Exfoliated graphene sheets decorated with metal/metal oxide nanoparticles: Simple preparation from cation exchanged graphite oxide

We produced carbon hybrid materials of graphene sheets decorated with metal or metal oxide nanoparticles of gold, silver, copper, cobalt, or nickel from cation exchanged graphite oxide. Measurements using powder X-ray diffraction, transmission electron microscopy, and X-ray absorption spectra revealed that the Au and Ag in the materials (Au–Gr and Ag–Gr) existed on graphene sheets as metal nanoparticles, whereas Cu and Co in the materials (Cu–Gr and Co–Gr) existed as a metal oxide. Most Ni particles in Ni–Gr were metal, but the surfaces of large particles were partly oxidized, producing a core–shell structure. The Ag–Gr sample showed a catalytic activity for the oxygen reduction reaction in 1.0 M KOH aq. under an oxygen atmosphere. Ag–Gr is superior as a cathode in alkaline fuel cells, which should not be disturbed by the methanol cross-over problem from the anode. We established an effective approach to prepare a series of graphene-nanoparticle composite materials using heat treatment.     

Synthesis of graphene decorated with silver nanoparticles by simultaneous reduction of graphene oxide and silver ions with glucose

A green and efficient approach for the synthesis of graphene decorated with silver nanoparticles is demonstrated by simultaneously reducing both graphene oxide (GO) sheets and silver ions with glucose as the reducing agent and poly(N-vinyl-2-pyrrolidone) (PVP) as the surface modifier. Different silver-containing materials are obtained by changing the synthesis temperature. The oxygen-containing groups of the substrate influence its decoration with the in situ formed silver nanoparticles. The combination of glucose and a silver–ammonia solution, as well as maintaining a good dispersion of GO by using PVP are crucial for the decoration of graphene with silver nanoparticles. The materials exhibit a distinct surface-enhanced Raman scattering effect.     

Preparation and characterization of tin oxide,SnO2 nanoparticles decorated graphene

SnO₂ nanoparticles/graphene (SnO₂/GP) nanocomposite was synthesized by a facile microwave method. The X-ray diffraction (XRD) pattern of the nanocomposite corresponded to the diffraction peak typical of graphene and the rutile phase of SnO₂ with tetragonal structure. The field emission scanning electron microscope (FESEM) images revealed that the graphene sheets were dotted with SnO₂ nanoparticles with an average size of 10 nm. The X-ray photoelectron spectroscopy (XPS) analysis indicated that the development of SnO₂/GP resulted from the removal of the oxygenous groups on graphene oxide (GO) by Sn²⁺ ions. The nanocomposite modified glassy carbon electrode (GCE) showed excellent enhancement of electrochemical performance when interacting with mercury(II) ions in potassium chloride supporting electrolyte. The current was increased by more than tenfold, suggesting its potential to be used as a mercury(II) sensor.     

The production of graphene nanosheets decorated with silver nanoparticles for use in transparent, conductive films

Aggregation and restacking of graphene nanosheets (GNS) can be efficiently inhibited by decorating the silver nanoparticles on the surface of GNS to form GNS/silver (GNS-Ag) composites, which can construct high transparent and electrically conductive thin films. Silver nanoparticles act as a useful nanospacer and conductor, which not only increase the interlayer distance but also improve the electrical conductivity between layers. A two-step reduction process using sodium borohydride and ethylene glycol was also demonstrated reducing graphene oxide to GNS efficiently. The GNS-Ag composite films showed a maximum sheet resistance of 93 Ω□⁻¹, while maintaining up to 78% light transmittance, which was two order of magnitude lower than that of GNS (8.2 × 10³ Ω□⁻¹, 81%), and the value of DC conductivity to optical conductivity ratio was 13.5 instead of 0.25.     

The preparation of graphene decorated with manganese dioxide nanoparticles by electrostatic adsorption for use in supercapacitors

Graphene decorated with manganese dioxide nanoparticles are prepared by electrostatic adsorption. The manganese dioxide is synthesized by a microemulsion route using the cationic surfactant hexadecyltrimethyl ammonium bromide, which dispersed in water is converted to be positively charged. The surface charge of graphene in water is negative, allowing two forms of manganese dioxide-decorated graphene to be synthesized by electrostatic adsorption: (a) free in situ synthesis and (b) layer-by-layer self-assembly. By electrochemical analysis, the specific capacitances of two materials are found to be about 40% and 250% larger than that of manganese dioxide. The improvement is because of the tighter contact between graphene and manganese dioxide, and the higher conductive and capacitive characteristics of graphene.     

