Raul Quesada-Cabrera

Where Do Photogenerated Holes Go in Anatase:Rutile TiO2? A Transient Absorption Spectroscopy Study of Charge Transfer and Lifetime

Anatase:rutile TiO2 junctions are often shown to be more photocatalytically active than anatase or rutile alone, but the underlying cause of this improvement is not fully understood. Herein, we employ transient absorption spectroscopy to study hole transfer across the anatase:rutile heterojunction in films as a function of phase composition. By exploiting the different signatures in the photoinduced absorption of trapped charges in anatase and rutile, we were able to separately track the yield and lifetime of holes in anatase and rutile sites within phase composites. Photogenerated holes transfer from rutile to anatase on submicrosecond time scales. This hole transfer can significantly increase the anatase hole yield, with a 20:80 anatase:rutile composite showing a 5-fold increase in anatase holes observed from the microsecond. Hole transfer does not result in an increase in charge-carrier lifetime, where an intermediate recombination dynamic between that of pure anatase (t1/2 ≈ 0.5 ms) and rutile (t1/2 ≈ 20 ms) is found in the anatase:rutile junction (t1/2 ≈ 4 ms). Irrespective of what the formal band energy alignment may be, we demonstrate the importance of trap-state energetics for determining the direction of photogenerated charge separation across heterojunctions and how transient absorption spectroscopy, a method that can specifically track the migration of trapped charges, is a useful tool for understanding this behavior.

A simple, low-cost CVD route to thin films of BiFeO3 for efficient water photo-oxidation

A novel method for preparation of BiFeO3 films via a simple solution-based CVD method is reported using for the first time a single-source heterobimetallic precursor [CpFe(CO)2BiCl2]. BiFeO3 films display ferroelectric and ferromagnetic ordering at room temperature and possess direct band-gaps between 2.0 and 2.2 eV. Photocatalytic testing for water oxidation revealed high activities under UVA (365 nm) and simulated solar irradiation, superior to that exhibited by a commercial standard (Pilkington Activ® TiO2 film) resulting in an apparent quantum yield of ∼24%.

Photo-induced enhanced Raman spectroscopy for universal ultra-trace detection of explosives, pollutants and biomolecules

Surface-enhanced Raman spectroscopy is one of the most sensitive spectroscopic techniques available, with single-molecule detection possible on a range of noble-metal substrates. It is widely used to detect molecules that have a strong Raman response at very low concentrations. Here we present photo-induced-enhanced Raman spectroscopy, where the combination of plasmonic nanoparticles with a photo-activated substrate gives rise to large signal enhancement (an order of magnitude) for a wide range of small molecules, even those with a typically low Raman cross-section. We show that the induced chemical enhancement is due to increased electron density at the noble-metal nanoparticles, and demonstrate the universality of this system with explosives, biomolecules and organic dyes, at trace levels. Our substrates are also easy to fabricate, self-cleaning and reusable.

Optimized Atmospheric-Pressure Chemical Vapor Deposition Thermochromic VO2 Thin Films for Intelligent Window Applications

Monoclinic vanadium(IV) oxide (VO2) has been widely studied for energy-efficient glazing applications because of its thermochromic properties, displaying a large change in transmission of near-IR wavelengths between the hot and cold states. The optimization of the reaction between VCl4 and ethyl acetate via atmospheric-pressure chemical vapor deposition (APCVD) was shown to produce thin films of monoclinic VO2 with excellent thermochromic properties (ΔTsol = 12%). The tailoring of the thermochromic and visible light transmission was shown to be possible by altering the density and morphology of the deposited films. The films were characterized by X-ray diffraction, atomic-force microscopy, scanning electron microscopy, ellipsometry, and UV–vis spectrometry. This article provides useful design rules for the synthesis of high-quality VO2 thin films by APCVD.

A simple and low-cost method for the preparation of self-supported TiO2–WO3 ceramic heterojunction wafers

Robust, bilayer heterojunction photodiodes of TiO2–WO3 were prepared successfully by a simple, low-cost powder pressing technique followed by heat-treatment. Exclusive photoirradiation of the TiO2 side of the photodiode resulted in a rapid colour change (dark blue) on the WO3 surface as a result of reduction of W6+ to W5+ (confirmed by X-ray photoelectron spectroscopy). This colour was long lived and shown to be stable in a dry environment in air for several hours. A similar photoirradiation experiment in the presence of a mask showed that charge transfer across the heterojunction occurred approximately normal to the TiO2 surface, with little smearing out of the mask image. As a result of the highly efficient vectorial charge separation, the photodiodes showed a tremendous increase in photocatalytic activity for the degradation of stearic acid, compared to wafers of the respective individual materials when tested separately.

High-Throughput Continuous Hydrothermal Synthesis of Nanomaterials (Part II): Unveiling the As-Prepared CexZryYzO2−δ Phase Diagram

High-throughput continuous hydrothermal flow synthesis was used to manufacture 66 unique nanostructured oxide samples in the Ce-Zr-Y-O system. This synthesis approach resulted in a significant increase in throughput compared to that of conventional batch or continuous hydrothermal synthesis methods. The as-prepared library samples were placed into a wellplate for both automated high-throughput powder X-ray diffraction and Raman spectroscopy data collection, which allowed comprehensive structural characterization and phase mapping. The data suggested that a continuous cubic-like phase field connects all three Ce-Zr-O, Ce-Y-O, and Y-Zr-O binary systems together with a smooth and steady transition between the structures of neighboring compositions. The continuous hydrothermal process led to as-prepared crystallite sizes in the range of 2-7 nm (as determined by using the Scherrer equation).

