Sulaiman N. Basahel

Influence of crystal structure of nanosized ZrO2 on photocatalytic degradation of methyl orange.

Nanosized ZrO2 powders with near pure monoclinic, tetragonal, and cubic structures synthesized by various methods were used as catalysts for photocatalytic degradation of methyl orange. The structural and textural properties of the samples were analyzed by X-ray diffraction, Raman spectroscopy, TEM, UV-vis, X-ray photoelectron spectroscopy (XPS), and N2 adsorption measurements. The performance of synthesized ZrO2 nanoparticles in the photocatalytic degradation of methyl orange under UV light irradiation was evaluated. The photocatalytic activity of the pure monoclinic ZrO2 sample is higher than that of the tetragonal and cubic ZrO2 samples under optimum identical conditions. The characterization results revealed that monoclinic ZrO2 nanoparticles possessed high crystallinity and mesopores with diameter of 100 Å. The higher activity of the monoclinic ZrO2 sample for the photocatalytic degradation of methyl orange can be attributed to the combining effects of factors including the presence of small amount of oxygen-deficient zirconium oxide phase, high crystallinity, large pores, and high density of surface hydroxyl groups.

Layered double hydroxides supported on multi-walled carbon nanotubes: preparation and CO2 adsorption characteristics

Layered double hydroxides (LDHs) are promising materials for CO2 sorption, although improvements in performance are required for practical applications. In the current study, the CO2 sorption capacity and multi-cycle stability were both increased by introducing an open supporting framework of multi-walled carbon nanotubes (MWNTs). This nanostructured inert network provides a high surface area, maximizing the gas accessibility and minimizing coarsening effects. Specifically, LDH nanoparticles were precipitated directly onto MWNTs, initially oxidised to ensure a favourable electrostatic interaction and hence a good dispersion. The dependence of the structural and physical properties of the Mg–Al LDH grown on MWNT supports has been studied, using electron microscopy, X-ray diffraction, thermogravimetric analysis (TGA), and BET surface area, and correlated with the CO2 sorption capacity, established via TGA and temperature programmed desorption measurements. The use of a MWNT support was found to improve the absolute capacity and cycle stability of the hybrid adsorbent under dry conditions.

Tungsten Doped TiO2 with Enhanced Photocatalytic and Optoelectrical Properties via Aerosol Assisted Chemical Vapor Deposition.

Tungsten doped titanium dioxide films with both transparent conducting oxide (TCO) and photocatalytic properties were produced via aerosol-assisted chemical vapor deposition of titanium ethoxide and dopant concentrations of tungsten ethoxide at 500 °C from a toluene solution. The films were anatase TiO2, with good n-type electrical conductivities as determined via Hall effect measurements. The film doped with 2.25 at.% W showed the lowest resistivity at 0.034 Ω.cm and respectable charge carrier mobility (14.9 cm3/V.s) and concentration (×1019 cm−3). XPS indicated the presence of both W6+ and W4+ in the TiO2 matrix, with the substitutional doping of W4+ inducing an expansion of the anatase unit cell as determined by XRD. The films also showed good photocatalytic activity under UV-light illumination, with degradation of resazurin redox dye at a higher rate than with undoped TiO2.

Aerosol assisted chemical vapour deposition of hydrophobic TiO2–SnO2 composite film with novel microstructure and enhanced photocatalytic activity