Reduced graphene oxide and ZnO decorated graphene for biomedical applications

The ability of graphene-based materials to enhance the conventional antibiotic resistance is well known and researchers have been interested in improving their antibacterial activity. The reduction of graphene oxide by eco-friendly reducing agents is of great interest on the basis of environmental and human health aspects. Herein we report the synthesis of two forms of graphene derivatives namely, reduced graphene oxide (RGO) through reduction using potato starch and zinc oxide decorated RGO (ZnO-RGO). In the case of ZnO-RGO, the reduction of graphene oxide and the conversion of ZnO to nano ZnO occur simultaneously. The characterization of all the graphene based materials and nanocomposites developed were carried out using FT-IR, XRD, Raman spectra and TEM techniques. The antibacterial activity of these modified materials against E. coli was also studied by well diffusion method. Our results show that ZnO-RGO is more efficient than RGO in their antibacterial properties which we attribute to the synergistic effect of ZnO and RGO towards the bacteria in the nanocomposite. Further we find that the antibacterial effect of ZnO-RGO towards E. coli is due to the disruption of the bacterial cell which could be confirmed by AFM images. Considering the fact that graphene-based materials are less toxic towards mammalian cells, both RGO and ZnO-RGO we have developed can find applications in the field of medicine and life sciences.     

A novel hydrogen peroxide sensor based on Ag nanoparticles decorated polyaniline/graphene composites

A novel electrochemical sensor based on Ag nanoparticles (AgNPs) decorated polyaniline/graphene composites (PANI/G) is developed, which can be used for sensitive determination of H₂O₂. For the construction of the H₂O₂ sensor, polyaniline (PANI) is first electrodeposited on the surface of graphene (G) to form PANI/G, and then horseradish peroxidase (HRP) loaded on AgNPs (HRP/AgNPs) is immobilized on to the PANI/G. H₂O₂ can be catalyzed by HRP to generate current response which can be significantly enhanced by AgNPs, and thus the PANI/G based sensor can be utilized for the detection of H₂O₂. Under the optimized conditions, the proposed H₂O₂ sensor exhibits wide linear response to H₂O₂ concentration ranging from 0.25 to 2.25 mM with a detection limit of 0.03 mM (signal‐to‐noise ratio of 3), and it also shows high selectivity and reproducibility. The method is simple and cost‐effective, and can be a promising candidate as the sensitive sensing platform for H₂O₂. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42409.     

Viscoelastic and mechanical characterization of graphene decorated with graphene quantum dots reinforced epoxy composites

The article explores viscoelastic and mechanical property analysis of graphene decorated with graphene quantum dots (GDGQD) reinforced epoxy composite. Tensile, nanoindentation, and nano-dynamic mechanical analysis (DMA) tests were conducted on the composite with 0 to 1 wt% filler variation (an interval of 0.25 wt% maintained). The hardness and elastic modulus for two different loading conditions under a frequency range of 10 to 250 Hz were performed. The viscoelastic properties described through loss tangent and storage modulus graphically and the various factors such as modulus and depth of penetration were influenced by force frequency and mobility of the molecular chain. The results revealed the role of GDGQDs as filler material for enhancing the nanomechanical and tensile properties of the epoxy matrix. The differences in the properties can be ascribed to the filler interfacial bonding with the polymer matrix at the molecular level. The macro-level properties like tensile properties following the same trend as that of the micro-level properties like nano-indentation and nano-DMA results. Further, with the GDGQD aspect ratio, and assuming three-dimensionally filled randomly orientation of filler, the Halpin-Tsai model was satisfied with the experimental tensile modulus values.     

Investigation of mechanical properties of graphene decorated with graphene quantum dot-reinforced epoxy nanocomposite

In this investigation, the mechanical properties such as compression, impact, and flexural properties of graphene decorated with graphene quantum dots (GDGQD) epoxy composites with concentration of GDGQD ranging from 0.25 to 1 wt % were studied. Ideal mechanical properties are obtained by systematically varying the filler weight in the epoxy matrix. The morphological studies of GDGQD have been characterized using transmission electron microscope, X-ray diffraction, and Fourier transform infrared technique. The compression, impact, and flexural strengths were enhanced effectively by the GDGQD loading. With the addition of 0.75 wt % of GDGQD, the compressive strength, compressive modulus, flexural strength, and flexural modulus of the composites were improved by 22, 29, 31, and 63%, respectively. Also an improvement in impact strength of 102% for 0.75 wt % GDGQD epoxy sample was also obtained. Examination of fractured test specimens was performed with scanning electron microscope. The enhancement in the mechanical properties is due to the better stress transfer that is attributed by enhanced interfacial bonding between GDGQDs and the epoxy. Using the GDGQD aspect ratio in the two-dimensional randomly oriented filler modified Halpin–Tsai model, the theoretical flexural modulus for the GDGQD/epoxy composites has been established. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48680.     

