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.     

静电自组装方法合成的具有多孔三维网络结构的Fe3O4/石墨烯复合材料作为高性能锂离子电池负极材料

采用静电自组装方法,分两步合成Fe（OH）₃/GO前驱体（GO：氧化石墨烯）,再通过水热反应和600 ℃高纯氮气气氛下煅烧,获得了Fe₃O₄/石墨烯复合材料. 通过X射线衍射（XRD）、扫描电镜（SEM）、高分辨透射电镜（HRTEM）、拉曼（Raman）光谱等多种分析,发现该复合材料具有三维多孔石墨烯网络结构. 把合成的这种Fe₃O₄/石墨烯复合材料作为锂离子电池负极材料,电化学测试结果表明其具有优良的电化学性能：首次放电容量为1390 mAh·g^-1,50次循环后容量为819 mAh·g^-1. 通过对比实验表明,三维石墨烯网络结构的形成对复合材料的电化学循环稳定性起着关键作用.     

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.     

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.     

Preparation,characterization and heterogeneous catalytic applications of GO/Fe3O4/HPW nanocomposite in chemoselective and green oxidation of alcohols with aqueous H2O2

Graphene oxide ‐ Fe₃O₄ ‐ NH₃⁺H₂PW₁₂O₄₀ ^‐ magnetic nanocomposite (GO/Fe₃O₄/HPW) was prepared by linking amino ‐ functionalized Fe₃O₄ nanoparticles (Fe₃O₄ ‐ NH₂) on the graphene oxide (GO), and then grafting 12 ‐ tungstophosphoric acid (H₃PW₁₂O₄₀) on the graphene oxide ‐ magnetite hybrid (GO ‐ Fe₃O₄ ‐ NH₂). The obtained GO/Fe₃O₄/HPW nanocomposite was well characterized with different techniques such as FT ‐ IR, TEM, SEM, XRD, EDX, TGA ‐ DTA, AGFM, ICP and BET measurements. The used techniques showed that the graphene oxide layers were well prepared and the various stages of preparation of the GO/Fe₃O₄/HPW nanocomposites successfully completed. This new nanocomposite displayed excellent performance as a heterogeneous catalyst in the oxidation of alcohols with H₂O₂. The as ‐ prepared GO/Fe₃O₄/HPW catalyst was more stable and recyclable at least five times without significantly reducing its catalytic activity.     

Sensitive Electrochemical Aptasensor for Thrombin Detection with Platinum Nanoparticles,Blocking Reagent‐Horseradish Peroxidase and Graphene Oxide as Enhancers

A highly sensitive thrombin electrochemical aptasensor with Pt nanoparticles, blocking reagent‐horseradish peroxidase (HRP) and inert graphene oxide (GO) as enhancers was successfully fabricated. Firstly, Pt nanoparticles with high surface to volume ratio could increase the amount of the immobilized redox probe hexacyanoferrate nanoparticles (NiHCFNPs) and effectively enhance the electron transfer. Secondly, HRP and Pt nanoparticles with high catalytic activity extremely amplify the electrochemical signal of NiHCFNPs toward H₂O₂. Lastly, inert graphene oxide (GO) labeled TBA could be used for enlarging the steric hindrance of thrombin. As a result, the aptasensor showed a high sensitivity with a detection limit of 500 fM.     

One-pot green synthesis of Prussian blue nanocubes decorated reduced graphene oxide using mushroom extract for efficient 4-nitrophenol reduction

One-pot green approach to the synthesis of Prussian blue nanocubes/reduced graphene oxide (PBNCs/RGO) nanocomposite had been attempted. It was based on the extract of mushroom with K₃[Fe(CN)₆] and graphene oxide (GO) as precursors, where the reduction of GO and the deposition of PBNCs occurred simultaneously. The obtained nanocomposite was characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and electrochemical techniques. With the introduction of β-cyclodextrin (β-CD), the β-CD/PBNCs/RGO system showed linear behavior in the range from 0.01 to 700 μM for 4-nitrophenol with a low detection limit of 2.34 nM (S/N = 3).     

