Since the discovery of mechanically exfoliated graphene in 2004, research on ultrathin two-dimensional (2D) nanomaterials has grown exponentially in the fields of condensed matter physics, material science, chemistry, and nanotechnology. Highlighting their compelling physical, chemical, electronic, and optical properties, as well as their various potential applications, in this Review, we summarize the state-of-art progress on the ultrathin 2D nanomaterials with a particular emphasis on their recent advances. First, we introduce the unique advances on ultrathin 2D nanomaterials, followed by the description of their composition and crystal structures. The assortments of their synthetic methods are then summarized, including insights on their advantages and limitations, alongside some recommendations on suitable characterization techniques. We also discuss in detail the utilization of these ultrathin 2D nanomaterials for wide ranges of potential applications among the electronics/optoelectronics, electrocat...

Recent Advances in Ultrathin Two-Dimensional Nanomaterials

Semiconductor-mediated photocatalysis has received tremendous attention as it holds great promise to address the worldwide energy and environmental issues. To overcome the serious drawbacks of fast charge recombination and the limited visible-light absorption of semiconductor photocatalysts, many strategies have been developed in the past few decades and the most widely used one is to develop photocatalytic heterojunctions. This review attempts to summarize the recent progress in the rational design and fabrication of heterojunction photocatalysts, such as the semiconductor–semiconductor heterojunction, the semiconductor–metal heterojunction, the semiconductor–carbon heterojunction and the multicomponent heterojunction. The photocatalytic properties of the four junction systems are also discussed in relation to the environmental and energy applications, such as degradation of pollutants, hydrogen generation and photocatalytic disinfection. This tutorial review ends with a summary and some perspectives on the challenges and new directions in this exciting and still emerging area of research.

Semiconductor heterojunction photocatalysts: design, construction, and photocatalytic performances

Graphene, a single layer of graphite, possesses a unique two-dimensional structure, high conductivity, superior electron mobility and extremely high specific surface area, and can be produced on a large scale at low cost. Thus, it has been regarded as an important component for making various functional composite materials. Especially, graphene-based semiconductor photocatalysts have attracted extensive attention because of their usefulness in environmental and energy applications. This critical review summarizes the recent progress in the design and fabrication of graphene-based semiconductor photocatalysts via various strategies including in situ growth, solution mixing, hydrothermal and/or solvothermal methods. Furthermore, the photocatalytic properties of the resulting graphene-based composite systems are also discussed in relation to the environmental and energy applications such as photocatalytic degradation of pollutants, photocatalytic hydrogen generation and photocatalytic disinfection. This critical review ends with a summary and some perspectives on the challenges and new directions in this emerging area of research (158 references).

Graphene-based semiconductor photocatalysts

The production of H2 by photocatalytic water splitting has attracted a lot attention as a clean and renewable solar H2 generation system. Despite tremendous efforts, the present great challenge in materials science is to develop highly active photocatalysts for splitting of water at low cost. Here we report a new composite material consisting of TiO2 nanocrystals grown in the presence of a layered MoS2/graphene hybrid as a high-performance photocatalyst for H2 evolution. This composite material was prepared by a two-step simple hydrothermal process using sodium molybdate, thiourea, and graphene oxide as precursors of the MoS2/graphene hybrid and tetrabutylorthotitanate as the titanium precursor. Even without a noble-metal cocatalyst, the TiO2/MoS2/graphene composite reaches a high H2 production rate of 165.3 μmol h–1 when the content of the MoS2/graphene cocatalyst is 0.5 wt % and the content of graphene in this cocatalyst is 5.0 wt %, and the apparent quantum efficiency reaches 9.7% at 365 nm. This unusu...

Synergetic Effect of MoS2 and Graphene as Cocatalysts for Enhanced Photocatalytic H2 Production Activity of TiO2 Nanoparticles

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

The production of clean and renewable hydrogen through water splitting using photocatalysts has received much attention due to the increasing global energy crises. In this study, a high efficiency of the photocatalytic H2 production was achieved using graphene nanosheets decorated with CdS clusters as visible-light-driven photocatalysts. The materials were prepared by a solvothermal method in which graphene oxide (GO) served as the support and cadmium acetate (Cd(Ac)2) as the CdS precursor. These nanosized composites reach a high H2-production rate of 1.12 mmol h–1 (about 4.87 times higher than that of pure CdS nanoparticles) at graphene content of 1.0 wt % and Pt 0.5 wt % under visible-light irradiation and an apparent quantum efficiency (QE) of 22.5% at wavelength of 420 nm. This high photocatalytic H2-production activity is attributed predominantly to the presence of graphene, which serves as an electron collector and transporter to efficiently lengthen the lifetime of the photogenerated charge carrier...

