The size and dispersion effect of modified graphene oxide sheets on the photocatalytic H2 generation activity of TiO2 nanorods

Nano graphene oxide (NGO) was produced by further refluxing graphene oxide (GO) sheets in HNO₃, and carboxylic acid functionalized graphene oxide (GO–COOH) was obtained by a simple etherification reaction between GO and chloroacetic acid. The GO, GO–COOH and NGO sheets are combined with TiO₂ nanorods by a two-phase assembling method, and confirmed by transmission electronic microscopy. The GO–TiO₂, GO–COOH–TiO₂ and NGO–TiO₂ composites are used in a comparative study of photocatalytic H₂ generation activity under UV light irradiation. The H₂ generation rate of TiO₂ nanorods was slightly increased from 15 to 30 mL h⁻¹ g⁻¹ by replacing oleic acid ligands with hydrophilic dopamine, and significantly increased to 105 mL h⁻¹ g⁻¹ after combining with GO sheets. The further comparative study shows that GO–COOH–TiO₂ composite has higher H₂ generation rate of 180 mL h⁻¹ g⁻¹ than that of GO–TiO₂ and NGO–TiO₂ composites.     

An easy one-step electrosynthesis of graphene/polyaniline composites and electrochemical capacitor

An easy electrochemical technique is proposed to prepare electrochemically reduced graphene oxide (ERGO)/polyaniline (PANI) composites in a single step. The technique uses a two-electrode cell in which a separator soaked with an acid solution is sandwiched between graphene oxide (GO)/aniline films deposited on conductive substrates and an alternating voltage was applied to the electrodes. Successful preparations of ERGO/PANI composites were evidenced by characterizations due to UV–vis-NIR, FT-IR, XPS, XRD, and SEM measurements with free-standing films of ERGO/PANI obtained easily by disassembling the two-electrode cells. The ERGO/PANI films exhibited a high mechanical stability, flexibility, and conductivity (68 S cm⁻¹ for the composite film containing 80% ERGO) with nanostructured PANI particles (smaller than 20 nm) embedded homogeneously between the ERGO layers. The two-electrode cells acted as electrochemical capacitors (ECs) after a sufficient voltage cycling and exhibited relatively large specific capacitances (195–243 F g⁻¹ at a scan rate of 100 mV s⁻¹) with an excellent cycle life (retention of 83% capacitance after 20,000 charge–discharge cycles). Influences of the GO/aniline ratio, the sort of electrolytes, and the weight of the composite on the energy storage characteristics of ECs comprising the ERGO/PANI composites were also studied.     

Porous nickel disulfide/reduced graphene oxide nanohybrids with improved electrocatalytic performance for hydrogen evolution

Single porous nickel disulfide (NiS₂) nanoballs and nanohybrids of NiS₂ with reduced graphene oxide (NiS₂/rGO) were successfully prepared by a simple hydrothermal process in the absence or presence of graphene oxide. NiS₂/rGO nanocomposites exhibit remarkable electrocatalytic performance for hydrogen evolution from water splitting due to the plentiful active sites in the porous NiS₂, the improved conductivity and the positive synergetic effect between NiS₂ and rGO. The nanocomposites displayed superior activity for the hydrogen evolution reaction (10 mA cm^− 2 vs. − 200 mV, Tafel slope of 52 mV dec^− 1) and an excellent electrocatalytic stability.     

Preparation of graphene film decorated TiO2 nano-tube array photoelectrode and its enhanced visible light photocatalytic mechanism

Graphene film decorated TiO₂ nano-tube array (GF/TiO₂ NTA) photoelectrodes were prepared through anodization, followed by electrodeposition strategy. Morphologies and structures of the resulting GF/TiO₂ NTA samples were characterized by scanning electrons microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. In addition, the optical and photoelectrochemical properties were investigated through UV–visible light diffuse reflection spectroscopy, photocurrent response and Mott–Schottky analysis. Furthermore, the photodecomposition performances were investigated through yield of hydroxyl radicals and photocatalytic (PC) degradation of methyl blue (MB) under visible light irradiation. It was found that GF/TiO₂ NTA photoelectrode exhibited intense light absorption both in UV light and visible region, higher transient photoinduced current of 0.107 mA cm⁻² and charge carrier concentration of 0.84 × 10¹⁹ cm⁻³, as well as effective PC performance of 65.9% for the degradation of MB. Furthermore, contribution of several reactive species to the PC efficiency of GF/TiO₂ NTA photoelectrode was distinguished. Moreover, the enhanced visible light PC mechanism was proposed and confirmed in detail.     

