Nanoscale insights into graphene oxide reduction by tip-enhanced Raman spectroscopy.

Graphene oxide (GO) has attracted substantial interest for its tunable properties and as a possible intermediate for the bulk manufacture of graphene. GO and its reduced derivatives display electronic and optical properties that depend strongly on their chemical structure, and with proper functionalization, GO can have a desirable bandgap for semiconductor applications. However, its chemical activity leads to a series of unclear chemical changes under ambient conditions, resulting in changes in color and solubility upon exposure to light. In this paper, we study the properties of fresh and spontaneously reduced GO under ambient conditions using tip-enhanced Raman spectroscopy (TERS) to map its nanometer scale chemical and structural heterogeneity. We observe different types of defect sites on reduced GO (rGO) by spatially mapping the D to G band peak ratio and D and G band spectral positions. The higher spatial resolution and out-of-plane polarization compared to conventional micro-Raman spectroscopy enables us to resolve unusual features, including D-band shifting on rGO. Based on statistical analysis of the spatial variations in modes and theoretical calculations for different functional groups, we conclude the reduction mechanism of GO is a self-photocatalytic reduction with the participation of water and visible light, in which the rate determining step is electron transport through the metal substrate and ion diffusion on the GO surface. These results demonstrate that TERS can reveal structural and chemical details elucidating reduction mechanisms, through the examination of samples at different time points.

Atmospheric-pressure CVD growth of two-dimensional 2H- and 1 T'-MoTe2films with high-performance SERS activity.

Two-dimensional (2D) molybdenum ditelluride (MoTe2) is a member of the transition-metal dichalcogenides family, which is an especially promising platform for surface-enhanced Raman scattering (SERS) applications, due to its excellent electronic properties. However, the synthesis of large-area highly crystalline 2D MoTe2with controllable polymorphism is a huge challenge due to the small free energy difference (∼40 meV per unit cell) between semiconducting 2H-MoTe2and semi-metallic 1 T'-MoTe2. Herein, we report an optimized route for the synthesis of 2H- and 1 T'-MoTe2films by atmospheric-pressure chemical vapor deposition. The SERS study of the as-grown MoTe2films was carried out using methylene blue (MB) as a probe molecule. The Raman enhancement factor on 1 T'-MoTe2was found to be three times higher than that on 2H-MoTe2and the 1 T'-MoTe2film is an efficient Raman-enhancing substrate that can be used to detect MB at nanomolar concentrations. Our study also imparts knowledge on the significance of a suitable combination of laser excitation wavelength and molecule-material platform for achieving ultrasensitive SERS-based chemical detection.

Direct observation of spatially heterogeneous single-layer graphene oxide reduction kinetics.

Graphene oxide (GO) is an important precursor in the production of chemically derived graphene. During reduction, GO's electrical conductivity and band gap change gradually. Doping and chemical functionalization are also possible, illustrating GO's immense potential in creating functional devices through control of its local hybridization. Here we show that laser-induced photolysis controllably reduces individual single-layer GO sheets. The reaction can be followed in real time through sizable decreases in GO's photoluminescence efficiency along with spectral blueshifts. As-produced reduced graphene oxide (rGO) sheets undergo additional photolysis, characterized by dramatic emission enhancements and spectral redshifts. Both GO's reduction and subsequent conversion to photobrightened rGO are captured through movies of their photoluminescence kinetics. Rate maps illustrate sizable spatial and temporal heterogeneities in sp(2) domain growth and reveal how reduction "flows" across GO and rGO sheets. The observed heterogeneous reduction kinetics provides mechanistic insight into GO's conversion to chemically derived graphene and highlights opportunities for overcoming its dynamic, chemical disorder.

Large Area Synthesis of Vertical Aligned Metal Oxide Nanosheets by Thermal Oxidation of Stainless Steel Mesh and Foil.

We report here the synthesis of metal oxide nanosheets (MONs) directly grown on stainless steel substrates by thermal oxidation in the presence of trace amounts of water. The morphology and microstructure of MONs were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and atomic force microscopy (AFM). The composition of MONs was determined by the energy dispersive system and X-ray diffraction patterns. The results showed that the as-synthesized MONs were ultrathin, vertically aligned, and mostly transparent. They were polycrystalline and were composed primarily of Cr2O3 and (Fe, Mn)3O4. The optimal condition to synthesize the MONs with an optimal ultra-high surface atom ratio were determined by varying the temperature and time required for the growth of the MONs. It was found that the lateral size of MONs gradually increases as the temperature rises from 1000 to 1100 °C. An optimal temperature of 1100 °C is obtained in terms of the growth density, size and transparency degree growth morphology, and quality. The structure of MONs changes from two-dimensional to three-dimensional networks when the synthesis time is prolonged to more than 1 h.