Graphene films decorated with metal sulfide nanoparticles for use as counter electrodes of dye-sensitized solar cells

The composite films of metal sulfide (MS, M = Ni, Co) nanoparticles (NPs)/graphene films were proposed to be novel transparent conductive oxide- and platinum (Pt)-free counter electrodes with high electrocatalytic activity for dye-sensitized solar cells (DSSCs). Such DSSCs show higher photovoltaic conversion efficiencies of 5.25% (NiS/graphene) and 5.04% (CoS/graphene), compared with 5.00% for (Pt/fluorine-doped tin oxide). The excellent DSSC efficiencies are mainly due to the superior electrocatalytic activity of the MS and graphene films, and highly electrical properties of graphene films (9.57 Ω/sq). The excellent charge transfer between MS NPs and graphene films is due to the unique MS NPs and high surface area graphene structure. The graphene films were directly grown on dielectric SiO₂ substrates by chemical vapor deposition. MS NPs were uniformly implanted on the graphene films by dip coating of MS precursors M(C₃H₅OS₂)₂, and further annealed at 400 °C for 30 min under Ar.     

Microwave-assisted one-pot synthesis of metal/metal oxide nanoparticles on graphene and their electrochemical applications

An effective synthesis strategy of hybrid metal (PtRu)/metal oxide (SnO₂) nanoparticles on graphene nanocomposites is developed using a microwave-assisted one-pot reaction process. The mixture of ethylene glycol (EG) and water is used as both solvent and reactant. In the reaction system for the synthesis of SnO₂/graphene nanocomposite, EG not only reduces graphene oxide (GO) to graphene, but also results in the formation of SnO₂ facilitated by the presence of a small amount of water. On the other hand, in the reaction system for preparation of PtRu/graphene nanocomposites, EG acts as solvent and reducing agent for reduction of PtRu nanoparticles from their precursors and reduction of graphene from graphene oxide. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) characterizations confirm the feasibility of the microwave-assisted reaction system to simultaneously reduce graphene oxide and to form SnO₂ or PtRu nanoparticles. The as-synthesized SnO₂/graphene hybrid composites show a much higher supercapacitance than the pure graphene, and the as-prepared PtRu/graphene show much better electrocatalytic activity for methanol oxidation compared to the commercial E-TEK PtRu/C electrocatalysts.     

Endocytosis behaviours of nanoparticles with helically decorated ligands

In this work, the receptor‐mediated endocytosis of nanoparticles with helically decorated ligands was investigated by performing coarse‐grained molecular dynamics simulations. The results showed that a helical distribution of ligands can generate a unique spinning stage during endocytosis in which the nanoparticle is internalized with precession. This precession behaviour is primarily caused by a lateral torque acting on the nanoparticle. Compared with nanoparticles that present uniformly distributed ligands, nanoparticles with helically decorated ligands present an enhanced endocytosis capacity. Additionally, a longer spin duration and larger precessional angle were obtained by decreasing the helical period of the ligands. Increasing the aspect ratio of the nanoparticles strengthens their capacity to take the spinning endocytosis pathway. The present study not only reveals the mechanism underlying a new endocytosis pathway of nanoparticles with helically structured surfaces but also provides valuable theoretical information for the design of novel drug delivery systems that primarily occur via cellular uptake. © 2019 Society of Chemical Industry     

A general and efficient method for decorating graphene sheets with metal nanoparticles based on the non-covalently functionalized graphene sheets with hyperbranched polymers

Multipyrene terminated hyperbranched polyglycidol (mPHP) has been synthesized and used to non-covalently functionalize pristine graphene sheets (GSs) through π-π stacking interactions. Mediated by the mPHP layer, a variety of metal nanoparticles (Au, Ag and Pt) were in situ generated and deposited onto the surface-modified GS, yielding versatile GS/mPHP/metal nanohybrids. As typical examples, by simply controlling the concentration of HAuCl(4) used, Au nanostructures ranging from isolated spheres to a continuous film were created and coated onto the surface-modified GS. The studies on the fluorescence properties of resulting GS/mPHP/Au hybrid nanostructures reveal that the GS and controllable content of Au components in the hybrids can effectively quench the fluorescence emission of mPHP in a controlled manner. Further investigation indicates that GS/mPHP/Au hybrids are promising surface enhanced Raman scattering (SERS) substrates. The SERS activities of these hybrids depend on the contents and form of the Au. The GS/mPHP/Au hybrid containing continuous Au films exhibits the strongest SERS activity. GS/mPHP/Au hybrids are also used as efficient heterogeneous catalysts for the reduction of 4-NP, and demonstrate excellent catalytic performance. The detailed reaction kinetics and the reusability of such catalysts have also been investigated.     