Electrochemically reduced graphene oxide sheets for use in high performance supercapacitors

Graphene oxide (GO) was reduced by a rapid, effective and eco-friendly electrochemical method of repetitive cathodic cyclic potential cycling, without using any reducing reagents. The electrochemically reduced graphene oxide (ERGO) was characterized by UV–vis, EIS and zeta-potential measurements. Most of the oxygen functional groups in ERGO were successfully removed resulting in smaller charge transfer resistance. However, some electrochemically stable residuals still remained, enabling ERGO to facilitate electrolyte penetration and pseudocapacitance. Since ERGO was readily stabilized by cathodic potential cycling, it exhibited an outstanding stability in cycle life, nearly with no capacitive loss from the second cycle on. A specific capacitance of 223.6 F g⁻¹ was achieved at 5 mV s⁻¹, which makes the ERGO a competitive material for electrochemical energy storage.     

High quality graphene sheets from graphene oxide by hot-pressing

We report a simple and effective route to convert graphene oxide sheets to good quality graphene sheets using hot pressing. The reduced graphene oxide sheets obtained from graphene oxide by low temperature thermal exfoliation are annealed at 1500 °C and 40 MPa uniaxial pressures for 5 min in vacuum. No appreciable oxygen content was observed from X-ray photoelectron spectroscopy and no D peak was detected in the Raman spectrum. The graphene sheets produced had a much higher electron mobility (1000 cm² V⁻¹ S⁻¹) than other chemically modified graphenes.     

Flexible free-standing graphene–TiO2 hybrid paper for use as lithium ion battery anode materials

Flexible and binder-free graphene–TiO₂ paper was prepared by a simple route. A unique 3-D nano-structure was achieved with nano-sized TiO₂ intercalated between graphene layers as pillars, significantly increasing the Li-ion insertion/extraction rate. At a current rate of 2 Ag⁻¹, the specific capacity can reach 122 mAhg⁻¹ after 100 charge/discharge cycles. More remarkably, the flexible graphene/TiO₂ hybrid paper shows an excellent stability when the rates decrease from 4 Ag⁻¹ back to 200 mAg⁻¹ with the retained capacity of 175 mAhg⁻¹.     

Iron-doped TiO2 nanotubes with high photocatalytic activity under visible light synthesized by an ultrasonic-assisted sol-hydrothermal method

A series of iron-doped anatase TiO₂ nanotubes (Fe/TiO₂ NTs) catalysts with iron concentrations ranging from 0.88 to 7.00 wt% were prepared by an ultrasonic-assisted sol-hydrothermal process. The structures and the properties of the fabricated Fe/TiO₂ NTs were characterized in detail and photocatalytic activity was examined using a reactive brilliant red X-3B aqueous solution as pollutant under visible light. The lengths of the NTs were determined to range from 20 nm to 100 nm. The incorporation of the iron ions (Fe³⁺) into the TiO₂ nanotubes shifted the photon absorbing zone from the ultraviolet (UV) to the visible wavelengths, reducing the band gap energy from 3.2 to 2.75 eV. The photocatalytic activity of the Fe/TiO₂ NTs was 2–4 times higher than the values measured for the pure TiO₂ nanotubes.     

Photocatalytic hydrogen production by Au–MxOy (MAg,Cu, Ni) catalysts supported on TiO2

Au–M_xO_y (MAg, Cu, Ni) nanoparticles supported on TiO₂–P25 were prepared by the deposition–precipitation method and were evaluated for the photocatalytic water splitting reaction for hydrogen production, using a mixture of water–methanol (1:1). The combinations of Au–Cu₂O/TiO₂ and Au–NiO/TiO₂ effectively increased the hydrogen production (2064 and 1636 μmol·h^− 1·g^− 1) obtained by Au/TiO₂ (1204 μmol·h^− 1·g^− 1). The higher photoactivities achieved by Au–Cu₂O and Au–NiO nanoparticles deposited on TiO₂ were attributed to an enhancement of the electron charge transfer from TiO₂ to the Au–M_xO_y systems and the effect of surface plasmon resonance of gold nanoparticles.     

