Facile hydrothermal synthesis and optical limiting properties of TiO2-reduced graphene oxide nanocomposites

TiO₂/reduced graphene oxide (RGO) nanocomposites Gx (RGO titania nanocomposite, x grams tetrabutyl titanate per 0.03 g RGO, x = 0.25, 0.50, 1.00) were prepared by a hydrothermal method: graphene oxide was reduced to RGO in a 2:1 water:ethanol mixture in the presence of varying quantities of tetrabutyl titanate, which deposited as TiO₂ on the RGO sheets. The nanocomposites were characterized by a combination of Fourier transform infrared spectroscopy, diffuse reflectance ultraviolet–visible spectroscopy, photoluminescence spectroscopy, Raman spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy studies. The nanocomposite G0.25 exhibits enhanced nonlinear optical properties compared to its individual components, which is ascribed to a combination of mechanisms. The role of defects and electron/energy transfer in the optical limiting performance of G0.25 was clarified with the help of Raman and photoluminescence spectroscopies. Intensity-dependent switching between reverse saturable absorption and saturable absorption behavior was observed with the G0.50 nanocomposite.     

One-pot synthesis of CdS sensitized TiO2 decorated reduced graphene oxide nanosheets for the hydrolysis of ammonia-borane and the effective removal of organic pollutant from water

A hybrid material of reduced graphene oxide (RGO) sheets decorated with CdS-TiO₂ NPs was prepared through a facile one-pot hydrothermal method. The assembly of CdS-TiO₂ nanoparticles (NPs) on RGO sheets was in-situ produced. As-synthesized nanocomposites were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy disperse X-ray spectrum (EDS), fourier transform infrared spectroscopy (FTIR), and photoluminescence spectroscopy (PL). The obtained nanocomposites exhibited a good photocatalytic activity for the visible-light-induced decomposition of methylene blue (MB) dye and hydrolysis of ammonia borane. The results showed that by incorporation of CdS and TiO₂ NPs on graphene oxide sheets the photocatalytic efficiency was enhanced. The significant enhancement in the photocatalytic activity of CdS-TiO₂/RGO nanocomposites under visible light irradiation can be ascribed to the effect of CdS by acting as electron traps in TiO₂ band gap. Reduced graphene oxide worked as the adsorbent, electron acceptor and a photo-sensitizer to efficiently enhance the dye photo decomposition. Such nanocomposite photocatalyst might find potential application in a wide range of fields, including hydrogen energy generation, air purification, and wastewater treatment.     

Sonochemical synthesis and characterization of amine‐modified graphene/conducting polymer nanocomposites

The objective of this work is to modify graphene and study the effect of modification of graphene in thermal and electrical properties of graphene/polypyrrole and graphene/polyaniline nanocomposites. The amine functionalization of graphene was confirmed by Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. The nanocomposites were prepared by insitu oxidative polymerization method using ammonium persulfate as oxidant. Field emission scanning electron microscopy and high‐resolution transmission electron microscopy were used to study the morphology of the nanocomposites which indicates toward the better dispersion of modified graphene within the polymer matrices as compared to unmodified composites. The modification of graphene played an important role in the noticeable improvements in electrical conductivity of the prepared composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Melt crystallization of poly(ethylene terephthalate): Comparing addition of graphene vs. carbon nanotubes

Poly(ethylene terephthalate) (PET)-based nanocomposites with graphene or multi-wall carbon nanotubes (MWCNT) were prepared by melt mixing. Aspect ratio, A_f, and interparticle distance, λ, of graphene in the nanocomposites were obtained from melt rheology and transmission electron microscopy respectively. λ of PET/graphene nanocomposites was much smaller than λ in PET/MWCNT. For PET/graphene with highest A_f, λ became <1 μm at more than 0.5 wt% graphene. Non-isothermal crystallization behavior from the melt was investigated by differential scanning calorimetry. The crystallization temperatures suggest that the nucleation effect of graphene was stronger than that of MWCNT. The half crystallization time of PET/graphene became longer than PET/MWCNT with increasing graphene loading, suggesting that confinement by graphene suppressed the crystal growth rate. XRD analysis indicated that smaller crystals formed in PET/graphene than in PET/MWCNT. From Raman spectroscopy, the π–π interaction between PET and graphene was stronger than that between PET and MWCNT. This stronger interaction in PET/graphene appears to result in formation of crystals with higher perfection.     

