Approaches, Derivatives and Applications Vasilios Georgakilas,† Michal Otyepka,‡ Athanasios B. Bourlinos,‡ Vimlesh Chandra, Namdong Kim, K. Christian Kemp, Pavel Hobza,‡,§,⊥ Radek Zboril,*,‡ and Kwang S. Kim* †Institute of Materials Science, NCSR “Demokritos”, Ag. Paraskevi Attikis, 15310 Athens, Greece ‡Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacky University Olomouc, 17. listopadu 12, 771 46 Olomouc, Czech Republic Center for Superfunctional Materials, Department of Chemistry, Pohang University of Science and Technology, San 31, Hyojadong, Namgu, Pohang 790-784, Korea Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, v.v.i., Flemingovo naḿ. 2, 166 10 Prague 6, Czech Republic

Functionalization of Graphene: Covalent and Non-Covalent Approaches, Derivatives and Applications

Graphene has attracted tremendous research interest in recent years, owing to its exceptional properties. The scaled-up and reliable production of graphene derivatives, such as graphene oxide (GO) and reduced graphene oxide (rGO), offers a wide range of possibilities to synthesize graphene-based functional materials for various applications. This critical review presents and discusses the current development of graphene-based composites. After introduction of the synthesis methods for graphene and its derivatives as well as their properties, we focus on the description of various methods to synthesize graphene-based composites, especially those with functional polymers and inorganic nanostructures. Particular emphasis is placed on strategies for the optimization of composite properties. Lastly, the advantages of graphene-based composites in applications such as the Li-ion batteries, supercapacitors, fuel cells, photovoltaic devices, photocatalysis, as well as Raman enhancement are described (279 references).

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Graphene-based composites

Graphene oxide: preparation, functionalization, and electrochemical applications.

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

Graphene, a two-dimensional, single-layer sheet of sp(2) hybridized carbon atoms, has attracted tremendous attention and research interest, owing to its exceptional physical properties, such as high electronic conductivity, good thermal stability, and excellent mechanical strength. Other forms of graphene-related materials, including graphene oxide, reduced graphene oxide, and exfoliated graphite, have been reliably produced in large scale. The promising properties together with the ease of processibility and functionalization make graphene-based materials ideal candidates for incorporation into a variety of functional materials. Importantly, graphene and its derivatives have been explored in a wide range of applications, such as electronic and photonic devices, clean energy, and sensors. In this review, after a general introduction to graphene and its derivatives, the synthesis, characterization, properties, and applications of graphene-based materials are discussed.

Graphene-Based Materials: Synthesis, Characterization, Properties, and Applications

A series of titanium dioxide and graphene sheets (GSs) composites were synthesized with a sol–gel method using tetrabutyl titanate and graphite oxide (GO) as the starting materials. The obtained TiO2/GSs photocatalysts are characterized by X-ray diffraction, N2 adsorption analysis, Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy. The photocatalytic activity of the as-prepared samples was evaluated by hydrogen evolution from water photo-splitting under UV-vis illumination. The influence of GSs content and calcinations atmosphere on the photocatalytic activity was also investigated. The results show that both GSs content and the calcinations atmosphere can affect the photocatalytic activity of the obtained composites.

Graphene/TiO2 nanocomposites: synthesis, characterization and application in hydrogen evolution from water photocatalytic splitting

Novel nanocomposite films, based on graphene oxide (GO) and TiO2 nanotube arrays, were synthesized by assembling GO on the surface of self-organized TiO2 nanotube arrays through a simple impregnation method. The composite films were characterized with field emission scanning electron microscopy, X-ray diffraction, Raman spectroscopy and UV–vis diffuse reflectance spectroscopy. The photoelectrochemical properties of the composite nanotube arrays were investigated under visible light illumination. Remarkably enhanced visible light photoelectrochemical response was observed for the GO decorated TiO2 nanotube composite electrode compared with pristine TiO2 nanotube arrays. The sensitizing effect of GO on the photoelectrochemical response of the TiO2 nanotube arrays was demonstrated and about 15 times enhanced maximum photoconversion efficiency was obtained with the presence of GO. An enhanced photocatalytic activity of the TiO2 nanotube arrays towards the degradation of methyl blue was also demonstrated after modification with GO. The results presented here demonstrate GO to be efficient for the improved utilization of visible light for TiO2 nanotube arrays.

Graphene oxide modified TiO2 nanotube arrays: enhanced visible light photoelectrochemical properties

This paper described the preparation, characterization, and electrochemical properties of a graphene-ZrO2 nanocomposite (GZN) and its application for both the enrichment and detection of methyl parathion (MP). GZN was fabricated using electrochemical deposition and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), which showed the successful formation of nanocomposites. Due to the strong affinity to the phosphoric group and the fast electron-transfer kinetics of GZN, both the extraction and electrochemical detection of organophosphorus (OP) agents at the same GZN modified electrochemical sensor was possible. The combination of solid-phase extraction and stripping voltammetric analysis allowed fast, sensitive, and selective determination of MP in garlic samples. The stripping response was highly linear over the MP concentrations ranging from 0.5 ng mL−1 to 100 ng mL−1, with a detection limit of 0.1 ng mL−1. This new nanocomposite-based electrochemical sensor provides an opportunity to develop a field-deployable, sensitive, and quantitative method for monitoring exposure to OPs.

One-step electrochemical deposition of a graphene-ZrO2 nanocomposite: Preparation, characterization and application for detection of organophosphorus agents

Preparing high-quality graphene through reduction of graphene oxide (GO) by oxalic acid is demonstrated in this paper. Transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectrometry, X-ray diffraction and Raman spectrometry were taken to confirm the reduction of GO and the formation of graphene under these mild conditions. Thermogravimetric analysis and conductivity measurements further testify the excellent thermal stability and conductivity of the obtained graphene. A possible mechanism for the reduction process was also proposed. Furthermore, a Pt–graphene composite was fabricated on a glassy carbon electrode and excellent electrocatalytic activity towards methanol oxidation was observed. With advantages of low toxicity, simple purification process and high quality of the product, oxalic acid provides a feasible route to prepare graphene from GO under mild conditions, thus facilitating the use of graphene-based materials for large-scale applications.

Xiaoyan Zhang

Papers

Graphene/TiO2 nanocomposites: synthesis, characterization and application in hydrogen evolution from water photocatalytic splitting

Graphene oxide modified TiO2 nanotube arrays: enhanced visible light photoelectrochemical properties

One-step electrochemical deposition of a graphene-ZrO2 nanocomposite: Preparation, characterization and application for detection of organophosphorus agents

Synthesis of graphene nanosheets via oxalic acid-induced chemical reduction of exfoliated graphite oxide

Thermal formation of silicon-doped TiO2 thin films with enhanced visible light photoelectrochemical response