An in situ oxidation route to fabricate graphene nanoplate-metal oxide composites

We report our studies on an improved soft chemical route to directly fabricate graphene nanoplate-metal oxide (Ag₂O, Co₃O₄, Cu₂O and ZnO) composites from the in situ oxidation of graphene nanoplates. By virtue of H⁺ from hydrolysis of the metal nitrate aqueous solution and NO₃⁻, only a small amount of functional groups were introduced, acting as anchor sites and consequently forming the graphene nanoplate-metal oxide composites. The main advantages of this approach are that it does not require cumbersome oxidation of graphite in advance and no need to reduce the composites due to the lower oxidation degree. The microstructures of as-obtained metal oxides on graphene nanoplates can be dramatically controlled by changing the reaction parameters, opening up the possibility for processing the optical and electrochemical properties of the graphene-based nanocomposites.     

Ultrasonic route synthesis,characterization and electrochemical study of graphene oxide and reduced graphene oxide

Research on Chemical Intermediates - In this study, an efficient route for graphene oxide (GO) and reduced GO (RGO) synthesis was developed by using an ultrasonic probe and bath alternatively. RGO...     

Aerosol-assisted route to low-E transparent conductive gallium-doped zinc oxide coatings from pre-organized and halogen-free precursor

Thermal control in low-emission windows is achieved by the application of glazings, which are simultaneously optically transparent in the visible and reflective in the near-infrared (IR). This phenomenon is characteristic of coatings with wide optical band gaps that have high enough charge carrier concentrations for the material to interact with electromagnetic radiation in the IR region. While conventional low-E coatings are composed of sandwiched structures of oxides and thin Ag films or of fluorinated SnO₂ coatings, ZnO-based glazing offers an environmentally stable and economical alternative with competitive optoelectronic properties. In this work, gallium-doped zinc oxide (GZO) coatings with properties for low-E coatings that exceed industrial standards (T_visible > 82%; R_{2500 nm} > 90%; λ_(plasma) = 1290 nm; ρ = 4.7 × 10⁻⁴ Ω cm; R_sh = 9.4 Ω·□⁻¹) are deposited through a sustainable and environmentally friendly halogen-free deposition route from [Ga(acac)₃] and a pre-organized zinc oxide precursor [EtZnOⁱPr]₄ (1) via single-pot aerosol-assisted chemical vapor deposition. GZO films are highly (002)-textured, smooth and compact without need of epitaxial growth. The method herein describes the synthesis of coatings with opto-electronic properties commonly achievable only through high-vacuum methods, and provides an alternative to the use of pyrophoric ZnEt₂ and halogenated SnO₂ coatings currently used in low-emission glazing and photovoltaic technology.

A pre-organised and halogen-free ZnO precursor is used to deposit GZO coatings via aerosol-assisted CVD with properties that exceed industrial standards for low-E coatings and photovoltaics.     

A facile method to fabricate ZnO hollow spheres and their photocatalytic property

This paper presents a novel and facile method for the fabrication of ZnO hollow spheres. In this approach, zinc ions were first adsorbed onto the surfaces of sulfonated polystyrene core-shell template spheres, and then reacted with NaOH to form a ZnO crystal nucleus, which was followed by a growth step to form ZnO nanoshells. During the formation of ZnO nanoshells or later on, the template spheres were "dissolved" in the same media to obtain ZnO hollow spheres directly. Neither additional dissolution nor calcination process was needed in this method to remove the templates, and the reaction conditions were very mild: neither high temperature nor long time was needed. Transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and Brunauer-Emmett-Teller analysis were used to investigate the morphology, surface composition, crystalline structure, specific surface area, and porosity of the ZnO hollow spheres, respectively. UV-visible spectra show that these ZnO hollow spheres had very good photocatalytic activity.     

Highly transparent solution processed In-Ga-Zn oxide thin films and thin film transistors

Highly transparent In-Ga-Zn oxide (IGZO) thin films were fabricated by spin coating using acetate- and chlorate-based precursors, and thin film transistors (TFTs) were further fabricated employing these IGZO films as the active channel layer. The impact of the post-annealing temperature on the physical properties of IGZO films and performance of IGZO TFTs were investigated. Compared to the nitrate-based IGZO precursor, the chlorate-based precursor increases the phase change temperature of IGZO thin films. The IGZO films changed from amorphous to nanocrystalline phase in an annealing temperature range of 600–700 °C. The transparency is more than 90% in the visible region for IGZO films annealed with temperatures higher than 600 °C. With the increase of post-annealing temperature, the carrier concentration of IGZO film decreases, while the sheet resistance increases firstly and then saturates. The bottom-gate TFT with IGZO channel annealed at 600 °C in oxygen showed the best performance, which was operated in n-type enhancement mode with a field effect mobility of 1.30 cm²/V s, a threshold voltage of 10 V, and a drain current on/off ratio of 2.5 × 10⁴.     