Aerosol assisted chemical vapour deposition (AACVD) was used to synthesise a TiO2–SnO2 composite film onto a glass substrate. For comparison a TiO2 film and a SnO2 film were also prepared. All films were characterised by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and wavelength dispersive X-ray spectroscopy (WDX). XPS and WDX of the composite film revealed a TiO2 rich film with a high level of SnO2 segregation at the surface. Highly structured pyramid-like features gave rise to hydrophobic films with static water contact angles of 134°. Photocatalytic activities were determined by monitoring the degradation of intelligent ink (containing Resazurin redox dye) via UV-visible spectroscopy. Under UVA irradiation, the TiO2 film only began to degrade the dye after being irradiated in excess of 100 minutes, whereas the composite TiO2–SnO2 film required only 6 minutes of irradiation before degradation was observed. The formal quantum efficiency (FQE) for the TiO2–SnO2 composite was determined to be 1.01 × 10−2 molecules per incident photon and the formal quantum yield (FQY) was 1.17 × 10−2 molecules per absorbed photon. This is an order of magnitude superior to Pilkington Activ™ self-cleaning glass a commercial self-cleaning TiO2 coating on glass. This improved photocatalytic activity is attributed to the presence of electron scavenging SnO2 sites that increase charge separation and the increased surface area due to the highly structured morphology.

Combinatorial Atmospheric Pressure Chemical Vapor Deposition of Graded TiO2–VO2 Mixed-Phase Composites and Their Dual Functional Property as Self-Cleaning and Photochromic Window Coatings

A combinatorial film with a phase gradient from V:TiO₂ (V: Ti ≥ 0.08), through a range of TiO₂-VO₂ composites, to a vanadium-rich composite (V: Ti = 1.81) was grown by combinatorial atmospheric pressure chemical vapor deposition (cAPCVD). The film was grown from the reaction of TiCl₄, VCl₄, ethyl acetate (EtAc), and H₂O at 550 °C on glass. The gradient in gas mixtures across the reactor induced compositional film growth, producing a single film with numerous phases and compositions at different positions. Seventeen unique positions distributed evenly along a central horizontal strip were investigated. The physical properties were characterized by wavelength dispersive X-ray (WDX) analysis, X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and UV-visible spectroscopy. The functional properties examined included the degree of photoinduced hydrophilicity (PIH), UVC-photocatalysis, and thermochromism. Superhydrophilic contact angles could be achieved at all positions, even within a highly VO₂-rich composite (V: Ti = 1.81). A maximum level of UVC photocatalysis was observed at a position bordering the solubility limit of V:TiO₂ (V: Ti ≈ 0.21) and fragmentation into a mixed-phase composite. Within the mixed-phase TiO₂: VO₂ composition region (V: Ti = 1.09 to 1.81) a decrease in the semiconductor-to-metal transition temperature of VO₂ from 68 to 51 °C was observed.

2D zeolite coatings: Langmuir-Schaefer deposition of 3 nm thick MFI zeolite nanosheets

Stable suspensions of zeolite nanosheets (3 nm thick MFI layers) were prepared in ethanol following acid treatment, which partially removed the associated organic structure-directing agent. Nanosheets from these suspensions could then be dispersed at the air-water interface and transferred to silicon wafers using Langmuir-Schaefer deposition. Using layer-by-layer deposition, control on coating thickness was demonstrated. In-plane X-ray diffraction (XRD) revealed that the deposited nanosheets contract upon calcination similar to bulk MFI crystals. Different methods for secondary growth resulted in preferentially oriented thin films of MFI, which had sub-12-nm thickness in certain cases. Upon calcination, there was no contraction detectable by in-plane XRD, indicating well-intergrown MFI films that are strongly attached to the substrate.

Aerosol assisted chemical vapor deposition of conductive and photocatalytically active tantalum doped titanium dioxide films

This paper shows the aerosol assisted chemical vapour deposition of transparent, blue coloured and conductive tantalum doped titanium dioxide films from the CVD reaction of Ti(OEt)4 and Ta(OEt)5. Hall effect measurements showed the doped films to have excellent n-type electrical conductivity showing, to the best of our knowledge, the lowest reported sheet resistance ever recorded for Ta-doped TiO2 of 14 Ω sq−1. The Ta 6 atom% doped TiO2 film also showed the best electrical results with a charge carrier concentration of 1.60 × 1021 cm−3 and mobility of 1.44 cm2 V−1 s−1 making it a suitable electrode in photovoltaic devices. The doped films were multifunctional, showing good photocatalytic activity under UV-light illumination. XPS and XRD studies gave strong evidence that the Ta was entering the TiO2 lattice as Ta5+ and that a reduction of some Ti4+ to Ti3+ was observed.

