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?

Sulfate radical-based advanced oxidation processes (SR-AOPs) employing heterogeneous catalysts to generate sulfate radical (SO4 −) from peroxymonosulfate (PMS) and persulfate (PS) have been extensively employed for organic contaminant removal in water. This article aims to provide a state–of–the–art review on the recent development in heterogeneous catalysts including single metal, mixed metal, and nonmetal carbon catalysts for organic contaminants removal, with particular focus on PMS activation. The hybrid heterogeneous catalyst/PMS systems integrated with other advanced oxidation technologies is also discussed. Several strategies for the identification of principal reactive radicals in SO4 −–oxidation systems are evaluated, namely (i) use of chemical probe or spin trapping agent coupled with analytical tools, and (ii) competitive kinetic approach using selective radical scavengers. The main challenges and mitigation strategies pertinent to the SR-AOPs are identified, which include (i) possible formation of oxyanions and disinfection byproducts, and (ii) dealing with sulfate produced and residual PMS. Potential future applications and research direction of SR-AOPs are proposed. These include (i) novel reactor design for heterogeneous catalytic system based on batch or continuous flow (e.g. completely mixed or plug flow) reactor configuration with catalyst recovery, and (ii) catalytic ceramic membrane incorporating SR-AOPs.

Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal: Current development, challenges and prospects

Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants: Review

Recently sulfate radical-based advanced oxidation processes (SR-AOPs) attract increasing attention due to their capability and adaptability in decontamination. The couple of cobalt and peroxymonosulfate (PMS) is an efficient way to produce reactive sulfate radicals. This article reviews the state-of-the-art progress on various heterogeneous cobalt-based catalysts for PMS activation, including cobalt oxides, cobalt-ferrite and supported cobalt by diverse substrates. We summarize the intrinsic properties of these catalysts and their fundamental behaviors in PMS activation, as well as synthetic approaches. In addition, influencing factors and synergistic techniques of Co/PMS systems in organic degradation and possible environmental applications are also discussed. Finally, we propose perspectives on challenges related to cobalt-based catalysts, heterogeneous Co/PMS systems and their potential applications in practical environmental cleanup.

Cobalt-catalyzed sulfate radical-based advanced oxidation: A review on heterogeneous catalysts and applications

Chemistry of persulfates in water and wastewater treatment: A review

We discovered that chemically reduced graphene oxide, with an ID/IG >1.4 (defective to graphite) can effectively activate peroxymonosulfate (PMS) to produce active sulfate radicals. The produced sulfate radicals (SO4•—) are powerful oxidizing species with a high oxidative potential (2.5–3.1 vs 2.7 V of hydroxyl radicals), and can effectively decompose various aqueous contaminants. Graphene demonstrated a higher activity than several carbon allotropes, such as activated carbon (AC), graphite powder (GP), graphene oxide (GO), and multiwall carbon nanotube (MWCNT). Kinetic study of graphene catalyzed activation of PMS was carried out. It was shown that graphene catalysis is superior to that on transition metal oxide (Co3O4) in degradation of phenol, 2,4-dichlorophenol (DCP) and a dye (methylene blue, MB) in water, therefore providing a novel strategy for environmental remediation.

Reduced graphene oxide for catalytic oxidation of aqueous organic pollutants.

Nanoscaled zerovalent iron (ZVI) encapsulated in carbon spheres (nano-Fe⁰@CS) were prepared via a hydrothermal carbonization method, using glucose and iron(III) nitrate as precursors. The properties of the nano-Fe⁰@CS were investigated by X-ray diffraction (XRD), thermogravimetric analysis-differential scanning calorimetry (TGA-DSC), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen adsorption/desorption isotherms. Nano-Fe⁰@CS was demonstrated, for the first time, as an effective material in activating Oxone (peroxymonosulfate, PMS) for the oxidation of organic pollutants. It was found that the efficiency of nano-Fe⁰@CS was higher than ZVI particles, iron ions, iron oxides, and a cobalt oxide. The mechanism of the high performance was discussed. The structure of the nano-Fe⁰@CS not only leads to high efficiency in the activation of PMS, but also good stability. This study extended the application of ZVI from reductive destruction of organics to oxidative degradation of organics by providing a green material for environmental remediation.

Nano-Fe0 Encapsulated in Microcarbon Spheres: Synthesis, Characterization, and Environmental Applications

Carbon nitride (C3N4) is a layered, stable, and polymeric metal-free material that has been discovered as a visible-light-response photocatalyst. Owing to C3N4 having a higher conduction band position, most previous studies have been focused on its reduction capability for solar fuel production, such as hydrogen generation from water splitting or hydrocarbon production from CO2. However, photooxidation ability of g-C3N4 is weak and has been less explored, especially for decomposition of chemically stable phenolics. Carbon spheres prepared by a hydrothermal carbonization of glucose have been widely applied as a support material or template due to their interesting physicochemical properties and the functional groups on the reactive surface. This study demonstrated that growth of carbon nanospheres onto g-C3N4 (CN-CS) can significantly increase the photooxidation ability (to about 4.79 times higher than that of pristine g-C3N4) in phenol degradation under artificial sunlight irradiations. The crystal struct...

Guanliang Zhou

Papers

Reduced graphene oxide for catalytic oxidation of aqueous organic pollutants.

Nano-Fe0 Encapsulated in Microcarbon Spheres: Synthesis, Characterization, and Environmental Applications

A new metal-free carbon hybrid for enhanced photocatalysis.

Visible light responsive titania photocatalysts codoped by nitrogen and metal (Fe, Ni, Ag, or Pt) for remediation of aqueous pollutants

Titanate supported cobalt catalysts for photochemical oxidation of phenol under visible light irradiations