Coconut Fiber Decorated with Bismuth Vanadate for Enhanced Photocatalytic Activity.

Bismuth vanadate/coconut fiber (BiVO4/CF) composites were synthesized by coprecipitation and calcination methods. All catalysts used in this work were prepared by a simple coprecipitation method and fully characterized by means of XRD, SEM-EDS, PL, BET N2 adsorption, zeta potential, and UV-vis DRS. Degradation of indigo carmine (IC) under visible light irradiation was tracked by the UV-vis technique. It was documented that XRD patterns of BiVO4 and BiVO4/CF samples retained the monoclinic structure. From SEM, the CF sheets were visualized, covering the surface of BiVO4 particles. The specific surface area of the synthesized catalysts increased from 1.77 to 24.82 m2/g. The shift of absorption edge to a longer wavelength corresponded to a decrease in band gap energy from 2.3 to 2.2 eV. The photocatalytic degradation rate of the BiVO4/CF composite was five times higher than that of pristine BiVO4. Moreover, the photocatalyst can be separated and recycled with little change after the third times recycling. The improved activity of the composite resulted from the combination of the adsorption performance of the substrate CF and the photocatalytic activity of BiVO4. In addition, the position of the specific mechanism could occur via both the active species of superoxide radical and hydroxyl radical.

Synthesis and Characterization of WO3/CeO2 Heterostructured Nanoparticles for Photodegradation of Indigo Carmine Dye.

WO3/CeO2 heterostructured nanocomposites containing different WO3 ratios (0.1, 0.3, 0.5, and 1.0 wt %) were synthesized by a precipitation method. The coupling of CeO2 and WO3 with a high specific surface area noticeably enhanced the photocatalytic activity of indigo carmine (IC) degradation under visible-light irradiation. The degradation rate constants (k) of 0.5 wt % WO3/CeO2 nanocomposites reached 4 and 5 times higher than those of CeO2 and WO3, respectively. Regarding the experimental results, the X-ray diffraction (XRD) patterns of the CeO2 spherical nanoparticles and rod-shaped WO3 were assigned to the cubic fluorite and orthorhombic phase structures, respectively. The increasing photocatalytic activity of nanocomposite samples could be attributed to the heterojunction of the photocatalysts with efficient charge separation and strong oxidative ability, which were confirmed by the photoluminescence spectra and diffuse reflectance spectrometry. The staggered heterojunction of the nanocomposite promoted efficient electron transfer and suppressed the recombination of photogenerated electrons and holes during the process.

Electrochemical Dopamine Biosensor Based on Poly(3-aminobenzylamine) Layer-by-Layer Self-Assembled Multilayer Thin Film.

Dopamine (DA) is an important neurotransmitter which indicates the risk of several neurological diseases. The selective determination with low detection limit is necessary for early diagnosis and prevention of neurological diseases associated with abnormal concentration of DA. The purpose of this study is to fabricate a poly(3-aminobenzylamine)/poly(sodium 4-styrenesulfonate) (PABA/PSS) multilayer thin film for use as an electrochemical DA biosensor. The PABA was firstly synthesized using a chemical oxidation method of 3-aminobenzylamine (ABA) monomer with ammonium persulfate (APS) as an oxidant. For electrochemical biosensor, the PABA/PSS thin film was fabricated on fluorine doped tin oxide (FTO)-coated glass substrate using the layer-by-layer (LBL) self-assembly method. The optimized number of bilayers was achieved using SEM and cyclic voltammetry (CV) results. The electroactivity of the optimized LBL thin film toward detection of DA in neutral solution was studied by CV and amperometry. The PABA/PSS thin film showed good sensitivity for DA sensing with sensitivity of 6.922 nA·cm-2·µM-1 and linear range of 0.1-1.0 µM (R2 = 0.9934), with low detection limit of 0.0628 µM, long-term stability and good reproducibility. In addition, the selectivity of the PABA/PSS thin film for detection of DA under the common interferences (i.e., ascorbic acid, uric acid and glucose) was also presented. The prepared PABA/PSS thin film showed the powerful efficiency for future use as DA biosensor in real sample analysis.

