Photocatalytic NO removal over calcium-bridged siloxenes under ultraviolet and visible light irradiation.

Ca-Bridged siloxenes (Ca-siloxenes) composed of two-dimensional siloxene planes with Ca bridging were prepared and their photocatalytic properties for nitrogen oxide (NO) removal were investigated. Ca-Siloxenes were synthesized via a solid-state metathesis reaction using TaCl5 to extract Ca from CaSi2 with different Cl2/Ca molar ratios of 0.25, 1.25 and 2.5 (CS0.25, CS1.25 and CS2.5, respectively) in an attempt to control the extent of Ca extraction. Ca-Siloxenes have a wide optical absorption band from the visible to ultraviolet region with absorption edges of 1.5, 2.9, and 3.1 eV for CS0.25, CS1.25, and CS2.5, respectively. Ca-Siloxenes exhibited photocatalytic activity for NO removal under irradiation with visible (λ > 400 nm (<3.10 eV)) and ultraviolet light (λ > 290 nm (<4.28 eV)). The photocatalytic activity was particularly improved by mixing the Ca-siloxene with acetylene black as a conductive material, which might have inhibited the recombination of photogenerated electrons and holes. The mixture of Ca-siloxene and acetylene black exhibited improved photocatalytic activity in the presence of 1O2 as one of the active oxygen species formed under ultraviolet light irradiation.

Multifunctionality in coating films including Nb-doped TiO2 and Cs x WO3: near infrared shielding and photocatalytic properties.

Various types of coating films were obtained from hydrothermally synthesized Nb-doped TiO2 (NTO) and Cs x WO3 (CWO) nanoparticles. The coating films possessed multifunctionality including near infrared (NIR) absorption and photocatalysis abilities. The NTO and CWO nanoparticles were synthesized by a unique solvothermal reaction in which water induced by an esterification reaction between alcohol and carboxylic acid can act as a hydrolyzing agent for metal precursors. NTO was synthesized by the unique solvothermal reaction for the first time. The reaction accompanied by the reduction of Ti4+ to Ti3+ led to the formation of nanoparticles with both NIR absorption and photocatalytic properties. The effect of the ethanol-acetic acid ratio on the morphology of the obtained NTO was investigated, and the larger amount of acetic acid led to a larger nanoparticle size, indicating the size controllability. The two types of coating film, including CWO and NTO nanoparticles, were obtained for comparison: (1) coexistent coating film: one side of the quartz glass was coated with a dispersion, including both CWO and NTO nanoparticles, and (2) double-sided coating film: a quartz glass coated with a CWO dispersion on one side and an NTO dispersion on the other side. The double-sided coating led to higher multifunctionality. Furthermore, the optimized condition for the double-sided coating was investigated by using various NTO particles obtained using different ethanol-acetic acid ratios.

Photocatalytic activity of silicon-based nanoflakes for the decomposition of nitrogen monoxide.

The photocatalytic decomposition of nitrogen monoxide (NO) was achieved for the first time using Si-based nanomaterials. Nanocomposite powders composed of Si nanoflakes and metallic particles (Ni and Ni3Si) were synthesized using a simple one-pot reaction of layered CaSi2 and NiCl2. The synthesized nanocomposites have a wide optical absorption band from the visible to the ultraviolet. Under the assumption of a direct transition, the photoabsorption behavior is well described and an absorption edge of ca. 1.8 eV is indicated. Conventional Si and SiO powders with indirect absorption edges of 1.1 and 1.4 eV, respectively, exhibit considerably low photocatalytic activities for NO decomposition. In contrast, the synthesized nanocomposites exhibited photocatalytic activities under irradiation with light at wavelengths >290 nm (<4.28 eV). The photocatalytic activities of the nanocomposites were confirmed to be constant and did not degrade with the light irradiation time.

A P25/(NH4)xWO3 hybrid photocatalyst with broad spectrum photocatalytic properties under UV, visible, and near-infrared irradiation.

