SiO2@AgCl:Ag纳米复合材料:一种可见光催化降解罗丹明B的高效等离子体光催化剂

采用多元醇沉淀以及光化学还原法制备了SiO₂担载AgCl:Ag等离子体纳米粒子。通过表征发现SiO₂@AgCl:Ag粒子呈立方-四足角状。同时,由于表面Ag簇的等离子共振效应,该催化剂在可见光区有很强的光吸收,可用于在高效降解稳定的有机染料,例如,罗丹明B。合成的SiO₂@AgCl:Ag复合催化剂可在2 min内将罗丹明B分子完全降解。自由基捕获实验进一步探究发现O₂·^-和·OH是参与降解反应的主要氧化活性物种。以上SiO₂@AgCl:Ag的这些特性使其在水净化和环境治理方面有着潜在的应用。     

SiO2@AgCl：Ag纳米复合材料：一种可见光催化降解罗丹明B的高效等离子体光催化剂

采用多元醇沉淀以及光化学还原法制备了SiO2担载AgCl:Ag等离子体纳米粒子。通过表征发现SiO2@AgCl:Ag粒子呈立方-四足角状。同时,由于表面Ag簇的等离子共振效应,该催化剂在可见光区有很强的光吸收,可用于高效降解稳定的有机染料,例如,罗丹明B。合成的SiO2@AgCl:Ag复合催化剂可在2 min内将罗丹明B分子完全降解。自由基捕获实验进一步探究发现O2.-和.OH是参与降解反应的主要氧化活性物种。以上SiO2@AgCl:Ag的这些特性使其在水净化和环境治理方面有着潜在的应用。     

Nanoflower-like composites of ZnO/SiO2 synthesized using bamboo leaves ash as reusable photocatalyst

In this study, the synthesis of ZnO/SiO₂ nanocomposites using bamboo leaf ash (BLA) and tested their photocatalytic activity for rhodamine B decolorization have been conducted. The nanocomposites were prepared by the sol–gel reaction of zinc acetate dihydrate, which was used as a zinc oxide precursor, with silica gel obtained from the caustic extraction of BLA. The effect of the Zn content (5, 10, and 20 wt%) on the physicochemical characteristics and photocatalytic activity of the nanocomposites was investigated. The results of X-ray diffraction, scanning electron microscopy, gas sorption, and transmission electron microscopy characterization confirmed the mesoporous structure of the composites containing nanoflower-like ZnO (wurtzite) nanoparticles of 10–30 nm in size dispersed on the silica support. Further, the nanocomposites were confirmed to be composed of ZnO/SiO₂ by X-ray photoelectron spectroscopy analysis. Meanwhile, diffuse-reflectance UV–visible spectrophotometry analysis of the nanocomposites revealed band gap energies of 3.38–3.39 eV. Of the tested nanocomposites, that containing 10 wt% Zn exhibited the highest decolorization efficiency (99%) and fastest decolorization rate. In addition, the degradation efficiencies were not reduced significantly after five repeated runs, demonstrating the reusability of the nanocomposite catalysts. Therefore, the ZnO/SiO₂ nanocomposite obtained from BLA is a promising reusable photocatalyst for the degradation of dye-polluted water.     

Parameters affecting carbofuran photocatalytic degradation in water using ZnO nanoparticles

Carbofuran photodegradation in water using zinc oxide nanoparticles as a catalyst was examined as well as some parameters influencing its percentage degradation rate such as zinc oxide load, initial concentration of carbofuran, the temperature of the reaction, the initial pH of the solution, and doping of zinc oxide nanoparticles with 5% (w:w) silver. Zinc oxide and Ag-doped zinc oxide nanoparticles were produced using solvothermal and photoreduction methods, respectively, and silver doping effects on the structural, optical, and photocatalytic properties of zinc oxide nanoparticles were investigated using XRD, UV-VIS spectrophotometer, TEM, SEM, SEM/EDX, and FTIR. The average diameter of the synthesized samples was 26.6, 30.55 nm for undoped zinc oxide and Ag-doped zinc oxide, respectively. Zinc oxide doping with silver did not change the shape of the zinc oxide crystal, but decreased the reflection in the visible region, as well as the energy of the bandgap, and increased the zinc oxide photocatalytic activity.     

