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

S-Scheme Heterojunction Photocatalyst

The appropriate interfacial contact of heterojunction photocatalysts plays a critical role in transfer/separation of interfacial charge carriers. Design of two-dimensional (2D)/2D surface-to-surface heterojunction is an effective method for improving photocatalytic activity since greater contact area can enhance interfacial charge transfer rate. Herein, ultrathin 2D/2D WO3/g-C3N4 step-like composite heterojunction photocatalysts were fabricated by electrostatic self-assembly of ultrathin tungsten trioxide (WO3) and graphitic carbon nitride (g-C3N4) nanosheets. The ultrathin WO3 and g-C3N4 nanosheets were obtained by electrostatic-assisted ultrasonic exfoliation of bulk WO3 and a two-step thermal-etching of bulk g-C3N4, respectively. The thickness of ultrathin WO3 and g-C3N4 nanosheets are 2.5–3.5 nm, which is equivalent to 5–8 atomic or molecular layer thickness. This ultrathin layered heterojunction structure can enhance surface photocatalytic rate because photogenerated electrons and holes at heterogeneous interface more easily transfer to surface of photocatalysts. Therefore, the obtained ultrathin 2D/2D WO3/g-C3N4 step-scheme (S-scheme) heterojunction photocatalysts exhibited better H2-production activity than pure g-C3N4 and WO3 with the same loading amount of Pt as cocatalyst. The mechanism and driving force of charge transfer and separation in S-scheme heterojunction photocatalysts are investigated and discussed. This investigation will provide new insight about designing and constructing novel S-scheme heterojunction photocatalysts.

Ultrathin 2D/2D WO3/g-C3N4 step-scheme H2-production photocatalyst

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.

Highly efficient removal of metal ion pollutants, such as toxic and nuclear waste-related metal ions, remains a serious task from the biological and environmental standpoint because of their harmful effects on human health and the environment. Recently, highly porous metal–organic frameworks (MOFs), with excellent chemical stability and abundant functional groups, have represented a new addition to the area of capturing various types of hazardous metal ion pollutants. This review focuses on recent progress in reported MOFs and MOF-based composites as superior adsorbents for the efficient removal of toxic and nuclear waste-related metal ions. Aspects related to the interaction mechanisms between metal ions and MOF-based materials are systematically summarized, including macroscopic batch experiments, microscopic spectroscopy analysis, and theoretical calculations. The adsorption properties of various MOF-based materials are assessed and compared with those of other widely used adsorbents. Finally, we propose our personal insights into future research opportunities and challenges in the hope of stimulating more researchers to engage in this new field of MOF-based materials for environmental pollution management.

Metal–organic framework-based materials: superior adsorbents for the capture of toxic and radioactive metal ions

Artificial photosynthesis of hydrocarbon fuels by utilizing solar energy and CO2 is considered as a potential route for solving ever-increasing energy crisis and greenhouse effect. Herein, hierarchical porous O-doped graphitic carbon nitride (g-C3 N4 ) nanotubes (OCN-Tube) are prepared via successive thermal oxidation exfoliation and curling-condensation of bulk g-C3 N4 . The as-prepared OCN-Tube exhibits hierarchically porous structures, which consist of interconnected multiwalled nanotubes with uniform diameters of 20-30 nm. The hierarchical OCN-Tube shows excellent photocatalytic CO2 reduction performance under visible light, with methanol evolution rate of 0.88 µmol g-1 h-1 , which is five times higher than bulk g-C3 N4 (0.17 µmol g-1 h-1 ). The enhanced photocatalytic activity of OCN-Tube is ascribed to the hierarchical nanotube structure and O-doping effect. The hierarchical nanotube structure endows OCN-Tube with higher specific surface area, greater light utilization efficiency, and improved molecular diffusion kinetics, due to the more exposed active edges and multiple light reflection/scattering channels. The O-doping optimizes the band structure of g-C3 N4 , resulting in narrower bandgap, greater CO2 affinity, and uptake capacity as well as higher separation efficiency of photogenerated charge carriers. This work provides a novel strategy to design hierarchical g-C3 N4 nanostructures, which can be used as promising photocatalyst for solar energy conversion.

Hierarchical Porous O-doped g-C3N4 with Enhanced Photocatalytic CO2 Reduction Activity

Recently, great attention has been paid to fabricating direct Z-scheme photocatalysts for solar-energy conversion due to their effectiveness for spatially separating photogenerated electron–hole pairs and optimizing the reduction and oxidation ability of the photocatalytic system. Here, the historical development of the Z-scheme photocatalytic system is summarized, from its first generation (liquid-phase Z-scheme photocatalytic system) to its current third generation (direct Z-scheme photocatalyst). The advantages of direct Z-scheme photocatalysts are also discussed against their predecessors, including conventional heterojunction, liquid-phase Z-scheme, and all-solid-state (ASS) Z-scheme photocatalytic systems. Furthermore, characterization methods and applications of direct Z-scheme photocatalysts are also summarized. Finally, conclusions and perspectives on the challenges of this emerging research direction are presented. Insights and up-to-date information are provided to give the scientific community the ability to fully explore the potential of direct Z-scheme photocatalysts in renewable energy production and environmental remediation.

A Review of Direct Z-Scheme Photocatalysts

Inspired by nature, artificial photosynthesis through the construction of direct Z-scheme photocatalysts is extensively studied for sustainable solar fuel production due to the effectiveness in enhancing photoconversion efficiency. However, there is still a lack of thorough understanding and direct evidence for the direct Z-scheme charge transfer in these photocatalysts. Herein, a recyclable direct Z-scheme composite film composed of titanium dioxide and cadmium sulfide (TiO2 /CdS) is prepared for high-efficiency photocatalytic carbon dioxide (CO2 ) reduction. In situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) confirms the direct Z-scheme charge-carrier migration pathway in the photocatalytic system. Furthermore, density functional theory simulation identifies the intrinsic cause for the formation of the direct Z-scheme heterojunction between the TiO2 and the CdS. Thanks to the significantly enhanced redox abilities of the charge carriers in the direct Z-scheme system, the photocatalytic CO2 reduction performance of the optimized TiO2 /CdS is 3.5, 5.4, and 6.3 times higher than that of CdS, TiO2 , and commercial TiO2 (P25), respectively, in terms of methane production. This work is a valuable guideline in preparation of highly efficient recyclable nanocomposite for photoconversion applications.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/adma.201807920

Chuanjia Jiang

Papers

g-C3N4-Based Heterostructured Photocatalysts

Ultrathin 2D/2D WO3/g-C3N4 step-scheme H2-production photocatalyst

Hierarchical Porous O-doped g-C3N4 with Enhanced Photocatalytic CO2 Reduction Activity

A Review of Direct Z-Scheme Photocatalysts

In Situ Irradiated X-Ray Photoelectron Spectroscopy Investigation on a Direct Z-Scheme TiO2 /CdS Composite Film Photocatalyst.