Single-step synthesis of doped TiO2 stratified thin-films by atmospheric-pressure chemical vapour deposition

Locally doped TiO2 thin-films were engineered by pulsed precursor delivery using atmospheric-pressure chemical vapour deposition. To our knowledge, this is the first example of stratified films deposited in this manner. The optical, structural and morphological properties of the films were investigated using absorption spectroscopy, X-ray diffraction and electron microscopy techniques. Nitrogen-doped TiO2 stratified thin-films were produced as proof that the new technique would work and that the nature and location of nitrogen species within the films could be studied by X-ray photoelectron spectroscopy. The photocatalytic performance of the films was investigated using the photodegradation of a model organic pollutant (stearic acid). The impact of a stratified configuration and the influence of the type of nitrogen species on enhanced photocatalytic activity are discussed.

Particle size, morphology and phase transitions in hydrothermally produced VO2(D)

Different morphologies and sizes of VO2(D) particles were synthesised via hydrothermal synthesis using ammonium metavanadate (NH4VO3) or vanadium pentoxide (V2O5) as a vanadium precursor. By adjusting the concentration of vanadium precursors and the pH of the starting solution, a variety of morphologies and sizes of VO2(D) particles from 20 nm to 3 μm could be produced. A flower-shape morphology was obtained under strongly acidic conditions, passing through star-shape particles of 1 μm at pH 2.5 and finally obtaining homogeneous round balls of around 3 μm at pH 6.9. Nanoparticles were produced hydrothermally using V2O5 as a precursor and hydrazine as a reducing agent. The transition from VO2(D) to thermochromic VO2(R) in micron scale particles occurred at 350 °C under vacuum. However, the nanoparticles of VO2(D) had a significantly lower VO2(D) to thermochromic VO2(R) transition temperature of 165 °C after annealing for only a few minutes. This is, to our knowledge, the lowest annealing temperature and time reported in the literature in order to obtain a thermochromic VO2 material via another VO2 phase. After the conversion of VO2(D) microparticles to thermochromic VO2(R), the metal to insulator transition temperature is 61 ± 1 °C for the heating cycle and 53 ± 1 °C for the cooling cycle. However, VO2(R) nanoparticles showed a significantly reduced metal insulator transition temperature of 59 ± 1 °C and 42 ± 1 °C for the cooling cycle lower than that reported in the literature for bulk VO2. This is important due to the need for having a compound with a switching temperature closer to room temperature to be used in smart window devices for energy consumption. W-VO2(D) star shape microparticle samples were prepared using 2–7 at% of the dopant (using ammonium metavanadate as a precursor), although unexpectedly this does not seem to be a viable route to a reduced metal to insulator transition in this system.

Silicalite-1/glass fibre substrates for enhancing the photocatalytic activity of TiO2

Silicalite-1 (S1) coatings were prepared on silica wool substrates by hydrothermal synthesis and subsequently immersed into a Ti-containing sol at a steady rate of 30 cm min−1. The material was annealed in a furnace at 90 °C for 2 h and 550 °C for 2 h to create a silica fibre core surrounded by concentric layers of silicalite-1 and TiO2. The resulting samples were characterised by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller (BET) surface area measurement. The photocatalytic activity of the samples was evaluated using the intelligent ink test and during degradation of stearic acid under UVA light (λ = 365 nm). The new coated-fibres were shown to be substantially better photocatalysts than comparable TiO2 coatings on plain glass fibres. The TiO2/S1/glass fibres have potential use in air/water cleaning applications.

Photocatalytic and electrically conductive transparent Cl-doped ZnO thin films via aerosol-assisted chemical vapour deposition

A simple, economical and effective solution-based chemical vapour deposition (CVD) technique, aerosol-assisted CVD, has been successfully applied to produce inexpensive Cl-doped ZnO films using Zn acetate dihydrate and FeCl3. X-ray photoelectron spectroscopy and the increase in cell parameters from powder X-ray diffraction determined that Cl had been doped into the wurtzite ZnO lattice. The Cl-doping had a significant effect on the morphology of the thin films synthesised and resulted in an improvement in the visible light transmission and lower electrical resistance (typical resistivities of doped films ∼10−2 Ω cm). The highest transmittance (% T) of 85% was obtained when 7 mol% FeCl3 was used in the precursor solution and the lowest resistivity of 4.28 ± 0.41 × 10−2 Ω cm was obtained with 5 mol% FeCl3. The greatest photocatalytic activity of stearic acid degradation under UVA irradiation was obtained on using 10 mol% FeCl3, resulting in the highest formal quantum efficiency (FQE) of 3.0 ± 0.1 × 10−4 molecule per photon. These films, therefore, display transparent conducting oxide and photocatalytic properties, giving multifunctional characteristics and promising applications.