Enhanced removal of naproxen from wastewater using silica magnetic nanoparticles decorated onto graphene oxide; parametric and equilibrium study

The present study describes the synthesis of silica and magnetic nanoparticle-decorated graphene oxide (GO-MNPs-SiO₂) and its application as an adsorbent for the removal of naproxen from wastewater. Nanocomposite was characterized utilizing FT-IR spectroscopy, FESEM microscopy, EDX and XPS spectroscopy. Under the optimum conditions, a high adsorption capacity (31 mg g^?1) was obtained toward naproxen at pH 5. The adsorption process was evaluated using isotherms; the Freundlich isotherm suggested a multilayer adsorption pattern for naproxen. Free energy confirmed a physisorption mechanism between naproxen and adsorbent. Lastly, the field application was performed in wastewater which obtained high removal efficiency percentages (83–94%).     

Photochemical loading of metal nanoparticles on reduced graphene oxide sheets using phosphotungstate

Well-dispersed reduced graphene oxide (r-GO) sheets loaded with metal nanoparticles were produced in dimethylformamide (DMF). The r-GO suspension was prepared through the photocatalytic reduction of graphene oxide (GO) using a phosphotungstate as a homogeneous photocatalyst under UV irradiation. Immediately after UV lamp was turned off, the injection of precursors of Ag, Au, and Pd caused the rapid nucleation because photoreduced phosphotungstates as well as electrons stored in r-GO directly reduced metal ions. Furthermore, the r-GO sheets not only provided the nucleation sites but also prohibited the metal nanoparticles from agglomeration. As a result, relatively uniform-sized metal nanoparticles were formed on the r-GO sheets. With phosphotungstates and UV light irradiation, both GO and metal ions can be reduced to form the hybrids of Ag, Au, and Pd/r-GO as a suspension in DMF or an isolated paper sheet without using any toxic reagents.     

Effect of metal nanoparticles decoration on electron field emission property of graphene sheets

The electron field emission from metal nanoparticle decorated hydrogen exfoliated graphene (metal/HEG) occurs at low turn on and threshold fields due to its low work function and high field enhancement factor.     

Large-scale synthesis of graphene by the reduction of graphene oxide at room temperature using metal nanoparticles as catalyst

A simple chemical approach has been developed for the synthesis of graphene through a mild reduction of graphene oxide (GO) using metal nanoparticles as the catalyst for the hydrolysis reaction of NaBH₄ at room temperature. The morphology and structure of the graphene were characterized with atomic force microscopy and transmission electron microscopy. The reduction process and quality of graphene were followed and examined by UV–vis absorption spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and X-ray diffraction. By this method, graphene can be prepared in large quantity without using toxic reducing agents such as hydrazine or its derivatives, making it environmentally benign. The reaction is conducted under mild conditions (room temperature), resulting in the formation of fewer defects. The method can be easily scaled up and the metal catalyst can be recycled.     

Fabrication of hybrids based on graphene and metal nanoparticles by in situ and self-assembled methods

In this work, we developed two novel strategies to attach metal nanoparticles (Au and Ag) to the surface of graphene nanosheets, in which graphene oxide was first modified by the linking molecule (3-mercaptopropyl)triethoxysilane and then subjected to different treatments including in situ and self-assembled techniques. The synthesis processes and the resulting hybrids were investigated by ultraviolet-visible measurements, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. It was found that both approaches could effectively immobilize metal nanoparticles onto a graphene surface, and that better distribution and size control of metal nanoparticles were obtained by the self-assembled method. Moreover, we prepared poly(vinylidene fluoride)/graphene-Ag nanocomposites by a solution blending method. The AC conductivity of the resulting nanocomposites could be increased significantly when the loading amount of graphene-Ag was only 2 wt%. We expect that such graphene-metal nanoparticle hybrids may be potentially useful in composite reinforcement, sensors, and electronic devices.     

Template-assisted syntheses of porous metal methylphosphonates

Neutral dibutyl methylphosphonate (DBMP) is used as a template to prepare porous metal methylphosphonates (metal = aluminum, titanium, zirconium). The removal of DBMP in the as-synthesized materials could be easily achieved by evaporation under vacuum without destroying the hybrid structure, as evidenced by elemental analyses, FT-IR spectra, ¹³C CP/MAS NMR and nitrogen adsorption-desorption isotherms. Thermal analyses show that three porous hybrid samples have high thermal stability in air. The exothermic weight losses due to oxidation combustion of organic species occluded in samples appear after 730 K. Furthermore, the templating effect of DBMP is also confirmed by comparing the hybrid materials synthesized in the presence or the absence of the template.