Self‐Assembled Platinum Nanoflowers on Polydopamine‐Coated Reduced Graphene Oxide for Methanol Oxidation and Oxygen Reduction Reactions

The morphology‐ and size‐controlled synthesis of branched Pt nanostructures on graphene is highly favorable for enhancing the electrocatalytic activity and stability of Pt. Herein, a facile approach is developed for the efficient synthesis of well‐dispersed Pt nanoflowers (PtNFs) on the surface of polydopamine (PDA)‐modified reduced graphene oxide (PDRGO), denoted as PtNFs/PDRGO, in high yield. The synthesis was performed by a simple heating treatment of an aqueous solution that contained K₂PtCl₄ and PDA‐modified graphene oxide (GO) without the need for any additional reducing agent, seed, surfactant, or organic solvent. The coated PDA serves not only as a reducing agent, but also as cross‐linker to anchor and stabilize PtNFs on the PDRGO support. The as‐prepared PtNFs/PDRGO hybrid, with spatially and locally separated PtNFs on PDRGO, exhibits superior electrocatalytic activity and stability toward both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in alkaline solutions.     

Effects of nano graphene oxide as support on the product properties and performance of Ziegler–Natta catalyst in production of UHMWPE

The synthesis of mono‐ and bi‐supported Ziegler–Natta catalysts using magnesium etoxide Mg(OEt)₂ and graphene oxide (GO) as catalyst support for production of Ultra High Molecular Weight Polyethylene (UHMWPE) is reported in this investigation. Nano‐graphene oxide was prepared by the modified Hummer's method and its structure was analyzed by XRD and FTIR indicating the presence of hydroxyl groups on graphene oxide and the formation of an exfoliated structure. The activity of TiCl₄/Mg(OEt)₂, TiCl₄/Mg(OEt)₂‐GO, and TiCl₄/GO catalysts in terms of grams of PE produced per mmol of Ti per hour was experimentally obtained for catalysts with different ratios of co‐catalyst (triisobutylaluminium) to TiCl₄. For all three series of catalysts, the activity curve showed an optimum point at a specific Al/Ti molar ratio. Catalyst activity was highest for TiCl₄/Mg(OEt)₂ and lowest for TiCl₄/GO. The characterization of UHMWPE products indicated that the viscosity average molecular weight (Mv) was highest for the polymer produced by TiCl₄/Mg(OEt)₂ and lowest for the polymer produced by TiCl₄/GO. Furthermore, thermogravimetric analysis (TGA), dynamic mechanical thermal analysis (DMTA), and mechanical tensile testing were conducted on the prepared polymers indicating that the polymer produced by TiCl₄/GO had the highest thermal and mechanical properties, while these properties were at their minimum for polymers produced by TiCl₄/Mg(OEt)₂. Copyright © 2015 John Wiley & Sons, Ltd.     

Exfoliated Single Layers of Layered Cobalt Hydroxide for Ultrafine Co3O4 Nanoparticles on Graphene Nanosheets as an Efficient Electrocatalyst for Oxygen Reduction

A highly effective way to produce an oxygen reduction electrocatalyst was developed through the self-assembly of exfoliated single layers of cobalt hydroxide (Co(OH)₂) and graphene oxide (GO). These 2D materials have complete contact with one another because of their physical flexibility and the electrostatic attraction between negatively charged GO and positively charged Co(OH)₂ layers. The strong coupling induces transformation of the Co(OH)₂ single layer into a discrete nanocrystal of spinel Co₃O₄ with an average size of 8 nm on reduced GO (RGO) during calcination, which could not be obtained with bulk-layered cobalt hydroxide because of its rapid layer collapse. The ultrafine Co₃O₄/RGO hybrid exhibited not only comparable performance in the oxygen reduction reaction but also higher durability compared with the commercial 20 wt % Pt/C catalyst.     

Preparing graphene oxide–copper composite material from spent lithium ion batteries and catalytic performance analysis

The wide use of lithium ion batteries (LIBs) has created much waste, which has become a global issue. It is vital to recycle waste LIBs considering their environmental risks and resource characteristics. Anode graphite from spent LIBs still possess a complete layer structure and contain some oxygen-containing groups between layers, which can be reused to prepare high value-added products. Given the intrinsic defect structure of anode graphite, copper foils in LIB anode electrodes, and excellent properties of graphene, graphene oxide–copper composite material was prepared in this work. Anode graphite was firstly purified to remove organic impurities by calcination and remove lithium. Purified graphite was used to prepare graphene oxide–copper composite material after oxidation to graphite oxide, ultrasonic exfoliation to graphene oxide (GO), and Cu²⁺ adsorption. Compared with natural graphite, preparing graphite oxide using anode graphite consumed 40% less concentrated H₂SO₄ and 28.6% less KMnO₄. Cu²⁺ was well adsorbed by 1.0 mg L^?1 stable GO suspension at pH 5.3 for 120 min. Graphene oxide–copper composite material could be successfully obtained after 6 h absorption, 3 h bonding between GO and Cu²⁺ with 3/100 of GO/CuSO₄ mass ratio. Compared to CuO, graphene oxide–copper composite material had better catalytic photodegradation performance on methylene blue, and the electric field further improved the photodegradation efficiency of the composite material.     

