A Direct Hybridization between Isocharged Nanosheets of Layered Metal Oxide and Graphene through a Surface‐Modification Assembly Process

An efficient and universal method to directly hybridize isocharged nanosheets of layered metal oxide and reduced graphene oxide (rGO) is developed on the basis of the surface modification and an electrostatically driven assembly process. On the basis of this synthetic method, the CoO₂–rGO nanocomposite can be synthesized with exfoliated CoO₂ and rGO nanosheets, and transformed into CoO–CoO₂–rGO nanocomposites with excellent electrode performance for lithium‐ion batteries. Also, this surface‐modification assembly route is successfully applied for the synthesis of another mesoporous TiO₂–rGO nanocomposite. This result provides clear evidence for the usefulness of the present method as a universal way of hybridizing isocharged anionic nanosheets of inorganic solids and graphene.     

Photocatalytic Oxidation Based on Modified Titanium Dioxide with Reduced Graphene Oxide and CdSe/CdS as Nanohybrid Materials

Photocatalytic activity of TiO₂ nanoparticles in the visible light region was enhanced. TiO₂–CdSe and TiO₂–CdSe/CdS nanohybrids were supported on the reduced graphene oxide. These nanohybrid materials were applied as photocatalyst toward oxidation of aromatic alcohols under a mild condition and the molecular oxygen as oxidant. A plausible mechanism for the photocatalytic oxidation was also proposed. Desired nanohybrids were obtained via in situ fixation of CdSe/CdS on the surface of nanosheets of reduced graphene oxide (rGO). Finally, it was modified by TiO₂ sol nanoparticles through a hydrothermal method. The obtained nanomaterials, were characterized by SEM, TEM imaging, XRD, EDAX, DRS and XPS analyses. The size of nanohybrids materials were distributed mostly in a narrow range of 50–65 and 60–75 nm for TiO₂–rGO–CdSe and TiO₂–rGO–CdSe/CdS, respectively. These photocatalysts showed high catalytic activity under visible light irradiation in a short reaction time and even higher selectivity rather than UV irradiation. The yield of catalytic oxidation increased at least 25–30% for TiO₂–CdSe/CdS on rGO, which could be related to its higher light sensitivity and lower energy band gap. The photocatalysts were recycled and reused 8 times without significant loss of their activities due to their stability under visible light.     

Doping of TiO2–GO and TiO2–rGO with Noble Metals: Synthesis,Characterization and Photocatalytic Performance for Azo Dye Discoloration

The nanocomposites of titania coupled with graphene oxide (GO) and reduced graphene oxide (rGO), respectively, were prepared by homogeneous hydrolysis with urea. Graphene was obtained by effect of high‐intensity cavitation field on natural graphite in the presence of strong aprotic solvents in pressurized ultrasonic reactor. The morphology of TiO₂–GO and TiO₂–rGO composites was assessed by scanning electron microscopy and atomic force microscopy. The nitrogen adsorption–desorption was used for determination of surface area (BET) and porosity. Raman and IR spectroscopy were used for qualitative analysis and diffuse reflectance spectroscopy was employed to estimate band‐gap energies. Further enhancement of the photocatalytic activity was attained by codoping of composites with noble metals—Au, Pd and Pt. The photocatalytic activity of TiO₂–GO and TiO₂–rGO were assessed by photocatalytic decomposition of Orange II dye in an aqueous slurry under UV and visible light irradiation. The photocatalytic activity of noble metals codoped samples was determined with decomposition of Reactive Black 5 azo dye.     

