Covalently functionalized graphene by thiourea for enhancing H2-evolution performance of TiO2 photocatalyst

Graphene as a well-known electron cocatalyst can enhance the hydrogen-production performance of photocatalysts due to its excellent conductivity. For highly efficient graphene-modified TiO₂ photocatalyst, besides the speedy electron transfer via graphene, it is significant to raise the interfacial hydrogen-generation reaction rate on the graphene surface. In this paper, thiourea (TU) can covalently functionalize graphene and act as effective H⁺-adsorbed active sites to improve the hydrogen-production efficiency of graphene-modified TiO₂ (TiO₂/rGO-TU). The TiO₂/rGO-TU sample was successfully prepared by a facile nucleophilic substitution reaction between the thiol (-SH) of thiourea and carboxyl (-COOH) of graphene. The TiO₂/rGO-TU could possess the maximum H₂-generation rate of 241.83 μmol h^?1 g^?1, which was 2.33 and 6.60 times greater than that of TiO₂/rGO and TiO₂, respectively. The enhanced photocatalytic activity of TiO₂/rGO-TU can be ascribed to the synergistic effect of graphene and thiourea, namely, the graphene functions as a cocatalyst to capture the photoexcited electrons of TiO₂ and the thiourea acts as effectual H⁺-adsorbed active sites to promote interfacial hydrogen generation. This study presents a feasible strategy for developing grephene-based photocatalysts for prospective applications in the hydrogen-production field.     

High-density oxygen-enriched graphene hydrogels for symmetric supercapacitors with ultrahigh gravimetric and volumetric performance

The contradiction between the porous structure and density of graphene materials makes it unable to meet the dual requirements of the next generation supercapacitors for gravimetric capacitance and volumetric capacitance. Herein, we successfully synthesized high-density oxygen-enriched graphene hydrogels (HOGHs) by a one-step hydrothermal method using high concentration graphene oxide (GO) solution and trometamol as precursors. The as-prepared HOGHs samples present a dense 3D network structure and moderate specific surface areas, which leads to a high packing density. In addition, the HOGHs samples also contain abundant oxygen-containing functional groups and some nitrogen-containing functional groups. These heteroatomic functional groups can provide pseudocapacitance for the electrode materials. Therefore, the HOGH-140 based symmetric supercapacitor shows ultrahigh gravimetric and volumetric specific capacitance (325.7 F g⁻¹, 377.8 F cm⁻³), excellent rate performance and cycling stability. Simultaneously, the symmetric binder-free supercapacitor exhibits high gravimetric specific energy density (11.3 Wh kg⁻¹) and volumetric specific energy density (13.1 Wh L⁻¹) in 6 M KOH, respectively. These outstanding properties make the material have a good application prospect in the field of compact energy storage devices.     

Influence of 2D rGO nanosheets on the properties of OPC paste

In this experimental study, the effects of 2D reduced graphene oxide (rGO) sheets on the properties of Portland cement paste in comparison to popularly reviewed nanomaterials like aluminium oxide nanopowder (n-Al₂O₃) and colloidal silicon dioxide nanoparticles (n-SiO₂) were investigated. The addition of 0.02% rGO sheets by weight of cement increased the 7 and 28 days flexural strength up to 70% and 23% respectively when compared to control paste. Moreover, its incorporation substantially decreased the sizes of pores/voids in the paste, even compared to the other nanomaterials, as characterized by Mercury Intrusion Porosimetry (MIP) and 3D X-ray Computed Tomography (CT) aided with image analysis technique. The assessment of Portlandite content by Thermo-gravimetric Analysis did not indicate major differences between the pastes, with the exception of the paste incorporating nano-silica. Microstructural analysis by Fourier Transform Infrared Spectroscopy, X-ray diffraction and Scanning Electron Microscopy did not reveal any major differences between the control paste and the pastes incorporating nanomaterials. The overall results suggest that the performance of rGO was better in comparison to other two nanomaterials, despite the significantly lower amounts that were used in the paste.     

Facile synthesis of three‐dimensional graphene networks by magnetron sputtering for supercapacitor electrode

Three‐dimensional (3D) graphene network deposition on Ni foam without any conductive agents and polymer binders was successfully synthesized by radio frequency magnetron sputtering at low temperature. The direct and close contact between graphene and Ni foam is beneficial to the enhanced conductivity of the electrode, as well as the improvement of ion diffusion/transport into the electrode. As a result, the 3D graphene network deposition on Ni foam electrode delivered a high specific capacitance of 122.0 F g⁻¹ at 1.0 A g⁻¹ and excellent cycle stability with capacitance retention of 99.0% after 1000 charge–discharge cycles. The work shows a new way to facile synthesis of 3D graphene network for various applications in the future. Copyright © 2016 John Wiley & Sons, Ltd.     