Enhanced Electrocatalytic Activity of Dual Template Based Pt/Cu‐zeolite A/Graphene for Methanol Electrooxidation

A novel Pt/Cu‐zeolite A/graphene based electrocatalyst was successfully prepared by chemical reduction method for methanol electrooxidation. Graphite oxide and Cu functionalized zeolite A were simultaneously reduced by NaBH₄ to prepare Cu‐zeolite A/graphene support which was used to deposit Pt nanoparticles. The nanostructure and composition of as‐prepared Pt/Cu‐zeolite A/graphene composites were characterized by X‐ray diffractometer, X‐ray fluorescence, Fourier transform infrared spectrometer and scanning electron microscopy. The electrocatalytic properties of Pt/Cu‐zeolite A/graphene modified electrode for methanol oxidation were investigated by cyclic voltammetry and chronoamperometry in 0.10 mol/L H₂SO₄ + 0.50 mol/L CH₃OH solution. Compared with Pt/zeolite A/graphene electrode and Pt/graphene electrode, Pt/Cu‐zeolite A/graphene based electrode exhibited obviously enhanced current and higher electrocatalytic activity for methanol electrooxidation. The increased electrocatalytic activity was attributed to the presence of zeolite A and reduced graphene oxide based dual template, which significantly increased the effective electrode surface and facilitated the diffusion of analytes into the electroactive catalyst.     

干燥方式对高氯酸铵/石墨烯复合材料的结构和热分解行为的影响

通过溶胶-凝胶法制备了石墨烯水凝胶, 并将其与高氯酸铵(AP)复合, 然后分别采用自然干燥、冷冻干燥和超临界CO₂干燥三种干燥方式制备了AP/石墨烯复合材料, 并通过扫描电镜(SEM)、元素分析、X射线衍射(XRD)、差示扫描量热仪(DSC)和热重-红外联用技术(TG-FTIR)研究了不同干燥方式对其结构和热分解行为的影响. 结果表明, 干燥方式对AP/石墨烯复合材料的形貌具有明显影响, 其中通过超临界CO₂干燥制备的AP/石墨烯复合材料基本能保持与石墨烯气凝胶相似的外观和多孔结构. 通过自然干燥、冷冻干燥和超临界CO₂干燥制备的AP/石墨烯复合材料中AP的质量分数分别为89.97%、92.41%和94.40%, 其中通过超临界CO₂干燥制备的复合材料中AP的粒径尺寸为69 nm. DSC测试结果表明, 石墨烯对AP的热分解过程具有明显的促进作用, 能使AP的低温分解过程大大减弱, 高温分解峰温明显降低. 三种干燥方式相比, 通过超临界CO₂干燥制备的AP/石墨烯复合材料中石墨烯的促进作用最明显. 与纯AP相比, 其高温分解峰温降低了83.7℃, 表观分解热提高到2110 J·g^-1. TG-FTIR分析结果表明, AP/石墨烯复合材料的热分解过程中, AP分解产生的氧化性产物与石墨烯发生了氧化反应, 生成了CO₂.     

High solar-light photocatalytic activity of using Cu3Se2/rGO nanocomposites synthesized by a green co-precipitation method

Current work presents a facile, cost-effective, and green method to synthesize copper selenide nanostructures and copper selenide/graphene nanocomposites. The products were synthesized by a co-precipitation method by glycine amino acid as a green surfactant and graphene oxide (GO) sheets as a graphene source. X-ray diffraction patterns (XRD) of the products indicated that the products were Cu₂Se₃ with tetragonal phase. Fourier transform infrared (FTIR) spectroscopy and the XRD patterns indicated that the GO sheets were changed into reduced GO (rGO) during the synthesis process. Scanning and transmission electron microscopy (SEM and TEM) images showed the nanoparticles (NPs) that were decorated on rGO sheets had the significantly smaller size in compared to the pristine NPs. UV-vis results revealed that, the absorption peak of the products were in the visible region with a band-gap value between 1.85 eV and 1.95 eV. Finally, the products were applied as photocatalytic materials to remove Methylene Blue (MB) dye under solar-light and visible-light irradiation conditions. It was observed; the rGO had a significant role in enhancing the photocatalytic performance of the products and Cu₂Se₃/rGO (15%) could degrade more than 91% and 73% of MB only during 1 h under solar-light and visible-light sources, respectively.     