Chemically modified graphene oxide/polybenzimidazobenzophenanthroline nanocomposites with improved electrical conductivity

Graphene/polybenzimidazobenzophenanthroline nanocomposites were prepared through the liquid-phase exfoliation of graphene oxide (GO) and reduced graphene oxide (rGO) in methanesulfonic acid with subsequent solution mixing. Various chemical and combined chemical-thermal methods were examined to be effective for producing rGO with highly graphitic structure and excellent electrical conductivity. Raman and X-ray photoelectron spectroscopy showed higher degree of reduction of the GO with the combined chemical-thermal method compared to other chemical reduction processes. Structural characterization of the nanocomposites by X-ray diffraction, scanning electron microscopy and transmission electron microscopy showed good exfoliation and dispersion of both GO and rGO fillers in the polymer matrix. The thermogravimetric analysis found that the nanocomposites with rGO have higher onset and maximum weight loss temperatures than those with GO. Compared with the pure polymer, the electrical conductivity of the nanocomposites containing 10 wt% GO and GO reduced by the combined chemical-thermal treatment showed a remarkable increase by four and seven orders of magnitude, respectively. Long-term in-situ thermal reduction was performed to further improve the conductivities of the nanocomposites.     

Preparation and characterization of CdS and CdS/polyacrylonitrile nanocomposites by γ‐irradiation and emulsion polymerization

CdS and CdS/polyacrylonitrile (PAN) nanocomposites were prepared by γ‐irradiation and emulsion polymerization. The CdS and CdS/PAN nanocomposites were characterized by powder X‐ray diffraction, infrared spectroscopy, Fourier transform Raman spectroscopy, transmission electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, and thermal analysis (thermogravimetric analysis/dynamic thermal analysis). In photoluminescence spectroscopy analysis, the maximum peak of CdS/PAN nanocomposites prepared by γ‐irradiation and emulsion polymerization was at about 485 nm, whereas the maximum peak of CdS nanocomposites was at about 460 nm. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2335–2342, 2004     

Synthesis and characterization of layer-aligned poly(vinyl alcohol)/graphene nanocomposites

Layer-aligned poly(vinyl alcohol)/graphene nanocomposites in the form of films are prepared by reducing graphite oxide in the polymer matrix in a simple solution processing. X-ray diffractions, scanning electron microscopy, Fourier-transform infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis are used to study the structure and properties of these nanocomposites. The results indicate that graphene is dispersed on a molecular scale and aligned in the poly(vinyl alcohol) (PVA) matrix and there exists strong interfacial interactions between both components mainly by hydrogen bonding, which are responsible for the change of the structures and properties of the PVA/graphene nanocomposites such as the increase in T_g and the decrease in the level of crystallization.     

Synthesis and characterization of polyurethane/reduced graphene oxide composite deposited on steel

There has been an ongoing effort by the coatings industry to improve surface properties in order to increase corrosion and wear resistances, as well as other material properties. In this work, we report a methodology for producing nanocomposite films of polyurethane and graphene oxide and polyurethane and reduced graphene oxide. The coatings were applied on steel. The nanocomposites coatings were characterized by optical microscopy, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, contact angle measurements, and electrochemical impedance spectroscopy. Corrosion tests reveal that the use of reduced graphene oxide increases corrosion resistance when compared with the use of graphene oxide as filler.     

Influence of graphene-based compounds on the mechanical toughness and thermal stability of polypropylene

A study of the improvement of the mechanical and thermal properties of nanocomposites prepared with polypropylene (PP) and different graphene samples [graphene oxide (GO), reduced GO (RGO), and commercial graphene (G)] is presented. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy characterization were applied to the graphene samples. The nanocomposites were characterized by thermogravimetric analysis, XRD, differential scanning calorimetry, transmission electron microscopy (TEM), tensile, and impact resistance tests. PP/RGO nanocomposites showed significant improvement in mechanical and thermal properties. Sample PP/RGO-0.75 resulted in an increment in Young's modulus (51%), tensile strength (24%), and elongation at break (15%). This is attributed to a good dispersion state, a higher crystallinity percentage, and a good interfacial adhesion between PP and RGO. Sample PP/RGO-0.50 exhibited an increase of 197 °C in the temperature at which a loss in weight of 5% occurred, compared to that for pure PP. The height of stacked layers calculated by XRD measurements was similar to the value observed by TEM. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48258.     