Transparent hydrophobic and superhydrophobic coatings fabricated using polyamide 12–SiO2 nanocomposite

Optically transparent hydrophobic and superhydrophobic coatings have been prepared using polyamide 12–SiO₂ nanocomposite (NC) on glass substrates by the spin‐coating method. The coatings have been optimized for their hydrophobicity and transparency. The transformation from hydrophobic to superhydrophobic is achieved with increase in roughness (R_a) which increases with SiO₂ content. These coatings are highly transparent in the entire visible region (400–800 nm). The influence of layer thickness on water contact angle (WCA) and optical transmittance of the coatings has been studied. Field emission scanning electron micrograph (FESEM) shows the presence of SiO₂ nanoparticles covered with polyamide homogenously on the surface and the particles are aggregated to form a rough structure. X‐ray diffraction (XRD) patterns show that the polyamide losses its crystalline structure in the composite. The preparation procedure reported here is simple and eco‐friendly. The dual nature of the coatings, that is, high transparency and superhydrophobicity in the entire visible region suggests for its potential usage in self‐cleanings, wind screen and optoelectronic applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Stepwise construction of Pt decorated oxygen-deficient mesoporous titania microspheres with core-shell structure and magnetic separability for efficient visible-light photocatalysis

Solid photocatalysts with high specific surface area,superior photoactivity and ease of recycling are highly desired in chemical process,water treatment and so on.In this study,a facile stepwise sol-gel coating approach was utilized to synthesize Pt decorated oxygen-deficient mesoporous titania microspheres with core-shell structure and convenient magnetic separability(denoted as Fe_3 O_4@-SiO_2@Pt/mTiO_(2-x)).These photocatalysts consist of magnetic Fe_3 O4 cores,nonporous insulating SiO_2 middle layer and mesoporous anatase TiO_(2-x) shell decorated by Pt nanoparticles(～3.5 nm) through wet impregnation and H_2 reduction.As a result of high activity of oxygen-deficiency of black TiO_(2-x) by H_2 reduction and efficient inhibition of electron-hole recombination by Pt nanoparticles,the rationally designed core-shell Fe_3 O_4@SiO_2@Pt/mTiO_(2-x) photocatalysts exhibit superior photocatalytic performance in rhodamine B(RhB) degradation under visible light irradiation,with more than 98% of RhB degraded within 50 min.These core-shell structured photocatalysts show excellent recyclability under the assistance of magnetic separation with well-retained photocatalytic performance even after running five cycles.This stepwise synthesis method paves the way for the rational design of a high-efficiency recyclable heterogeneous catalyst,including photocatalysts,for various applications.     

Control of Spatially Homogeneous Distribution of Heteroatoms to Produce Red TiO2 Photocatalyst for Visible-Light Photocatalytic Water Splitting

The strong band-to-band absorption of photocatalysts spanning the whole visible-light region (400–700 nm) is critically important for solar-driven photocatalysis. Although it has been actively and widely used as a photocatalyst for various reactions in the past four decades, TiO₂ has a very poor ability to capture the whole spectrum of visible light. In this work, by controlling the spatially homogeneous distribution of boron and nitrogen heteroatoms in anatase TiO₂ microspheres with a predominance of high-energy {001} facets, a strong visible-light absorption spectrum with a sharp edge beyond 680 nm has been achieved. The red TiO₂ obtained with homogeneous doping of boron and nitrogen shows no increase in defects like Ti³⁺ that are commonly observed in doped TiO₂. More importantly, it has the ability to induce photocatalytic water oxidation to produce oxygen under the irradiation of visible light beyond 550 nm and also the photocatalytic reduction of water to produce hydrogen under visible light. These results demonstrate the great promise of using red TiO₂ for visible-light photocatalytic water splitting and also reveal an attractive strategy for realizing the wide-spectrum visible-light absorption of wide-band-gap oxide photocatalysts.     