Bridging TiO2 nanoparticles using graphene for use in dye‐sensitized solar cells

The use of graphene to bridge TiO₂ particles in the photoanode of dye‐sensitized solar cell for reduced electrical resistance has been investigated. The difficulty in dispersing graphene in TiO₂ paste was overcome by first dispersing graphene oxide (GO) into the TiO₂ paste. The GO was then reduced to graphene after the sintering of TiO₂. This is shown through transmission electron microscopy and X‐ray photoelectron spectroscopy analysis. Cell performance was evaluated using a solar simulator, incident photon to electron conversion efficiency, intensity modulated photocurrent/photovoltage spectroscopy under blue light, and electrochemical impedance spectroscopy. Depending on the amount of graphene in the photoanode, the cell performance was enhanced to different degrees. A maximum increase of 11.4% in the cell efficiency has been obtained. In particular, the inclusion of graphene has reduced the electron diffusion time by as much as 23.4%, i.e. from 4.74 to 3.63 ms and increased the electron lifetime by as much as 42.3%, i.e. from 19.58 to 27.85 ms. Copyright © 2014 John Wiley & Sons, Ltd.     

Spinel CoFe2O4 supported by three dimensional graphene as high-performance bi-functional electrocatalysts for oxygen reduction and evolution reaction

Spinel CoFe₂O₄ supported on three dimensional graphene (3DG) is prepared by hydrothermal reaction, which is denoted as CoFe₂O₄/3DG. The 3DG is prepared by the templated method, where coal tar pitch (CTP) and MgO are used as the carbon source and the template, respectively. The microstructure and composition of the resultant have been investigated by X-ray diffraction as well as X-ray photoelectron spectroscopy indicating the formation of spinel CoFe₂O₄ and composite of CoFe₂O₄/3DG. The multilayer structure of 3DG and CoFe₂O₄/3DG is also examined by the Raman spectra. Electrochemically, CoFe₂O₄/3DG shows high-performance half-wave potential is 0.80 V vs. RHE in O₂-saturated 0.1 M KOH, which is compared to 20 wt% Pt/C. When evaluated for OER activity, CoFe₂O₄/3DG obtains a low overpotential 1.63 V vs. RHE (at j = 10 mA cm⁻²), which is 180 mV better than 20 wt% Pt/C. Moreover, it possesses excellent durability superior to 20 wt% Pt/C.     

Monodisperse rutheniumcopper alloy nanoparticles decorated on reduced graphene oxide for dehydrogenation of DMAB

In this study, we report a superior dehydrogenation catalyst for dimethylamine borane, which exhibited one of the best catalytic activities. The newly formed catalyst system contains well dispersed ruthenium-copper nanomaterials on reduced graphene oxide (3.86 ± 0.47 nm), which was prepared by using the ultrasonic double reduction technique. The characterization of monodisperse ruthenium-copper alloy nanoparticles was performed using some advanced analytical methods such as TEM, HRTEM, XPS, Raman spectroscopic analysis. The experiments results revealed that the monodisperse ruthenium-copper alloy catalyst (RuCu@rGO) has one of the highest catalytic activity compared to previous studies, having a high turnover frequency value (256.70 h⁻¹). The detailed kinetic parameters such as activation energy, enthalpy, and entropy values were also calculated for the dehydrogenation of dimethylamine borane at room temperature. Also, the results showed that the monodisperse RuCu@rGO catalyst has high durability and reusability as retained its 81% initial catalytic activity even after 4th runs for the dehydrogenation of dimethylamine borane.     

A remarkable three-component RuO2-MnCo2O4/rGO nanocatalyst towards methanol electrooxidation

A three-part nano-catalyst including ruthenium oxide, manganese cobalt oxide, and reduced graphene oxide nanosheet in form of RuO₂-MnCo₂O₄/rGO is synthesized by one-step hydrothermal synthesis. The material is placed on a glassy carbon electrode (GCE) for electrochemical studies. The ability of these nano-catalysts in the oxidation process of methanol in an alkaline medium for usage in direct methanol fuel cells (DMFC) was examined with electrochemical tests of cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS). The effect of the addition of rGO to the nanocatalyst structure in the methanol oxidation reaction (MOR) process was investigated. We introduced the RuO₂-MnCo₂O₄/rGO as a nanocatalyst with excellent cyclic stability of 97% after 5000 cycles in the MOR process. Besides, the study of the Tafel plots and the effect of temperature and scan rate in the MOR process showed that RuO₂-MnCo₂O₄/rGO nanocatalyst has better electrochemical properties than MnCo₂O₄ and RuO₂-MnCo₂O₄. This high electrocatalytic activity could be related to the synergistic effect of placement of metal oxides of ruthenium, manganese, and cobalt near each other and putting them on rGO, which enhances conductivity and surface area and improve electron transfer. The decrease in the resistance against charge transfer and the increment in the anodic current density illustrated that the reaction rate is enhanced at higher temperature. Thus RuO₂-MnCo₂O₄/rGO shows robust stability and superior performance for MOR.