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?

Rising atmospheric levels of carbon dioxide and the depletion of fossil fuel reserves raise serious concerns about the ensuing effects on the global climate and future energy supply. Utilizing the abundant solar energy to convert CO2 into fuels such as methane or methanol could address both problems simultaneously as well as provide a convenient means of energy storage. In this Review, current approaches for the heterogeneous photocatalytic reduction of CO2 on TiO2 and other metal oxide, oxynitride, sulfide, and phosphide semiconductors are presented. Research in this field is focused primarily on the development of novel nanostructured photocatalytic materials and on the investigation of the mechanism of the process, from light absorption through charge separation and transport to CO2 reduction pathways. The measures used to quantify the efficiency of the process are also discussed in detail.

Photocatalytic reduction of CO2 on TiO2 and other semiconductors.

The detection methods and generation mechanisms of the intrinsic reactive oxygen species (ROS), i.e., superoxide anion radical (•O2–), hydrogen peroxide (H2O2), singlet oxygen (1O2), and hydroxyl radical (•OH) in photocatalysis, were surveyed comprehensively. Consequently, the major photocatalyst used in heterogeneous photocatalytic systems was found to be TiO2. However, besides TiO2 some representative photocatalysts were also involved in the discussion. Among the various issues we focused on the detection methods and generation reactions of ROS in the aqueous suspensions of photocatalysts. On the careful account of the experimental results presented so far, we proposed the following apprehension: adsorbed •OH could be regarded as trapped holes, which are involved in a rapid adsorption–desorption equilibrium at the TiO2–solution interface. Because the equilibrium shifts to the adsorption side, trapped holes must be actually the dominant oxidation species whereas •OH in solution would exert the reactivity...

Generation and Detection of Reactive Oxygen Species in Photocatalysis

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.

The most widely used oxide for photocatalytic applications owing to its low cost and high activity is TiO2. The discovery of the photolysis of water on the surface of TiO2 in 19721 launched four decades of intensive research into the underlying chemical and physical processes involved2, 3, 4, 5. Despite much collected evidence, a thoroughly convincing explanation of why mixed-phase samples of anatase and rutile outperform the individual polymorphs has remained elusive6. One long-standing controversy is the energetic alignment of the band edges of the rutile and anatase polymorphs of TiO2 (ref. 7). We demonstrate, through a combination of state-of-the-art materials simulation techniques and X-ray photoemission experiments, that a type-II, staggered, band alignment of ~ 0.4 eV exists between anatase and rutile with anatase possessing the higher electron affinity, or work function. Our results help to explain the robust separation of photoexcited charge carriers between the two phases and highlight a route to improved photocatalysts.

Band alignment of rutile and anatase TiO2

A Patterned TiO2(Anatase)/TiO2(Rutile) Bilayer-Type Photocatalyst: Effect of the Anatase/Rutile Junction on the Photocatalytic Activity

http://web.tuat.ac.jp/~empat/wl/article/lenggoro-JAerosolSci.pdf

Preparation of ZnS Nanoparticles by Electrospray Pyrolysis

The effects of UV-irradiation on the properties of ZrO2 and TiO2 gel films prepared from corresponding metal-butoxides modified with acetylacetone (AcAc) or benzoylacetone (BzAc) have been studied. It was found that the chelate bonds of β-diketones remaining in the gel films were dissociated by the UV-irradiation. The UV-irradiation also changed the properties of the gel films such as solubility; the solubility in acidic solutions was decreased for ZrO2 gel films modified with AcAc and TiO2 gel films modified with BzAc became insoluble in alcohol. Based on these findings, a new fine-patterning process has been established, which enables us to make fine-patterns of ZrO2 and TiO2 films on a variety of substrates.

Effects of UV-irradiation on the formation of oxide thin films from chemically modified metal-alkoxides

TiO2 films with a thickness of 75 ± 5 nm (anatase) were formed on SnO2-film (580 ± 80 nm) coated soda-lime glass substrates (SnO2/SL-glass) by a sol-gel method. Although the photocatalytic activity for CH3CHO oxidation (λex > 300 nm) significantly exceeded that of a standard TiO2/quartz sample, it decayed with illumination time (t) at t > 0.75 h. Stripes of anatase TiO2 films of 40 nm in thickness and 1 mm in width were prepared on the SnO2/SL-glass substrate in a 1-mm pitch by photolysis of an organically modified sol-gel film. The TiO2 patterning further increased the photocatalytic activity by a factor of 4.1 as compared to the non-patterned sample, and it was also maintained at 0 < t < 2 h. The flat band potentials of the TiO2 and SnO2 films are determined to be −0.34 and +0.07 V (vs. SHE), respectively, at pH = 7 by the Mott-Schottky plots. On the basis of the results, the outstanding patterning effects could be rationalized in terms of the vectorial charge separation at the interface between TiO2 and SnO2.

Noboru Tohge

Papers

A Patterned TiO2(Anatase)/TiO2(Rutile) Bilayer-Type Photocatalyst: Effect of the Anatase/Rutile Junction on the Photocatalytic Activity

Preparation of ZnS Nanoparticles by Electrospray Pyrolysis

Effects of UV-irradiation on the formation of oxide thin films from chemically modified metal-alkoxides

Patterning effect of a sol-gel TiO2 overlayer on the photocatalytic activity of a TiO2/SnO2 bilayer-type photocatalyst

Photosensitive gel films prepared by the chemical modification and their application to surface-relief gratings