Photocatalysis and photoinduced hydrophilicity of WO3 thin films with underlying Pt nanoparticles

The photocatalytic oxidation and photoinduced hydrophilicity of thin tungsten trioxide (WO(3)) films coupled with platinum (Pt) nanoparticles were investigated. WO(3) films with underlying Pt nanoparticles (WO(3)/Pt/substrate) and those with overlying Pt nanoparticles (Pt/WO(3)/substrate) were synthesized by sputtering and sol-gel methods. Between these films, underlying Pt nanoparticles greatly enhanced the photocatalytic oxidation activity of WO(3) without decreasing the photoinduced hydrophilic conversion. However, overlying Pt nanoparticles deteriorated the hydrophilicity of WO(3) because the Pt nanoparticle surface was hydrophobic. The enhanced photocatalytic reaction by the Pt nanoparticles was attributed to the multi-electron reduction in Pt, which is caused by the injected electrons from the conduction band of WO(3). The relationship between photocatalytic activity and thin film structure, including the size of Pt nanoparticles, the thickness and porosity of the WO(3) layer, were investigated. Consequently, the optimum structure for high performance in both photocatalysis and photoinduced hydrophilicity was WO(3) (50 nm)/Pt(1.5 nm)/substrate, and this film exhibited a significant self-cleaning property even under visible light irradiation.     

Photocatalytic Oxidation Based on Modified Titanium Dioxide with Reduced Graphene Oxide and CdSe/CdS as Nanohybrid Materials

Photocatalytic activity of TiO₂ nanoparticles in the visible light region was enhanced. TiO₂–CdSe and TiO₂–CdSe/CdS nanohybrids were supported on the reduced graphene oxide. These nanohybrid materials were applied as photocatalyst toward oxidation of aromatic alcohols under a mild condition and the molecular oxygen as oxidant. A plausible mechanism for the photocatalytic oxidation was also proposed. Desired nanohybrids were obtained via in situ fixation of CdSe/CdS on the surface of nanosheets of reduced graphene oxide (rGO). Finally, it was modified by TiO₂ sol nanoparticles through a hydrothermal method. The obtained nanomaterials, were characterized by SEM, TEM imaging, XRD, EDAX, DRS and XPS analyses. The size of nanohybrids materials were distributed mostly in a narrow range of 50–65 and 60–75 nm for TiO₂–rGO–CdSe and TiO₂–rGO–CdSe/CdS, respectively. These photocatalysts showed high catalytic activity under visible light irradiation in a short reaction time and even higher selectivity rather than UV irradiation. The yield of catalytic oxidation increased at least 25–30% for TiO₂–CdSe/CdS on rGO, which could be related to its higher light sensitivity and lower energy band gap. The photocatalysts were recycled and reused 8 times without significant loss of their activities due to their stability under visible light.     

Nanoplasmonic zirconium nitride photocatalyst for direct overall water splitting

The ability of plasmonic nanostructures to efficiently harvest light energy and generate energetic hot carriers makes them promising materials for utilization in photocatalytic water spitting.Apart from the traditional Au and Ag based plasmonic photocatalysts,more recently the noble-metal-free alternative plasmonic materials have attracted ever-increasing interest.Here we report the first use of plasmonic zirconium nitride（ZrN） nanoparticles as a promising photocatalyst for water splitting.Highl...     