Highly Sensitive and Selective Sensing of H2S Gas Using Precipitation and Impregnation-Made CuO/SnO2 Thick Films.

In this work, CuO-loaded tetragonal SnO2 nanoparticles (CuO/SnO2 NPs) were synthesized using precipitation/impregnation methods with varying Cu contents of 0-25 wt% and characterized for H2S detection. The material phase, morphology, chemical composition, and specific surface area of NPs were evaluated using X-ray diffraction, transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller analysis. From gas-sensing data, the H2S responses of SnO2 NPs were greatly enhanced by CuO loading particularly at the optimal Cu content of 20 wt%. The 20 wt% CuO/SnO2 sensor showed an excellent response of 1.36 × 105 toward 10 ppm H2S and high H2S selectivity against H2, SO2, CH4, and C2H2 at a low optimum working temperature of 200 °C. In addition, the sensor provided fast response and a low detection limit of less than 0.15 ppm. The CuO-SnO2 sensor could therefore be a potential candidate for H2S detection in environmental applications.

Chemophysical acetylene-sensing mechanisms of Sb2O3/NaWO4-doped WO3 heterointerfaces.

Sb2O3-loaded NaWO4-doped WO3 nanorods were fabricated with varying Sb contents from 0 to 2 wt% by precipitation/impregnation methods and their p-type acetylene (C2H2) gas-sensing mechanisms were rigorously analyzed. Material characterization by X-ray diffraction, X-ray photoelectron spectroscopy, scanning transmission electron microscopy and nitrogen adsorption indicated the construction of short NaWO4-doped monoclinic WO3 nanorods loaded with very fine Sb2O3 nanoparticles. The sensors were fabricated by powder pasting and spin coating and their gas-sensing characteristics were evaluated towards 0.08-1.77 vol% C2H2 at 200-350 °C in dry air. The gas-sensing properties of the NaWO4-doped WO3 sensor with the optimum Sb content of 1 wt% showed the highest p-type response of ∼250.2 to 1.77 vol% C2H2, which was more than 20 times as high as that of the unloaded one at the best working temperature of 250 °C. Furthermore, the Sb2O3-loaded sensor offered high C2H2 selectivity against CH4, H2, C3H6O, C2H5OH, HCHO, CH3OH, C8H10, C7H8, C2H4 and NO2. Mechanisms responsible for the observed p-type sensing and response enhancement behaviors were proposed based on the NaWO4-doped WO3-Sb2O3 (p-n) heterointerfaces and catalytic spillover effects. Consequently, the Sb2O3-loaded NaWO4-doped WO3 nanorods have potential as alternative p-type gas sensors for selective and sensitive C2H2 detection in various industrial applications.

Correction: Influence of Cu doping on the visible-light-induced photocatalytic activity of InVO4.

[This corrects the article DOI: 10.1039/C6RA27138C.].

Visible-light-driven WO3/BiOBr heterojunction photocatalysts for oxidative coupling of amines to imines: Energy band alignment and mechanistic insight.

The visible-light-driven WO3/BiOBr heterojunction was for the first time determined for its photocatalytic activity toward oxidative coupling of amines at room temperature using molecular oxygen as a green oxidant. The WO3/BiOBr heterojunction exhibits superior photocatalytic activity and photostability compared with pure BiOBr and WO3 due to an increased oxygen vacancy concentration, an effective separation of photogenerated electron-hole pairs and an efficient interfacial charge transfer. Additionally, the WO3/BiOBr also shows 2.3 and 41.1 times higher activity than that of TiO2 P25 and BiVO4 Alfa Aesar, respectively. Determination of energy band line-up indicates that the WO3/BiOBr is a type II-heterojunction where electron-hole pairs are efficiently separated. Mechanistic studies based on radical quenching experiment, EPR trapping study and Hammett plot reveal that the main reaction pathway is the electron transfer route mediated by superoxide radical. A possible surface reaction mechanism, the insightful information on the structure-activity relationship and the involvement of reactive oxygen species elucidated in this work lay an important background for the material design and encourage a further development of highly efficient photocatalysts toward organic fine chemical syntheses.

Evaluating the photocatalytic efficiency of the BiVO4/rGO photocatalyst.

