Probing the Catalytic Activity of Reduced Graphene Oxide Decorated with Au Nanoparticles Triggered by Visible Light

Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO–Au NPs) were obtained by the in situ reduction of GO and AuCl₄^?_(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O₂ through the transfer of SPR‐excited hot electrons to O₂ molecules adsorbed from air. The SPR‐mediated catalytic oxidation of p‐aminothiophenol (PATP) to p,p′‐dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR‐mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge‐transfer processes from rGO to Au took place and contributed to improved SPR‐mediated activity. Since the transfer of electrons from Au to adsorbed O₂ molecules is the crucial step for PATP oxidation, in addition to the SPR‐excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au‐to‐O₂ charge‐transfer process.     

Polymerization of graphene oxide nanosheet by using of aminoclay: Electrocatalytic activity of its platinum nanohybrids

This study describes the polymerization of graphene oxide (GO) nanosheet to reduced‐GO‐aminoclay (RGC) by covalent functionalization of chemically reactive epoxy groups on the basal planes of GO with amine groups of magnesium phyllosilicate clay (known as aminoclay). The resulting RGC sheets were characterized and applied to support platinum nanostructures at toluene/water interface. Pt nanoparticles (NPs) with diameters about several nanometers were adhered to RGC sheets by chemical reduction of [PtCl₂(cod)] (cod = cis,cis‐1,5‐cyclooctadiene) complex. Catalytic activity of Pt NPs thin films were investigated in the methanol oxidation reaction. Cyclic voltammetry results exhibit that the Pt/reduced‐GO (RGO) and Pt/RGC thin films showed improved catalytic activity in methanol oxidation reaction in comparison to other Pt NPs thin films, demonstrating that the prepared Pt/RGO and Pt/RGC thin films are promising catalysts for direct methanol fuel cell.     

Gold Nanoparticles Decorated Graphene as a High Performance Sensor for Determination of Trace Hydrazine Levels in Water

Electrochemical sensors provide a selective, sensitive and an easy approach to detect hazardous substances such as hydrazine. Herein, we investigate a facile route for the fabrication of a nanostructured composite based on Au nanoparticles (AuNPs) decorated graphene and present its sensing performance towards hydrazine. Our strategy involves electrophoretic deposition (EPD) of graphene oxide (GO) on Au substrate to obtain a uniform layer EPD‐GO, followed by electrochemical reduction of GO to yield high quality graphene ERGO and electrodeposition of monodispersed AuNPs on ERGO (AuNPs/ERGO/Au). The modified AuNPs/ERGO/Au electrode was characterized using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT‐IR) techniques. The sensor exhibited an improved catalytic activity with a peak potential of +87 mV (vs. Ag/AgCl) for hydrazine oxidation. The high performance of this hybrid electrode is due to the presence of a synergistic effect between AuNPs and ERGO at their interface. Insights into the mechanism and kinetics of hydrazine oxidation are withdrawn from varying the voltage scan rate as the reaction is fully irreversible and diffusion‐controlled. The proposed hydrazine sensor showed suitability for nanomolar detection (detection limit of 74 nM), high selectivity in the presence of common ions and efficiency for application in water samples.     

Synthesis and characterization of silver nanoparticle and graphene oxide nanosheet composites as a bactericidal agent for water disinfection

Graphene oxide (GO) nanosheets impregnated with silver nanoparticles (Ag NPs) were fabricated by the in situ reduction of adsorbed Ag(+) by hydroquinone (HQ) in a citrate buffer solution. Paper-like Ag NP/GO composite materials were fabricated owing to convenient structure characterization and antibacterial tests. The Ag NP/GO composites were characterized by UV-vis spectra, transmission electron microscope, electron diffraction, Raman spectroscopy, and field emission scanning electron microscope coupled with Energy Dispersive Spectrometer. Antibacterial activity was tested using Escherichia coli and Staphylococcus aureus as model strains of Gram negative and Gram positive bacteria, respectively. The as-prepared composites exhibit stronger antibacterial activity against both. The Ag NP/GO composites performed efficiently in bringing down the count of E. coli from 10(6) cfu/mL to zero with 45 mg/L GO in water. The micron-scale GO nanosheets (lateral size) enable them to be easily deposited on porous ceramic membranes during water filtration; making them a promising biocidal material for water disinfection.     