In this study, a series of hybrid nanostructured photocatalysts P25/(NH4)xWO3 nanocomposites with the average crystallite size of P25 and (NH4)xWO3 of the sample was calculated to be about 30 nm and 130 nm, were successfully synthesized via a simple one-step hydrothermal method. The as-obtained samples was characterized by transmission electron microscopy (TEM), which implies that the P25/(NH4)xWO3 nanocomposites are fabricated with favourable nanosizd interfacial. The XPS results confirmed that the obtained sample consists of mixed chemical valences of W5+ and W6+, the low-valance W5+ sites could be the origin of NIR absorption. As revealed by optical absorption results, P25/(NH4)xWO3 nanocomposites possess high optical absorption in the whole solar spectrum of 200-2500 nm. Benefiting from this unique photo-absorption property and the synergistic effect of P25 and (NH4)xWO3, broad spectrum response photocatalytic activities covering UV, visible and near infrared regions on degradation of Rhodamine B have been realized by P25/(NH4)xWO3 nanocomposites. Meanwhile, the stability of photocatalysts was examined by the XRD and XPS of the photocatalysts after the reaction. The results show that P25/(NH4)xWO3 photocatalysts has a brilliant application prospect in the energy utilization to solve deteriorating environmental issues.

Smart window coating based on F-TiO2-KxWO3 nanocomposites with heat shielding, ultraviolet isolating, hydrophilic and photocatalytic performance.

A series of smart window coated multifunctional NIR shielding-photocatalytic films were fabricated successfully through KxWO3 and F-TiO2 in a low-cost and environmentally friendly process. Based on the synergistic effect of KxWO3 and F-TiO2, the optimal proportion of KxWO3 to F-TiO2 was investigated and the FT/2KWO nanocomposite film exhibited strong near-infrared, ultraviolet light shielding ability, good visible light transmittance, high photocatalytic activity and excellent hydrophilic capacity. This film exhibited better thermal insulation capacity than ITO and higher photocatalytic activity than P25. Meanwhile, the excellent stability of this film was examined by the cycle photocatalytic degradation and thermal insulation experiments. Overall, this work is expected to provide a possibility in integrating KxWO3 with F-TiO2, so as to obtain a multifunctional NIR shielding-photocatalytic nanocomposite film in helping solve the energy crisis and deteriorating environmental issues.

Enhanced Photocatalytic Performance of Luminescent g-C3N4 Photocatalyst in Darkroom.

Graphitic-C3N4(g-C3N4), a low-cost visible-light-driven photocatalyst, was used for the photocatalytic oxidation of aqueous methylene blue (MB) in the dark with Sr4Al14O25:(Eu,Dy) assistance. The Sr4Al14O25:(Eu,Dy)/g-C3N4 photocatalysts were fabricated through the ultrasonic dispersion method. The commercial Sr4Al14O25:(Eu,Dy) phosphor was used as a long afterglow supplier for exciting g-C3N4 in the dark. The results demonstrated that the metal-free g-C3N4 photocatalyst could use the eye-visible long afterglow to photocatalytically decompose MB dyes in the dark. This work may expand the appealing application of g-C3N4 for the environmental cleanup.

Cs(x)WO3 Nanoparticles for the Near-Infrared Shielding Film.

Cs0.3WO3 nanoparticles with broad near infrared (NIR) absorptive ability were fabricated by a high-temperature solvothermal process. It has been found that there was a strong size-dependent effect for the NIR absorption, that was, the smaller size led to stronger optical absorption. The thin film containing the Cs(x)WO3 nanoparticles can effectively shield out the most part of NIR light without the loss of brightness from the visible lights.

Bi(1-x)Ni(x)VO(4-y) Solid Solution with a High Visible-Light Photocatalytic Activity for Degradation Methyl Orange.

Particulate solid solutions Bi(1-x)Ni(x)VO(4-y) were synthesized by solid-state reaction at high temperature. The samples were characterized by X-ray Diffraction (XRD), Field-Emission Scanning Electron Microscopy (FE-SEM), Energy Dispersive Spectrometer (EDS), Brunauer-Emmett-Teller (BET) surface area and Ultraviolet-Visible spectroscopy (UV-Vis). The photocatalytic activity of BiVO4 for photocatalytic degradation of organic contaminants ability in visible light region could be improved by doping of Ni(2+). The high visible light photocatalytic activity of Bi(1-x)Ni(x)VO(4-y) solid solution might be due to the generation of a new band gap and expanding the range of visible light response. It was suggested that the Ni(2+) doping was beneficial to effective charge separation of Bi(1-x)Ni(x)VO(4-y) solid solution, thus improved the photocatalytic activity.

