Efficient Solar Light Photocatalyst Made of Ag3PO4 Coated TiO2-SiO2 Microspheres.

Solar light active photocatalyst was prepared as silver phosphate (Ag3PO4) coating on titania-silica (TiO2-SiO2) microspheres. Titania-silica microsphere was obtained by spray drying TiO2-SiO2 colloidal solutions, whereas Ag3PO4 was applied by wet impregnation. XRD on the granules and SEM analysis show that the silver phosphate particles cover the surface of the titania-silica microspheres, and UV-visible diffuse reflectance analysis highlights that Ag3PO4/TiO2-SiO2 composites can absorb the entire visible light spectrum. BET measurements show higher specific surface area of the composite samples compared to bare Ag3PO4. Photocatalytic activity was evaluated by dye degradation tests under solar light irradiation. The prepared catalysts follow a pseudo-first-order rate law for dye degradation tests under solar light irradiation. The composite catalysts with an Ag3PO4/TiO2-SiO2 ratio of 1:1.6 wt% show better catalytic activity towards both rhodamine B and methylene blue degradation and compared with the results with uncoated TiO2-SiO2 microspheres and the benchmark commercial TiO2 (Evonik-P25) as a reference. The composite photocatalyst showed exceptional efficiency compared to its pristine counterparts and reference material. This is explained as having a higher surface area with optimum light absorption capacity.

Mechanistic Insights into WO3 Sensing and Related Perspectives.

Tungsten trioxide (WO3) is taking on an increasing level of importance as an active material for chemoresistive sensors. However, many different issues have to be considered when trying to understand the sensing properties of WO3 in order to rationally design sensing devices. In this review, several key points are critically summarized. After a quick review of the sensing results, showing the most timely trends, the complex system of crystallographic WO3 phase transitions is considered, with reference to the phases possibly involved in gas sensing. Appropriate attention is given to related investigations of first principles, since they have been shown to be a solid support for understanding the physical properties of crucially important systems. Then, the surface properties of WO3 are considered from both an experimental and first principles point of view, with reference to the paramount importance of oxygen vacancies. Finally, the few investigations of the sensing mechanisms of WO3 are discussed, showing a promising convergence between the proposed hypotheses and several experimental and theoretical studies presented in the previous sections.

WO3-Based Gas Sensors: Identifying Inherent Qualities and Understanding the Sensing Mechanism.

Semiconducting metal oxide-based gas sensors are an attractive option for a wide array of applications. In particular, sensors based on WO3 are promising for applications varying from indoor air quality to breath analysis. There is a great breadth of literature which examines how the sensing characteristics of WO3 can be tuned via changes in, for example, morphology or surface additives. Because of variations in measurement conditions, however, it is difficult to identify inherent qualities of WO3 from these reports. Here, the sensing behavior of five different WO3 samples is examined. The samples show good complementarity to SnO2 (the most commonly used material)-based sensors. A surprising homogeneity, despite variation in morphology and preparation method, is found. Using operando diffuse reflectance infrared Fourier transform spectroscopy, it is found that the oxygen vacancies are the dominant reaction partner of WO3 with the analyte gas. This surface chemistry is offered as an explanation for the homogeneity of WO3-based sensors.

Surface modification by vanadium pentoxide turns oxide nanocrystals into powerful adsorbents of methylene blue.

HYPOTHESIS: If nanocrystals of such semiconductor as SnO2 and TiO2, which are not known as powerful adsorbents, have their surface modified by layer of V2O5, how will the adsorption properties be affected? Answering this question would provide a new set of surface properties to be designed by surface engineering of oxide nanocrystals. EXPERIMENTS: SnO2 and TiO2 colloidal nanocrystals were prepared by coupling sol-gel and solvothermal synthesis. By co-processing with V chloroalkoxide and subsequent heat-treatment at 400-500 °C, surface deposition of V2O5 layers was obtained. The methylene blue adsorption onto the prepared materials was tested and compared with the pure oxide supports. Cycling of the materials and analysis of the adsorption process was also investigated. FINDINGS: The V-modified nanocrystals extracted ∼80% methylene blue from 1.5 × 10-5 M aqueous solution after 15 min only, contrarily to pure materials, which took up only 30% of the dye even after 120 min. Comparison with pure commercial V2O5 showed that the peculiar adsorption properties were imparted by the surface deposition of the V2O5-like layers. This report demonstrates that new classes of adsorbing materials can be conceived by suitably coupling different metal oxides.

Corrigendum: Inorganic Photocatalytic Enhancement: Activated RhB Photodegradation by Surface Modification of SnO2 Nanocrystals with V2O5-like species.

This corrects the article DOI: 10.1038/srep44763.

Inorganic Photocatalytic Enhancement: Activated RhB Photodegradation by Surface Modification of SnO2 Nanocrystals with V2O5-like species.