The present study reported the preparation of BiVO4 by co-precipitation method. The as-prepared BiVO4 photocatalyst were deposited on rGO sheets to form BiVO4/rGO via the hydrothermal method. The crystalline structure, morphological, optical properties, and surface properties of the synthesized pure BiVO4 compared to BiVO4/rGO composite were studied using X-ray diffraction (XRD), scanning electronmicroscopy (SEM), photoluminescence (PL) spectrophotoscopy, UV-vis spectrophotometer with an integrating sphere, and N2 adsorption-desorption isotherm based on BET theory. The photocatalytic activity of the prepared samples were evaluated by the degradation of MB dye in aqueous medium under visible light irradiation. The result showed that the BiVO4/rGO composite exhibited greater photocatalytic efficiency compared to pure BiVO4 with the photocatalytic degradation efficiency remains stable up to fifth cycle. The improved activity of the BiVO4/rGO composite might be attributed to the high surface area available to adsorb more MB molecules, and efficient charge separation of BiVO4 through π electron on the rGO structure. According to experimental results, the possible photocatalytic mechanism of the BiVO4/rGO composite were determined and the active species hydroxyl radical were reported. Based on photocatalytic activity inhibition in the presence of both h+ (VB) and O2•- (CB) scavengers over the BiVO4 photocatalyst, it can be proposed that the hydroxyl radical generated during the photocatalytic degradation mechanism is mainly responsible by the main active species of h+ and O2•- at VB and CB positions, respectively.

H2S Gas Sensor Based on Ru-MoO3 Nanoflake Thick Film.

In this study, H2S-sensing characteristics of the spincoated ruthenium loaded molybdenum trioxide nanoflake (Ru-MoO3 NFs) thick films with 0-1.00 wt% Ru concentrations have been studied. The morphologies, cross section and elemental compositions of sensing films were characterized by SEM and EDS line-scan analyses. The influence of Ru concentration on H2S response of the thick film sensor was studied at the operating temperatures ranging from 200 to 350 °C. It was found that 0.5 wt% RuMoO3 film exhibited an enhanced response of ~30 to 10 ppm H2S, which was more than one order of magnitude higher than that of unloaded one. Plausible mechanisms responsible for the enhanced H2S response by sensing films of Ru-MoO3 NFs were discussed on the basis of the catalytic spill-over effects and enhanced specific surface area provided by Ru nanoparticles.

Adsorption and Photocatalytic Processes of Mesoporous SiO2-Coated Monoclinic BiVO4.

The silicon dioxide (SiO2)-coated bismuth vanadate (BiVO4) composites as visible-driven-photocatalysts were successfully synthesized by the co-precipitation method. The effects of SiO2 coating on the structure, optical property, morphology and surface properties of the composites were investigated by X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM) and Brunauer-Emmette-Teller (BET) measurements. The photocatalytic activity of monoclinic BiVO4 and BiVO4/SiO2 composites were evaluated according to the degradation of methylene blue (MB) dye aqueous solution under visible light irradiation. The SiO2-coated BiVO4 composites showed the enhancing photocatalytic activity approximately threefold in comparison with the single phase BiVO4.

Low temperature preparation of oxygen-deficient tin dioxide nanocrystals and a role of oxygen vacancy in photocatalytic activity improvement.

The introduction of oxygen vacancies (Vos) into tin dioxide crystal structure has been found as an effective method to improve its photocatalytic performance. Herein, oxygen-deficient tin dioxide (SnO2-x) nanocrystals were successfully prepared via a facile, one-step hydrothermal method at the temperature lower than those reported previously. The effect of hydrothermal temperature on phase composition and Vos content was also firstly investigated. Due to its high oxygen vacancy concentration, the SnO2-x prepared at 80 °C provides the best photocatalytic degradation of methyl orange under UV-visible light. Scavenger trapping and nitroblue tetrazolium experiments also show that the Vos act as electron trapped sites and molecular oxygen adsorption sites, therefore increasing the production of active O2- radical which is the main species governing the photocatalytic activity of SnO2-x nanocrystals. Raman spectroscopy, X-ray photoelectron spectroscopy, photoluminescence measurement and electron spin resonance investigation clearly indicate that increasing the hydrothermal temperature results in the coexistence of SnO2-x and Sn3O4 phases and the reduction of Vos concentration which are detrimental to the photocatalytic performance. Density functional theory calculations also reveal that the presence of Vos is responsible for the upshift of valence band maximum and an extended conduction band minimum, hence a valence band width broadening and band gap narrowing which consequently enhance the photocatalytic performance of the oxygen-deficient SnO2-x.