A Facile One-Step Solvothermal Synthesis and Electrical Properties of Reduced Graphene Oxide/Rod-Shaped Potassium Tungsten Bronze Nanocomposite.

Reduced graphene oxide (rGO)/rod-shaped potassium tungsten bronze nanocomposites with the different ratio were successfully synthesized by solvothermal reaction and followed by the reduction in H2(5 vol.%)/N2 atmosphere at 550 degrees C. The coupled samples showed excellent shielding ability of NIR light as well as certain visible lights transparency. The synergistic effects could be observed in the composites, i.e., when 15 wt% and 20 wt% of rGO which was fabricated by chemical reduction of graphene oxide, were composed into K(x)WO3, the composite showed the higher electrical conductivity than those of rGO and potassium tungsten bronze.

Synthesis of ZrB2 and ZrB2-SiC Powders Using a Sucrose-Containing System.

ZrB2 and ZrB2-SiC powders are synthesized by a sol-gel method from zirconium n-propoxide, tetraethyl orthosilicate (only for ZrB2-SiC), boric acid, and sucrose. After reduction at 1550 degrees C, both ZrB2 and ZrB2-SiC are unconsolidated, soft gray powders. The ZrB2-SiC particles have an equiaxed shape with a diameter of about 800 nm and a uniform size distribution. The SiC may be very finely distributed, because we barely find SiC among ZrB2 particles when using energy dispersive X-ray spectroscopy (EDS), although both ZrB2 and SiC are identified by X-ray diffractometry (XRD).

A Cs(x)WO3/ZnO nanocomposite as a smart coating for photocatalytic environmental cleanup and heat insulation.

A novel CsxWO3/ZnO smart coating was proposed to achieve multiple functions, such as heat insulation, photodecomposition of toxic NO gas, blocking of harmful UV light, etc. In this composite coating, CsxWO3 nanorods were used as a NIR and UV light shielding material while ZnO nanoparticles were utilized as a photocatalyst and a material to enhance visible light transmittance and block UV light. When the mass ratio of CsxWO3/ZnO was 1, the composite coating possessed a very good visible light transmittance of over 80% and an excellent UV-shielding ability. This novel coating showed heat insulation that is superior to the ITO coating and photocatalytic decontamination of NO gas that is superior to the standard TiO2 (P25). The proposed CsxWO3/ZnO smart coating is a promising material not only for energy saving but also for environmental cleanup.

Visible Light-Driven Photocatalytic Activity of Oleic Acid-Coated TiO2 Nanoparticles Synthesized from Absolute Ethanol Solution.

The one-step synthesis of oleic acid-coated TiO2 nanoparticles with visible light-driven photocatalytic activity was reported by this manuscript, using oleic acid-ethanol as crucial starting materials. The photocatalytic degradation of nitrogen monoxide (deNOx) in the gas phase was investigated in a continuous reactor using a series of TiO2 semiconductors, prepared from oleic acid- or acetic acid-ethanol solution. The surface modification on TiO2 by organic fatty acid, oleic acid, could reinvest TiO2 photocatalyst with the excellent visible light response. The deNOx ability is almost as high as 30 % destruction in the visible light region (λ > 510 nm) which is similar to the nitrogen-doped TiO2. Meanwhile, acetic acid, a monobasic acid, has a weaker ability on visible light modification of TiO2.

Preparation and visible light induced photocatalytic activity of C-NaTaO3 and C-NaTaO3-Cl-TiO2 composite.