Enhanced photoluminescence and photocatalytic activity of ZnO-ZnWO4 nanocomposites synthesized by a precipitation method

Zinc oxide (ZnO)-zinc tungstate (ZnWO₄) nanocomposites ((ZnO)_1−x(ZnWO₄)_x, x=0, 0.1, 0.2, 0.3, 0.5, 0.7, 0.9, 1) were prepared using a convenient precipitation method. The structural, morphological and optical properties of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), Ultraviolet-visible (UV–vis) absorbance measurements and photoluminescence (PL) spectroscopy. The photocatalytic performance of the samples was evaluated utilizing methyl orange (MO) under UV light irradiation. The SEM and HR-TEM analyses revealed that an intimate contact was possibly formed at the ZnO-ZnWO₄ interface. The PL spectra of the composites of ZnO and ZnWO₄ exhibited a stronger blue-green emission band in the range of 400–540 nm under 272 nm radiations compared with that of single phase ZnWO₄. And their photocatalytic performances were also elevated significantly when the value of the x was 0.1, 0.2, 0.3 and 0.5, almost twice as much to that of ZnO. The superior fluorescent and photocatalytic performances might be ascribed to the suitable energy levels related to the intimate contact between two different semiconductors, which are beneficial to the interfacial charge transfer between the conduction and valence bands.     

Enhanced interfacial interaction for effective reinforcement of poly(vinyl alcohol) nanocomposites at low loading of graphene

The graphene/poly(vinyl alcohol) (PVA) nancomposites with homogeneous dispersion of the nanosheet and enhanced nanofiller–matrix interfacial interaction were fabricated via water blending partially reduced graphene oxide and PVA. The nanocomposites were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetry. The graphene nanosheets were fully exfoliated in the PVA matrix and a new covalent linkage was formed between graphene and PVA matrix. Uncommon to conventional method, the enhanced interfacial adhesion resulted from covalent interaction and hydrogen bondings between graphene and PVA backbone. The mechanical and thermal properties of the nanocomposites were significantly improved at low graphene loadings. An 116% increase in tensile strength and a 19 °C improvement of onset thermal degradation temperature were achieved by the addition of only 0.8 wt% graphene.     

Mg Doped Copper Ferrite with Polyaniline Matrix Core–Shell Ternary Nanocomposite for Electromagnetic Interference Shielding

Electromagnetic interference shielding materials based on polyaniline/Mg_0.6Cu_0.4Fe₂O₄ ternary nanocomposites were prepared using in situ chemical oxidation polymerization method. The crystalline, structural and morphology analyses of the synthesized material were studied by X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FTIR) and high resolution transmission electron microscopy (HR-TEM). The nanocomposites were examined by UV–Vis spectroscopy (UV–Vis), four probe resistivity, vibrating sample magnetometer (VSM), thermal gravimetric analysis (TGA) and vector network analyzer (VNA) for the optical, electrical, thermal, magnetic and shielding properties. XRD, FTIR and UV–Vis spectra analyses confirmed the formation of ferrites and polyaniline phases in the composites. The particle sizes of Mg_0.6Cu_0.4Fe₂O₄ are lying in the range of 15–40 nm verified by the HR-TEM. VSM study proved the presence of magnetic nanoparticles in the polyaniline matrix. TGA results revealed that the mixing of ferrites particles in polyaniline has improved its thermal stability. The nanocomposites are showing the significant shielding effectiveness value up to 32.8 dB in the X-band frequency range which makes them potential shielding material for electromagnetic interference shielding applications due to lightweight, good processability and low cost.     

Eco-friendly one-pot synthesis of gold decorated reduced graphene oxide using beer as a reducing agent

A facile, eco-friendly and economical approach was demonstrated for the synthesis of gold-decorated reduced graphene oxide nanocomposites (rGO–Au_nano) using beer as a reducing agent via a hydrothermal method. The phenolic compounds of beer play a key role in the reduction of graphene oxide and the gold precursor. The obtained rGO–Au_nano was characterized by X-ray diffraction, UV–vis absorption spectroscopy, electron microscopy, atomic force microscopy and the electrochemical impedance spectroscopy. Analysis revealed that the electron-transfer resistance of rGO–Au_nano/GCE was much lower than that of the GCE and GO/GCE. The proposed nanocomposites have excellent electrocatalytical properties for catalytic reduction of O₂ in solution.     