A sol-gel route for the development of rare-earth aluminum borate nanopowders and transparent thin films

A new sol-gel route was applied to obtain Y_0.9Er_0.1Al₃(BO₃)₄ crystalline powders and amorphous thin films by using Al(acac)₃, B(OPrⁱ)₃, Y(NO₃)₃·6H₂O, and Er(NO₃)₃·5H₂O as starting materials dissolved in propionic acid and ethyl alcohol mixtures. Our study shows that propionic acid acts as good chelant agent for yttrium and erbium ions while ethyl alcohol allows to dissolve Al(acac)₃. This process makes the resulting sols very stable to obtain homogeneous gels and transparent amorphous thin films. In addition, the propionic acid prevents the sol precipitation, making easy porous- and crack-free thin film depositions. Chemical reactions involved in the complexation were discussed. As-prepared powders and films are amorphous and present a good thermal stability due to their high glass transition (746 °C) and crystallization temperatures (830 °C). This new sol-gel route showed to be adequate to obtain dense and crack-free thin films free of organic and hydroxyl groups that can be considered as promising materials to be used in integrated optical systems.     

A simple route to ordered metal oxide nanoparticle arrays using block copolymer thin films

Oxide nanoparticles arrays are easily synthesized in a 3-steps method including (i) the deposition of poly(styrene)-b-poly(4-vinylpyridine) (PS-b-PVP) thin films, (ii) the selective deposition of inorganic precursors and (iii) the synthesis of oxide nanoparticles and the elimination of the polymer scaffold by thermal annealing. The specific staining of the PVP domains by inorganic precursors is obtained in this study thanks to a simple and fast spin coating process using an alcoholic solution of the precursors. This simple lab-procedure is used to synthesize a wide range of metallic (silicon, titanium, cerium, ruthenium, zinc and manganese) oxides, showing that this method can be extended to the synthesis of all kinds of oxides with all kinds of precursors as long as the precursor is soluble in P4VP solvent. It is shown that this strategy can be extended to the synthesis of oxide nanorods.     

Highly transparent and conductive thin films fabricated with nano-silver/double-walled carbon nanotube composites

This study develops a technique for enhancing the electrical conductivity and optical transmittance of transparent double-walled carbon nanotube (DWNT) film. Silver nanoparticles were modified with a NH(2)(CH(2))(2)SH self-assembled monolayer terminated by amino groups and subsequent surface condensation that reacted with functionalized DWNTs. Ag nanoparticles were grafted on the surface of the DWNTs. The low sheet resistance of the resulting thin conductive film on a polyethylene terephthalate (PET) substrate was due to the increased contact areas between DWNTs and work function by grafting Ag nanoparticles on the DWNT surfaces. Increasing the contact area between DWNTs and work function improved the conductivity of the DWNT-Ag thin films. The prepared DWNT-Ag thin films had a sheet resistance of 53.4 Ω/sq with 90.5% optical transmittance at a 550 nm wavelength. After treatment with HNO(3) and annealing at 150 °C for 30 min, a lower sheet resistance of 45.8 Ω/sq and a higher transmittance of 90.4% could be attained. The value of the DC conductivity to optical conductivity (σ(DC)/σ(OP)) ratio is 121.3.     

Double laminated reduced graphene/Cu_2S/reduced graphene/graphene oxide nanofilms and their photoelectrochemical properties

In this work,an efficient photocatalytic material was prepared directly on Indium tin oxide(ITO)glass substrates by fabricating Cu_2 S and graphene oxide onto graphene for photoelectrochemical(PEC) water splitting.The double laminated reduced graphene/Cu_2S/reduced graphene/graphene oxide(RG/Cu_2S/RG/GO) nanofilms were characterized,and an enhanced photoelectrochemical response in the visible region was discovered.The photocurrent density of the nanofilms for PEC water splitting was measured to be up to 1.98 m A/cm~2,which could be ascribed to the followings:(i) a higher efficiency of light-harvesting because of GO coupling with Cu_2 S that could broaden the absorbing solar spectrum and enhance the light utilization efficiency;(ii) a stepwise structure of band-edge levels in the Cu_2S/GO electrode was constructed;(iii) double laminated electron accelerator(RG) was used in the Cu_2S/GO materials to get better electron-injecting efficiency.     