Composite Photocatalysts Containing BiVO4 for Degradation of Cationic Dyes.

The creation of composite structures is a commonly employed approach towards enhanced photocatalytic performance, with one of the key rationales for doing this being to separate photoexcited charges, affording them longer lifetimes in which to react with adsorbed species. Here we examine three composite photocatalysts using either WO3, TiO2 or CeO2 with BiVO4 for the degradation of model dyes Methylene Blue and Rhodamine B. Each of these materials (WO3, TiO2 or CeO2) has a different band edge energy offset with respect to BiVO4, allowing for a systematic comparison of these different arrangements. It is seen that while these offsets can afford beneficial charge transfer (CT) processes, they can also result in the deactivation of certain reactions. We also observed the importance of localized dye concentrations, resulting from a strong affinity between it and the surface, in attaining high overall photocatalytic performance, a factor not often acknowledged. It is hoped in the future that these observations will assist in the judicious selection of semiconductors for use as composite photocatalysts.

Visible light photocatalytic performance and mechanism of highly efficient SnS/BiOI heterojunction.

Novel SnS/BiOI heterostructures with excellent photocatalytic degradation of methyl orange were successfully prepared by a facile hydrothermal-coprecipitation method. The maximum methyl orange degradation activity under visible light irradiation (λ>400nm) was found for 10wt% SnS/BiOI. The composite also showed better stability and good recyclability compared to BiOI. The energy band diagram and band offsets from X-ray photoelectron spectroscopy investigation indicated that the novel composite was a type-II heterojunction where the photogenerated electron-hole can be efficiently separated and transferred. Results from UV-vis DRS, PL-TA and photocurrent response measurement suggested that the improved photodegradation efficiency of the SnS/BiOI heterojunction was mainly attributed to enhanced light absorption capability, strong ability to generate and transfer photoexcited charge carriers and high active species formation. Additionally, radical scavenging experiments demonstrated that holes and superoxide radicals are dominant active species, whereas hydroxyl radicals are of secondary importance in this system. A plausible photocatalytic mechanism of the SnS/BiOI composite was also discussed.

Photocatalytic degradation of dye using CeO2/SCB composite catalysts.

The main task of the present work is to enhance the photocatalytic degradation efficiency of methylene blue (MB) by using CeO2/sugarcane bagasse (SCB) composite catalysts. Homogeneous precipitation method was used to synthesis CeO2-SCB composite catalysts by adding SCB powder to precursor solution of Ce base-metal. The structural analytical data indicated the pure cubic fluorite structure of CeO2. Morphological images revealed the coating of CeO2 layer on high surface area of SCB core-shell. The chemical analysis presented spectrum of the Ce 3d in CeO2/SCB sample existed in the form of the Ce3+ and Ce4+ mixed- valence states. Optical spectra showed the shift of absorption edge towards longer visible region upon supporting CeO2 with SCB. The main chemical composition of the SCB was K, Ca, and Si. Furthermore, recombination of the photogenerated electrons and holes was identified by photoluminescence techniques (PL), the data suggested inhibition of electron-hole pairs recombination by the cations from SCB loaded in CeO2/SCB composite. Photocatalytic activity of CeO2/SCB catalyst was investigated via the degradation of MB under UV-A irradiation. Experimental kinetic data followed the pseudo-first order model. CeO2 supported with SCB adsorbent had higher photocatalytic activity in dye wastewater treatment compared to the pure CeO2. The proposed mechanism explaining the high photocatalytic efficiency of CeO2/SCB was associated with high surface properties and the suppression of recombination of the photogenerated electron-hole pairs by the SCB adsorbent.

Ultrasensitive NO2 Sensor Based on Ohmic Metal-Semiconductor Interfaces of Electrolytically Exfoliated Graphene/Flame-Spray-Made SnO2 Nanoparticles Composite Operating at Low Temperatures.