Stability of Ag@SiO_2 core–shell particles in conditions of photocatalytic overall water-splitting

Core–shell nanoparticles containing plasmonic metals(Ag or Au) have been frequently reported to enhance performance of photo-electrochemical(PEC) devices. However, the stability of these particles in water-splitting conditions is usually not addressed. In this study we demonstrate that Ag@SiO_2 core–shell particles are instable in the acidic conditions in which WO_3-based PEC cells typically operate, Ag in the core being prone to oxidation, even if the SiO_2 shell has a thickness in the order of 10 nm. This is evident from in situ voltammetry studies of several anode composites. Similar to the results of the PEC experiments, the Ag@SiO_2 core–shell particles are instable in slurry-based, Pt/ZnO induced photocatalytic water-splitting. This was evidenced by in situ photodeposition of Ag nanoparticles on the Pt-loaded ZnO catalyst, observed in TEM micrographs obtained after reaction. We explain the instability of Ag@SiO_2 by OH-radical induced oxidation of Ag, yielding dissolved Ag+. Our results imply that a decrease in shell permeability for OH-radicals is necessary to obtain stable, Ag-based plasmonic entities in photo-electrochemical and photocatalytic water splitting.     

Interface-directed sol-gel: direct fabrication of the covalently attached ultraflat inorganic oxide pattern on functionalized plastics

For plastic electronics and optics, the fabrication of smooth, transparent and stable crack-free inorganic oxide films (and patterning) on flexible polymeric substrates with strong bonding strength and controllable thickness from nanometers to micrometers is a key but still remains a challenge. Among versatile inorganic oxides, silica oxide film as SiO _x is especially important because this semiconductor material could provide crucial properties in devices or serve as a base layer for further multilayer construction. In this paper, we describe a new interface-directed sol-gel method to fabricate flexible high quality silicon oxide film onto commodity plastics. The resulting crack-free silica film has strong covalent bonding with polymer substrates, homogeneous morphology with ultralow roughness, highly optical transparency, tunable thickness from nm to μm, and easy patterning ability. Such fabrication strategy relies on a novel photocatalytic oxidation reaction by photosensitive ammonium persulfate (APS), which is able to fabricate highly reactive hydroxyl monolayer surface on inert polymeric substrates. This kind of hydroxylated surface could serve as nucleation and growth sites to initiate surface sol-gel process. As a result, well-defined SiO _x film deposition (gelation) occurs, and patterned hydroxylation regions could be easily utilized to induce the formation of patterned oxide film arrays. Our strategy also excludes the requirements of clean room and vacuum devices so as to fulfill low-cost and fast fabrication demands. Two application examples from such high quality SiO _x layer onto plastics are given but should not be limited within these. One is that oxygen permeation rate of SiO _x deposited polymer film decreases 25 times than pristine polymer substrate, which is good for the potential packaging materials. The other one is that silanization monolayer, for example, 3-aminopropyltriethoxysilane (APTES), could be successfully constructed onto silica layer through classical silanization reaction, which is applicable for many potential purposes, for instance, proteins could be accordingly immobilized onto plastic support with effective signal-to-background ratio. Moreover, we further demonstrate that this interface-directed sol-gel strategy is a general method which could be successfully extended to other high quality oxide film fabrication, e.g., TiO₂.     

Preparation of Titania Nanosheet-Precipitated Coatings on Glass Substrates by Treating SiO2-TiO2 Gel Films with Hot Water Under Vibrations

Titania nanosheet-precipitated coatings have been prepared by treating SiO₂-TiO₂ gel films on glass substrates with hot water at 90°C under vibration. Longitudinal vibrations at about 6 Hz during the treatment enhanced the formation of titania nanosheet. The titania nanosheet consisted of several layers with a spacing of about 0.6 nm and was identified as hydrated titania with a lepidocrocite-type structure. The morphology of the titania nanosheet-precipitated coatings is probably achieved by lowering of the concentration of hydrolyzed titania species at the surface due to rapid water flow driven by the vibrations. The coatings were transparent in the visible range and showed high photocatalytic activity and antifogging property.     