Transparent and conductive thin films of graphene/polyaniline nanocomposites prepared through interfacial polymerization

This communication reports a simple, one-pot procedure for the synthesis and processing of transparent and conductive thin films of graphene/polyaniline nanocomposites based on an interfacial polymerization. Thin films presenting transmittance of 89% and sheet resistance of 60.6 ? sq(-1) are spontaneously obtained and can be easily transferred to suitable substrates.     

Double laminated reduced graphene/Cu2S/reduced graphene/graphene oxide nanofilms and their photoelectrochemical properties

In this work,an efficient photocatalytic material was prepared directly on Indium tin oxide（ITO）glass substrates by fabricating Cu₂ S and graphene oxide onto graphene for photoelectrochemical（PEC） water splitting.The double laminated reduced graphene/Cu₂S/reduced graphene/graphene oxide（RG/Cu₂S/RG/GO） nanofilms were characterized,and an enhanced photoelectrochemical response in the visible region was discovered.The photocurrent density of the nanofilms for PEC water splitting was measured to be up to 1.98 m A/cm²,which could be ascribed to the followings:（i） a higher efficiency of light-harvesting because of GO coupling with Cu₂ S that could broaden the absorbing solar spectrum and enhance the light utilization efficiency;（ii） a stepwise structure of band-edge levels in the Cu₂S/GO electrode was constructed;（iii） double laminated electron accelerator（RG） was used in the Cu₂S/GO materials to get better electron-injecting efficiency.     

A new route to fabricate large-area, compact Ag metal mesh films with ordered pores

Ordered Si nanowire (SiNW) arrays can be fabricated by metal-assisted chemical etching. The metal mesh films (MMFs) are extremely important for achieving a high quality of the SiNWs. We have developed a two-step chemical deposition method to obtain compact porous Ag MMFs. By the separation of the nucleation and growth stages of the metal in the two-step deposition processes, the overgrowth of the metals to form randomly aggregated irregular metal particles can be overcome. Hexagonally arranged polystyrene (PS) latex microspheres have been employed as a template for the deposition of porous Ag MMFs. The spacing of the pores in the Ag MMFs is determined by the diameter of PS microspheres, and the pore size can also be tuned by changing Ar plasma etching time. One of the main advantages of the two-step deposition method lies in that Ag MMFs can be produced with PS microspheres that are not limited to a single layer, which dramatically simplifies the tedious processes of producing a monolayered PS template. The two-step chemical deposition method shows great potential in metal-assisted chemical etching.     

PE-CPE blends and their graphene oxide nanocomposites with reduced low temperature brittleness

The low-temperature flexibility of polyethylene (PE)–chlorinated polyethylene (CPE) blends and their composites with a small amount of graphene oxide filler was studied. Quantitative height variation in the AFM images, rheological as well as fracture analyses were employed to gain insights into the generation of flexibility in the matrix phase. The semi-crystalline CPE (CPE25) polymer did not induce viscoelastic behavior at temperatures lower than the glass transition temperature of PE, whereas the amorphous CPE (CPE35) had completely different behavior. The samples with CPE35 could not be sufficiently hardened even at ?180 °C and remained too soft for cryosectioning. Therefore, compression, which results in a 30–60 % reduction in length along the cutting direction with no change in the dimension perpendicular to it, was very prominent for both thin section and block face of the sample. The composites had even higher degree of compression due to additional effect of weak filler matrix interactions and as a consequence, the topographical variations led to filler pull out during sectioning. It was also confirmed using the rheological analysis that composites (and blends with 10 % CPE35 content) had phase immiscibility as CPE phase was suspected to concentrate near the graphene oxide phase leading to generation of chlorine-rich phases. The addition of graphene oxide did not lead to reduced flexibility and the composites also retained the modulus similar to pure polymer. The mechanical fracture of the samples also confirmed the flexibility of the CPE containing blends and composites as these samples were still flexible at ?195 °C.     

Cobalt oxide thin films for high capacity and stable Li-ion battery anode

Journal of Solid State Electrochemistry - Here, we report reactive DC-sputter deposited Co3O4 thin films as a promising and stable Li-ion battery anode. Thin films were deposited on stainless steel...     

