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.     

Thorium adsorption on graphene oxide nanoribbons/manganese dioxide composite material

A functional graphene oxide nanoribbons/manganese dioxide composite material (MnO₂-GONRs) was synthesized by hydrothermal method using graphene oxide nanoribbons (GONRs) as raw material which were formed by longitudinal unzipping of multi-walled carbon nanotubes with KMnO₄ and H₂SO₄. The microstructure of MnO₂-GONRs was characterized by SEM and FT-IR. The various factors affecting the adsorption of Th(IV) in aqueous solution such as pH, solid–liquid ratio, contact time, initial concentration and temperature were investigated by batch static adsorption experiments, and the adsorption mechanism is also discussed. The results showed that MnO₂-GONRs had a good adsorption effect on Th(IV) with a maximum adsorption of 166.11 mg/g.

     

Fabrication of a graphene–cuprous oxide composite

A composite of graphene–cuprous oxide (Cu₂O) was prepared using copper acetate-adsorbed graphene oxide (GO) sheets as precursors. In this composite, in-situ formed Cu₂O particles were derived from the adsorbed copper acetate which attached to graphene sheets and prevented the aggregation of the reduced graphene oxide sheets. The as-synthesized Cu₂O crystals were cube-like particles distributed randomly on the sheets due to the template effect of GO, consequently forming a graphene–Cu₂O cubes composite. A preliminary study on the electrochemical behavior of the graphene–Cu₂O composite used as anode material for lithium ion batteries was carried out.     

氧化石墨烯浓度对还原氧化石墨烯/ZnS电化学性能的影响

以氧化石墨烯(GO)、乙酸锌(Zn(CH₃COO)₂)和硫脲为原料,采用水热法成功制备了还原氧化石墨烯/ZnS(rGO/ZnS)复合材料,并将该材料用作锂离子电池负极。高导电性的 rGO可以为锂离子和电子的传输提供有效的路径,ZnS可以提供较高的理论比容量。rGO/ZnS复合材料在rGO与纳米级高度分散的类球形ZnS颗粒协同作用下展现了较好的嵌锂容量和循环性能。当GO质量浓度为2 mg·mL^-1时制备的rGO/ZnS复合材料的倍率性能最好,循环稳定性最佳。     

Synthesis of graphene oxide nanosheet: A novel glucose sensor based on nickel-graphene oxide composite film

The graphene oxide (GO) nanosheets were produced by chemical conversion of graphite, and were characterized by transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR). An electrochemical sensor based on Ni/graphene (GR) composite film was developed by incorporating Ni²⁺ into the graphene oxide film modified glassy carbon electrode (Ni/GO/GCE) through the electrostatic interactions with negatively charged graphene oxide. The Ni²⁺/graphene modified glassy carbon electrode (Ni/GR/GCE) was prepared by cyclic voltammetric scanning of Ni/GO/GCE in the potential range from ?1.5 to 0.2 V at 50 mV s^?1 for 5 cycles. The electrochemical activity of Ni/GR/GCE was illustrated in 0.10 M NaOH using cyclic voltammetry. The Ni/GR/GCE exhibits the characteristic of improved reversibility and enhanced current responses of the Ni(III)/Ni(II) couple. The introduction of conductive graphene not only greatly facilitates the electron transfer of Ni²⁺, but also dramatically improves the long-term stability of the sensor by providing the electrostatic interactions. Ni/GR/GCE also shows good electrocatalytic activity toward the oxidation of glucose. The Ni/GR/GCE gives a good linear range over 10 to 2700 μM with a detection limit of 5 μM towards the determination of glucose by amperometry. This sensor keeps over 85% activity towards 0.1 mM glucose after being stored in air for a month, respectively. Furthermore, the modified sensor was successfully applied to the sensitive determination of glucose in blood samples.     

A novel nonenzymatic hydrogen peroxide sensor based on MnO2/graphene oxide nanocomposite

A new electrocatalyst, MnO₂/graphene oxide hybrid nanostructure was successfully synthesized for the nonenzymatic detection of H₂O₂. The morphological characterization was examined by scanning electron microscopy and transmission electron microscopy. The MnO₂/graphene oxide based electrodes showed high electrochemical activity for the detection of H₂O₂ in alkaline medium. The nonenzymatic biosensors displayed good performance along with low working potential, high sensitivity, low detection limit, and long-term stability, which could be attributed to the high surface area of graphene oxide providing for the deposition of MnO₂ nanoparticles. These results demonstrate that this new nanocomposite with the high surface area and electrocatalytic activity offers great promise for new class of nanostructured electrode for nonenzymatic biosensor and energy conversion applications.     

