The nanocomposites of TiO(2)-graphene (TiO(2)-GR) have been prepared via a facile hydrothermal reaction of graphene oxide and TiO(2) in an ethanol-water solvent. We show that such a TiO(2)-GR nanocomposite exhibits much higher photocatalytic activity and stability than bare TiO(2) toward the gas-phase degradation of benzene, a volatile aromatic pollutant in air. By investigating the effect of different addition ratios of graphene on the photocatalytic activity of TiO(2)-GR systematically, we find that the higher weight ratio in TiO(2)-GR will decrease the photocatalytic activity. Analogous phenomenon is also observed for the liquid-phase degradation of dyes over TiO(2)-GR. In addition, the key features for TiO(2)-GR including enhancement of adsorptivity of pollutants, light absorption intensity, electron-hole pairs lifetime, and extended light absorption range have also been found in the composite of TiO(2) and carbon nanotubes (TiO(2)-CNT). These strongly manifest that TiO(2)-GR is in essence the same as other TiO(2)-carbon (carbon nanotubes, fullerenes, and activated carbon) composite materials on enhancement of photocatalytic activity of TiO(2), although graphene by itself has unique structural and electronic properties. Notably, this key fundamental question remains completely unaddressed in a recent report ( ACS Nano 2010 , 4 , 380 ) regarding liquid-phase degradation of dyes over the TiO(2)-GR photocatalyst. Thus, we propose that TiO(2)-GR cannot provide truly new insights into the fabrication of TiO(2)-carbon composite as high-performance photocatalysts. It is hoped that our work could avert the misleading message to the readership, hence offering a valuable source of reference on fabricating TiO(2)-carbon composites for their application as a photocatalyst in the environment cleanup.

Increasing interest has been devoted to synthesizing graphene (GR)-semiconductor nanocomposites as photocatalysts for potential applications, which is very similar to its forebear carbon nanotube (CNT)-semiconductor photocatalysts. Unfortunately, a thoughtful and inevitable comparison between GR- and CNT-semiconductors as photocatalysts is often neglected in literature. This situation may give incomplete or exaggerated information on the contribution role of GR to enhance the semiconductor photocatalytic activity, as compared to CNT. Thus, our knowledge regarding the specific advantage of GR over CNT on how to design more efficient GR-semiconductor nanocomposites and understanding the origin of their enhanced photocatalytic performance is far from satisfactory. By taking the TiO(2) semiconductor as an example, we conceptually demonstrate how to synthesize a more efficient GR-TiO(2) nanocomposite as a visible light photocatalyst toward selective oxidation of alcohols under mild conditions. Comparison between GR-TiO(2) and CNT-TiO(2) discloses the prominent advantage of GR over CNT on both controlling the morphology of GR-TiO(2) nanocomposite and enhancing the photocatalytic activity of TiO(2). This work clearly highlights the importance and necessity for a comparison investigation between GR- and CNT-semiconductors as photocatalysts, which will promote our in-depth fundamental understanding on the analogy and difference between GR and CNT on controlling the morphology of GR (or CNT)-semiconductor nanocomposites and enhancing the photocatalytic performance. Therefore, we appeal the photocatalysis community to pay attention to this respect rather than separately imposing hype on the miracle of GR in much the same way as its carbon forebears, which could significantly advance our rational fabrication of smart GR-semiconductor nanocomposites for artificial photosynthesis.

We report the assembly of nanosized ZnS particles on the 2D platform of a graphene oxide (GO) sheet by a facile two-step wet chemistry process, during which the reduced graphene oxide (RGO, also called GR) and the intimate interfacial contact between ZnS nanoparticles and the GR sheet are achieved simultaneously. The ZnS-GR nanocomposites exhibit visible light photoactivity toward aerobic selective oxidation of alcohols and epoxidation of alkenes under ambient conditions. In terms of structure-photoactivity correlation analysis, we for the first time propose a new photocatalytic mechanism where the role of GR in the ZnS-GR nanocomposites acts as an organic dye-like macromolecular "photosensitizer" for ZnS instead of an electron reservoir. This novel photocatalytic mechanism is distinctly different from all previous research on GR-semiconductor photocatalysts, for which GR is claimed to behave as an electron reservoir to capture/shuttle the electrons photogenerated from the semiconductor. This new concept of the reaction mechanism in graphene-semiconductor photocatalysts could provide a new train of thought on designing GR-based composite photocatalysts for targeting applications in solar energy conversion, promoting our in-depth thinking on the microscopic charge carrier transfer pathway connected to the interface between the GR and the semiconductor.

The recent progress in the synthesis, properties and photocatalytic applications of carbon quantum dots (CQDs) has been elaborately demonstrated, and some perspectives on the challenges and opportunities for future exploration in this arena are discussed.

