As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The constructi...

Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability?

Semiconductor photocatalysis has received much attention as a potential solution to the worldwide energy shortage and for counteracting environmental degradation. This article reviews state-of-the-art research activities in the field, focusing on the scientific and technological possibilities offered by photocatalytic materials. We begin with a survey of efforts to explore suitable materials and to optimize their energy band configurations for specific applications. We then examine the design and fabrication of advanced photocatalytic materials in the framework of nanotechnology. Many of the most recent advances in photocatalysis have been realized by selective control of the morphology of nanomaterials or by utilizing the collective properties of nano-assembly systems. Finally, we discuss the current theoretical understanding of key aspects of photocatalytic materials. This review also highlights crucial issues that should be addressed in future research activities.

Nano‐photocatalytic Materials: Possibilities and Challenges

Graphitic (g)-C3N4 with a layered structure has the potential of forming graphene-like nanosheets with unusual physicochemical properties due to weak van der Waals forces between layers. Herein is shown that g-C3N4 nanosheets with a thickness of around 2 nm can be easily obtained by a simple top-down strategy, namely, thermal oxidation etching of bulk g-C3N4 in air. Compared to the bulk g-C3N4, the highly anisotropic 2D-nanosheets possess a high specific surface area of 306 m2 g-1, a larger bandgap (by 0.2 eV), improved electron transport ability along the in-plane direction, and increased lifetime of photoexcited charge carriers because of the quantum confinement effect. As a consequence, the photocatalytic activities of g-C3N4 nanosheets have been remarkably improved in terms of OH radical generation and photocatalytic hydrogen evolution.

Graphene-Like Carbon Nitride Nanosheets for Improved Photocatalytic Activities

Semiconductor-based photocatalysis is considered to be an attractive way for solving the worldwide energy shortage and environmental pollution issues. Since the pioneering work in 2009 on graphitic carbon nitride (g-C3N4) for visible-light photocatalytic water splitting, g-C3N4 -based photocatalysis has become a very hot research topic. This review summarizes the recent progress regarding the design and preparation of g-C3N4 -based photocatalysts, including the fabrication and nanostructure design of pristine g-C3N4 , bandgap engineering through atomic-level doping and molecular-level modification, and the preparation of g-C3N4 -based semiconductor composites. Also, the photo-catalytic applications of g-C3N4 -based photocatalysts in the fields of water splitting, CO2 reduction, pollutant degradation, organic syntheses, and bacterial disinfection are reviewed, with emphasis on photocatalysis promoted by carbon materials, non-noble-metal cocatalysts, and Z-scheme heterojunctions. Finally, the concluding remarks are presented and some perspectives regarding the future development of g-C3N4 -based photocatalysts are highlighted.

Polymeric Photocatalysts Based on Graphitic Carbon Nitride

Graphene, a single layer of graphite, possesses a unique two-dimensional structure, high conductivity, superior electron mobility and extremely high specific surface area, and can be produced on a large scale at low cost. Thus, it has been regarded as an important component for making various functional composite materials. Especially, graphene-based semiconductor photocatalysts have attracted extensive attention because of their usefulness in environmental and energy applications. This critical review summarizes the recent progress in the design and fabrication of graphene-based semiconductor photocatalysts via various strategies including in situ growth, solution mixing, hydrothermal and/or solvothermal methods. Furthermore, the photocatalytic properties of the resulting graphene-based composite systems are also discussed in relation to the environmental and energy applications such as photocatalytic degradation of pollutants, photocatalytic hydrogen generation and photocatalytic disinfection. This critical review ends with a summary and some perspectives on the challenges and new directions in this emerging area of research (158 references).

Graphene-based semiconductor photocatalysts

Single atomic layer nanosheet materials show great application potential in many fields due to their enhanced intrinsic properties compared to their counterparts and newly born properties. Herein, g-C3N4 nanosheets with a single atomic layer structure are prepared by a simple chemical exfoliation method. The as-prepared nanosheets show a single atomic thickness of 0.4 nm and a lateral size of micrometers. The structure and photocatalytic properties of the as-prepared single layer g-C3N4 are then studied. Compared with the bulk g-C3N4, single layer g-C3N4 nanosheets show great superiority in photogenerated charge carrier transfer and separation. Accordingly, the photocatalytic H2 production and pollutant decomposition activities and photocurrent generation of single layer g-C3N4 nanosheets are much higher than those of the bulk g-C3N4, indicating the great application potential of single layer g-C3N4 nanosheets in photocatalysis and photosynthesis.