Ruthenium-catalyzed asymmetric transfer hydrogenation of ketones in ethanol

A ruthenium catalyst formed in situ by combining [Ru(p-cymene)Cl₂]₂ and an amino acid hydroxy-amide was found to catalyze efficiently the asymmetric reduction of aryl alkyl ketones under transfer hydrogenation conditions using ethanol as the hydrogen donor. The secondary alcohol products were obtained in moderate to good yields and with good to excellent enantioselectivity (up to 97% ee).     

Morphology,structure, and photoactivity of two types of graphene oxide-TiO<Subscript>2</Subscript> composites

Two types of graphene oxide-TiO₂ composites were prepared: one by including graphene oxide flakes in the TiO₂ sol, followed by thermal treatment (GI composite) at 300°C, and the second by including graphene oxide flakes in the calcined (at 500°C) TiO₂ xerogel (GII composite). The composites were characterized by SEM, TEM-EDS, TEM-SADP, STEM-HAADF, HRTEM coupled with FT, XRD, and XPS. Photocatalysis results were fitted to different kinetic models (pseudo-first and pseudo-second kinetics, intraparticle Weber-Morris diffusion, film diffusion, and external mass transfer). The results showed that by introducing graphene oxide flakes in the TiO₂ sol, followed by thermal treatment at 300°C (GI composite), an efficient graphene oxide-TiO₂ catalyst with high specific surface area, heterogeneity, and many graphitized areas can be obtained. Complete crystallization of the composite is not the key issue for the best photoactivity achievement. The rate limiting step in the photocatalytic process is the photooxidation of SA molecules on the TiO₂ surface.     

Preparation and study of bi-supported Ziegler-Natta catalyst with nano graphene oxide and magnesium ethoxide supports for polymerization of polyethylene

In this study, we have reported the preparation of bi-supported Ziegler-Natta catalysts using magnesium ethoxide and graphene oxide as support. The polymerization process was carried out in slurry phase using triisobutylaluminum as a co-catalyst.The XRD analysis of TiCl₄/graphene oxide/Mg(OEt)₂ catalyst demonstrated that the space between the layers of graphene oxide had increased to 0.2 nm.The catalyst was characterized by XPS, BET, BJH, SEM, and TGA. The catalyst activity was studied for various Al/Ti molar ratios, and the catalyst activity was optimum at Al/Ti molar ratio of 315.     

One-step synthesis of Pt nanoparticles/reduced graphene oxide composite with enhanced electrochemical catalytic activity

A one-step electrochemical approach for synthesis of Pt nanoparticles/reduced graphene oxide(Pt/RGO) was demonstrated.Graphene oxide(GO) and chloroplatinic acid were reduced to RGO and Pt nanoparticles(Pt NPs) simultaneously,and Pt/RGO composite was deposited on the fluorine doped SnO 2 glass during the electrochemical reduction.The Pt/RGO composite was characterized by field emission-scanning electron microscopy,Raman spectroscopy and X-ray photoelectron spectroscopy,which confirmed the reduction of GO and chloroplatinic acid and the formation of Pt/RGO composite.In comparison with Pt NPs and RGO electrodes obtained by the same method,results of cyclic voltammetry and electrochemical impedance spectroscopy measurements showed that the composite electrode had higher catalytic activity and charge transfer rate.In addition,the composite electrode had proved to have better performance in DSSCs than the Pt NPs electrode,which showed the potential application in energy conversion.     

Immobilization of In2O3 nanoparticles on the surface of reduced graphene oxide

This communication describes a new method for immobilizing indium oxide nanoparticles (∼20 nm) on the surface of reduced graphene oxide. Dispersion of graphene oxide with added In₂O₃ nanoparticles was treated in supercritical isopropanol, both a reducing agent of graphene oxide and a reaction medium. The resulting nanocomposite was characterized by different methods of physical and chemical analysis.     

Two step hydrothermal synthesis of flowerbud-like magnetite/graphene oxide hybrid with high-performance microwave absorption

A novel flowerbud-like magnetite/graphene oxide (GO) hybrid was synthesized from facile two-step hydrothermal process by using FeCl₃ as iron source, ethylene glycol as the reducing agent, and graphene oxide as template. The magnetite nanoparticles with the diameters of 70–80 nm were attached onto the surface of graphene oxide through the two-step self-assembly process which enhanced the magnetic properties of the hybrids. The final flowerbud-like magnetite/graphene oxide hybrid emerged with the saturated magnetization of ~84.5 emu g^–1. More importantly, owing to the combined contribution of enhanced dielectric and magnetic properties, the maximum microwave absorption of as-prepared magnetite/GO hybrid reached 30 dB with a thickness of 4 mm. Besides, the absorption bandwidth with a reflection loss above 23 dB ranged from 6.0 to 11.5 GHz.     