Bimetallic NiCo Functional Graphene: An Efficient Catalyst for Hydrogen‐Storage Properties of MgH2

Bimetallic NiCo functional graphene (NiCo/rGO) was synthesized by a facile one‐pot method. During the coreduction process, the as‐synthesized ultrafine NiCo nanoparticles (NPs), with a typical size of 4–6 nm, were uniformly anchored onto the surface of reduced graphene oxide (rGO). The NiCo bimetal‐supported graphene was found to be more efficient than their single metals. Synergetic catalysis of NiCo NPs and rGO was confirmed, which can significantly improve the hydrogen‐storage properties of MgH₂. The apparent activation energy (E_a) of the MgH₂? NiCo/rGO sample decreases to 105 kJ mol^?1, which is 40.7 % lower than that of pure MgH₂. More importantly, the as‐prepared MgH₂? NiCo/rGO sample can absorb 5.5 and 6.1 wt % hydrogen within 100 and 350 s, respectively, at 300 °C under 0.9 MPa H₂ pressure. Further cyclic kinetics investigation indicates that MgH₂? NiCo/rGO nanocomposites have excellent cycle stability.     

Enhancing Hematite Photoanode Activity for Water Oxidation by Incorporation of Reduced Graphene Oxide

Two effective methods to prepare reduced graphene oxide (rGO)/hematite nanostructured photoanodes and their photoelectrochemical characterization towards water splitting reactions are presented. First, graphene oxide (GO) is reduced to rGO using hydrazine in a basic solution containing tetrabutylammonium hydroxide (TBAOH), and then deposited over the nanostructured hematite photoanodes previously treated at 750 °C for 30 min. The second method follows the deposition of a paste containing a mixture of hematite nanoparticles and rGO sheets by the doctor‐blade method, varying the rGO concentration. Since hematite suffers from low electron mobility, a low absorption coefficient, high recombination rates and slow reaction kinetics, the incorporation of rGO in the hematite can overcome such limitations due to graphene's exceptional properties. Using the first method, the rGO incorporation results in a photocurrent density increase from 0.56 to 0.82 mA cm^?2 at 1.23 V_RHE. Our results indicate that the rGO incorporation in the hematite photoanodes shows a positive effect in the reduction of the electron–hole recombination rate.     

Manganese Oxide Nanoparticles/Reduced Graphene Oxide as Novel Electrochemical Platform for Immobilization of FAD and its Application as Highly Sensitive Persulfate Sensor

In this study, manganese oxide nanoparticles/reduced graphene oxide(MnOxNPs/rGO) was used as support for strong immobilization of flavin adenine dinucleotide(FAD). A thin film of rGO cast on the electrode surface, followed by performing electrodeposition of MnOxNPs at applied constant potential of +1.4 V vs. Ag/AgCl for 200 s. Finally, FAD was electrodeposited onto the rGO/MnOxNPs film by potential cycling between 1.0 to ?1.0 V in solution containing 1 mg ml^?1 FAD. Electrochemical properties and catalytic activity of GCE/rGO‐MnOxNPs/FAD toward persulfate (S₂O₈^2?) reduction was investigated. Under optimized condition, the concentration calibration range, detection limit, and sensitivity were 0.1 μM–2 mM, 90 nM and 125.8 nA/μM, respectively, using hydrodynamic amperometry technique.     

Complementary combinative strategy of defect engineering and graphene coupling for efficient energy-functional materials

The synergetic combination of defect engineering and graphene coupling enables to develop an effective way of exploring efficient bifunctional electrocatalyst/electrode materials. Defect-engineered amorphous MoO₂-reduced graphene oxide (rGO) nanohybrid was synthesized by soft-chemical reduction of K₂MoO₄ in graphene oxide colloids. Mo K-edge X-ray absorption spectroscopy clearly demonstrates the rutile-type local atomic structure of amorphous MoO₂ with significant oxygen vacancies and intimate electronic coupling with rGO. The defect-introduced MoO₂-rGO nanohybrid shows excellent bifunctionality as electrocatalyst for hydrogen evolution reaction and electrode for sodium-ion batteries, which are superior to those of crystalline MoO₂-rGO homologue. The beneficial effect of simultaneous defect control and rGO coupling can be ascribed to the provision of oxygen vacancies acting as active sites, the increase of electrical conductivity, and the improvement of reaction kinetics.     