SnO2 nanocrystals were prepared by precipitation in dodecylamine at 100 °C, then they were reacted with vanadium chloromethoxide in oleic acid at 250 °C. The resulting materials were heat-treated at various temperatures up to 650 °C for thermal stabilization, chemical purification and for studying the overall structural transformations. From the crossed use of various characterization techniques, it emerged that the as-prepared materials were constituted by cassiterite SnO2 nanocrystals with a surface modified by isolated V(IV) oxide species. After heat-treatment at 400 °C, the SnO2 nanocrystals were wrapped by layers composed of vanadium oxide (IV-V mixed oxidation state) and carbon residuals. After heating at 500 °C, only SnO2 cassiterite nanocrystals were obtained, with a mean size of 2.8 nm and wrapped by only V2O5-like species. The samples heat-treated at 500 °C were tested as RhB photodegradation catalysts. At 10-7 M concentration, all RhB was degraded within 1 h of reaction, at a much faster rate than all pure SnO2 materials reported until now.

Surface modification of TiO2 nanocrystals by WO(x) coating or wrapping: solvothermal synthesis and enhanced surface chemistry.

TiO2 anatase nanocrystals were prepared by solvothermal processing of Ti chloroalkoxide in oleic acid, in the presence of W chloroalkoxide, with W/Ti nominal atomic concentration (R(w)) ranging from 0.16 to 0.64. The as-prepared materials were heat-treated up to 500 °C for thermal stabilization and sensing device processing. For R(0.16), the as-prepared materials were constituted by an anatase core surface-modified by WO(x) monolayers. This structure persisted up to 500 °C, without any WO3 phase segregation. For R(w) up to R(0.64), the anatase core was initially wrapped by an amorphous WO(x) gel. Upon heat treatment, the WO(x) phase underwent structural reorganization, remaining amorphous up to 400 °C and forming tiny WO3 nanocrystals dispersed into the TiO2 host after heating at 500 °C, when part of tungsten also migrated into the TiO2 structure, resulting in structural and electrical modification of the anatase host. The ethanol sensing properties of the various materials were tested and compared with pure TiO2 and WO3 analogously prepared. They showed that even the simple surface modification of the TiO2 host resulted in a 3 orders of magnitude response improvement with respect to pure TiO2.

Solvothermal, chloroalkoxide-based synthesis of monoclinic WO(3) quantum dots and gas-sensing enhancement by surface oxygen vacancies.

We report for the first time the synthesis of monoclinic WO3 quantum dots. A solvothermal processing at 250 °C in oleic acid of W chloroalkoxide solutions was employed. It was shown that the bulk monoclinic crystallographic phase is the stable one even for the nanosized regime (mean size 4 nm). The nanocrystals were characterized by X-ray diffraction, High resolution transmission electron microscopy, X-ray photoelectron spectroscopy, UV-vis, Fourier transform infrared and Raman spectroscopy. It was concluded that they were constituted by a core of monoclinic WO3, surface covered by unstable W(V) species, slowly oxidized upon standing in room conditions. The WO3 nanocrystals could be easily processed to prepare gas-sensing devices, without any phase transition up to at least 500 °C. The devices displayed remarkable response to both oxidizing (nitrogen dioxide) and reducing (ethanol) gases in concentrations ranging from 1 to 5 ppm and from 100 to 500 ppm, at low operating temperatures of 100 and 200 °C, respectively. The analysis of the electrical data showed that the nanocrystals were characterized by reduced surfaces, which enhanced both nitrogen dioxide adsorption and oxygen ionosorption, the latter resulting in enhanced ethanol decomposition kinetics.

Chemoresistive sensing of light alkanes with SnO2 nanocrystals: a DFT-based insight.

Density functional theory (DFT) modelling of the alkane-SnO2 surface interaction correctly predicts the results of the chemoresistive alkane sensing tests, provided that the highly reduced nature of the SnO2 nanocrystal surface is properly inserted in the model.

Capping ligand effects on the amorphous-to-crystalline transition of CdSe nanoparticles.

Amorphous CdSe nanoparticles were prepared by a base-catalyzed room-temperature reaction between cadmium nitrate and selenourea, with dodecanethiol as a capping ligand. The nanoparticle size could be controlled from 1.9 to 3.6 nm by increasing the water concentration in the reaction. When the nanoparticles were heated in a pyridine suspension, excitonic peaks appeared in the initially featureless optical absorption spectra. By changing the suspension solvent and the capping ligand and its concentration, it was shown that the dynamic surface exchange between the ligand and pyridine controls the crystallization process. This phenomenon was interpreted as a surface rigidity effect imposed by the ligand, whose importance was separately evidenced on the dried nanoparticles by the evolution of X-ray diffraction patterns and Raman spectra. In particular, both techniques showed that a threshold temperature is needed before crystallization occurs, and such a threshold was related to ligand desorption. The surface effect was directly visualized by high-resolution transmission electron microscopy observations of the amorphous particles, where crystallization under the electron beam was observed to start by the formation of a crystalline nucleus in the nanoparticle interior and then to extend to the whole structure.

Ambient pressure synthesis of corundum-type IN2O3.

This communication reports the formation of the high-pressure modification of indium (III) oxide (so-called corundum-type or hexagonal In2O3) under ambient pressure. Corundum-type In2O3 was obtained by precipitation from the solution of indium nitrate in methanol by adding concentrated ammonia solution and subsequent calcination of the obtained precipitate at 250-500 degrees C. The role of the impurities and the additives in the stabilization of corundum-type In2O3 is discussed.