MOCVD of crystalline Bi2O3 thin films using a single-source bismuth alkoxide precursor and their use in photodegradation of water

Bismuth(III) tert-butoxide [Bi((OBu)-Bu-t)(3)] was utilised as a single-source precursor to controllably deposit thin films of different phases of bismuth oxide (Bi2O3) on glass substrates via low-pressure chemical vapour deposition (LPCVD). Band gaps for the different phases have been measured (E-g = 2.3-3.0 eV) and the films displayed excellent photodegradation of water under near-UV irradiation

A novel route to Pt-Bi2O3 composite thin films and their application in photo-reduction of water

A novel homoleptic bismuth(III) β-diketonate (dibenzoylmethane – dbm) complex [Bi(dbm)3]2 has been used as a precursor to thin films of crystalline β-Bi2O3, and hexachloroplatinic acid (H2PtCl6·6H2O) has been demonstrated as a suitable precursor for deposition of platinum nanoparticles, both deposited via aerosol-assisted chemical vapour deposition (AACVD). Thin films of Pt–Bi2O3 were co-deposited from a mixture of [Bi(dbm)3]2 and H2PtCl6·6H2O; the introduction of Pt particles into β-Bi2O3 causes hydrogen to be evolved during photolysis of water over the composite material, a property not found for Pt particles or β-Bi2O3 alone

Gas-phase synthesis of hybrid nanostructured materials

Nanoparticles (NPs) of noble metals and their oxides, which have many applications in catalysis, electrocatalysis and photocatalysis, are frequently loaded onto metal oxide supports to enhance performance due to the presence of strong metal-metal oxide or metal oxide-metal oxide interactions. Here we present a flexible aerosol-assisted chemical vapour deposition (AACVD) method for constructing nanostructured thin films of noble metal (Au, Pt, Pd or Ru) and metal oxide (PdO or RuOx) NPs supported on 1D WO3 nanorod arrays. The size of the NPs (1.6 to 7.3 nm) is directly controlled by the deposition time (0.5 to 36 minutes)

Analysis of transferred fragrance and its forensic implications

Perfumes are widely used by many people in developed countries, and a large number of both men and women wear perfumes on a daily basis. Analysis of perfume trace materials from clothing is not commonly employed within forensic casework, yet as a form of trace evidence it has the potential to provide valuable intelligence. In order to appreciate the value of trace evidence there is a fundamental need for an evidence base that can both offer insight into how a trace material behaves under different scenarios and activities, and from which inferences can be made. With this purpose a gas chromatography-mass spectrometry method for trace analysis of perfumes was developed. This paper presents two different series of experiments that investigate the dynamics of perfume transfer as a factor of perfume ageing time, and as a factor of perfume contact time. Empirical data showed that both perfume ageing time, and perfume contact time play a key role in the number of perfume components transferred. These studies have implication for forensic protocols, specifically for perfume trace evidence collection, analysis, interpretation, and presentation, and there is potentially great value in analysing perfumes from clothing exhibits in forensic enquiries that involve close contact between individuals, such as sexual assaults

Photocatalytic Oxygen Evolution from Cobalt-Modified Nanocrystalline BiFeO3 Films Grown via Low-Pressure Chemical Vapor Deposition from beta-Diketonate Precursors

BiFeO3 is an interesting multifunctional narrow band gap semiconductor that exhibits simultaneous multiferroic, photovoltaic, and photocatalytic behavior. Hence there is much interest in the growth of thin films of BiFeO3 via chemical vapor deposition (CVD); however, the number of suitable bismuth precursors is severely limited. A series of homoleptic bismuth(III) β-diketonate complexes were synthesized via simple room temperature ligand-exchange reactions from [Bi(N(SiMe3)2)3] and free diketonate ligands, which yielded the crystal structure of [Bi(acac)3] as a 1-D polymer. We attempted to use these complexes for low pressure CVD (LPCVD) growth of BiFeO3 films with [Fe(acac)3]; however, all bismuth complexes exhibited poor volatilities and decomposition characteristics, and as a result film growth was unsuccessful. Subsequently, the volatile alkoxide [Bi(OtBu)3], with [Fe(acac)3], was used to grow dense BiFeO3 films via low pressure CVD. The BiFeO3 films possessed multiferroic properties at room temperature and exhibited activity for visible light-driven water oxidation in the presence of a Ag+ electron scavenger, which improved significantly when modified with a cobalt surface cocatalyst. The increase in activity, probed by time-resolved photoluminescence spectroscopy, was attributed to improved charge carrier separation arising from the in-built internal electric field of BiFeO3 in addition to the presence of an efficient cobalt oxygen evolution catalyst