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Highly efficient visible-light-driven photocatalytic hydrogen production of CdS-cluster-decorated graphene nanosheets.

Bright two-photon fluorescent probes are highly desirable to be able to optically probe biological activities deep inside living organisms with larger imaging depth, minor autofluorescence background, and less photodamage. In this study, we report the biocompatible nitrogen-doped graphene quantum dots (N-GQDs) as efficient two-photon fluorescent probes for cellular and deep-tissue imaging. The N-GQD was prepared by a facile solvothermal method using dimethylformamide as a solvent and nitrogen source. The two-photon absorption cross-section of N-GQD reaches 48 000 Goppert-Mayer units, which far surpasses that of the organic dyes and is comparable to that of the high performance semiconductor QDs, achieving the highest value ever reported for carbon-based nanomaterials. More importantly, a study of penetration depth in tissue phantom demonstrates that the N-GQD can achieve a large imaging depth of 1800 μm, significantly extending the fundamental two-photon imaging depth limit. In addition, the N-GQD is nont...

Strong two-photon-induced fluorescence from photostable, biocompatible nitrogen-doped graphene quantum dots for cellular and deep-tissue imaging.

Graphene, a new material for the electron-device community, has many extraordinary properties. Especially, it provides a perfect platform to explore the unique electronic property in absolutely two-dimensions. However, most electronic applications are handicapped by the absence of a semiconducting gap in pristine graphene. To control the semiconducting properties of graphene, doping is regarded as one of the most feasible methods. Herein, a brief review is given on the recent research progress of graphene doping, which is roughly divided into three categories: First, the hetero atom doping, including arc discharge, chemical vapor deposition, electrothermal reaction and ion-irradiation approaches; Second, the chemical modification strategy; Third, the method of electrostatic field tuning. In addition, the various potential applications of the above doping methods are also introduced.

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Graphene Doping: A Review

a b s t r a c t Selective photocatalysis offers an alternative green approach for valuable fine chemical synthesis and environmental remediation. In this work, high selectivity in visible-light-driven partial photocatalytic oxidation of benzyl alcohol over single-crystalline rutile TiO2 nanorods was achieved. The nanorods were prepared by a hydrothermal reaction using rutile TiO2 nanofibers obtained from calcination of compos- ite electrospun nanofibers as a substrate. The selectivity of partial photocatalytic oxidation of benzyl alcohol over the obtained rutile TiO2 nanorods under visible-light irradiation was over 99%, much better than the results reported over nanoparticle counterparts under UV light irradiation. A tentative reaction mechanism was proposed, that is, benzyl alcohol was first adsorbed on the surface of rutile TiO2 to form a complex which could absorb visible-light to generate electrons and holes, then was oxidized into the benzaldehyde by electrons transfer and holes-attracted release of H atom. In addition, the unidirectional property of nanorods favored the electron transfer and thus the selectivity. To the best of our knowledge, it is the first report of the rutile TiO2 nanorods for the visible-light-driven selective photocatalysis. Our work extends the selective photocatalysts to one-dimensional nanomaterials instead of limiting to the commonly used nanoparticles and will open up an intriguing perspective for green synthesis and efficient energy conversion.

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High selectivity in visible-light-driven partial photocatalytic oxidation of benzyl alcohol into benzaldehyde over single-crystalline rutile TiO2 nanorods

Chiral Zn(II)/D-,L-phenylalanine (Phe) bio-coordination polymer nanofibers with fluorescence were prepared by fast coordination-assisted assembly. The synthetic strategy is based on the fact that the Zn2+ ions were linked to oxygen atoms from carboxylate groups of the D- or L-amino acid by coordination interactions to form the chiral polymers. The Zn(II)/D-,L-Phe nanofibers had homogeneous diameters in the range of 700-900 nm and ultra-long length in several hundred micrometers, and the surface of the fiber was extremely smooth. In addition, the enantiomers of Zn(II)/Phe nanofibers exhibited both optical activity and fluorescent property in the solid state, which has great potential for application in the field of biomimetic nanofabrication and micro-/nano-optoelectronics.

Baohong Zhang

Papers

Highly efficient visible-light-driven photocatalytic hydrogen production of CdS-cluster-decorated graphene nanosheets.

Strong two-photon-induced fluorescence from photostable, biocompatible nitrogen-doped graphene quantum dots for cellular and deep-tissue imaging.

Graphene Doping: A Review

High selectivity in visible-light-driven partial photocatalytic oxidation of benzyl alcohol into benzaldehyde over single-crystalline rutile TiO2 nanorods

Chiral Zinc Phenylalanine Nanofibers with Fluorescence