Visible light-driven water oxidation by Ir oxide clusters coupled to single Cr centers in mesoporous silica

Visible light-induced water oxidation has been demonstrated at an Ir oxide nanocluster coupled to a single CrVI site on the pore surface of MCM-41 mesoporous silica. The photocatalytic unit was assembled by the reaction of surface Cr=O groups with Ir(acac)3 precursor followed by calcination at 300 degrees C and bond formation monitored by FT-Raman and FT-IR spectroscopy. High-resolution Z-contrast electron micrographs of the calcined material combined with energy-dispersive X-ray spot analysis confirmed the occlusion of Ir oxide nanoparticles inside the mesopores. Oxygen evolution of an aqueous suspension of the IrxOy-CrMCM-41 upon visible light irradiation of the CrVI-O ligand-to-metal charge-transfer absorption was monitored mass-spectrometrically. Comparison of the product yields for samples with low Cr content (Cr/Si 相似文献   

Composition/structural evolution and optical properties of ZnO/Zn nanoparticles by laser ablation in liquid media

We present composition-controlled synthesis of ZnO-Zn composite nanoparticles by laser ablation of a zinc metal target in pure water or in aqueous solution of sodium dodecyl sulfate (SDS). By SDS concentration, composition and size of the nanoparticles can be controlled in a wide range. Relative amounts of the components Zn and ZnO, the particle size, and the microstructure can evolve with SDS concentration in solution. High SDS concentration corresponds to high relative amount of Zn nanoparticles existing as the core in the core/shell nanostructures, whereas low SDS concentration leads to high ZnO amount. This was explained by a dynamic mechanism on the basis of the competition between aqueous oxidation and SDS capping protection. Correspondingly, optical absorption spectra evolve from the excitonic peak of ZnO (about 350 nm) to the Zn surface plasmon resonance (about 242 nm) with rise of SDS concentration. A blue (about 450 nm) photoluminescence was observed in the obtained ZnO nanoparticles, which was attributed to existence of interstitial zinc in ZnO lattices. This study has revealed that laser ablation of active metal in liquid media is an appropriate method to synthesize a series of metal oxide semiconductor-metal composite nanoparticles with controlled composition and size.     

Cathodoluminescence depth analysis in SiO2-Si-systems

SEM cathodoluminescence (CL) is extended to luminescence center spatial depth profiling by means of electron beam energy E₀ variation and consequently variation of CL excitation range. In this way the CL profile of SiO₂-layers on Si substrate offers a dead layer of luminescence beneath the surface (10–75) nm as well as the SiO₂ oxide thickness with an accuracy of better 10% across a small spot area of less than 1 μm.     

Tuning the properties of a black TiO2-Ag visible light photocatalyst produced by a rapid one-pot chemical reduction

A highly efficient black TiO₂-Ag photocatalytic nanocomposite, active under both UV and visible light illumination, was synthesized by decorating the surface of 25 nm TiO₂ particles with Ag nanoparticles. The material was obtained via a rapid, one-pot, simple (surfactant and complexing agent free) chemical reduction method using silver nitrate and formaldehyde as a metal salt and reducing agent, respectively. The nanocomposite shows an increase of over 800% in the rate of photocatalytic methylene blue dye degradation, compared to commercial unmodified TiO_2, under UV-VIS illumination. Unlike pure TiO₂, the nanocomposite exhibits visible light activation, with a corresponding drop in optical reflectance from 100% to less than 10%. The photocatalytic properties were shown to be strongly enhanced by post-reduction annealing heat treatments in air, which were observed to decrease, rather than coarsen, silver particle size, and increase particle distribution. This, accompanied by a variation in the silver surface oxidation states, appear to dramatically affect the photocatalytic efficiency under both UV and visible light. This highly active photocatalyst could have wide ranging applications in water and air pollution remediation and solar fuel production.     