Core–Shell LiFePO4/Carbon‐Coated Reduced Graphene Oxide Hybrids for High‐Power Lithium‐Ion Battery Cathodes

Core‐shell carbon‐coated LiFePO₄ nanoparticles were hybridized with reduced graphene (rGO) for high‐power lithium‐ion battery cathodes. Spontaneous aggregation of hydrophobic graphene in aqueous solutions during the formation of composite materials was precluded by employing hydrophilic graphene oxide (GO) as starting templates. The fabrication of true nanoscale carbon‐coated LiFePO₄‐rGO (LFP/C‐rGO) hybrids were ascribed to three factors: 1) In‐situ polymerization of polypyrrole for constrained nanoparticle synthesis of LiFePO₄, 2) enhanced dispersion of conducting 2D networks endowed by colloidal stability of GO, and 3) intimate contact between active materials and rGO. The importance of conducting template dispersion was demonstrated by contrasting LFP/C‐rGO hybrids with LFP/C‐rGO composites in which agglomerated rGO solution was used as the starting templates. The fabricated hybrid cathodes showed superior rate capability and cyclability with rates from 0.1 to 60 C. This study demonstrated the synergistic combination of nanosizing with efficient conducting templates to afford facile Li⁺ ion and electron transport for high power applications.     

In Situ Reduction of Graphene Oxide in Waterborne Polyurethane Matrix and the Healing Behavior of Nanocomposites by Multiple Ways

Smart polymers are advanced materials that continue to attract scientific community. In this work, self‐healing waterborne polyurethane/reduced graphene oxide (SHWPU/rGO) nanocomposites were prepared by in situ chemical reduction of graphene oxide in a waterborne polyurethane matrix. The chemical structure, morphology, thermal stability, mechanical property, and electrical conductivity of the SHWPU/rGO nanocomposites were characterized. The prepared SHWPU/rGO nanocomposites were further treated under heating, microwave radiating, and electrifying conditions to investigate their healing property. The results showed that chemical reduction of graphene oxide was achieved using hydrazine hydrate as a reducing agent and the rGO was well dispersed in the SHWPU matrix. The thermal stability and mechanical properties of SHWPU/rGO nanocomposites were significantly increased. The SHWPU/rGO nanocomposites can be healed via different methods including heating, microwave radiating, and electrifying. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 202–209     

Microwave-Assisted Synthesis of ZnO–rGO Core–Shell Nanorod Hybrids with Photo- and Electro-Catalytic Activity

The unique two-dimensional structure and surface chemistry of reduced graphene oxide (rGO) along with its high electrical conductivity can be exploited to modify the electrochemical properties of ZnO nanoparticles (NPs). ZnO–rGO nanohybrids can be engineered in a simple new two-step synthesis, which is both fast and energy-efficient. The resulting hybrid materials show excellent electrocatalytic and photocatalytic activity. The structure and composition of the as-prepared bare ZnO nanorods (NRs) and the ZnO–rGO hybrids have been extensively characterised and the optical properties subsequently studied by UV/Vis spectroscopy and photoluminescence (PL) spectroscopy (including decay lifetime measurements). The photocatalytic degradation of Rhodamine B (RhB) dye is enhanced using the ZnO–rGO hybrids as compared to bare ZnO NRs. Furthermore, potentiometry comparing ZnO and ZnO–rGO electrodes reveals a featureless capacitive background for an Ar-saturated solution whereas for an O₂-saturated solution a well-defined redox peak was observed using both electrodes. The change in reduction potential and significant increase in current density demonstrates that the hybrid core–shell NRs possess remarkable electrocatalytic activity for the oxygen reduction reaction (ORR) as compared to NRs of ZnO alone.     

Comparison of photocatalytic and antibacterial activities of allotropes of graphene doped Sm2O3 nanocomposites: Optical,thermal, and structural studies