A nice visible light responsive C-doped NaTaO3 (C-NaTaO3) particle has been successfully prepared by a facile solvothermal method using water-ethylene glycol mixed solutions as solvent. The results presented that the carbon could be easily incorporated in NaTaO3 from ethylene glycol during a solvothermal reaction, finally leading to excellent visible light absorption. The as-synthesized C-NaTaO3 showed excellent visible light induced photocatalytic activity superior to those of pure NaTaO3 and commercial P25. In addition, in order to further improve the visible light driven photocatalytic performance of C-NaTaO3, a new C-doped NaTaO3-Cl-doped TiO2 (C-NaTaO3-Cl-TiO2) core-shell type of composite was also fabricated. After coupling C-NaTaO3 with Cl-TiO2, the visible light induced NOx gas destruction ability of C-NaTaO3-Cl-TiO2 composite was significantly enhanced as compared to those of sole C-NaTaO3 and Cl-TiO2, probably due to the hindrance of the recombination rate of photogenerated electron-hole pairs. The C-NaTaO3 particle and C-NaTaO3-Cl-TiO2 composite prepared in this work would probably provide a new way to prepare high performance of visible light induced perovskite-type NaTaO3 based photocatalysts.

UV, visible and near-infrared lights induced NOx destruction activity of (Yb,Er)-NaYF4/C-TiO2 composite.

Titanium dioxide (TiO2) is a well-known photocatalyst for environmental cleaning and energy conversion. However, it can only be excited by ultraviolet light for photocatalysis due to its wide band gap (3.2 eV). In this paper, we present a novel (Yb,Er)-NaYF4/C-TiO2 composite which can be perfectly induced not only by ultraviolet light but also weak visible and near infrared lights, owing to the increased carbon doping contents and optimal energy transfer between up-conversion phosphor and C doped TiO2 compared with that of solely C-TiO2. Consequently, the (Yb,Er)-NaYF4/C-TiO2 composite can present the outstanding continuous NOx gas destruction ability under the irradiation of ultraviolet, weak visible and infrared lights much superior to pure C-TiO2, P25 titania and even that of (Yb,Er)-NaYF4/N-TiO2 composite, due to the nice synergetic effect of (Yb,Er)-NaYF4 and C-TiO2, indicating a promising potential in the photocatalyst application with high efficiency of ultraviolet, visible and infrared lights induced photocatalysis simultaneously.

The visible-light driven photocatalytic destruction of NO(x) using mesoporous TiO2 spheres synthesized via a "water-controlled release process".

Mesoporous anatase TiO2 spheres with tunable sizes ranging from 400 nm to 3 µm were synthesized using an original so-called "water-controlled solvothemal release process". In this method, the well-known esterification reaction between ethanol and acetic acid was creatively employed to generate water gradually during a solvothermal process. Thereafter, the slowly released water molecules functioned as nucleation centers for completing the hydrolysis of titanium tetraisopropoxide to produce homogenous mesoporous TiO2 spheres. In reality, these samples consisted of densely packed nanoparticles that formed spherical secondary particles with interparticle pores. Research has demonstrated that the diameter of the TiO2 spheres can be easily tuned by controlling the concentration of the Ti source in the starting solution. Regardless of their diameter, all of these TiO2 spheres exhibited a high specific surface area (above 150 m(2) g(-1)) originating largely from the contribution of mesopores. On the merits of their porous structure and related high specific surface area, the mesoporous TiO2 spheres showed a higher photocatalytic activity than P25 for the oxidative photo-destruction of NOx gas.

Solvothermal fabrication of rubidium tungsten bronze for the absorption of near infrared light.

For fabricating the crystal of Rb(x)WO3, the solvothermal process was performed using a mixed medium of water and ethanol as solvent. It has been found that the morphological evolutions of samples were greatly changed as disordered nanoparticles, bundle of nanorods and microfibers with increasing content of water in the starting solution. Among them, sample synthesized with assistance of 3 ml water consisted of the nanorods with a diameter in the range of 80-150 nm, showing suitable size and morphology as near-infrared shielding material. On the merits of this nanostructure, the thin film of the Rb(x)WO3 nanorods realized excellent shielding of near-infrared light, meanwhile, it selectively transmitted the major part of visible light.

Dual functions of YF3:Eu³âº for improving photovoltaic performance of dye-sensitized solar cells.