Preparation of silver/graphene/polymer hybrid microspheres and the study of photocatalytic degradation

Three-dimensional silver/graphene/polymer hybrid microspheres were prepared to depress the aggregation of two-dimensional graphene. Graphene oxide (GO) sheets were successfully wrapped on the surface of amine-functionalized polystyrene-poly (glycidyl methacrylate) (PS-PGMA) microspheres (～3 μm in diameter) to form graphene oxide/amino-microsphere (GO/AMS) core–shell structure. Subsequently, the wrapped GO sheets were reduced by using hydrazine hydrate as the reducing agents, meanwhile decorated with silver nanoparticles on the wrinkled surface to form Ag-rGO/AMS hybrid microspheres with monodisperse distributions in shape and diameter. The resulting materials were characterized by power X-ray diffraction, scanning electron microscope, Raman spectra, and ultraviolet–visible (UV–vis) absorption spectra. Since Ag nanoparticles behave surface plasmon resonance effect and rGO structure can improve the separation of photogenerated electrons and holes, the Ag-rGO/AMS composites present good photocatalytic activities for the degradation of methylene blue (MB) as 93 % MB were degraded after 2.5 h under irradiation.     

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.     

Green synthesis of Pt/CeO2/graphene hybrid nanomaterials with remarkably enhanced electrocatalytic properties

We developed a facile strategy for clean synthesis of Pt/CeO(2)/graphene nanomaterials with remarkably enhanced catalytic properties. The graphene oxide (GO) could be used as an oxidant to oxidize Ce(3+) into CeO(2) NPs, and l-lysine was used as a linker to realize the in situ growth of Pt NPs around CeO(2) NPs dispersed on graphene.     

Mild Synthesis of Pt/SnO2/Graphene Nanocomposites with Remarkably Enhanced Ethanol Electro‐oxidation Activity and Durability

We have designed a new Pt/SnO₂/graphene nanomaterial by using L ‐arginine as a linker; this material shows the unique Pt‐around‐SnO₂ structure. The Sn²⁺ cations reduce graphene oxide (GO), leading to the in situ formation of SnO₂/graphene hybrids. L ‐Arginine is used as a linker and protector to induce the in situ growth of Pt nanoparticles (NPs) connected with SnO₂ NPs and impede the agglomeration of Pt NPs. The obtained Pt/SnO₂/graphene composites exhibit superior electrocatalytic activity and stability for the ethanol oxidation reaction as compared with the commercial Pt/C catalyst owing to the close‐connected structure between the Pt NPs and SnO₂ NPs. This work should have a great impact on the rational design of future metal–metal oxide nanostructures with high catalytic activity and stability for fuel cell systems.     

Graphene‐Oxide‐Catalyzed Direct CH−CH‐Type Cross‐Coupling: The Intrinsic Catalytic Activities of Zigzag Edges

The development of graphene oxide (GO)‐based materials for C?C cross‐coupling represents a significant advance in carbocatalysis. Although GO has been used widely in various catalytic reactions, the scope of reactions reported is quite narrow, and the relationships between the type of functional groups present and the specific activity of the GO are not well understood. Herein, we explore CH?CH‐type cross‐coupling of xanthenes with arenes using GO as real carbocatalysts, and not as stoichiometric reactants. Mechanistic studies involving molecular analogues, as well as trapped intermediates, were carried out to probe the active sites, which were traced to quinone‐type functionalities as well as the zigzag edges in GO materials. GO‐catalyzed cross‐dehydrogenative coupling is operationally simple, shows reusability over multiple cycles, can be conducted in air, and exhibits good functional group tolerance.     