Enhancing polymer/graphene oxide gas barrier film properties by introducing new crystals

A transparent, gas barrier film comprised of poly(vinyl alcohol) (PVA) and graphene oxide (GO) is synthesized through combined methods of solution blending and isothermal recrystallization. The recrystallized PVA/GO film with only 0.07 vol% GO gives an O₂ transmission rate <0.005 cc m⁻² day⁻¹ and an O₂ permeability <5.0 × 10⁻²⁰ cm³ cm cm⁻² Pa⁻¹ s⁻¹; hence, it is far superior to other blend polymer/inorganic composites. The excellent O₂ barrier properties are attributed to a unique hybrid of PVA crystals and GO sheets. PVA crystals form around the GO during isothermal recrystallization, indicating that a GO sheet can act as a nucleating agent. The newly formed PVA crystals fill in the spaces between the GO sheets, and together they become ultra-large impermeable regions, which can prevent the passage of O₂. The hybrid film has potential applications in flexible electronics, pharmaceuticals, and food packaging.     

Preparation and characterization of transparent indium- doped TiO2 films deposited by MOCVD

Titanium dioxide (TiO₂) films doped with different indium (In) concentrations have been prepared on SrTiO₃ (STO) substrates by high vacuum metalorganic chemical vapor deposition (MOCVD). X-ray diffraction (XRD) analyses revealed the TiO₂ films doped with low In concentrations to be [001] oriented anatase phase and the films with high In concentrations to present polycrystalline structures. The 1.8% In-doped TiO₂ film exhibited the best electrical conductivity properties with the lowest resistivity of 8.68×10⁻² Ω cm, a Hall mobility of 10.9 cm² V⁻¹ s⁻¹ and a carrier concentration of 6.5×10¹⁸ cm⁻³. The films showed excellent transparency with average transmittances of over 85% in the visible range.     

Improved activity of a graphene–TiO2 hybrid electrode in an electrochemical supercapacitor

We present a simple and fast approach for the synthesis of a graphene–TiO₂ hybrid nanostructure using a microwave-assisted technique. The microstructure, composition, and morphology were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, Raman microscopy, X-ray photoelectron spectroscopy, and field-emission scanning electron microscopy. The electrochemical properties were evaluated using cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge–discharge tests. Structural analysis revealed a homogeneous distribution of nanosized TiO₂ particles on graphene nanosheets. The material exhibited a high specific capacitance of 165 F g⁻¹ at a scan rate of 5 mV s⁻¹ in 1 M Na₂SO₄ electrolyte solution. Theenhanced supercapacitance property of these materials could be ascribed to the increased conductivity of TiO₂ and better utilization of graphene. Moreover, the material exhibited long-term cycle stability, retaining ∼90% specific capacitance after 5000 cycles, which suggests that it has potential as an electrode material for high-performance electrochemical supercapacitors.     

Synthesis and electrochemical performance of reduced graphene oxide/maghemite composite anode for lithium ion batteries

Reduced graphene oxide (rGO) tethered with maghemite (γ-Fe₂O₃) was synthesized using a novel modified sol–gel process, where sodium dodecylbenzenesulfonate was introduced into the suspension to prevent the undesirable formation of an iron oxide 3D network. Thus, nearly monodispersed and homogeneously distributed γ-Fe₂O₃ magnetic nanoparticles could be obtained on surface of graphene sheets. The utilized thermal treatment process did not require a reducing agent for reduction of graphene oxide. The morphology and structure of the composites were investigated using various characterization techniques. As-prepared rGO/Fe₂O₃ composites were utilized as anodes for half lithium ion cells. The 40 wt.%-rGO/Fe₂O₃ composite exhibited high reversible capacity of 690 mA h g⁻¹ at current density of 500 mA g⁻¹ and good stability for over 100 cycles, in contrast with that of the pure-Fe₂O₃ nanoparticles which demonstrated rapid degradation to 224 mA h g⁻¹ after 50 cycles. Furthermore, the composite showed good rate capability of 280 mA h g⁻¹ at 10C (∼10,000 mA g⁻¹). These characteristics could be mainly attributed to both the use of an effective binder, poly(acrylic acid) (PAA), and the specific hybrid structures that prevent agglomeration of nanoparticles and provide buffering spaces needed for volume changes of nanoparticles during insertion/extraction of Li ions.     

