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?

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

A review on g-C3N4-based 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.

Solar-driven water splitting provides a leading approach to store the abundant yet intermittent solar energy and produce hydrogen as a clean and sustainable energy carrier. A straightforward route to light-driven water splitting is to apply self-supported particulate photocatalysts, which is expected to allow solar hydrogen to be competitive with fossil-fuel-derived hydrogen on a levelized cost basis. More importantly, the powder-based systems can lend themselves to making functional panels on a large scale while retaining the intrinsic activity of the photocatalyst. However, all attempts to generate hydrogen via powder-based solar water-splitting systems to date have unfortunately fallen short of the efficiency values required for practical applications. Photocatalysis on photocatalyst particles involves three sequential steps: (i) absorption of photons with higher energies than the bandgap of the photocatalysts, leading to the excitation of electron-hole pairs in the particles, (ii) charge separation and migration of these photoexcited carriers, and (iii) surface chemical reactions based on these carriers. In this review, we focus on the challenges of each step and summarize material design strategies to overcome the obstacles and limitations. This review illustrates that it is possible to employ the fundamental principles underlying photosynthesis and the tools of chemical and materials science to design and prepare photocatalysts for overall water splitting.

Particulate Photocatalysts for Light-Driven Water Splitting: Mechanisms, Challenges, and Design Strategies

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.

A composite Sr2TiO4/SrTiO3(La,Cr) heterojunction photocatalyst has been prepared by a simple in situ polymerized complex method. Upon Pt cocatalyst loading, this catalyst shows higher photocatalytic activity towards hydrogen production than individual SrTiO3(La,Cr) and Sr2TiO4(La,Cr) in the presence of methanol sacrificial reagent. Microscopic morphology studies show that well defined heterojunctions are formed by matching the lattice fringes of SrTiO3(La,Cr) and Sr2TiO4(La,Cr), and Pt was preferentially loaded on the surface of the Sr2TiO4(La,Cr) component in the composite Sr2TiO4/SrTiO3(La,Cr) photocatalyst. XPS and EPR analyses show that the composite photocatalyst also has the lowest amount of Cr6+ electron trapping sites. Band structure analysis by combining absorption spectroscopy and Mott–Schottky plots shows that, in the composite photocatalyst, the photogenerated electrons and holes tend to migrate from SrTiO3(La,Cr) to Sr2TiO4(La,Cr) and from Sr2TiO4(La,Cr) to SrTiO3(La,Cr), respectively. This kind of band structure can facilitate charge transfer and separation driven by the minor potential difference between the two components, which is further confirmed by the observation of long lived electrons in the time resolved FT-IR spectroscopic study. It is concluded that the superior photocatalytic activity of the composite heterojunction photocatalyst is due to efficient charge transfer and separation by well defined heterojunctions formed between SrTiO3(La,Cr) and Sr2TiO4(La,Cr), preferential loading of Pt nanoparticles on the Sr2TiO4(La,Cr) component, and the lowest amount of Cr6+ in the composite photocatalyst. The tailored design and synthesis of the composite heterojunction structure is a promising approach for the improvement of the photocatalytic activity of a photocatalyst.

Composite Sr2TiO4/SrTiO3(La,Cr) heterojunction based photocatalyst for hydrogen production under visible light irradiation

A Novel Sr2CuInO3S p-type semiconductor photocatalyst for hydrogen production under visible light irradiation

Time-resolved infrared spectroscopic investigation of roles of valence states of Cr in (La,Cr)-doped SrTiO3 photocatalysts

The invention relates to a semiconductor material photocatalyst based on a layered structure and hydrogen production applications thereof. The photocatalyst and the applications are characterized in that: a semiconductor material comprises a group-IIA metal element, a metal element in the IB group, a group-VIB or group-VIIB or group-IIB or group-IIIA metal element, and one or two group-VIA nonmetal element. A hydrogen production reaction under visible light is performed by adopting the semiconductor material as the photocatalyst, with or without a small amount of a transition metal and a precious metal supported on the catalyst surface by in-situ photodeposition as a cocatalyst. The semiconductor material can be compounded with a known n type semiconductor to form a p-n heterojunction water decomposition system, and can be adopted as a photocathode material for a photoelectrochemistry water decomposition system.

Yushuai Jia

Papers

Titanium dioxide-based nanomaterials for photocatalytic fuel generations.

Composite Sr2TiO4/SrTiO3(La,Cr) heterojunction based photocatalyst for hydrogen production under visible light irradiation

A Novel Sr2CuInO3S p-type semiconductor photocatalyst for hydrogen production under visible light irradiation

Time-resolved infrared spectroscopic investigation of roles of valence states of Cr in (La,Cr)-doped SrTiO3 photocatalysts

A semiconductor material photocatalyst based on a layered structure and hydrogen production applications thereof