We report a simple and general approach to improve the transfer efficiency of photogenerated charge carriers across the interface between graphene (GR) and semiconductor CdS by introducing a small amount of metal ions (Ca(2+), Cr(3+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), and Zn(2+)) as "mediator" into their interfacial layer matrix, while the intimate interfacial contact between GR and CdS is maintained. This simple strategy can not only significantly improve the visible-light-driven photoactivity of GR-CdS semiconductor composites for targeting selective photoredox reaction, including aerobic oxidation of alcohol and anaerobic reduction of nitro compound, but also drive a balance between the positive effect of GR on retarding the recombination of electron-hole pairs photogenerated from semiconductor and the negative "shielding effect" of GR resulting from the high weight addition of GR. Our current work highlights that the significant issue on improving the photoactivity of GR-semiconductor composites via strengthening interfacial contact is not just a simple issue of tighter connection between GR and the semiconductor, but it is also the optimization of the atomic charge carrier transfer pathway across the interface between GR and the semiconductor.

Incessant interest has been shown in the synthesis of graphene (GR)-semiconductor nanocomposites as photocatalysts aiming to utilize the excellent electron conductivity of GR to lengthen the lifetime of photoexcited charge carriers in the semiconductor and, hence, improve the photoactivity. However, research works focused on investigating how to make sufficient use of the unique electron conductivity of GR to design a more efficient GR-semiconductor photocatalyst have been quite lacking. Here, we show a proof-of-concept study on improving the photocatalytic performance of GR-TiO(2) nanocomposites via a combined strategy of decreasing defects of GR and improving the interfacial contact between GR and the semiconductor TiO(2). The GR-TiO(2) nanocomposite fabricated by this approach is able to make more sufficient use of the electron conductivity of GR, by which the lifetime and transfer of photoexcited charge carriers of GR-TiO(2) upon visible light irradiation will be improved more efficiently. This in turn leads to the enhancement of visible-light-driven photoactivity of GR-TiO(2) toward selective transformation of alcohols to corresponding aldehydes using molecular oxygen as a benign oxidant under ambient conditions. It is anticipated that our current work would inform ongoing efforts to exploit the rational design of smart, more efficient GR-semiconductor photocatalysts for conversion of solar to chemical energy by heterogeneous photocatalysis.

One-dimensional (1D) CdS@TiO₂ core-shell nanocomposites (CSNs) have been successfully synthesized via a two-step solvothermal method. The structure and properties of 1D CdS@TiO₂ core-shell nanocomposites (CdS@TiO₂ CSNs) have been characterized by a series of techniques, including X-ray diffraction (XRD), ultraviolet-visible-light (UV-vis) diffuse reflectance spectra (DRS), field-emission scanning electron microscopy (FESEM), photoluminescence spectra (PL), and electron spin resonance (ESR) spectroscopy. The results demonstrate that 1D core-shell structure is formed by coating TiO₂ onto the substrate of CdS nanowires (NWs). The visible-light-driven photocatalytic activities of the as-prepared 1D CdS@TiO₂ CSNs are evaluated by selective oxidation of alcohols to aldehydes under mild conditions. Compared to bare CdS NWs, an obvious enhancement of both conversion and yield is achieved over 1D CdS@TiO₂ CSNs, which is ascribed to the prolonged lifetime of photogenerated charge carriers over 1D CdS@TiO₂ CSNs under visible-light irradiation. Furthermore, it is disclosed that the photogenerated holes from CdS core can be stuck by the TiO₂ shell, as evidenced by controlled radical scavenger experiments and efficiently selective reduction of heavy-metal ions, Cr(VI), over 1D CdS@TiO₂ CSNs, which consequently leads to the fact that the reaction mechanism of photocatalytic oxidation of alcohols over 1D CdS@TiO₂ CSNs is apparently different from that over 1D CdS NWs under visible-light irradiation. It is hoped that our work could not only offer useful information on the fabrication of various specific 1D core-shell nanostructures, but also open a new doorway of such 1D core-shell semiconductors as visible-light photocatalysts in the promising field of selective transformations.

Merging hydrogen (H 2 ) evolution with oxidative organic synthesis in a semiconductor-mediated photoredox reaction is extremely attractive because the clean H 2 fuel and high-value chemicals can be coproduced under mild conditions using light as the sole energy input. Following this dual-functional photocatalytic strategy, a dreamlike reaction pathway for constructing C−C/C−X (X = C, N, O, S) bonds from abundant and readily available X−H bond-containing compounds with concomitant release of H 2 can be readily fulfilled without the need of external chemical reagents, thus offering a green and fascinating organic synthetic strategy. In this review, we begin by presenting a concise overview on the general background of traditional photocatalytic H 2 production and then focus on the fundamental principles of cooperative photoredox coupling of selective organic synthesis and H 2 production by simultaneous utilization of photoexcited electrons and holes over semiconductor-based catalysts to meet the economic and sustainability goal. Thereafter, we put dedicated emphasis on recent key progress of cooperative photoredox coupling of H 2 production and various selective organic transformations, including selective alcohol oxidation, selective methane conversion, amines oxidative coupling, oxidative cross-coupling, cyclic alkanes dehydrogenation, reforming of lignocellulosic biomass, and so on. Finally, the remaining challenges and future perspectives in this flourishing area have been critically discussed. It is anticipated that this review will provide enlightening guidance on the rational design of such dual-functional photoredox reaction system, thereby stimulating the development of economical and environmentally benign solar fuel generation and organic synthesis of value-added fine chemicals.