Bismuth ferrite based acetone gas sensor: evaluation of graphene oxide loading.

We report a BiFeO3/graphene oxide (BFO/GO) perovskite, synthesized using a CTAB-functionalized glycine combustion route, as a potential material for acetone gas sensing applications. The physicochemical properties of the developed perovskite were analysed using XRD, FE-SEM, TEM, HRTEM, EDAX and XPS. The gas sensing performance was analysed for various test gases, including ethanol, acetone, propanol, ammonia, nitric acid, hydrogen sulphide and trimethylamine at a concentration of 500 ppm. Among the test gases, the developed BFO showed the best selectivity towards acetone, with a response of 61% at an operating temperature of 250 °C. All the GO-loaded BFO samples showed an improved gas sensing performance compared with pristine BFO in terms of sensitivity, the response/recovery times, the transient response curves and the stability. The 1 wt% GO-loaded BiFeO3 sensor showed the highest sensitivity of 89% towards acetone (500 ppm) at an operating temperature of 250 °C. These results show that the developed perovskites have significant potential for use in acetone gas sensing applications.

RGO/WO3 hierarchical architectures for improved H2S sensing and highly efficient solar-driving photo-degradation of RhB dye.

Surface area and surface active sites are two important key parameters in enhancing the gas sensing as well as photocatalytic properties of the parent material. With this motivation, herein, we report a facile synthesis of Reduced Graphene Oxide/Tungsten Oxide RGO/WO3 hierarchical nanostructures via simple hydrothermal route, and their validation in accomplishment of improved H2S sensing and highly efficient solar driven photo-degradation of RhB Dye. The self-made RGO using modified Hummer's method, is utilized to develop the RGO/WO3 nanocomposites with 0.15, 0.3 and 0.5 wt% of RGO in WO3 matrix. As-developed nanocomposites were analyzed using various physicochemical techniques such as XRD, FE-SEM, TEM/HRTEM, and EDAX. The creation of hierarchic marigold frameworks culminated in a well affiliated mesoporous system, offering efficient gas delivery networks, leading to a significant increase in sensing response to H2S. The optimized sensor (RGO/WO3 with 0.3 wt% loading) exhibited selective response towards H2S, which is ~ 13 times higher (Ra/Rg = 22.9) than pristine WO3 (Ra/Rg = 1.78) sensor. Looking at bi-directional application, graphene platform boosted the photocatalytic activity (94% degradation of Rhodamine B dye in 210 min) under natural sunlight. The RGO's role in increasing the active surface and surface area is clarified by the H2S gas response analysis and solar-driven photo-degradation of RhB dye solution. The outcome of this study provides the new insights to RGO/WO3 based nanocomposites' research spreadsheet, in view of multidisciplinary applications.

Microwave-Epoxide-Assisted Hydrothermal Synthesis of the CuO/ZnO Heterojunction: a Highly Versatile Route to Develop H2S Gas Sensors.

A robust synthesis approach to develop CuO/ZnO nanocomposites using microwave-epoxide-assisted hydrothermal synthesis and their proficiency toward H2S gas-sensing application are reported. The low-cost metal salts (Cu and Zn) as precursors in aqueous media and epoxide (propylene oxide) as a proton scavenger/gelation agent are used for the formation of mixed metal hydroxides. The obtained sol was treated using the microwave hydrothermal process to yield the high-surface area (34.71 m2/g) CuO/ZnO nanocomposite. The developed nanocomposites (1.25-10 mol % Cu doping) showcase hexagonal ZnO and monoclinic CuO structures, with an average crystallite size in the range of 18-29 nm wrt Cu doping in the ZnO matrix. The optimized nanocomposite (2.5 mol % Cu doping) showed a lowest crystallite size of 21.64 nm, which reduced further to 18.06 nm upon graphene oxide addition. Morphological analyses (scanning electron microscopy and transmission electron microscopy) exhibited rounded grains along with copious channels typical for sol-gel-based materials . Elemental mapping displayed the good dispersion of Cu in the ZnO matrix. When these materials are employed as a gas sensor, they demonstrated high sensitivity and selectivity toward H2S gas in comparison with the reducing gases and volatile organic compounds under investigation. The systematic doping of Cu in the ZnO matrix exhibited an improved response from 76.66 to 94.28%, with reduction in operating temperature from 300 to 250 °C. The 2.5 mol % doped Cu in ZnO was found to impart a response of 23 s for 25 ppm of H2S. Gas-sensing properties are described using an interplay of epoxide-assisted sol-gel chemistry and structural and morphological properties of the developed material.