This study mainly focuses on the synthesis of two allotropes of graphene, graphene oxide (GO) and reduced graphene oxide (rGO), by the modified Hummers' method and chemical reduction method, respectively. Sm₂O₃/GO and Sm₂O₃/rGO nanocomposites were further synthesized in the presence of the cationic surfactant CTAB via the sol–gel method followed by the reflux method. Synthesized nanocomposites were subjected to characterization by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and UV–Visible spectroscopy to explore structural, thermal, optical, and photocatalytic properties. Characteristic FTIR peaks were observed in nanocomposites, and the bond length of the Sm-O bond was calculated. The Coats-Redfern method was employed to calculate the kinetics and thermodynamic parameters. Hexagonal crystallite shapes of Sm₂O₃/GO and Sm₂O₃/rGO nanocomposites with 11.8 and 13.13 nm crystallite sizes and 3.9 and 2.5 eV optical band gaps were observed. The photocatalytic efficiency of Sm₂O₃/GO and Sm₂O₃/rGO nanocomposites was assessed against the degradation of methylene blue in the presence of sunlight, and its degradation was confirmed through FTIR. The antimicrobial activities were also performed against the bacterial strains Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus.     

Reduced graphene oxide-porous In2O3 nanocubes hybrid nanocomposites for room-temperature NH3 sensing

Metal oxide semiconductors (MOS)-reduced graphene oxide (rGO) nanocomposites have attracted great attention for room-temperature gas sensing applications. The development of novel sensing materials is the key issue for the effective detection of ammoniagas at room temperature. In the present work, the novel reduced graphene oxide (rGO)-In₂O₃ nanocubes hybrid materials have been prepared via a simple electrostatic self-assembly strategy. Characterization results exhibit that the intimate interfacial contact between In₂O₃ nanocubes and the rGO sheets are achieved. Particularly, the as-prepared rGO/In₂O₃ nanocomposites displayed high sensitivity, fast response and excellent selectivity towards ammonia (NH₃) at room-temperature, which clearly uncovers the merit of structural design and rational integration with rGO sheets. The superior gas sensing performance of the rGO/In₂O₃ nanocomposites can be attributed to the synergetic effects of rGO sheets and porous In₂O₃ nanocubes. The reported synthesis offers a general approach to rGO/MOS-based semiconductor composites for room-temperature gas sensing applications.     

Free‐standing and Flexible MoS2/rGO Paper Electrode for Amperometric Detection of Folic Acid

The development of flexible electrodes is of considerable current interest because of the increasing demand for modern electronics, portable medical products, and compact devices. We report a new type of flexible electrochemical sensor fabricated by integrating graphene and MoS₂ nanosheets. A highly flexible and free‐standing conductive MoS₂ nanosheets/reduced graphene oxide (MoS₂/rGO) paper was prepared by a two‐step process: vacuum filtration and chemical reduction treatment. The MoS₂/graphene oxide (MoS₂/GO) paper obtained by a simple filtration method was transformed into MoS₂/rGO paper after a chemical reduction process. The obtained MoS₂/rGO paper was characterized by scanning electron microscopy, X‐ray diffraction spectroscopy, X‐ray photoelectron spectroscopy, Raman spectroscopy, electrochemical impedance spectroscopy. The electrochemical behavior of folic acid (FA) on MoS₂/rGO paper electrode was investigated by cyclic voltammetry and amperometry. Electrochemical experiments indicated that flexible MoS₂/rGO composite paper electrode exhibited excellent electrocatalytic activity toward the FA, which can be attributed to excellent electrical conductivity and high specific surface area of the MoS₂/rGO paper. The resulting biosensor showed highly sensitive amperometric response to FA with a wide linear range.     

A Vanadium(V) Oxide Nanorod Promoted Platinum/Reduced Graphene Oxide Electrocatalyst for Alcohol Oxidation under Acidic Conditions

A Pt‐V₂O₅/rGO ternary hybrid electrocatalyst was designed by using active vanadium(V) oxide (V₂O₅) nanorods and reduced graphene oxide (rGO) components. The V₂O₅ nanorods were synthesized by a simple polyol‐assisted solvothermal method and were incorporated uniformly onto rGO sheets by intermittent microwave heating. Subsequently, Pt nanoparticles (2–3 nm in size) were deposited over the V₂O₅/rGO composite by the conventional polyol reflux method. The electrocatalytic performance of the Pt‐V₂O₅/rGO ternary hybrid and bare Pt/rGO catalysts towards the oxidation of simple alcohols was evaluated in acidic media. The ternary hybrid catalyst exhibited higher electrocatalytic activity than bare Pt/rGO and also showed good stability. The higher electrocatalytic activity of the Pt‐V₂O₅/rGO ternary hybrid was attributed to a synergistic effect among the Pt, V₂O₅, and rGO components. In addition, oxygen‐containing species, such as OH groups, were generated on V₂O₅ at lower potentials. These groups were able to scavenge intermediate species such as CO_ads on the Pt surfaces and helped to regenerate the active sites on the Pt surface more effectively for the routine alcohol oxidation reaction.     