A colloidal route to fabricate hierarchical sticky and non-sticky substrates

Ginsenoside Ro (Ro), a natural anionic biosurfactant derived from ginseng, has been found to markedly increase the solubility of saikosaponin a (SSa), which is the active ingredient of Radix Bupleuri. SSa is minimally soluble in water. To determine the mechanism by which Ro solubilizes SSa, the self-assembly behavior of Ro and the phase behavior of blended Ro and SSa systems were studied by mesoscopic dynamics (MesoDyn) and dissipative particle dynamics (DPD) simulations. The simulation results show that Ro can form vesicles via the closure of oblate membranes. At low concentrations, SSa molecules are solubilized in the palisade layer of the Ro vesicles. At high concentrations, they interact with Ro molecules to form mixed vesicles with Ro adsorbing on the surfaces of the vesicles. The evaluation of the SSa solubilization process reveals that, at low concentrations, Ro aggregates preferentially to form vesicles, which then absorb SSa into themselves. However, at high concentrations, SSa first self-aggregates and then dissolves. This is because the solubilization behavior of Ro shifts the precipitation-dissolution equilibrium in the direction of dissolution. These results of the simulations are consistent with those of transmission electron microscopy (TEM) and dynamic light scattering (DLS).     

A facile route to 4,5,6,7-tetrahydrothiophenes and benzothiophenes

2-Substituted tetrahydro- and cyclopentathiophenes 2 were produced in high yields by treatment of the semi-cyclic trisubstituted 1,4-diketones 1 such as 2-phenacylcyclohexan-1-one, 2-acetonylcyclohexan-1-one, and 2-phenacylcyclopentan-1-one, with Lawesson's reagent.     

A facile route to ruthenium–carbene complexes and their application in furfural hydrogenation

A number of new N‐heterocyclic carbene (NHC) ligands were synthesized via a multicomponent reaction, wherein an aldehyde or ketone, a primary amine and an α‐acidic isocyanide were reacted, giving the corresponding 2H‐2‐imidazolines. These were easily alkylated with an alkyl halide at position N‐3, yielding the final NHC precursors, that were then complexed with Ru in situ. The resulting complexes are shown to be active and selective catalysts for the transfer hydrogenation of furfural to furfurol, using isopropanol as the hydrogen source. Importantly, the carbene ligand remains coordinated to the ruthenium center throughout the reaction. Copyright © 2009 John Wiley & Sons, Ltd.     

A facile route to temperature determination in hot-wire electrochemistry

The determination of the actual electrode surface temperature is important for all electrochemical methods using in situ heating of electrodes. Existing methods of temperature measurement of a heated thin-wire electrode are of restricted use and critically discussed in the introduction. The use of the electrode wire itself as a resistive thermometer is improved in the present method. With the new thermoelectrochemical method temperature pulse voltammetry, the reliability of different thermometric methods can be compared. In this way, it is ensured to have correct temperature measurements at wire microelectrodes in all common solvents available.     

A facile route to electronically conductive polyelectrolyte brushes as platforms of molecular wires

A facile strategy for the synthesis of conjugated polyelectrolyte brushes grafted from a conductive surface is presented. Such brushes form a platform of molecular wires oriented perpendicularly to the surface, enabling efficient directional transport of charge carriers. As the synthesis of conjugated polymer brushes using chain-growth polymerization via a direct “grafting from” approach is very challenging, we developed a self-templating surface-initiated method. It is based on the formation of multimonomer template chains in the first surface-initiated polymerization step, followed by the second polymerization leading to conjugated chains in an overall ladder-like architecture. This strategy exploits the extended conformation of the surface-grafted brushes, thereby enabling alignment of the pendant polymerizable groups along the template chains. We synthesized a new bifunctional monomer and used the developed approach to obtain quaternized poly(ethynylpyridine) chains on a conductive indium tin oxide surface. A catalyst-free quaternization polymerization was for the first time used here for surface grafting. The presence of charged groups makes the obtained brushes both ionically and electronically conductive. After doping with iodine, the brushes exhibited electronic conductivity, in the direction perpendicular to the surface, as high as 10^–1–10⁰ S m^–1. Tunneling AFM was used for mapping the surface conductivity and measuring the conductivity in the spectroscopic mode. The proposed synthetic strategy is very versatile as a variety of monomers with pendant polymerizable groups and various polymerization techniques may be applied, leading to platforms of molecular wires with the desired characteristics.