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?

Photocatalytic water splitting represents a promising strategy for clean, low-cost, and environmental-friendly production of H2 by utilizing solar energy. There are three crucial steps for the photocatalytic water splitting reaction: solar light harvesting, charge separation and transportation, and the catalytic H2 and O2 evolution reactions. While significant achievement has been made in optimizing the first two steps in the photocatalytic process, much less efforts have been put into improving the efficiency of the third step, which demands the utilization of cocatalysts. To date, cocatalysts based on rare and expensive noble metals are still required for achieving reasonable activity in most semiconductor-based photocatalytic systems, which seriously restricts their large-scale application. Therefore, seeking cheap, earth-abundant and high-performance cocatalysts is indispensable to achieve cost-effective and highly efficient photocatalytic water splitting. This review for the first time summarizes all the developed earth-abundant cocatalysts for photocatalytic H2- and O2-production half reactions as well as overall water splitting. The roles and functional mechanism of the cocatalysts are discussed in detail. Finally, this review is concluded with a summary, and remarks on some challenges and perspectives in this emerging area of research.

Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting

Generations Yi Ma,† Xiuli Wang,† Yushuai Jia,† Xiaobo Chen,‡ Hongxian Han,*,† and Can Li*,† †State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences and Dalian National Laboratory for Clean Energy, 457 Zhongshan Road, Dalian 116023, China ‡Department of Chemistry, College of Arts and Sciences, University of Missouri-Kansas City, 5100 Rockhill Road, Kansas City, Missouri 64110, United States

Titanium dioxide-based nanomaterials for photocatalytic fuel generations.

Titania is one of the most widely used benchmark standard photocatalysts in the field of environmental applications. However, the large band gap of titania and massive recombination of photogenerated charge carriers limit its overall photocatalytic efficiency. The former can be overcome by modifying the electronic band structure of titania including various strategies like coupling with a narrow band gap semiconductor, metal ion/nonmetal ion doping, codoping with two or more foreign ions, surface sensitization by organic dyes or metal complexes, and noble metal deposition. The latter can be corrected by changing the surface properties of titania by fluorination or sulfation or by the addition of suitable electron acceptors besides molecular oxygen in the reaction medium. This review encompasses several advancements made in these aspects, and also some of the new physical insights related to the charge transfer events like charge carrier generation, trapping, detrapping, and their transfer to surface are d...

Review on Modified TiO2 Photocatalysis under UV/Visible Light: Selected Results and Related Mechanisms on Interfacial Charge Carrier Transfer Dynamics

https://chemical.eng.usm.my/bassim/PDF/photocatalytic%20degradation.pdf

Parameters affecting the photocatalytic degradation of dyes using TiO2-based photocatalysts: a review.

Heterogeneous photocatalysis has become a comprehensively studied area of research during the past three decades due to its practical interest in applications including water–air depollution, cancer therapy, sterilization, artificial photosynthesis (CO2 photoreduction), anti-fogging surfaces, heat transfer and heat dissipation, anticorrosion, lithography, photochromism, solar chemicals production and many others. The utilization of solar irradiation to supply energy or to initiate chemical reactions is already an established idea. Excited electron–hole pairs are generated upon light irradiation of a wide-band gap semiconductor which can be applied to solar cells to generate electricity or in chemical processes to create/degrade specific compounds. While the field of heterogeneous photocatalysis for pollutant abatement and mineralisation of contaminants has been extensively investigated, a new research avenue related to the selective valorisation of residues has recently emerged as a promising alternative to utilise solar light for the production of valuable chemicals and fuels. This tutorial review will focus on the potential and applications of solid photonanocatalysts for the selective transformation of biomass-derived substrates.