In this work, flame-spray-made undoped SnO2 nanoparticles were loaded with 0.1-5 wt % electrolytically exfoliated graphene and systematically studied for NO2 sensing at low working temperatures. Characterizations by X-ray diffraction, transmission/scanning electron microscopy, and Raman and X-ray photoelectron spectroscopy indicated that high-quality multilayer graphene sheets with low oxygen content were widely distributed within spheriodal nanoparticles having polycrystalline tetragonal SnO2 phase. The 10-20 µm thick sensing films fabricated by spin coating on Au/Al2O3 substrates were tested toward NO2 at operating temperatures ranging from 25 to 350 °C in dry air. Gas-sensing results showed that the optimal graphene loading level of 0.5 wt % provided an ultrahigh response of 26,342 toward 5 ppm of NO2 with a short response time of 13 s and good recovery stabilization at a low optimal operating temperature of 150 °C. In addition, the optimal sensor also displayed high sensor response and relatively short response time of 171 and 7 min toward 5 ppm of NO2 at room temperature (25 °C). Furthermore, the sensors displayed very high NO2 selectivity against H2S, NH3, C2H5OH, H2, and H2O. Detailed mechanisms for the drastic NO2 response enhancement by graphene were proposed on the basis of the formation of graphene-undoped SnO2 ohmic metal-semiconductor junctions and accessible interfaces of graphene-SnO2 nanoparticles. Therefore, the electrolytically exfoliated graphene-loaded FSP-made SnO2 sensor is a highly promising candidate for fast, sensitive, and selective detection of NO2 at low operating temperatures.

CoTiO3/Ag3VO4 composite: A study on the role of CoTiO3 and the active species in the photocatalytic degradation of methylene blue.

The role of CoTiO3 and the possible active species in the methylene blue (MB) degradation over the visible-light-driven CoTiO3/Ag3VO4 catalyst have firstly been investigated in this work. CoTiO3 is found to play important roles in enhancing the visible light-harvesting ability of the composite and increasing electron-hole separation efficiency due to the hybrid effect between Ag3VO4 and CoTiO3. The indirect probe experiments reveal that CoTiO3/Ag3VO4 heterostructure provides large amount of active species, therefore a high photocatalytic activity could be obtained. The results clearly suggest that the photocatalytic MB degradation over this hybrid catalyst is mainly governed by direct hole oxidation.

Electrolytically exfoliated graphene-loaded flame-made Ni-doped SnO2 composite film for acetone sensing.

In this work, flame-spray-made SnO2 nanoparticles are systematically studied by doping with 0.1-2 wt % nickel (Ni) and loading with 0.1-5 wt % electrolytically exfoliated graphene for acetone-sensing applications. The sensing films (∼12-18 µm in thickness) were prepared by a spin-coating technique on Au/Al2O3 substrates and evaluated for acetone-sensing performances at operating temperatures ranging from 150 to 350 °C in dry air. Characterizations by X-ray diffraction, transmission/scanning electron microscopy, Brunauer-Emmett-Teller analysis, X-ray photoelectron spectroscopy and Raman spectroscopy demonstrated that Ni-doped SnO2 nanostructures had a spheriodal morphology with a polycrystalline tetragonal SnO2 phase, and Ni was confirmed to form a solid solution with SnO2 lattice while graphene in the sensing film after annealing and testing still retained its high-quality nonoxidized form. Gas-sensing results showed that SnO2 sensing film with 0.1 wt % Ni-doping concentration exhibited an optimal response of 54.2 and a short response time of ∼13 s toward 200 ppm acetone at an optimal operating temperature of 350 °C. The additional loading of graphene at 5 wt % into 0.1 wt % Ni-doped SnO2 led to a drastic response enhancement to 169.7 with a very short response time of ∼5.4 s at 200 ppm acetone and 350 °C. The superior gas sensing performances of Ni-doped SnO2 nanoparticles loaded with graphene may be attributed to the large specific surface area of the composite structure, specifically the high interaction rate between acetone vapor and graphene-Ni-doped SnO2 nanoparticles interfaces and high electronic conductivity of graphene. Therefore, the 5 wt % graphene loaded 0.1 wt % Ni-doped SnO2 sensor is a promising candidate for fast, sensitive and selective detection of acetone.