Novel Ag2S nanoparticles on reduced graphene oxide sheets as a super-efficient catalyst for the reduction of 4-nitrophenol

Here,Ag_2S nanoparticles on reduced graphene oxide(Ag_2S NPs/RGO) nanocomposites with relatively good distribution are synthesized for the first time by conversing Ag NPs/RGO to Ag_2S NPs/RGO via a facile hydrothermal sulfurization method.As an noval catalyst for the reduction of 4-nitrophenol(4-NP),it only takes 5 min for Ag_2S NPs/RGO to reduce 98% of 4-NP,and the rate constant of the composites is almost 13 times higher than that of Ag NPs/RGO composites.The high catalytic activity of Ag_2S NPs/RGO can be attributed to the following three reasons:(1) Like metal complex catalysts,the Ag_2S NPs is also rich with metal center Ag(δ~+),with pendant base S(δ) close to it,and thus the Ag and basic S function as the electron-acceptor and proton-acceptor centers,respectively,which facilitates the catalyst reaction;(2)RGO features the high adsorption ability toward 4-NP which provides a high concentration of 4-NP near the Ag_2S NPs;and(3) electron transfer from RGO to Ag_2S NPs,facilitating the uptake of electrons by 4-NP molecules.     

Magnetic GO‐PANI decorated with Au NPs: A highly efficient and reusable catalyst for reduction of dyes and nitro aromatic compounds

Due to the high activity of Au nanoparticles (NPs) for various reactions, many researchers have tried to develop heterogeneous catalysts in order to prevent irreversible agglomeration of Au NPs. Herein, magnetic graphene oxide modified with polyaniline (PANI) was used as a support for Au NPs that brings together advantages including: uniform dispersal of the catalyst in water,alarge surface area related to the graphene oxide; easy electron transfer in chemical reactions and good attachment of Au NPs to the support associated with PANI; and finally facile recovery in the presence of a magnetic field. Catalytic reduction of different analytes (Congo red, methylene blue, rhodamine B and 4‐nitro phenol) was evaluated in the presence of NaBH₄ and the results show high catalytic activity of the catalyst. The catalyst was thoroughly characterized using various methods including FTIR, XRD, XPS, FE‐SEM and HRTEM analyses while its catalytic activity was evaluated via reduction of different analytes.     

Polyacrylamide/reduced graphene oxide-Ag nanocomposite as highly efficient antibacterial transparent film

In this study, preparation and characterization of polyacrylamide/reduced graphene oxide-Ag (PAM/rGO-Ag) nanocomposites as a new nanocomposite film were investigated. First, PAM/GO nanocomposite was synthesized by in situ polymerization strategy. Afterward, highly stable and uniformly distributed silver nanoparticles (Ag NPs) have been obtained with PAM/GO nanocomposite as nanoreactors via in situ reduction of silver nitrate (AgNO₃) using sodium borohydride (NaBH₄) as reducing agent. In addition, the prepared PAM/rGO-Ag nanocomposite was thermally annealed in order to achieve high-performance nanocomposite film with antimicrobial activities. The prepared nanocomposite was characterized by XRD, FT-IR, SEM, TEM and TGA. The obtained results demonstrate that the silver nanoparticles were well decorated and dispersed on the graphene oxide nanosheets. In fact, the GO nanosheets and polyacrylamide chains act as a support and stabilize the Ag nanoparticles. Moreover, antimicrobial activities of the films were also examined, and the films containing well-dispersed and stabilized Ag nanoparticles showed outstanding antibacterial activity.     