Unique photocatalytic oxidation reactivity and selectivity of TiO₂-graphene nanocomposites

Mesoporous TiO(2)-graphene nanocomposites are fabricated in high yield via two successive steps: (1) hydrothermal hydrolysis of Ti(SO(4))(2) in an acidic suspension of graphene oxide to gain TiO(2)-graphene oxide nanocomposites; (2) UV-assisted photocatalytic reduction of graphene oxide to get the TiO(2)-graphene nanocomposites. The anatase TiO(2) nanocrystals with a crystallite size of 10-20 nm are densely packed and supported on meshy graphene sheets with close interfacial contacts, which is confirmed by transmission electron microscopy (TEM) together with Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Although a low graphene loading (0-2 wt%) slightly influences the textural properties (including the crystallite size, specific surface areas, and pore volume etc.), the incorporation of graphene in TiO(2)-graphene nanocomposites greatly increases the adsorption capacity towards azo dyes such as MO and MB, which is possibly associated with their unique surface properties. Significantly, the incorporated graphene exerts combined effects on the adsorption and charge transfer dynamics in TiO(2)-graphene nanocomposites, which together endow them with good photocatalytic reactivity and tunable photocatalytic selectivity in decomposing MO and MB in aqueous solution.     

Large scale synthesis of N-doped multi-layered graphene sheets by simple arc-discharge method

N-doped multi-layered graphene sheets were synthesized in large scale by the method of direct current arc-discharge between pure graphite rods. For the use of NH₃ as one of the buffer gas, the multi-layered graphene sheets were doped with N without the addition of other nitrogen source. The product so obtained has been characterized by transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy and element analysis. The graphene sheets are mainly of 2-6 layers and their sizes are about 100-200 nm. The multi-layered graphene sheets can be purified by a simple heat treatment process. The content of N atoms on the multi-layered graphene sheets can be tuned by simply changing the proportion of NH₃ in the atmosphere.     

Physical and electrochemical characterization of nanocomposites formed from polythiophene and titaniumdioxide

A simple method for covering titanium dioxide particles with a polythiophene film by chemical preparation was developed. The resulting nanocomposites consisted of a titanium dioxide core with a grain size of 25-250 nm and a polythiophene shell between 1 and 2 nm thickness. The composites were characterized by scanning electron microscopy, thermogravimetry, X-ray photoelectron spectroscopy, cyclovoltammetry, impedance spectroscopy and photocurrent spectroscopy. The content of polythiophene in the composite (determined by thermogravimetry), was between 2% and 5%. Disk-like electrodes were prepared by pressing and then characterized by various electrochemical methods. A reversible redox potential of the polythiophene of +1.0 V (NHE) was determined by cyclic voltammetry. The reduced form of polythiophene behaved as a p-type semiconductor so that the composite with n-type TiO₂ contained the properties of a p/n-junction. In the photocurrent spectra (depending on the applied potential), the characteristic anodic peaks of the TiO₂ at λ=320 nm and cathodic peaks of the polythiophene around λ=500 nm were found. A new cathodic peak observed at 370 nm was explained as a new feature of the pn interface.     

Pulsed laser ablation in liquid synthesis of ZnO/TiO2 nanocomposite catalyst with enhanced photovoltaic and photocatalytic performance

In this work, we employed an impurity-free nanoparticle synthesis technique, known as pulsed laser ablation in liquid (PLAL), to integrate titanium dioxide nanoparticles (TiO₂ NPs) into zinc oxide nanorods (ZnO NRs) with varying relative proportions. The main objective of this integration was to enhance the charge carrier separation of photo-generated electron hole pairs during solar irradiation. For the synthesis process, an Nd:YAG laser at 532 nm wavelength was applied as an ablation source, along with deionized water as a solvent medium in which the precursor materials were dispersed prior to laser irradiation. The nanocomposites were characterized by X-ray diffraction (XRD), UV–vis absorption and in-situ Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HR-TEM) and field emission scanning electron microscopy (FE-SEM). The synthesized nanocomposites were primarily utilised in two applications: firstly, as a catalyst in the degradation of methyl orange (MO) and secondly, as photo-anode in dye sensitized solar cell (DSSC). Our research has demonstrated that optimal performance was obtained for the nanocomposite containing 10% and 90% (by weight) TiO₂ NPs and ZnO respectively, which we define as the ideal nanocomposite. Relative to pure ZnO, the photo-conversion efficiency of the ideal composite was improved substantially by 63.73%, whilst the photo-degradation rate was enhanced by 3 fold. The oxidation state and the microstructural of the segregated ideal nanocomposite confirms that oxygen vacancy defects were created when perfect surface integration occurs between TiO₂ and ZnO. Nonetheless, we believe that the performance enhancement is predominantly due to the excellent charge carrier separation and fast interfacial electron flow in this nanocomposite.     