Palladium oxide nanoparticles supported on graphene oxide: A convenient heterogeneous catalyst for reduction of various carbonyl compounds using triethylsilane

Palladium oxide nanoparticles supported on graphene oxide ‐ triethylsilane was found to be an effective reductive system for a broad range of reduction processes, including the reduction of various carbonyl compounds such as aromatic aldehydes to their corresponding alcohols or methyl arene compounds, aromatic ketones to their respective alcohols or saturated compounds, aromatic acyl chlorides to their reduced compounds. The desired products were obtained in good to excellent yields under mild conditions. The heterogeneous environmentally friendly catalyst can be easily separated from the reaction mixture through a simple filtration, facilitating purification of the prepared compounds.     

Elaboration of nano titania-magnetic reduced graphene oxide for degradation of tartrazine dye in aqueous solution

In this paper, magnetic nanocomposites are synthesized by loading reduced graphene oxide (RG) with two components of nanoparticles consisting of titanium dioxide (TiO₂) and magnetite (Fe₃O₄) with varying amounts. The structural and magnetic features of the prepared composite photocatalysts were investigated by powder X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectra (UV–vis/DRS), Raman and vibrating sample magnetometer (VSM). The resulting TiO₂/magnetite reduced graphene oxide (MRGT) composite demonstrated intrinsic visible light photocatalytic activity, on degradation of tartrazine (TZ) dye from a synthetic aqueous solution. Specifically, it exhibits higher photocatalytic activity than magnetite reduced graphene oxide (MRG) and TiO₂ nanoparticles. The photocatalytic degradation of TZ dye when using MRG and TiO₂ for 3 h under visible light was 35% and 10% respectively, whereas for MRGT it was more than 95%. The higher photocatalytic efficiency of MRGT is due to the existence of reduced graphene oxide and magnetite which enhances the photocatalytic efficiency of the composite in visible light towards the degradation of harmful soluble azo dye (tartrazine).     

Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized in sol–gel-derived tin oxide/gelatin composite films

Horseradish peroxidase (HRP) was immobilized into a new type of sol–gel-derived nano-sized tin oxide/gelatin composite film (SnO₂ composite film) using a sol–gel film/enzyme/sol–gel film “sandwich” configuration. Direct electrochemistry and electrocatalysis of HRP incorporated into the composite films were investigated. HRP/SnO₂ composite film exhibited a pair of stable and quasi-reversible cyclic voltammetric peaks for the HRP Fe(III)/HRP Fe(II) redox couple with a formal potential of about −0.25 V (vs. SCE) in a pH 6.0 phosphate buffer solution. The electron transfer between the enzyme and the underlying electrode was greatly enhanced in the microenvironment with nano-SnO₂ particles and nanoporous structures. Morphologies and microstructures of the composite films and HRP/composite films were characterized with TEM, AFM. Electrochemical impedance spectroscopy (EIS) was also used to feature the HRP incorporated into composite films. FTIR and UV–Vis spectroscopy demonstrated that HRP in the composite film could retain its native secondary structure. With the advantages of organic–inorganic hybrid materials, the HRP/SnO₂ composite film modified electrode displayed good stability and electrocatalytic activity to the reduction of H₂O₂, The apparent Michaelis-Menten constant was estimated to be 0.345 mM, indicating a high affinity of HRP entrapped into the composite film toward H₂O₂.     

Application of biosynthesized palladium nanoparticles (Pd NPs) on Rosa canina fruit extract‐modified graphene oxide as heterogeneous nanocatalyst for cyanation of aryl halides

A green palladium (Pd)‐based catalyst supported on Rosa canina fruit extract‐modified graphene oxide [Pd nanoparticles (NPs)/reduced graphene oxide (RGO)‐Rosa canina] hybrid materials has been used as a recoverable and heterogeneous nanocatalyst for cyanating aryl halides using K₄[Fe (CN)₆] as the resource of cyanide. The nitriles were achieved in good to high yield, and the catalyst can be recovered and reused for up to seven cycles with no remarkable decrease in its catalytic activity.     