Fibrillar Networks of Glycyrrhizic Acid for Hybrid Nanomaterials with Catalytic Features

Self‐assembly of the naturally occurring sweetening agent, glycyrrhizic acid (GA) in water is studied by small‐angle X‐ray scattering and microscopic techniques. Statistical analysis on atomic force microscopy images reveals the formation of ultralong GA fibrils with uniform thickness of 2.5 nm and right‐handed twist with a pitch of 9 nm, independently of GA concentration. Transparent nematic GA hydrogels are exploited to create functional hybrid materials. Two‐fold and three‐fold hybrids are developed by introducing graphene oxide (GO) and in situ‐synthesized gold nanoparticles (Au NPs) in the hydrogel matrix for catalysis applications. In the presence of GO, the catalytic efficiency of Au NPs in the reduction of p‐nitrophenol to p‐aminophenol is enhanced by 2.5 times. Gold microplate single crystals are further synthesized in the GA hydrogel, expanding the scope of these hybrids and demonstrating their versatility in materials design.     

Preparation of Nanoscrolls by Rolling up Graphene Oxide–Polydopamine–Au Sheets using Lyophilization Method

Graphene oxide–polydopamine–Au (GO–PDA–Au) nanoscrolls were prepared by rolling up GO–PDA–Au sheets through a simple lyophilization method. The structure of GO–PDA–Au nanoscrolls and GO–PDA–Au sheets were compared by powder X‐ray diffraction, Raman spectra, transmission electron microscopy, and scanning electron microscopy. The results demonstrated that the heterogeneous GO–PDA–Au nanoscrolls were synthesized successfully. Polydopamine (PDA) attached at the surface of GO sheets served as binding reagents to anchor and disperse Au nanoparticles (NPs). The electrocatalytic activity of methanol with GO–PDA–Au nanoscrolls and GO–PDA–Au sheets as electrodes were conducted. Compared to GO–PDA–Au sheets, GO–PDA–Au nanoscrolls showed better electrocatalytic activity and electrochemical stability owing to their scrolled structure. This article provides a simple and effective method to prepare GO nanoscrolls containing metal NPs that broadens the applications of the graphene‐based materials in optical, magnetic, and catalytic fields.     

Comparative Studies on Electrocatalytic Activities of Chemically Reduced Graphene Oxide and Electrochemically Reduced Graphene Oxide Noncovalently Functionalized with Poly(methylene blue)

This study compares the electrocatalytic activities of chemically reduced graphene oxide (crGO) and electrochemically reduced graphene oxide (erGO), which are both noncovalently functionalized with a polyaromatic dye, poly(methylene blue) (polyMB), toward the oxidation of β‐nicotinamide adenine dinucleotide (NADH). PolyMB‐crGO and polyMB‐erGO composites were obtained via electropolymerization of methylene blue on crGO and GO modified glassy carbon (GC) electrodes, respectively. Cyclic voltammetry (CV) results indicate that these two types of integrated electrodes reveal different electrocatalytic activities. PolyMB‐crGO integrated electrode possesses lower catalytic oxidation potential, suggesting higher catalytic activity. The present study is helpful for the understanding and screening of graphene‐based advanced carbon nanomaterials for potential electrochemical applications.     

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.     

Covalent polymeric modification of graphene nanosheets via surface‐initiated single‐electron‐transfer living radical polymerization

Graphene nanosheets offer intriguing electronic, thermal, and mechanical properties and are expected to find a variety of applications in high‐performance nanocomposite materials. Dispersal of graphene nanosheets in polymer hosts and precise interface control are challenging due to their strong interlayer cohesive energy and surface inertia. Here, an efficient strategy is presented for growing polymers directly from the surface of reduced graphene oxide (GO). This method involves the covalent attachment of Br‐containing initiating groups onto the surface of hydrazine hydrate reduced GO via a diazonium addition and the succeeding linking of poly(tert‐butyl methacrylate) (PtBMA) chains (71.7 wt % grafting efficiency) via surface‐initiated single‐electron‐transfer living radical polymerization (SET‐LRP) to graphene nanosheets. The resulting materials were characterized by using a range of testing techniques and it was proved that polymer chains were successfully introduced to the surface of exfoliated graphene sheets. After grafting with PtBMA, the modified graphene sheets still maintained the separated single layers, and the dispersibility was improved significantly. The method is believed to offer possibilities for optimizing the processing properties and interface structure of graphene–polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Ag/Fe_3O_4/rGO纳米复合材料的制备及抗菌性能