A greener approach towards the development of graphene-Ag loaded ZnO nanocomposites for acetone sensing applications.

We report a facile, green synthesis of graphene/Ag/ZnO nanocomposites and their use as acetone sensors via a medicinal plant extraction assisted precipitation process. The choice of plant extract in combination with metal nitrates led to self-sustaining colloid chemistry. Along with the green synthesis strategy, structural, morphological and gas sensing properties are described.

Ru-Loaded mesoporous WO3 microflowers for dual applications: enhanced H2S sensing and sunlight-driven photocatalysis.

We report a facile synthesis of Ru-loaded WO3 marigold structures through a hydrothermal route and their bidirectional applications as enhanced H2S gas sensors and efficient sunlight-driven photocatalysts. The developed hierarchical marigold structures provide effective gas diffusion channels via a well-aligned mesoporous framework, resulting in remarkable enhancement in the sensing response to H2S. The temperature and gas concentration dependence on the sensing properties reveals that Ru loading not only improves the sensing response, but also lowers the operating temperature of the sensor from 275 to 200 °C. The 0.5 wt% Ru-loaded WO3 shows selective response towards H2S, which is 45 times higher (142) than that of pristine WO3 (3.16) sensor, whereas the 0.25 wt% Ru-loaded WO3 exhibits the highest photocatalytic activity, as shown by the degradation of rhodamine B (RhB) under natural sunlight. The gas sensing and photocatalytic properties are explained through the role of Ru and the structural and morphological properties of the developed material.

Synthesis of single crystalline CdS nanocombs and their application in photo-sensitive field emission switches.

Single crystalline CdS nanocombs were synthesized by a thermal evaporation route. The photo-sensitive field emission current shows a reproducible switching behavior, with a rise in current level of nearly five times the initial preset value of ∼1 µA. An ultra low turn-on field, required to draw an emission current density of ∼0.1 µA cm(-2) (100 nA), is found to be ∼0.26 V µm(-1) (260 V), which is much lower than the reported values for various other CdS nanostructures. Upon illumination with visible light the CdS nanocombs act as a photo field emission switch. At an applied field of ∼0.65 V µm(-1) the current densities are observed to be ∼14.6 µA cm(-2) and ∼26.9 µA cm(-2), without and with light illumination, respectively. The average emission current is seen to be stable over the duration of measurement for two preset values. The high sensitivity and fast response in the visible range indicates that the CdS nanocombs can be used as a photo-sensitive field emitting switch in device applications, and also in pulsed electron beam technology.

The Fowler-Nordheim plot behavior and mechanism of field electron emission from ZnO tetrapod structures.

Field emission measurements of current-voltage characteristics are reported for tetrapod structures of ZnO. The nonlinear Fowler-Nordheim (FN) plot is analyzed according to a model of calculation based on saturation of conduction band current and predominance of valence band current at high-field values. The simulated FN plot exhibits similar features to those observed experimentally. The model of calculation suggests that the slope variation of the FN plot, in the high-field and low-field regions, does not depend on the magnitude of saturation. Instead, it is a characteristic of the energy band structure and voltage-to-barrier-field conversion factor of the emitting material.

Electrochemical sensing of sulphur dioxide: a comparison using dodecanethiol and citrate capped gold nanoclusters.

A comparison of cyclic voltammograms of dodecanethiol (DDT) capped Au nanoclusters (5.0 0.5 nm) and trisodium citrate (Cit) capped Au nanoclusters (approximately 10-15 nm) modified glassy carbon electrode shows a dramatic variation in the current when exposed to a small amount of sulphur dioxide. This is explained using the electrocatalytic properties of Au nanoclusters towards the oxidation of SO2, thus facilitating the fabrication of electrochemical sensors for the detection of SO2. The intrinsic redox changes observed for gold nanocluster-modified glassy carbon electrodes disappear on passing SO2, despite a dramatic current increase, which indeed scales up with the amount of dissolved SO2. Interestingly, a complete rejuvenation of the redox behavior of gold is also observed on subsequent removal of SO2 from the solution by passing pure nitrogen for 15 minutes. Further, these nanoclusters when characterized with X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) after SO2 passage reveal a variety of SO2 adsorption modes on gold surface. XP spectra also show a shift of 1.03 eV towards higher binding energy indicating a strong adsorption of SO2 gas, while FTIR gives conclusive evidence for the interaction of SO2 with gold nanoparticles.

'All-solid-state' electrochemistry of a protein-confined polymer electrolyte film.