Gas sensing properties of conducting polymer/Au-loaded ZnO nanoparticle composite materials at room temperature.

In this work, a new poly (3-hexylthiophene):1.00 mol% Au-loaded zinc oxide nanoparticles (P3HT:Au/ZnO NPs) hybrid sensor is developed and systematically studied for ammonia sensing applications. The 1.00 mol% Au/ZnO NPs were synthesized by a one-step flame spray pyrolysis (FSP) process and mixed with P3HT at different mixing ratios (1:1, 2:1, 3:1, 4:1, and 1:2) before drop casting on an Al2O3 substrate with interdigitated gold electrodes to form thick film sensors. Particle characterizations by X-ray diffraction (XRD), nitrogen adsorption analysis, and high-resolution transmission electron microscopy (HR-TEM) showed highly crystalline ZnO nanoparticles (5 to 15 nm) loaded with ultrafine Au nanoparticles (1 to 2 nm). Film characterizations by XRD, field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX) spectroscopy, and atomic force microscopy (AFM) revealed the presence of P3HT/ZnO mixed phases and porous nanoparticle structures in the composite thick film. The gas sensing properties of P3HT:1.00 mol% Au/ZnO NPs composite sensors were studied for reducing and oxidizing gases (NH3, C2H5OH, CO, H2S, NO2, and H2O) at room temperature. It was found that the composite film with 4:1 of P3HT:1.00 mol% Au/ZnO NPs exhibited the best NH3 sensing performances with high response (approximately 32 to 1,000 ppm of NH3), fast response time (4.2 s), and high selectivity at room temperature. Plausible mechanisms explaining the enhanced NH3 response by composite films were discussed.

Enhanced visible-light photocatalytic activity of g-C3N4/TiO2 films.

Enhanced photocatalytic degradation of methylene blue (MB) using graphitic carbon nitride/titanium dioxide (g-C3N4/TiO2) catalyst films has been demonstrated in this present work. The g-C3N4/TiO2 composites were prepared by directly heating the mixture of melamine and pre-synthesized TiO2 nanoparticles in Ar gas flow. The g-C3N4 contents in the g-C3N4/TiO2 composites were varied as 0, 20, 50 and 70 wt%. It was found that the visible-light-induced photocatalytic degradation of MB was remarkably increased upon coupling TiO2 with g-C3N4 and the best degradation performance of ~70% was obtained from 50 wt% g-C3N4 loading content. Results from UV-vis absorption study, Electron microscopy, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggest that the improved photoactivity is due to a decrease in band gap energy, an increased light absorption in visible light region and possibly an enhanced electron-hole separation efficiency as a result of effective interfacial electron transfer between TiO2 and g-C3N4 of the g-C3N4/TiO2 composite film. Based on the obtained results, the possible MB degradation mechanism is ascribed mainly to the generation of active species induced by the photogenerated electrons.

In situ electrochemical-transmission surface plasmon resonance spectroscopy for poly(pyrrole-3-carboxylic acid) thin-film-based biosensor applications.

In this study, we describe the combination of transmission surface plasmon resonance (TSPR) and electrochemical techniques for the application to biosensors with conducting polymers. Electropolymerization was employed to construct poly(pyrrole-3-carboxylic acid) (PP3C) film on a gold-coated grating substrate using pyrrole-3-carboxylic acid (P3C) monomer solution in 0.5 M H(2)SO(4). In situ electrochemical-transmission surface plasmon resonance (EC-TSPR) measurements were carried out to study the kinetic and electroactivity properties of PP3C film. Immobilization of antihuman IgG on the activated surface and the binding process of human IgG and antihuman IgG in neutral solution could be detected in situ by EC-TSPR measurement. The surface modification steps on the PP3C layer led to an increase in intensity of the transmission peak. The performance, sensitivity, and utility of EC-TSPR spectroscopy showed obvious advantages for the detection of binding process with the simple experimental setup, and could be applied to the study of biomolecular interactions in various systems.