以四水合氯化亚铁和硝酸银为原料,硼氢化钠为还原剂,氧化石墨烯(GO)为载体,通过原位还原法制备了具有磁分离功能的银/四氧化三铁/还原氧化石墨烯(Ag/Fe_3O_4/rGO)纳米复合抗菌材料.采用X射线粉末衍射仪(XRD)、X射线光电子能谱仪(XPS)、透射电子显微镜(TEM)等对复合材料进行了表征.结果显示,Fe_3O_4和Ag纳米颗粒均匀分布在rGO片层上.复合材料的饱和磁化率(Ms)为40.5 A·m~2·kg·(-1),表明其具有较强的磁性,将其与菌液混合后,在磁场作用下10 min即可吸附沉降完成磁分离.以大肠杆菌(E.coli)和金黄色葡萄球菌(S.aureus)为实验菌株,通过琼脂扩散法评价了复合材料的抗菌性能.结果表明,该复合材料具有良好的抗菌效果,对E.coli和S.aureus的抑菌圈直径分别为18 mm和13 mm,最低抑菌浓度值(MIC)分别为50 mg/L和80 mg/L,最低杀菌浓度值(MBC)分别为30 mg/L和50 mg/L.     

Ag−Co3O4 @ Nr GO Material Synthesized by One‐pot Hydrothermal Method for Carcinoembryonic Antigen (CEA) Detection of Enzyme‐mimetic Electrochemical Immunosensor

A high‐sensitivity carcinoembryonic antigen immunosensor was successfully prepared via a one‐step hydrothermal method, wherein nitrogen‐doped graphene oxide (Nr GO) loaded Ag and Co₃O₄ nanomaterials were synthesized using ammonia as the nitrogen source. Doping nitrogen atoms into the graphene structure forms a new type of N‐type semiconductor with an increased number of graphene layers and more active sites for bonding with chemicals, thereby providing excellent in biocompatibility and good electrical conductivity. The electrical signal of the sensor is further amplified due to the good catalytic effect of Co₃O₄ and Ag NPs on H₂O₂. The signal probe requires neither pretreatment nor acid treatment, and can be easy to loaded with metal‐immobilized antibodies, which greatly simplifies the detection step not shorten the detection time. The sensor has good sensitivity to detecting carcinoembryonic antigen (CEA) and can easily operate, and requires mild reaction conditions. Under optimal experimental conditions, the linear range of the sensor is 0.001–200 ng ? mL^?1, the detection limit is 0.18 pg ? mL^?1, and the linear correlation coefficient is 0.991, which can be used for CEA determination of the actual sample.     

一步微波法制备石墨烯-硫化镉纳米复合材料

石墨烯-硫化镉量子点纳米复合材料在光电领域具有广阔的应用前景,而其性能依赖于良好的硫化镉纳米颗粒均匀地分布在单片石墨烯片上。为此,我们发展了一种简便的一步制备高质量石墨烯-硫化镉纳米复合材料的方法。该方法以氧化石墨烯为原料,二水乙酸镉作为镉源,硫代乙酰胺作为硫源,通过微波加热处理数分钟直接制得石墨烯-硫化镉纳米复合材料。电镜照片显示获得的石墨烯-硫化镉纳米复合材料中硫化镉纳米粒子均匀生长在石墨烯表面,无明显聚集产生。以氧化石墨烯为起始原料一步合成保证了最终纳米复合材料中石墨烯主要以单片形式存在,而在微波加热合成过程中,氧化石墨烯也同时还原成石墨烯。