Copper Schiff base complex immobilized on magnetic graphene oxide: Efficient heterogeneous nanocatalyst for treating environmental pollutants and synthesis of chromenes

Herein, a new Cu(II) Schiff base complex was immobilized onto the magnetic graphene oxide surface through a stepwise procedure. The as-synthesized nanostructure (GO/Fe₃O₄/CuL) was characterized by various techniques including Fourier transform infrared (FT-IR), Raman spectroscopies, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), energy-dispersive X-ray (EDX) and inductively coupled plasma (ICP) spectroscopies, N₂ adsorption–desorption analysis, vibrating sample magnetometry (VSM), and X-ray diffraction (XRD). The catalytic activity of the synthesized nanocatalyst was examined in 4-nitrophenol (4-NP), Congo red (CR), and methylene blue (MB) reduction using NaBH₄ in an aqueous solution at room temperature. The reaction progress was monitored by UV–Vis spectroscopy. Also, the synthesized nanostructure was evaluated as an efficient catalyst for the synthesis of 2-amino-4H-benzopyrans via three-component reactions of 1-naphthol, malononitrile, and various aldehydes in ethanol/water at 50°C. The use of green solvents, the short reaction time, the high product yield, and easy separation from the reaction environment are the main benefits of this catalytic system. By covalent grafting of the complex on the graphene oxide surface, its catalytic performance significantly increased compared with graphene oxide; this is probably related to the chemical change of the graphene oxide surface. The results show the high chemical stability and the improved reusability of the synthesized nanocatalyst (six times) without significant loss in the catalytic activity of GO/Fe₃O₄/CuL nanocomposite.     

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.     

Electrochemical reduction of CO2 to CO using graphene oxide/carbon nanotube electrode in ionic liquid/acetonitrile system

Electrochemical reduction of CO₂ to CO is an interesting topic. In this work, we prepared metal-free electrodes by depositing graphene oxide (GO), multi-walled carbon nanotube (MWCNT), and GO/MWCNT composites on carbon paper (CP) using electrophoretic deposition (EPD) method. The electrodes were characterized by different methods, such as X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The electrochemical reduction of CO₂ to CO was conducted on the electrodes in 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄)/acetonitrile (MeCN) electrolyte, and the composition of the electrolyte influenced the reaction significantly. It was demonstrated that GO/MWCNT-CP electrode was very effective for the reaction in IL (90 wt%)/MeCN binary mixture, the Faradaic efficiency of CO and current density were even higher than those on Au and Ag electrodes in the same electrolyte.     

A study of novel macrocyclic copper complex/graphene‐based composite materials for counter electrodes of dye‐sensitized solar cells

In this study, a newly synthesized macrocyclic copper complex, [Cu(C₁₀H₂₀N₈)(C₄H₈N₄)](BF₄)₂, was used for a reaction with graphene oxide. Macrocyclic copper complex/graphene‐based composite materials were prepared and applied to the counter electrodes (CEs) of dye‐sensitized solar cells (DSSCs). As the level of the macrocyclic copper complex increased, the catalytic sites on the surface of the CE increased. The results showed that the device efficiency of the composite GO/Cu (1:10) CE was 7.61%, which was better than that of the Platinum (Pt) CE (7.04%). The device efficiency of the DSSC was enhanced effectively because the electrocatalytic activity of the CE was enhanced, and the interface impedance of the device was reduced. Therefore, the macrocyclic copper complex/graphene‐based composite materials may have the potential to replace traditional Pt to increase efficiency and reduce the fabrication cost of DSSCs.     

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.     

一种可分散性石墨烯的制备

先通过γ-氨丙基三乙氧基硅烷(KH-550)与氧化石墨反应得到改性氧化石墨, 再经水合肼还原制备了改性石墨烯. 未烘干的改性石墨烯经超声处理后, 可稳定分散于体积比为9∶1的N,N-二甲基甲酰胺/水或丙酮/水的混合溶液中, 而且在N,N-二甲基甲酰胺/水体系中超声得到的改性石墨烯分散液可在乙醇、丙酮中稳定存在. 采用红外光谱、X光电子能谱及X射线衍射分析等手段研究了KH-550改性氧化石墨及石墨烯的结构. 结果表明, KH-550上的氨基与氧化石墨的羧基反应生成了酰胺键, 与环氧基发生了加成反应, 干燥的改性石墨烯层间通过Si-O-Si键连接在一起.