In order to enhance the photovoltaic performance of dye-sensitized solar cell (DSSC), a novel design is demonstrated by introducing rare-earth compound europium ion doped yttrium fluoride (YF3:Eu³âº) in TiO2 film in the DSSC. As a conversion luminescence medium, YF3:Eu³âº transfers ultraviolet light to visible light via down-conversion, and increases incident harvest and photocurrent of DSSC. As a p-type dopant, Eu³âº elevates the Fermi level of TiO2 film and thus heightens photovoltage of the DSSC. The conversion luminescence and p-type doping effect are demonstrated by photoluminescence spectra and Mott-Schottky plots. When the ratio of YF3:Eu³âº/TiO2 in the doping layer is optimized as 5 wt.%, the light-to-electric energy conversion efficiency of the DSSC reaches 7.74%, which is increased by 32% compared to that of the DSSC without YF3:Eu³âº doping. Double functions of doped rare-earth compound provide a new route for enhancing the photovoltaic performance of solar cells.

Photothermal ablation cancer therapy using homogeneous CsxWO3 nanorods with broad near-infra-red absorption.

Recently, photothermal ablation therapy (PTA) employing near-infrared radiation (NIR) has been extensively investigated as an emerging modality for cancer management. However, the clinical translation of this promising approach is limited by the lack of PTA agents with broad NIR absorption, low cost and high photothermal conversion efficiency. Herein, we have developed PEGylated homogeneous CsxWO3 nanorods (a mean size ∼69.3 nm × 12.8 nm) with broad photo-absorption (780-2500 nm) as a novel NIR absorbent for PTA treatment of human cancer. The prepared CsxWO3 nanocrystals displayed strong near-infrared optical absorption with a high molar extinction coefficient (e.g. 4.8 × 10(10) M(-1) cm(-1) at 980 nm), thus generated significant amounts of heat upon excitation with near-infrared light. The PTA study in two human carcinoma cell lines (i.e. A549 lung cancer cells and HeLa ovarian cancer cells) demonstrated that CsxWO3 nanorods can efficiently cause cell death via hyperthermia induced lysosome destruction, cytoskeleton protein degradation, DNA damage and thereafter cellular necrosis or apoptosis. Our study also confirmed the migration of healthy cells migrated from unirradiated areas to dead cell cycle, which is essential for tissue reconstruction and wound healing after photodestruction of tumor tissue. The prompted results reported in the current study imply the promising potential of CsxWO3 nanorods for application in PTA cancer therapy.

An ultraviolet responsive hybrid solar cell based on titania/poly(3-hexylthiophene).

Here we present an ultraviolet responsive inorganic-organic hybrid solar cell based on titania/poly(3-hexylthiophene) (TiO(2)/P3HT) heterojuction. In this solar cell, TiO(2) is an ultraviolet light absorber and electronic conductor, P3HT is a hole conductor, the light-to-electrical conversion is realized by the cooperation for these two components. Doping ionic salt in P3HT polymer can improve the photovoltaic performance of the solar cell. Under ultraviolet light irradiation with intensity of 100 mW·cm(-2), the hybrid solar cell doped with 1.0 wt.% lithium iodide achieves an energy conversion efficiency of 1.28%, which is increased by 33.3% compared to that of the hybrid solar cell without lithium iodide doping. Our results open a novel sunlight irradiation field for solar energy utilization, demonstrate the feasibility of ultraviolet responsive solar cells, and provide a new route for enhancing the photovoltaic performance of solar cells.

Synthesis of hierarchically structured ZnO spheres by facile methods and their photocatalytic deNOx properties.

This paper presents novel and facile methods for the fabrication of a series ZnO spheres by template-free, carbon template and hydrated-salt assisted solvothermal process, respectively. Phase purity and crystalline structure of the products were studied by X-ray diffraction analysis. SEM was employed to investigate the morphology and the fabrication of the monodisperse. BET analysis revealed that the as-prepared samples possessed huge specific surface area. UV-vis diffuse reflectance spectroscopy showed that these ZnO hollow spheres have a higher absorption. The as-prepared samples showed excellent photocatalytic activity for the decomposition of NOx gas under both visible-light and UV light irradiation (λ>510, 400, 290nm), being superior to that of commercial TiO2 powders.