Chemical exfoliation of graphitic carbon nitride for efficient heterogeneous photocatalysis

A ZnO photocatalyst was hybridized with graphite-like C3N4via a monolayer-dispersed method. After hybridization with C3N4, the photocurrent of ZnO was enhanced by 5 times under UV irradiation and a photocurrent under visible light irradiation was observed. The photocatalytic activity of C3N4/ZnO under UV irradiation was increased by 3.5 times, the visible light photocatalytic activity was generated and the photocorrosion of ZnO was suppressed completely after ZnO was hybridized with C3N4. The enhancement in performance and photocorrosion inhibition under UV irradiation was induced by the high separation efficiency of photoinduced holes from ZnO to the HOMO of C3N4. Under visible light irradiation, the electron excited from the HOMO to the LUMO of C3N4 could directly inject into the CB of ZnO, making C3N4/ZnO present visible light photocatalytic activity. The optimum synergetic effect of C3N4/ZnO was found at a weight ratio of 3%, which corresponded to a monolayer dispersion of C3N4 on the surface of ZnO.

Enhancement of photocurrent and photocatalytic activity of ZnO hybridized with graphite-like C3N4

Graphene-like carbon/TiO2 photocatalysts were prepared via a facile in situ graphitization approach. The introduction of graphene-like carbon to TiO2 effectively enhanced its photocatalytic activity. A graphene-like carbon/TiO2 photocatalyst with a monolayer carbon shell (0.468 nm) showed the highest photocatalytic activity which is about 2.5 times as high as that of pristine TiO2 (P25) under UV light irradiation. The mechanism of the enhanced photocatalytic activity is based on the synergetic effect between graphene-like carbon and TiO2. The synergetic effect caused a rapid photoinduced charge separation and decreased the possibility of recombination of electron–hole pairs, which increased the number of holes participated in the photooxidation process and enhanced the photocatalytic activity.

Significant photocatalytic enhancement in methylene blue degradation of TiO2 photocatalysts via graphene-like carbon in situ hybridization

First-principles density functional theory incorporating the LDA + U formalism has been used to investigate the origin of photocatalytic activation of Ag3PO4. The approach provides an improved band gap and the position of the valence band if both Up and Ud are used. Through examining the energy band structure and density of states, we can understand why Ag3PO4 is a promising photocatalyst for oxidizing water as well as degrading organic contaminants. The results show that Ag3PO4 has a large dispersion of conduction band and the inductive effect of PO43−, which help the separation of electron−hole pairs. It is demonstrated theoretically that Ag vacancies in Ag3PO4 with high concentration have a significant effect on the separation of electron−hole pairs and optical absorbance in the visible-light region. These findings present a reasonable explanation of recent experimental results.

Origin of Photocatalytic Activation of Silver Orthophosphate from First-Principles

F− substituted Bi2WO6 (Bi2WO6−XF2X) photocatalysts with high activity have been successfully synthesized by a two-step process. The effects of F− substitution on the crystal structure and photocatalytic activity of Bi2WO6 were investigated. F− substitution could change the original coordination around the W and Bi atoms. Comparing with Bi2WO6, the photocatalytic activity of Bi2WO6−XF2X increased about 2 times for degradation of MB under visible-light (λ > 420 nm) irradiation. Density functional calculations revealed that Bi2WO6−XF2X has a wider valence bandwidth and lower valence band position. The high activities of Bi2WO6−XF2X photocatalysts come from its valence band which increase the mobility of photoexcited charge carriers and possess a stronger oxidation power.

Rui Shi

Papers

Chemical exfoliation of graphitic carbon nitride for efficient heterogeneous photocatalysis

Enhancement of photocurrent and photocatalytic activity of ZnO hybridized with graphite-like C3N4

Significant photocatalytic enhancement in methylene blue degradation of TiO2 photocatalysts via graphene-like carbon in situ hybridization

Origin of Photocatalytic Activation of Silver Orthophosphate from First-Principles

Photocatalytic Activity Enhancement for Bi2WO6 by Fluorine Substitution