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Heterogeneous photocatalytic nanomaterials: prospects and challenges in selective transformations of biomass-derived compounds

A simple, low-temperature synthesis approach is reported for planting CdS-sensitized 1D ZnO nanorod arrays on the 2D graphene (GR) sheet to obtain the ternary hierarchical nanostructures, during which graphene oxide (GO) as the precursor of GR acts as a flexible substrate for the formation of ZnO nanorod arrays. The hierarchical CdS-1D ZnO-2D GR hybrids can serve as an efficient visible-light-driven photocatalyst for selective organic transformations. The fast electron transport of 1D ZnO nanorods, the well-known electronic conductivity of 2D GR, the intense visible-light absorption of CdS, the unique hierarchical structure, and the matched energy levels of CdS, ZnO and GR efficiently boost the photogenerated charge carriers separation and transfer across the interfacial domain of hierarchical CdS-1D ZnO-2D GR hybrids under visible light irradiation via three-level electron transfer process. Furthermore, the superior reusability of ternary hybrids is achieved by controlling the reaction parameters, i.e., using visible light irradiation and holes scavenger to prevent ZnO and CdS from photocorrosion. This work demonstrates a facile way of fabricating hierarchical CdS-1D ZnO-2D GR hybrids in a controlled manner and highlights a promising scope of adopting integrative photosensitization and co-catalyst strategy to design more efficient semiconductor-based composite photocatalysts toward solar energy capture and conversion.

Hierarchically CdS Decorated 1D ZnO Nanorods‐2D Graphene Hybrids: Low Temperature Synthesis and Enhanced Photocatalytic Performance

The severe consequences of fossil fuel consumption have resulted in a need for alternative sustainable sources of energy. Conversion and storage of solar energy via a renewable method, such as photocatalysis, holds great promise as such an alternative. One-dimensional (1D) nanostructures have gained attention in solar energy conversion because they have a long axis to absorb incident sunlight yet a short radial distance for separation of photogenerated charge carriers. In particular, well-ordered spatially high dimensional architectures based on 1D nanostructures with well-defined facets or anisotropic shapes offer an exciting opportunity for bridging the gap between 1D nanostructures and the micro and macro world, providing a platform for integration of nanostructures on a larger and more manageable scale into high-performance solar energy conversion applications. In this review, we focus on the progress of photocatalytic solar energy conversion over controlled one-dimension-based spatially ordered architecture hybrids. Assembly and classification of these novel architectures are summarized, and we discuss the opportunity and future direction of integration of 1D materials into high-dimensional, spatially organized architectures, with a perspective toward improved collective performance in various artificial photoredox applications.

One-dimension-based spatially ordered architectures for solar energy conversion

Different titania-based systems doped with diverse transition metals (Ag, Fe, Pd, Pt, Zn and Zr) were synthesized by the sol‐gel method. Samples were characterized by a wide range of physical techniques (ICP-MS, N2-isotherms, TGA‐DTA, TEM, XRD, FT-Raman and UV‐vis spectroscopies). The effect of aging of the gel either under magnetic stirring (ST) or ultrasonic irradiation (US) on the characteristics of the resulting solids was studied. Sonication ensured the obtention of pure anatase nanoparticles and generally led to an increase in surface area. All the solids were tested for gas phase selective photooxidation of 2-propanol. Irrespective of the aging method, doping with Pd, Pt or Ag resulted in an increase in molar conversion as compared to bare-TiO2, whereas the presence of Fe and Zr had a detrimental effect. Those solids for which sonication hadthegreatestimpactontexturalandstructuralcharacteristics (bare-TiO2andZn-containingsamples)exhibitedthegreatestdifference in molar conversion. Moreover, high selectivities to acetone were achieved in most of the cases. # 2006 Elsevier B.V. All rights reserved.

Juan Carlos Colmenares

Papers

Heterogeneous photocatalytic nanomaterials: prospects and challenges in selective transformations of biomass-derived compounds

Hierarchically CdS Decorated 1D ZnO Nanorods‐2D Graphene Hybrids: Low Temperature Synthesis and Enhanced Photocatalytic Performance

One-dimension-based spatially ordered architectures for solar energy conversion

Synthesis, characterization and photocatalytic activity of different metal-doped titania systems

A sustainable approach for lignin valorization by heterogeneous photocatalysis