Photo-electro-Fenton-like process for rapid ciprofloxacin removal: The indispensable role of polyvalent manganese in Fe-free system

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 construction and characteristics of each classification of the heterojunction system will be critically reviewed, namely metal-g-C3N4, semiconductor-g-C3N4, isotype g-C3N4/g-C3N4, graphitic carbon-g-C3N4, conducting polymer-g-C3N4, sensitizer-g-C3N4, and multicomponent heterojunctions. The band structures, electronic properties, optical absorption, and interfacial charge transfer of g-C3N4-based heterostructured nanohybrids will also be theoretically discussed based on the first-principles density functional theory (DFT) calculations to provide insightful outlooks on the charge carrier dynamics. Apart from that, the advancement of the versatile photoredox applications toward artificial photosynthesis (water splitting and photofixation of CO2), environmental decontamination, and bacteria disinfection will be presented in detail. Last but not least, this comprehensive review will conclude with a summary and some invigorating perspectives on the challenges and future directions at the forefront of this research platform. It is anticipated that this review can stimulate a new research doorway to facilitate the next generation of g-C3N4-based photocatalysts with ameliorated performances by harnessing the outstanding structural, electronic, and optical properties for the development of a sustainable future without environmental detriment.

In recent years, semiconductor photocatalytic process has shown a great potential as a low-cost, environmental friendly and sustainable treatment technology to align with the "zero" waste scheme in the water/wastewater industry. The ability of this advanced oxidation technology has been widely demonstrated to remove persistent organic compounds and microorganisms in water. At present, the main technical barriers that impede its commercialisation remained on the post-recovery of the catalyst particles after water treatment. This paper reviews the recent R&D progresses of engineered-photocatalysts, photoreactor systems, and the process optimizations and modellings of the photooxidation processes for water treatment. A number of potential and commercial photocatalytic reactor configurations are discussed, in particular the photocatalytic membrane reactors. The effects of key photoreactor operation parameters and water quality on the photo-process performances in terms of the mineralization and disinfection are assessed. For the first time, we describe how to utilize a multi-variables optimization approach to determine the optimum operation parameters so as to enhance process performance and photooxidation efficiency. Both photomineralization and photo-disinfection kinetics and their modellings associated with the photocatalytic water treatment process are detailed. A brief discussion on the life cycle assessment for retrofitting the photocatalytic technology as an alternative waste treatment process is presented. This paper will deliver a scientific and technical overview and useful information to scientists and engineers who work in this field.