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?

http://ieeexplore.ieee.org/iel5/5610941/5624686/05624745.pdf

Power electronics

A review on g-C3N4-based photocatalysts

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.

P-doped g-C3N4 has been successfully synthesized using hexachlorocyclotriphosphazene, a low cost and environmentally benign compound, as phosphorus source, and guanidiniumhydrochloride as g-C3N4 precursor, via a thermally induced copolymerization route. The obtained P-doped g-C3N4 showed excellent photocatalytic performance both in the photoreduction of H2O to produce H2 and the photodegradation of Rhodamine B (RhB). H2 evolution rate on modified g-C3N4 reached 50.6 μmol h−1, which is 2.9 times higher than that of the pure g-C3N4. RhB (10 mg L−1) was completely photodegraded within 10 min. The structure and texture properties of the P-doped g-C3N4 have been investigated in detail by XRD, FTIR, TEM, EDS and STEM. With the results of XPS and 31P NMR, a possible existing form of P atom in the framework g-C3N4 has been put forward. The introduction of a P atom significantly changes the electronic property of g-C3N4 and suppresses the recombination of photogenerated charge carriers, thus improving its photocatalytic performance.

Brand new P-doped g-C3N4: enhanced photocatalytic activity for H2 evolution and Rhodamine B degradation under visible light

A highly efficient visible-light-driven acidified g-C3N4 (ACNS)/g-C3N4 isotype heterojunction photocatalysts were synthesized by ultrasonic dispersion assisted electrostatic self-assembly strategy for the first time. The photocatalytic oxidation ability of the novel photocatalysts were evaluated using methyl orange (MO) as a target pollutant. The obtained ACNS/g-C3N4 photocatalysts were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectrometry (FTIR), UV–vis diffuse reflection spectroscopy (DRS), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) methods. The photocatalysts exhibited a significantly enhanced photocatalytic performance in degrading MO under visible light illumination (λ > 420 nm) compared with the pristine ACNS and g-C3N4 solely. The optimal ACNS content for the photocatalytic activity of the heterostructured composites was determined. The 30 wt.% ACNS/g-C3N4 exhibited the highest photocatalytic activity, which showed a reaction rate constant as high as 0.0216 min−1, 4.3 times higher than that of bare g-C3N4. The mechanism of the photocatalysts was investigated by determination of reactive species in the photocatalytic reactions and photoluminescence technique. The quenching effects of different scavengers displayed that the reactive h+ and O2− played major role in the reaction systems. The synergic effect between the ACNS and g-C3N4 was found to lead to an improved photo-generated carrier separation and hence the photocatalytic activities of the composite photocatalysts were increased significantly.

Facile fabrication of acidified g-C3N4/g-C3N4 hybrids with enhanced photocatalysis performance under visible light irradiation

Mesostructured CeO2/g-C3N4 nanocomposites: Remarkably enhanced photocatalytic activity for CO2 reduction by mutual component activations

CO2 is highly stable and therefore extremely difficult to be reduced at room temperature even by photocatalysis. Herein, a series of g-C3N4/Bi2WO6 composites have been synthesized through a facile in situ hydrothermal approach, which demonstrated greatly enhanced response to visible light, and consequently a remarkably enhanced CO2 selective photoreduction to CO. The g-C3N4 content and synthesis parameters of these composites have been tuned to obtain the optimized photocatalytic activity with a peak CO production rate of 5.19 μmol g−1 h−1 under visible light irradiation at room temperature, which was 22 and 6.4 times that on pure g-C3N4 and Bi2WO6, respectively. Based on the matched band energy potentials between g-C3N4 and Bi2WO6 in the synthesized composites, a possible Z-scheme mechanism, which features a significantly promoted separation of photo-generated carriers under visible light irradiation by the composites, has been proposed to account for the distinctive CO2 photoreduction performance.

Highly selective CO2 photoreduction to CO over g-C3N4/Bi2WO6 composites under visible light

Introducing O vacancies into the lattice of a semiconductor photocatalyst can alter its intrinsic electronic properties and band gap, thus enhancing the visible light absorption, promoting the sepa...

Mengli Li

Papers

Brand new P-doped g-C3N4: enhanced photocatalytic activity for H2 evolution and Rhodamine B degradation under visible light

Facile fabrication of acidified g-C3N4/g-C3N4 hybrids with enhanced photocatalysis performance under visible light irradiation

Mesostructured CeO2/g-C3N4 nanocomposites: Remarkably enhanced photocatalytic activity for CO2 reduction by mutual component activations

Highly selective CO2 photoreduction to CO over g-C3N4/Bi2WO6 composites under visible light

Oxygen Vacancy Generation and Stabilization in CeO2–x by Cu Introduction with Improved CO2 Photocatalytic Reduction Activity