Synthesis and Study of Plasmon‐Induced Carrier Behavior at Ag/TiO2 Nanowires

Nanocomposites of Ag/TiO₂ nanowires with enhanced photoelectrochemical performance have been prepared by a facile solvothermal synthesis of TiO₂ nanowires and subsequent photoreduction of Ag⁺ ions to Ag nanoparticles (AgNPs) on the TiO₂ nanowires. The as‐prepared nanocomposites exhibited significantly improved cathodic photocurrent responses under visible‐light illumination, which is attributed to the local electric field enhancement of plasmon resonance effect near the TiO₂ surface rather than by the direct transfer of charge between the two materials. The visible‐light‐driven photocatalytic performance of these nanocomposites in the degradation of methylene blue dye was also studied, and the observed improvement in photocatalytic activity is associated with the extended light absorption range and efficient charge separation due to surface plasmon resonance effect of AgNPs.     

Correlation of SiO x layer thickness and properties of BOPP/SiO x composite films with spin coating process parameters

The effects of the spin coating process parameters on the thickness of the SiOx layer of the BOPP/SiOx composite film were investigated. When the concentration of tetraethoxysilane (TEOS) increased from 12.5 vol% to 55% vol%, the SiOx thickness increased from about 80 nm to 470 nm. In the sol time range of 1.5 h to 5 h the SiOx layer thickness reached a maximum at about 4 h and the change of the thickness roughly matched the change of the silica colloidal sphere sizes in sol. When the spin-coating speed of the dispensing stage increased from 450 r/min to 500 r/min, the SiOx layer thickness drastically decreased from about 1.67 μm to 400 nm. While the spin-coating speed of the thinning and drying stage went up to 1200 r/min, the SiOx layer thickness was in the range of 330 nm to 390 nm. It was also found that the SiOx layer thickness was almost increased linearly from about 500 nm to 1.02 μm with the ratio of the commercial silica colloidal to the TEOS from 0.2 to 1.0. The water contact angles decreased to about 23.0° for the BOPP/Si-Sol composite film with 1.67 μm SiOx layer and about 4.0° for the BOPP/mixing Si-Sol composite film with 1.02 μm SiOx layer. Compared to BOPP, the light transparency of the BOPP/Si-Sol composite films decreased by about 5.5% with the SiOx layer from about 80 nm to 1.67 μm and by 7.0% for the BOPP/mixing Si-Sol composite film with the SiOx layer from about 350 nm to 1.02 μm respectively.     

Indium-doped ZnOas efficient photosensitive material for sunlight driven hydrogen generation and DSSC applications: integrated experimental and computational approach

Electricity generation using simple and cheap dye-sensitized solar cells and photocatalytic water splitting to produce future fuel, hydrogen, directly under natural sunlight fascinated the researchers worldwide. Herein, synthesis of indium-doped wurtzite ZnO nanostructures with varying molar percentage of indium from 0.25 to 3.0% with concomitant characterization indicating wurtzite structure is reported. The shift of (002) reflection plane to higher 2θ degree with increase in indium-doping thus is a clear evidence of doping of indium in zinc oxide nanoparticles. Surface morphological as well as microstructural studies of In@ZnO exhibited generation of ZnO nanoparticles and nanoplates of diameter 10–30 nm. The structures have been correlated well using computational density functional (DFT) studies. Diffuse reflectance spectroscopy depicted the extended absorbance of these materials in the visible region. Hence, the photocatalytic activity towards hydrogen generation from water under natural sunlight as well as efficient DSSC fabrication of these newly synthesized materials has been demonstrated. In-doped ZnO exhibited enhanced photocatalytic activity towards hydrogen evolution (2465 μmol/h/g) via water splitting under natural sunlight. DSSC fabricated using 2% In-doped ZnO exhibited an efficiency of 3.46% which is higher than other reported In-doped ZnO based DSSCs.