Synthesis of Ultrastable Ag Nanoplates/Polyethylenimine–Reduced Graphene Oxide and Its Application as a Versatile Electrochemical Sensor

Investigations on Ag nanostructures/reduced graphene oxide composites have been frequently reported, yet the morphology control of those loaded Ag nanocrystals is still challenging. We herein develop a facile method to grow triangular Ag nanoplates (AgP) on polyethylenimine‐modified reduced graphene oxide (AgP/PEI‐rGO). The AgP/PEI‐rGO hybrids show unexpected high stability against chloride ions (Cl^?) and hydrogen peroxide (H₂O₂), which is possibly due to the strong interaction between surface Ag atoms with the amine groups of PEI. In the chronoamperometry measurements for detecting H₂O₂, N₂H₄, and NaNO₂, the AgP/PEI‐rGO hybrid shows very wide linear ranges (usually 10^?6–10^?2 mol L^?1 for H₂O₂, N₂H₄, and NaNO₂) and low detection limits (down to ≈1×10^?7 mol L^?1), which demonstrate the promising electrochemical sensor applications of these metal/graphene hybrids with well‐defined morphologies and facets. In addition, this strategy could be extended to the deposition of other noble metals on rGO with controlled morphologies.     

Nanocomposites of Sulfonic Polyaniline Nanoarrays on Graphene Nanosheets with an Improved Supercapacitor Performance

A new nanocomposite, poly(aniline‐co‐diphenylamine‐4‐sulfonic acid)/graphene (PANISP/rGO), was prepared by means of an in situ oxidation copolymerization of aniline (ANI) with diphenylamine‐4‐sulfonic acid (SP) in the presence of graphene oxide, followed by the chemical reduction of graphene oxide using hydrazine hydrate as a reductant. The morphology and structure of PANISP/rGO were characterized by field‐emission (FE) SEM, TEM, X‐ray photoelectron spectroscopy (XPS), Raman, FTIR, and UV/Vis spectra. The electrochemical performance was evaluated by cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy. The PANISP/rGO nanocomposite showed a nanosized structure, with sulfonic polyaniline nanoarrays coated homogeneously on the surface of graphene nanosheets. This special structure of the nanocomposite also facilitates the enhancement of the electrochemical performance of the electrodes. The PANISP/rGO nanocomposite exhibits a specific supercapacitance up to 1170 F g^?1 at the current density of 0.5 A g^?1. The as‐prepared electrodes show excellent supercapacitive performance because of the synergistic effects between graphene and the sulfonic polyaniline copolymer chains.     

Application of a highly sensitive magnetic solid phase extraction for phytochemical compounds in medicinal plant and biological fluids by ultra‐high performance liquid chromatography coupled with quadrupole time‐of‐flight tandem mass spectrometry

A highly sensitive method using reduced graphene oxide with iron oxide (rGO/Fe₃O₄) as the sorbent in magnetic SPE has been developed for the purification of five anthraquinones (emodin, rhein, aloeemodin, physcion, and chrysophanol) in rhubarb and rat urine by ultra‐HPLC coupled with quadrupole TOF/MS. The extraction was accomplished by adding trace amount rGO/Fe₃O₄ suspension to 200 mL of aqueous mixture, and the excellent adsorption capacity of the nanoparticles was fully demonstrated in this procedure. Under the optimized conditions, the calibration curves were linear in the concentration range of 0.05–27.77 ng/mL with correlation coefficients varying from 0.9902 to 0.9978. The LODs ranged from 0.28 to 58.99 pg/mL. The experimental results indicated that the proposed method was feasible for the analysis of anthraquinones in rhubarb and urine samples.     

