Photocatalysis is considered as one of the promising routes to solve the energy and environmental crises by utilizing solar energy. Graphitic carbon nitride (g-C3N4) has attracted worldwide attention due to its visible-light activity, facile synthesis from low-cost materials, chemical stability, and unique layered structure. However, the pure g-C3N4 photocatalyst still suffers from its low separation efficiency of photogenerated charge carriers, which results in unsatisfactory photocatalytic activity. Recently, g-C3N4-based heterostructures have become research hotspots for their greatly enhanced charge carrier separation efficiency and photocatalytic performance. According to the different transfer mechanisms of photogenerated charge carriers between g-C3N4 and the coupled components, the g-C3N4-based heterostructured photocatalysts can be divided into the following categories: g-C3N4-based conventional type II heterojunction, g-C3N4-based Z-scheme heterojunction, g-C3N4-based p–n heterojunction, g-C3N4/metal heterostructure, and g-C3N4/carbon heterostructure. This review summarizes the recent significant progress on the design of g-C3N4-based heterostructured photocatalysts and their special separation/transfer mechanisms of photogenerated charge carriers. Moreover, their applications in environmental and energy fields, e.g., water splitting, carbon dioxide reduction, and degradation of pollutants, are also reviewed. Finally, some concluding remarks and perspectives on the challenges and opportunities for exploring advanced g-C3N4-based heterostructured photocatalysts are presented.

g-C3N4-Based Heterostructured Photocatalysts

Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution to simultaneously overcome both environmental problems and energy crisis. The low selectivity of challenging multi-electron CO2 photoreduction reactions makes it one of the holy grails in heterogeneous photocatalysis. This Review highlights the important roles of cocatalysts in selective photocatalytic CO2 reduction into solar fuels using semiconductor catalysts. A special emphasis in this review is placed on the key role, design considerations and modification strategies of cocatalysts for CO2 photoreduction. Various cocatalysts, such as the biomimetic, metal-based, metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area. This Review provides useful information for the design of highly selective cocatalysts for photo(electro)reduction and electroreduction of CO2 and complements the existing reviews on various semiconductor photocatalysts.

Cocatalysts for Selective Photoreduction of CO2 into Solar Fuels.

Ever-increasing fossil-fuel combustion along with massive CO2 emissions has aroused a global energy crisis and climate change. Photocatalytic CO2 reduction represents a promising strategy for clean, cost-effective, and environmentally friendly conversion of CO2 into hydrocarbon fuels by utilizing solar energy. This strategy combines the reductive half-reaction of CO2 conversion with an oxidative half reaction, e.g., H2 O oxidation, to create a carbon-neutral cycle, presenting a viable solution to global energy and environmental problems. There are three pivotal processes in photocatalytic CO2 conversion: (i) solar-light absorption, (ii) charge separation/migration, and (iii) catalytic CO2 reduction and H2 O oxidation. While significant progress is made in optimizing the first two processes, much less research is conducted toward enhancing the efficiency of the third step, which requires the presence of cocatalysts. In general, cocatalysts play four important roles: (i) boosting charge separation/transfer, (ii) improving the activity and selectivity of CO2 reduction, (iii) enhancing the stability of photocatalysts, and (iv) suppressing side or back reactions. Herein, for the first time, all the developed CO2 -reduction cocatalysts for semiconductor-based photocatalytic CO2 conversion are summarized, and their functions and mechanisms are discussed. Finally, perspectives in this emerging area are provided.

Cocatalysts in Semiconductor-based Photocatalytic CO2 Reduction: Achievements, Challenges, and Opportunities.

A direct Z-scheme g-C3N4/SnS2 photocatalyst with superior visible-light CO2 reduction performance

Product selectivity of photocatalytic CO2 reduction reactions

As a promising approach to achieving two objectives with one strategy, photocatalytic CO2 conversion for C1/C2 “solar fuels” production can provide a package solution to the current global warming and growing energy demand by using inexhaustible solar energy and increasing atmospheric CO2. Although numerous efforts have been made to enhance the CO2 conversion efficiency through developing photocatalysts and CO2 reduction systems in recent years, some challenges still remain in improving the activity and selectivity of the CO2 photoreduction reactions. This review gives an overview of fundamental aspects and recent research advances of heterogeneous photocatalytic CO2 conversion systems in the last 3 years, and the catalysts are categorized as one-step excitation semiconductor systems, one-step excitation photosensitized semiconductor systems, and two-step excitation hybrid systems such as semiconductor heterojunction and Z-scheme systems. Also, some suggestions are given for further confirming that the ca...

Recent Advances in Heterogeneous Photocatalytic CO2 Conversion to Solar Fuels

A new kind of brookite TiO 2 /g-C 3 N 4 nanocomposite, in which g-C 3 N 4 nanodots (CNDs) with a mean size of ∼2.8 nm are decorated on brookite TiO 2 quasi nanocube (BTN) surfaces (hereafter referred as BTN-CNDs heterojunction), is prepared via a facile calcination process of the mixture of urea and the home-made BTN powders, and then used as visible-light-responsive photocatalyst for CO 2 reduction. Electron microscopy, X-ray powder diffraction (XRD), ultraviolet-visible light (UV-vis) diffuse reflectance absorption spectra (DRS), X-ray photoelectron spectra (XPS) and its valance band (VB) spectra are adopted to investigate the microstructure, composition, energy band structure, and the possible photogenerated electron transfer processes between BTN and CNDs. After optimizing the photocatalytic condition, enhanced visible-light-driven CO 2 -reduction activity and selectivity for CH 4 generation as compared to g-C 3 N 4 and BTN alone are observed, and a photosensitization mechanism is proposed to explain the differences in the photocatalytic performance among g-C 3 N 4 , BTN, and BTN-CNDs. The pronounced CH 4 generation activity and selectivity over BTN-CNDs heterojunction demonstrate a new strategy for improving the interfacial charge transfer and the photocatalytic CO 2 reduction performance though tailoring the microstructures of the semiconductor-based nanocomposites.

Bosi Peng

Papers

Recent Advances in Heterogeneous Photocatalytic CO2 Conversion to Solar Fuels

Carbon nitride nanodots decorated brookite TiO2 quasi nanocubes for enhanced activity and selectivity of visible-light-driven CO2 reduction

Graphene-nanopocket-encaged PtCo nanocatalysts for highly durable fuel cell operation under demanding ultralow-Pt-loading conditions

Experimental Sabatier plot for predictive design of active and stable Pt-alloy oxygen reduction reaction catalysts

A general one-step plug-and-probe approach to top-gated transistors for rapidly probing delicate electronic materials