Graphene-gold nanostructure composites fabricated by electrodeposition and their electrocatalytic activity toward the oxygen reduction and glucose oxidation

A gold nanoparticles (Au NPs)-graphene nanocomposite (Au-graphene nanocomposite) was prepared by electrochemically depositing Au NPs on the surface of graphene sheets, and characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray powder diffraction (XRD), and electrochemical methods. The morphology and size of the Au NPs could be easily controlled by adjusting the electrodeposition time and the concentration of precursor (AuCl₄⁻). The electrocatalytic activities of the nanocomposites toward oxygen reduction and glucose oxidation were investigated by cyclic voltammetry. The results indicated that the nanocomposites had a higher catalytic activity than the Au NPs or graphene alone, indicating the synergistic effect of graphene and Au NPs. Therefore, this study has provided a general route for fabrication of graphene-based noble metal nanomaterials composite, which could be potential utility to fuel cells and bioelectroanalytical chemistry.     

TiO2 nanofibers assembled on graphene-silver platform as a visible-light photo and bio-active nanostructure

The heterogeneous titanium oxide-reduced graphene oxide-silver (TiO₂/RGO/Ag) nanocomposites were successfully prepared by incorporation of two dimensional (2D) RGO nanosheets and spherical silver nanoparticles (NPs) into the 1D TiO₂ nanofibers. The novel TiO₂/RGO/Ag nanocomposites were synthesized by loading TiO₂ nanofibers, prepared via electrospinning technique, on the RGO/Ag platform. The resulting nanocomposites have been characterized using various techniques containing transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and ultra-violet-visible (UV–vis) spectroscopy. Microscopic studies clearly verified the existence of TiO₂ nanofibers with Ag NPs on the surface of RGO sheet and formation of TiO₂/RGO/Ag nanocomposites. Moreover, the results of UV–vis spectroscopy demonstrated that TiO₂/RGO/Ag nanocomposites extended the light absorption spectrum toward the visible region and significantly enhanced the visible-light photocatalytic performance of the prepared samples on degradation of rhodamine B (Rh. B) as a model dye. It was found that, incorporation of 50 µl RGO/Ag into the TiO₂ nanofibers lead to a maximum photocatalytic performance. Also, the improvement of the inactivation of Escherichia coli (E. coli) bacteria under visible-light irradiation was revealed by introduction of RGO/Ag into the TiO₂ matrix. The significant enhancement in the photo and bio-activity of TiO₂/RGO/Ag nanocomposites under visible-light irradiation can be ascribed to the RGO/Ag content by acting as electron traps in TiO₂ band gap.     

Synthesis and characterizations of Ni-NiO nanoparticles on PDDA-modified graphene for oxygen reduction reaction

We are presenting our recent research results about the Ni-NiO nanoparticles on poly-(diallyldimethylammonium chloride)-modified graphene sheet (Ni-NiO/PDDA-G) nanocomposites prepared by the hydrothermal method at 90°C for 24 h. The Ni-NiO nanoparticles on PDDA-modified graphene sheets are measured by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and selected area electron diffraction (SAED) pattern for exploring the structural evidence to apply in the electrochemical catalysts. The size of Ni-NiO nanoparticles is around 5 nm based on TEM observations. The X-ray diffraction (XRD) results show the Ni in the (012), (110), (110), (200), and (220) crystalline orientations, respectively. Moreover, the crystalline peaks of NiO are found in (111) and (220). The thermal gravimetric analysis (TGA) result represents the loading content of the Ni metal which is about 34.82 wt%. The electron spectroscopy for chemical analysis/X-ray photoelectron spectroscopy (ESCA/XPS) reveals the Ni⁰ to Ni^II ratio in metal phase. The electrochemical studies with Ni-NiO/PDDA-G in 0.5 M aqueous H₂SO₄ were studied for oxygen reduction reaction (ORR).