Detection of Dexamethasone Sodium Phosphate in Blood Plasma: Application of Hematite in Electrochemical Sensors

We studied sensor application of a graphene oxide and hematite (α‐Fe₂O₃/GO) composite electrode well‐characterized by the SEM and XRD. Through differential pulse voltammetry (DPV), oxidation of dexamethasone sodium phosphate (DSP) was studied at the surface of a glassy carbon electrode (GCE) modified with graphene oxide nanosheets (GO) and the α‐Fe₂O₃/GO composite. The values of the transfer coefficient (α) and the diffusion coefficient (D) of DSP were 0.5961 and 4.71×10^?5 cm² s^?1 respectively. In the linear range of 0.1–50 μM, the detection limit (DL) was 0.076 μM. In the second step, a GCE was modified with α‐Fe₂O₃/GO composite and the DSP measurement step was repeated to analyzed and compare the effects of hematite nanoparticles present on graphene oxide surfaces. According to the results, α and D were 0.52 and 2.406×10^?4 cm² s^?1 respectively and the DL was 0.046 μM in the linear range of 0.1–10.0 μM. The sensor is simple, inexpensive and uses blood serum.     

One‐pot synthesis of magnetic zeolitic imidazolate framework/grapheme oxide composites for the extraction of neonicotinoid insecticides from environmental water samples

Magnetic zeolitic imidazolate framework 67/graphene oxide composites were synthesized by one‐pot method at room temperature for the first time. Electrostatic interactions between positively charged metal ions and both negatively charged graphene oxide and Fe₃O₄ nanoparticles were expected to chemically stabilize magnetic composites to generate homogeneous magnetic products. The additional amount of graphene oxide and stirring time of graphene oxide, Co²⁺, and Fe₃O₄ solution were investigated. The zeolitic imidazolate framework 67 and Fe₃O₄ nanoparticles were uniformly attached on the surface of graphene oxide. The composites were applied to magnetic solid‐phase extraction of five neonicotinoid insecticides in environmental water samples. The main experimental parameters such as amount of added magnetic composites, extraction pH, ionic strength, and desorption solvent were optimized to increase the capacity of adsorbing neonicotinoid insecticides. The results show limits of detection at signal‐to‐noise ratio of 3 were 0.06–1.0 ng/mL under optimal conditions. All analytes exhibited good linearity with correlation coefficients of higher than 0.9915. The relative standard deviations for five neonicotinoid insecticides in environmental samples ranged from 1.8 to 16.5%, and good recoveries from 83.5 to 117.0% were obtained, indicating that magnetic zeolitic imidazolate framework 67/graphene oxide composites were feasible for analysis of trace analytes in environmental water samples.     

p-Aminophenylacetic acid-mediated synthesis of monodispersed titanium oxide hybrid microspheres in ethanol solution

Monodispersed TiO₂ hybrid microspheres were prepared via the hydrolysis of titanium isopropoxide (TTIP) in ethanol solution containing p-aminophenylacetic acid (APA). The effects of the APA:TTIP molar ratio, water content, reaction time and reaction temperature on the morphology of the resultant spheres were investigated. The products were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. It was demonstrated that the diameters of the resultant TiO₂ spheres could be tuned in the range of 380–800 nm by changing the APA:TTIP molar ratio (1:3 to 3:1) and water content (1–3 v/v%) in the reaction medium, and that increasing the APA:TTIP molar ratio led to larger TiO₂ hybrid spheres while increasing the water content decreased their size. The loading content of APA in the hybrid spheres could reach 20 wt.% as they were prepared with the APA:TTIP ratio of 3:1. The possible formation mechanism of the hybrid spheres was also investigated. It was found that APA slowed down the hydrolysis rate of the titanium precursor so that resulted in the formation of the TiO₂ spheres. In addition, the APA present in TiO₂ spheres acted as a reducing agent to in situ convert HAuCl₄ into metallic Au on the surface of the TiO₂ spheres. The catalytic activity of the resultant Au/APA–TiO₂ composite was examined using transfer hydrogenation of phenylacetone with 2-propanol, and it was indicated that the catalyst displayed high efficiency for this reaction.     

Pd supported on graphene modified g-C3N4 hybrid: a highly efficient catalyst for hydrogenation of nitroarenes

Graphitic carbon nitride (g-C₃N₄) and graphene (GO) have been greatly utilized as supports in the field of heterogeneous catalysis. In this work, layered C₃N₄ polymer/graphene hybrid (CNNS/rGO₂₀) with heterostructure was fabricated by a hydrothermal method followed by loading Pd nanoparticles on the hybrid. The palladium was well dispersed uniformly (1.31 nm) owing to the layered and porous heterostructure of CNNS/rGO₂₀. The obtained catalyst was used for the transfer hydrogenation of a series of nitro-compounds to give the corresponding aromatic amines with outstanding activity by employing formic acid as hydrogen donor under mild conditions. The catalytic activity of the heterogeneous catalyst showed no significant loss after five continuous use.