Enhanced Performance of E-Bike Motive Power Lead-Acid Batteries with Graphene as an Additive to the Active Mass.

The effects of both graphene nanoplatelets and reduced graphene oxide as additives to the negative active material in valve-regulated lead-acid batteries for electric bikes were investigated. Low-temperature performance, charge acceptance, cycle performance, and water loss were investigated. The test results show that the low-temperature performance, charge acceptance, and large-current discharge performance of the batteries with graphene additives were significantly improved compared to the control battery, and the cycle life under 100% depth of discharge condition was extended by more than 52% from 250 to 380 cycles. Meanwhile, the amount of water loss from the batteries with graphene changed only slightly compared with the control cells. The excellent performance of the batteries can be ascribed to the graphene promoting the negative-plate charge and discharge processes and suppressing the growth of lead sulfate crystals.

Influence of electron storing, transferring and shuttling assets of reduced graphene oxide at the interfacial copper doped TiO2 p-n heterojunction for increased hydrogen production.

Herein we report simple, low-cost and scalable preparation of reduced graphene oxide (rGO) supported surfactant-free Cu2O-TiO2 nanocomposite photocatalysts by an ultrasound assisted wet impregnation method. Unlike the conventional preparation techniques, simultaneous reduction of Cu(2+) (in the precursor) to Cu(+) (Cu2O), and graphene oxide (GO) to rGO is achieved by an ultrasonic method without the addition of any external reducing agent; this is ascertained by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses. UV-visible diffused reflectance spectroscopy (DRS) studies (Tauc plots) provide evidence for the loading of Cu2O tailoring the optical band gap of the photocatalyst from 3.21 eV to 2.87 eV. The photoreactivity of the as-prepared Cu2O-TiO2/rGO samples is determined via H2 evolution from water in the presence of glycerol as a hole (h(+)) scavenger under visible light irradiation. Very interestingly, the addition of rGO augments the carrier mobility at the Cu2O-TiO2 p-n heterojunction, which is evidenced by the significantly reduced luminescence intensity of the Cu2O-TiO2/rGO photocatalyst. Hence rGO astonishingly enhances the photocatalytic activity compared with pristine TiO2 nanoparticles (NPs) and Cu2O-TiO2, by factors of ∼14 and ∼7, respectively. A maximum H2 production rate of 110 968 µmol h(-1) gcat(-1) is obtained with a 1.0% Cu and 3.0% GO photocatalyst composition; this is significantly higher than previously reported graphene based photocatalysts. Additionally, the present H2 production rate is much higher than those of precious/noble metal (especially Pt) assisted (as co-catalysts) graphene based photocatalysts. Moreover, to the best of our knowledge, this is the highest H2 production rate (110 968 µmol h(-1) gcat(-1)) achieved by a graphene based photocatalyst through the splitting of water under visible light irradiation.

Soluble reduced graphene oxide sheets grafted with polypyridylruthenium-derivatized polystyrene brushes as light harvesting antenna for photovoltaic applications.

Soluble graphene nanosheets, prepared by grafting polystyrene-based polymer chains from the surface of reduced graphene oxide (RGO), have been functionalized with pendant Ru(II) polypyridine chromophores. N-Hydroxysuccinimide (NHS) derivatized p-vinylbenzoic acid polymer chains were grown from methyl bromoisobutyrate initiation sites on the surface of RGO by atom transfer radical polymerization (ATRP). Deprotection of the resulting NHS polystyrene chains followed by amide coupling with the amine-derivatized Ru(II) polypyridyl complex [Ru(4-CH2NH2-4'-CH3-bpy)(bpy)2](2+) (4-CH2NH2-4'-CH3-bpy = 4-aminomethyl-4'-methyl 2,2'-bipyridine and bpy = 2,2'-bipyridine) afforded the covalently linked RGO-metallopolymer. The hybrid graphene-polymer assembly has been fully characterized with clear evidence for covalent attachment of the metallopolymer brushes to the graphene substrate. On the basis of thermal gravimetric analysis, one polymer strand is grafted to the surface of RGO for every hundred graphene carbons. The covalently linked polymer brushes feature controlled chain lengths of ∼30 repeat units with a small polydispersity index (PDI, ∼ 1.2). Photovoltaic cells based on the derivatized polymers and graphene-polymer assemblies were evaluated. The graphene-polymer assembly in the configuration, ITO/PEDOT:PSS/RGO-PSRu/PC60BM/Al, exhibited enhanced photocurrent and power conversion efficiencies (∼5 fold) relative to devices with the configuration, ITO/PEDOT:PSS/PSRu/PC60BM/Al.