Interfacial redox behavior of a heme protein (hemoglobin) confined in a solid polymer electrolyte membrane, Nafion (a perfluoro sulfonic acid ionomer) is investigated using a unique 'all-solid-state' electrochemical methodology. The supple phase-separated structure of the polymer electrolyte membrane, with hydrophilic pools containing solvated protons and water molecules, is found to preserve the incorporated protein in its active form even in the solid-state, using UV-visible, Fluorescence (of Tryptophan and Tyrosine residues) and DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy. More specifically, solid-state cyclic voltammetry and electrochemical impedance of the protein-incorporated polymer films reveal that the Fe2+-form of the entrapped protein is found to bind molecular oxygen more strongly than the native protein. In the 'all-solid-state' methodology, as there is no need to dip the protein-modified electrode in a liquid electrolyte (like the conventional electrochemical methods), it offers an easier means to study a number of proteins in a variety of polymer matrices (even biomimetic assemblies). In addition, the results of the present investigation could find interesting application in a variety of research disciplines, in addition to its fundamental scientific interest, including protein biotechnology, pharmaceutical and biomimetic chemistry.

ZnO multipods, submicron wires, and spherical structures and their unique field emission behavior.

A simple method of vapor deposition for the shape selective synthesis of ZnO structures, namely, multipods, submicron wires, and spheres, has been successfully demonstrated. A plausible growth mechanism based on the studies of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) is proposed. Our studies suggest that the growth of a multipod structure is governed by the screw dislocation propagation while the vapor-liquid-solid (VLS) mechanism is responsible for the formation of submicron wires and spheres. Moreover, the flow rate of the carrier gas plays a crucial role in governing the morphology. Further, these structures exhibit an enhanced field emission behavior. The nonlinearity in the Fowler-Nordheim (F-N) plot, a characteristic feature of electron emission from semiconductors, is explained by considering the contributions from both the conduction and the valence bands of ZnO.

Suppression of electron-transfer characteristics of ferrocene by OTS monolayer on a silicon/electrolyte interface.

The passivating behavior of self-assembled monolayers (SAMs) of octadecyltrichlorosilane (OTS) on an n-type Si(100) electrode with and without a redox species like ferrocene in a polar non-aqueous medium has been investigated using techniques like contact angle measurements, Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to understand the role of the monolayer. The electron-transfer behavior of ferrocene is found to be drastically affected by the presence of monolayer and the reasons for these are analyzed as a function of the change in resistance, dielectric thickness and coverage of the monolayer. Electrochemical impedance analysis in the presence of ferrocene gives the monolayer coverage as 0.998 and the apparent rate constant calculated from this gives 4.85 x 10(-12) cm s(-1) in comparison with 4.4 x 10(-8) cm s(-1) for a similar electrode without any monolayer. A positive shift of 200 mV in the flat-band potential after monolayer formation also suggests the covalent coupling of the silane monolayer offering a protective barrier.

Micropencils and microhexagonal cones of ZnO.

Shape selective synthesis of ZnO micropencils and microhexagonal cones has been demonstrated using a controlled method of modified vapor deposition. A plausible growth mechanism based on the results of scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetry, and differential thermal analysis is proposed. Our results suggest that growth of micropencil takes place as per the vapor-liquid-solid progression while the microhexagonal cones grow in two steps following a vapor-solid/vapor-liquid-solid mechanism. Moreover, the geometry, the location of substrate and temperature are found to have key roles in governing the morphology. XPS studies clearly demonstrate the presence of Si species as SiO and SiO2, which act as catalysts enabling nucleating sites for ZnO microstructural growth.

Effect of RuO2 in the shape selectivity of submicron-sized SnO2 structures.

Several dissimilar types of tin oxide microstructures including bipyramids, cubes, and wires synthesized effectively by means of a simple approach were investigated using X-ray diffraction (XRD), thermogravimetry/differential thermometric analysis (TG-DTA), and X-ray photoelectron spectroscopy (XPS). A possible growth mechanism is proposed using the results of these studies. The texture coefficient values of all the structures, indexed to a tetragonal lattice, exhibit amazing variation in the preferred orientation with respect to their shapes. Although XPS data indicate that wires and cubes have a strong SnO(2) type signal, bipyramids interestingly exhibit both SnO and SnO(2) signals and a correlation of the binding energy helps in understanding the growth kinetics of such submicron structures. The results suggest that the bipyramids are formed because of the vapor-solid process (VS) while wires and cubes are formed by the vapor-liquid-solid (VLS) progression.