Monolithic Fe2O3/graphene hybrid for highly efficient lithium storage and arsenic removal

We fabricated a monolithic Fe₂O₃/graphene hybrid directly by hydrothermal reaction of ferrous oxalate dihydrate and graphene oxide without using a reducing agent. The reduced graphene oxide formed an interconnected network structure that can be used as a support for homogeneous distribution of active Fe₂O₃ nanoparticles. The graphene network and the pore channels in the hybrid facilitate fast electron transfer and ion transport. This hybrid can be directly used as a free-standing anode for lithium ion batteries, which simplifies the fabrication procedure of electrodes, and also exhibited a high capacity of 1062 mA h g⁻¹ at 100 mA g⁻¹, high rate capability and excellent cyclic stability over 100 cycles. Furthermore, as a self-supported adsorbent, it provides a new idea on loading active materials to the suitable substrate, which can be used as a promising material for water purification due to its easy collection and excellent capability in removing As(V) from water. The results demonstrate the promising applications of bulk reduced assembly of graphene with functional metal oxides, which will be helpful for future development of graphene-based multifunctional materials.     

Enhanced rate capability of nanostructured three-dimensional graphene/Ni3S2 composite for supercapacitor electrode

Three-dimensional graphene/Ni₃S₂ (3DG/Ni₃S₂) composite electrodes were produced by a facile two-step synthesis route involving chemical vapor deposition (CVD) growth of graphene foam and in situ hydrothermal synthesis of Ni₃S₂. The porous structure of the prepared 3DG is ideal for use as a scaffold for fabricating monolithic composite electrodes. The relative content of Ni₃S₂ initially increased and then decreased with increasing hydrothermal reaction time. The basal surface of the electrode was completely covered after 6 h of hydrothermal reaction. The size of the Ni₃S₂ microspheres also increased with increasing hydrothermal reaction time. The composite electrodes exhibited good specific capacitance (11.529 F cm⁻² at 2 mA cm⁻², i.e., 2611.9 F g⁻¹ at 5 mV s⁻¹) and cyclability (retention of 88.97% capacitance after 1000 charge/discharge cycles at 20 mA cm⁻²). These results are attributed to the fact that the uniform distribution of the Ni₃S₂ microspheres increased the specific surface area of the electrode and facilitated electron transfer and ion diffusion. The 3D multiplexed and highly conductive pathways provided by the defect-free graphene foam also ensured rapid charge transfer and conduction to improve the rate capability of the supercapacitors.     

Bio-inspired cross-linking with borate for enhancing gas-barrier properties of poly(vinyl alcohol)/graphene oxide composite films

The demand for flexible and transparent barrier films in industries has been increasing. Learning from nature, borate ions were used to cross-link poly(vinyl alcohol) (PVA) and graphene oxide (GO) to produce flexible, transparent high-barrier composite films with a bio-inspired structure. PVA/GO films with only 0.1 wt% GO and 1 wt% cross-linker exhibited an O₂ transmission rate <0.005 cc m⁻² day⁻¹, an O₂ permeability <5.0 × 10⁻²⁰ cm³ cm cm⁻² Pa⁻¹ s⁻¹, and a transmittance at 550 nm >85%; thus, they can be used for flexible electronics. Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy indicated that the outstanding barrier properties are attributed to the formation of chemical cross-linking involving borate ions, GO sheets, and PVA, similar to the borate cross-links in high-order plants. Comparing our experimental data with the Cussler model, we found that the effective aspect ratio was significantly increased after cross-linking, suggesting that cross-linking networks connected GO with each other to form ultra-large impermeable regions. A feasible green technique, with potential for commercial production of barrier films for flexible electronics was presented.     