Visible-light driven water splitting over BiFeO₃ photoanodes grown via the LPCVD reaction of [Bi(OtBu)₃] and [Fe(OtBu)₃]₂ and enhanced with a surface nickel oxygen evolution catalyst

Phase-pure BiFeO3 films were grown directly via dual-source low-pressure CVD (LPCVD) from the ligand-matched precursors [Bi(O(t)Bu)3] and [Fe(O(t)Bu)3]2, without the requirement for oxidising gas or post deposition annealing. Photocatalytic testing for water oxidation revealed extremely high activity for PEC water splitting and photocatalytic water oxidation under visible light irradiation (λ > 420 nm) with a benchmark IPCE for BiFeO3 of 23% at 400 nm. The high activity is ascribed to the ultrafine morphology achieved via the LPCVD process. The performance was enhanced by over four times when the BiFeO3 photoanode is coupled to a Ni-B surface OEC

Chemical vapour deposition of group Vb metal phosphide thin films

The atmospheric pressure chemical vapour deposition (APCVD) reaction of VCl4 or VOCl3 with cyclohexylphosphine at substrate temperatures of 600 degreesC deposits thin films of amorphous vanadium phosphide. The films are black - gold, hard, chemically resistant and conductive. The APCVD reaction of MCl5 (where M = Nb or Ta) with cyclohexylphosphine at 500 - 600 degreesC deposits films of crystalline beta-MP and at 400 degreesC - 450 degreesC amorphous films of stoichiometry MP are formed. The MP films are metallic, conductive, adherent and chemically resistant

Chemical vapour deposition of crystalline thin films of tantalum phosphide

Tantalum phosphide coatings were prepared by chemical vapour deposition reaction of TaCl5 and PH2Cy at 350-500 degreesC. The films are hard, stable to corrosive environments and show reflection properties in the infrared. (C) 2002 Elsevier Science B.V. All rights reserved

Persistence of transferred fragrance on fabrics for forensic reconstruction applications

It has recently been established that volatile organic compounds (VOCs) successfully transfer between clothing even with a short contact of 10 s, highlighting the potential to use VOCs in forensic reconstruction scenarios, such as sexual assault cases. The mid and low volatility compounds transferred in greater amounts than high volatility compounds. This study presents empirical data addressing the persistence of transferred VOCs on clothing for the first time. A series of experiments were carried out to determine the persistence of VOCs on clothing for time periods of up 4 weeks, on natural and synthetic fibres, and at three different environmental temperatures. The data indicate that the highest VOC amounts are generally obtained for shorter persistence times of up to 1 d. Whilst high volatility compounds were not recovered in sufficient amounts to allow quantification, the four other transferred VOCs were successfully quantified for persistence times of up to 4 weeks. The persistence for mid-volatility compounds follows decay curve trends in line with those previously obtained for fibres, glass and pollen. When comparing the persistence of VOCs on a natural and a synthetic fibre, for a persistence time of 1 h, the transferred VOCs were retained on a natural fibre in higher amounts than on a synthetic fibre. However, for longer persistence times the concentration of VOCs was similar between the two fabrics. Lastly, lower environmental temperatures resulted in higher recoveries for most VOCs, especially for short persistence times. These findings demonstrate that optimal recovery of VOCs from clothing occurs when the fabric is kept at cooler temperatures and analysed soon after the fragrance transfer occurred, although VOC recovery was possible at higher temperatures and after longer persistence times. Given the transfer and persistence characteristics of VOCs from fragrance, there is potential for fragrance to be used as a form of trace in forensic reconstruction approaches

An array of WO3 and CTO heterojunction semiconducting metal oxide gas sensors used as a tool for explosive detection

Terrorists frequently use explosives and they represent an imminent threat to national and global security. Recent events highlight the necessity of explosive detection, demonstrating the need for developing and applying new sensors for explosive gas detection. Semiconducting metal oxide gas sensors can be incorporated into electronic noses, which provide a cheap, portable and highly sensitive device. Using unmodified, admixed and 2-layered sensors consisting of WO3 and chromium titanium oxide (CTO), an array of seven heterojunction semiconducting metal oxide sensors was produced. All seven sensors were tested against four gases associated with explosive materials. The sensitivity was improved by using 2-layered sensors in response to ethanol, ammonia and nitromethane, whereas the admixed sensors showed high sensitivity when exposed to nitrogen dioxide. The selectivity of the array of sensors was tested using machine-learning techniques with a support vector machine. The technique produced good data classification when classifying the gases used within the study