n‐Type Reduced Graphene Oxide Field‐Effect Transistors (FETs) from Photoactive Metal Oxides

Graphene is of considerable interest as a next‐generation semiconductor material to serve as a possible substitute for silicon. For real device applications with complete circuits, effective n‐type graphene field effect transistors (FETs) capable of operating even under atmospheric conditions are necessary. In this study, we investigated n‐type reduced graphene oxide (rGO) FETs of photoactive metal oxides, such as TiO₂ and ZnO. These metal oxide doped FETs showed slight n‐type electric properties without irradiation. Under UV light these photoactive materials readily generated electrons and holes, and the generated electrons easily transferred to graphene channels. As a result, the graphene FET showed strong n‐type electric behavior and its drain current was increased. These n‐doping effects showed saturation curves and slowly returned back to their original state in darkness. Finally, the n‐type rGO FET was also highly stable in air due to the use of highly resistant metal oxides and robust graphene as a channel.     

Monodisperse CuPt alloy nanoparticles assembled on reduced graphene oxide as catalysts in the transfer hydrogenation of various functional organic groups

We present herein a new nanocatalyst, namely binary CuPt alloy nanoparticles (NPs) supported on reduced graphene oxide (CuPt‐rGO), as a highly active heterogeneous catalyst for the transfer hydrogenation (TH) protocol that is demonstrated to be applicable over the reduction of various unsaturated organic compounds (olefins, aldehydes/ketones and nitroarenes) in aqueous solutions at room temperature. CuPt alloy NPs were synthesized by the co‐reduction of metal (II) acetylacetonates by borane‐tert‐butylamine (BTB) complex in hot oleylamine (OAm) solution and then assembled on reduced graphene oxide (rGO) via ultrasonic‐assisted liquid phase self‐assembly method. The structure of yielded CuPt NPs and CuPt‐rGO nanocatalyst were characterized by TEM, XRD and ICP‐MS. The activity of Cu₇Pt₃‐rGO nanocatalysts were then tested for the THs that were conducted in a commercially available high‐pressure tube using water as sole solvent and ammonia borane as a hydrogen donor at room temperature. The presented catalytic TH protocol was successfully applied over nitroarenes, olefines and aldehydes/ketones, and all the tested compounds were converted to corresponding reduction products with the yields reaching up to 99% under ambient conditions. Moreover, the Cu₇Pt₃‐rGO nanocatalyst was also reusable in the TH by providing 99% yield after five consecutive runs in TH of nitrobenzene as an example.     

Palladium Nanoparticles Bonded to Two‐Dimensional Iron Oxide Graphene Nanosheets: A Synergistic and Highly Reusable Catalyst for the Tsuji–Trost Reaction in Water and Air

Low cost, high activity and selectivity, convenient separation, and increased reusability are the main requirements for noble‐metal‐nanocatalyst‐catalyzed reactions. Despite tremendous efforts, developing noble‐metal nanocatalysts to meet the above requirements remains a significant challenge. Here we present a general strategy for the preparation of strongly coupled Fe₃O₄ and palladium nanoparticles (PdNPs) to graphene sheets by employing polyethyleneimine as the coupling linker. Transmission electron microscopic images show that Pd and Fe₃O₄ nanoparticles are highly dispersed on the graphene surface, and the mean particle size of Pd is around 3 nm. This nanocatalyst exhibits synergistic catalysis by Pd nanoparticles supported on reduced graphene oxide (rGO) and a tertiary amine of polyethyleneimine (Pd/Fe₃O₄/PEI/rGO) for the Tsuji–Trost reaction in water and air. For example, the reaction of ethyl acetoacetate with allyl ethyl carbonate afforded the allylated product in more than 99 % isolated yield, and the turnover frequency reached 2200 h^?1. The yield of allylated products was 66 % for Pd/rGO without polyethyleneimine. The catalyst could be readily recycled by a magnet and reused more than 30 times without appreciable loss of activity. In addition, only about 7.5 % of Pd species leached off after 20 cycles, thus rendering this catalyst safer for the environment.