Synthesis of highly dispersed titanium dioxide nanoclusters on reduced graphene oxide for increased glucose sensing

Highly dispersed titanium dioxide nanocluster (TDN) was synthesized on reduced graphene oxide (RGO) in a toluene–water system under microwave irradiation. The prepared RGO–TDN hybrids were used to modify glassy carbon electrode for loading glucose oxidase. The fabricated glucose biosensor exhibits excellent performance for glucose sensing including low work potential (−0.7 V), high sensitivity (35.8 μA mM⁻¹ cm⁻²), low detection limit (4.8 μM), wide linear range from 0.032 to 1.67 mM, small Michaelis–Menten constant (K_m) (0.81 mM), and short response time (10 s).     

Synthesis of ruthenium complex and its application in dye-sensitized solar cells

An amphiphilic bipyridyl ligand, 4,4′-dicarboxy-octyl-2,2′-bipyridine, and its ruthenium(□) complex (termed as S8) were synthesized and characterized by UV/Vis, IR and NMR spectroscopy. The performance of this S8 complex as charge transfer photo-sensitizer in TiO₂-based dye-sensitized solar cells was studied under standard AM 1.5 sunlight and by using an electrolyte consisting of 0.70 M 1,2-dimethyl-3-propyl-imidazolium iodide, 0.10 M LiI, 40 mM iodine and 0.125 M 4-tert-butylpyridine in acetonitrile. Aliphatic chains linking to carboxylate groups of S8 act as an effective electron donor and carboxylate groups act as an effective electron withdrawing between the TiO₂ layer and the carboxylate linking TiO₂ layer leading to increasing of electron density at this interface, which is attributed to increasing efficiency of electron injection to the TiO₂ conduction band from the excited state of dye. The complex, S8, gave a photocurrent density of 13.02 mA/cm², 0.60 V open circuit voltage and 0.69 fill factor yielding 5.36% efficiency. The S8 dye with aliphatic chain improved conversion efficiency of the resulting DSSCs compared with a cell fabricated using the N3 dye.     

Integration of tailored reduced graphene oxide nanosheets and electrospun polyamide-66 nanofabrics for a flexible supercapacitor with high-volume- and high-area-specific capacitance

Nanofiber fabric is firstly introduced to replace common microfiber fabrics as the platform for flexible supercapacitors. Nanofiber and microfiber electrodes can be simply fabricated using a dipping process that impregnates reduced graphene oxide (RGO) nanosheets into electrospun polyamide-66 (PA66) nanofiber and microfiber fabrics. RGO nanosheets are tailored to various sizes and only RGO with a medium diameter of 250–450 nm (denoted as M-RGO) can effectively penetrate the pores of nanofiber fabrics for constructing smooth conductive paths within PA66 nanofiber fabrics. The synergistic effect between suitable sizes of RGO nanosheets and nanofiber fabrics with a high specific area provides a symmetric supercapacitor composed of M-RGO/PA66 nanofiber fabric electrodes with high-volume and high-area specific capacitance (C_S,V and C_S,A, equal to 38.79 F cm⁻³ and 0.931 F cm⁻² at 0.5 A g⁻¹, respectively), which are much larger than that of a symmetric supercapacitor composed of RGO/PA66 microfiber fabric electrodes (8.52 F cm⁻³ and 0.213 F cm⁻² at 0.5 A g⁻¹). The effect of impregnating nanofiber fabrics with suitably sized RGO to promote C_S,V and C_S,A of flexible supercapacitors has been demonstrated.     

Novel one-step preparation of tungsten loaded TiO2 nanotube arrays with enhanced photoelectrocatalytic activity for pollutant degradation and hydrogen production

Highly ordered tungsten doped TiO₂ nanotube arrays (W-TiO₂NTs) were prepared in glycerol/fluoride electrolyte solution containing sodium tungstate via the electrochemical oxidation of a Ti substrate. The resulting arrays were characterized by XRD, SEM, and XPS. The 15 mM W-TiO₂NTs exhibited better photoelectrochemical activity than the TiO₂NTs and W-TiO₂NTs fabricated using other W concentrations under Xe illumination. The W ion was successfully introduced into the TiO₂ crystal lattice in the W^6 + form according to the XPS analysis, which enhanced the photoelectrocatalytic activity of the W-TiO₂NTs, as indicated by the efficient removal of Rhodamine B and the production of hydrogen.