H 2 production and then focus on the fundamental principles of cooperative photoredox coupling of selective organic synthesis and H 2 production by simultaneous utilization of photoexcited electrons and holes over semiconductor-based catalysts to meet the economic and sustainability goal. Thereafter, we put dedicated emphasis on recent key progress of cooperative photoredox coupling of H 2 production and various selective organic transformations, including selective alcohol oxidation, selective methane conversion, amines oxidative coupling, oxidative cross-coupling, cyclic alkanes dehydrogenation, reforming of lignocellulosic biomass, and so on. Finally, the remaining challenges and future perspectives in this flourishing area have been critically discussed. It is anticipated that this review will provide enlightening guidance on the rational design of such dual-functional photoredox reaction system, thereby stimulating the development of economical and environmentally benign solar fuel generation and organic synthesis of value-added fine chemicals.

Heterogeneous photocatalysis is a promising strategy for addressing the worldwide environmental pollution and energy shortage issues. However, unlike TiO2 with good photostability, the intrinsic drawback of photoinduced decomposition, i.e., photocorrosion, of semiconductors significantly challenges durable photocatalysis. In this review, the photocorrosion mechanisms of typical semiconductors and different characterization methods proposed for monitoring the photocorrosion process of semiconductor-based composite photocatalysts are elaborated. Dedicated emphasis is put on the strategies for improving the anti-photocorrosion property of semiconductor-based photocatalysts, including modifying the crystal structure or morphology of semiconductors, doping with heteroatoms, hybridizing with various semiconductors and/or cocatalysts, and regulating the photocatalytic reaction conditions. Finally, we cast a personal prospect on the future development of the rational design of corrosion-controlled semiconductor-based photocatalysts toward versatile photoredox applications.

Highly-efficient oxygen evolution reaction (OER) and reduction of carbon dioxide (CO2RR) represent the two biggest scientific challenges in artificial photosynthesis. Many efficient and cost-affordable electrocatalysts have been reported in the...

The performance of transition metal hydroxides, as cocatalysts for CO2 photoreduction, is significantly limited by their inherent weaknesses of poor conductivity and stacked structure. Herein, we report the rational assembly of a series of transition metal hydroxides on graphene to act as a cocatalyst ensemble for efficient CO2 photoreduction. In particular, with the Ru-dye as visible light photosensitizer, hierarchical Ni(OH)2 nanosheet arrays-graphene (Ni(OH)2-GR) composites exhibit superior photoactivity and selectivity, which remarkably surpass other counterparts and most of analogous hybrid photocatalyst system. The origin of such superior performance of Ni(OH)2-GR is attributed to its appropriate synergy on the enhanced adsorption of CO2, increased active sites for CO2 reduction and improved charge carriers separation/transfer. This work is anticipated to spur rationally designing efficient earth-abundant transition metal hydroxides-based cocatalysts on graphene and other two-dimension platforms for artificial reduction of CO2 to solar chemicals and fuels.

Photocatalytic reduction of CO2 to solar fuels and/or fine chemicals is a promising way to increase the energy supply and reduce greenhouse gas emissions. However, the conventional reaction system for CO2 photoreduction with pure H2O or sacrificial agents usually suffers from low catalytic efficiency, poor stability, or cost‐ineffective atom economy. A recent surge of developments, in which photocatalytic CO2 valorization is integrated with selective organic synthesis into one reaction system, indicates an efficient modus operandi that enables sufficient utilization of photogenerated electrons and holes to achieve the goals for sustainable economic and social development. In this Review we discuss current advances in cooperative photoredox reaction systems that integrate CO2 valorization with organics upgrading based on heterogeneous photocatalysis. The applications and virtues of this strategy and the underlying reaction mechanisms are discussed. The ongoing challenges and prospects in this area are critically discussed.