Photocatalytic Activity of Doped and Undoped Titanium Dioxide 32 Nanoparticles Synthesised by Flame Spray Pyrolysis

*Email: felicity.sartain@bio-nano-consulting.com The photocatalytic activities of a series of titanium dioxide (TiO2) based nanoparticles, synthesised via flame spray pyrolysis (FSP), have been investigated and compared with the commercially available Evonik Aeroxide TiO2 P 25 (P 25). The effects of metal ions aluminium, tin and platinum, respectively, on the physical and chemical properties of the TiO2 nanoparticles are reported. The set of six samples were characterised by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), inductively coupled plasma-mass spectrometry (ICP-MS) and ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy. Specific surface areas were determined using nitrogen adsorption and desorption measurements. Subsequent photocatalytic studies of the degradation of methyl orange (MO) dye under UV irradiation demonstrated that addition of Al and Sn had a negative effect on catalytic performance, whereas the addition of ≤0.7 at% Pt to each sample enhanced photocatalytic activity. Most interestingly, the Pt-doped composite samples (TiO2-Sn/Pt and TiO2-Al/Pt) both showed a significantly higher rate of degradation of MO, when compared to P 25. All Pt-doped samples show an increased visible photon absorption capacity. The relationships between the physical and chemical characteristics are discussed in relation to photocatalytic performance.

Activation and local structural stability during the thermal decomposition of Mg/Al-hydrotalcite by total neutron scattering

The activation of synthetic hydrotalcite, the carbonated layered double hydroxide (LDH) with ratio Mg2+/Al3+ = 3 and structural formula [Mg6Al2(OH)16]2+·CO32−n(H2O), has been investigated using neutron and X-ray diffraction. In situneutron diffraction was used to follow the structural phase transformations during the thermal decomposition (calcination) of hydrotalcite under vacuum in the temperature range 298–723 K, and during which the residual gas evolved by the sample was analysed by mass spectrometry. Detailed structural information of the LDH and mixed metal oxides (MMOs) was extracted from both the Bragg peaks and the total scattering. These two analysis techniques provide complementary insight into the relevant transition mechanisms, since Bragg diffraction originates from long-range periodicities within the samples while total scattering reveals the subtleties of the local atomic environment. This latter information is particularly important for our understanding of catalytic activity since it elucidates the local metal coordination. We find that, during the calcination process, the local environment around the metal centres is robust, as the various stages during the phase transition have identical local structures. The implications of these new results for the nature of the MMOs is discussed in relation to the well-studied, reverse, rehydration reaction, and the high propensity of trivalent Al ions to migrate to tetrahedrally-coordinated lattice sites.

Combinatorial aerosol assisted chemical vapour deposition of a photocatalytic mixed SnO2/TiO2 thin film

Combinatorial Aerosol Assisted Chemical Vapour Deposition (cAACVD) was used to grow a thin film that graduated across its width from tin dioxide to titanium dioxide. This is a relatively new technique that can be used to create a variety of mixed phase and composition thin films on a single substrate. Here cAACVD was used to deposit a mixed phase TiO2 and SnO2 film and composition was related to UV photocatalysis, hydrophobicity and microstructure not inherent to anatase TiO2 or cassiterite SnO2. Characterisation was achieved using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and UV-Vis spectroscopy. Functional testing to elucidate the differences in functional properties across the film was undertaken by the photo-induced degradation of a resazurin ‘intelligent’ ink, a photo-induced wettability study and two-point resistivity measurements. Functional properties showed enhanced photocatalysis in comparison to Pilkington Activ™ with similar formal quantum yield (molecules destroyed per absorbed photon) and formal quantum efficiency (molecules destroyed per incident photon) values.