In-situ fabrication of self-supported cobalt molybdenum sulphide on carbon paper for bifunctional water electrocatalysis.

The fabrication of highly efficient yet stable noble-metal-free bifunctional electrocatalysts that can simultaneously catalyse both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) remains challenging. Herein, we employ the heterostructure coupling strategy, showcasing an aerosol-assisted chemical vapour deposition (AACVD) aided synthetic approach for the in-situ growth of cobalt molybdenum sulphide nanocomposites on carbon paper (CoMoS@CP) as a bifunctional electrocatalyst. The AACVD allows the rational incorporation of Co in the Mo-S binary structure, which modulates the morphology of CoMoS@CP, resulting in enhanced HER activity (ŋ10 = 171 mV in acidic and ŋ10 = 177 mV in alkaline conditions). Furthermore, the CoS2 species in the CoMoS@CP ternary structure extends the OER capability, yielding an ŋ100 of 455 mV in 1 M KOH. Lastly, we found that the synergistic effect of the Co-Mo-S interface elevates the bifunctional performance beyond binary counterparts, achieving a low cell voltage (1.70 V at 10 mA cm-2) in overall water splitting test and outstanding catalytic stability (∼90 % performance retention after 50-/30-h continuous operation at 10 and 100 mA cm-2, respectively). This work has opened up a new methodology for the controllable synthesis of self-supported transition metal-based electrocatalysts for applications in overall water splitting.

A Single-Step Route to Robust and Fluorine-Free Superhydrophobic Coatings via Aerosol-Assisted Chemical Vapor Deposition.

Robust fluorine-free superhydrophobic films were produced from a mixture of two fatty acids (stearic acid and palmitic acid), SiO2 nanoparticles, and polydimethylsiloxane. These simple and nontoxic compounds were deposited via aerosol-assisted chemical vapor deposition to provide the rough topography required for superhydrophobicity, formed through island growth of the aggregates. The optimum conditions for well-adhered superhydrophobic films produced films with a highly textured morphology, which possessed a water contact angle of 162 ± 2° and a sliding angle of <5°. Superhydrophobicity was maintained after ultraviolet exposure (14 days at 365 nm), heat treatment (5 h at 300 °C and 5 h at 400 °C), 300 tape peel cycles, and exposure to ethanol and toluene (5 h each).

Dynamics of Photo-Induced Surface Oxygen Vacancies in Metal-Oxide Semiconductors Studied Under Ambient Conditions.

Surface-enhanced Raman spectroscopy (SERS) is a powerful analytical technique commonly used in the detection of traces of organic molecules. The mechanism of SERS is of a dual nature, with Raman scattering enhancements due to a combination of electromagnetic (EM) and chemical contributions. In conventional SERS, the EM component is largely responsible for the enhancement, with the chemical contribution playing a less significant role. An alternative technique, called photo-induced enhanced Raman spectroscopy (PIERS) has been recently developed, using a photo-activated semiconductor substrate to give additional chemical enhancement of Raman bands over traditional SERS. This enhancement is assigned to surface oxygen vacancies (V o) formed upon pre-irradiation of the substrate. In this work, the exceptional chemical contribution in PIERS allows for the evaluation of atomic V o dynamics in metal oxide surfaces. This technique is applied to study the formation and healing rates of surface-active V o in archetypical metal-oxide semiconductors, namely, TiO2, WO3, and ZnO. Contrary to conventional analytical tools, PIERS provides intuitive and valuable information about surface stability of atomic defects at ambient pressure and under operando conditions, which has important implications in a wide range of applications including catalysis and energy storage materials.

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).

The Effect of Film Thickness on the Gas Sensing Properties of Ultra-Thin TiO2 Films Deposited by Atomic Layer Deposition.

Analyte sensitivity for gas sensors based on semiconducting metal oxides should be highly dependent on the film thickness, particularly when that thickness is on the order of the Debye length. This thickness dependence has previously been demonstrated for SnO2 and inferred for TiO2. In this paper, TiO2 thin films have been prepared by Atomic Layer Deposition (ALD) using titanium isopropoxide and water as precursors. The deposition process was performed on standard alumina gas sensor platforms and microscope slides (for analysis purposes), at a temperature of 200 °C. The TiO2 films were exposed to different concentrations of CO, CH4, NO2, NH3 and SO2 to evaluate their gas sensitivities. These experiments showed that the TiO2 film thickness played a dominant role within the conduction mechanism and the pattern of response for the electrical resistance towards CH4 and NH3 exposure indicated typical n-type semiconducting behavior. The effect of relative humidity on the gas sensitivity has also been demonstrated.

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.

The spatial distribution patterns of condensed phase post-blast explosive residues formed during detonation.

The continued usage of explosive devices, as well as the ever growing threat of 'dirty' bombs necessitates a comprehensive understanding of particle dispersal during detonation events in order to develop effectual methods for targeting explosive and/or additive remediation efforts. Herein, the distribution of explosive analytes from controlled detonations of aluminised ammonium nitrate and an RDX-based explosive composition were established by systematically sampling sites positioned around each firing. This is the first experimental study to produce evidence that the post-blast residue mass can distribute according to an approximate inverse-square law model, while also demonstrating for the first time that distribution trends can vary depending on individual analytes. Furthermore, by incorporating blast-wave overpressure measurements, high-speed imaging for fireball volume recordings, and monitoring of environmental conditions, it was determined that the principle factor affecting all analyte dispersals was the wind direction, with other factors affecting specific analytes to varying degrees. The dispersal mechanism for explosive residue is primarily the smoke cloud, a finding which in itself has wider impacts on the environment and fundamental detonation theory.

Morphological Variations of Explosive Residue Particles and Implications for Understanding Detonation Mechanisms.

The possibility of recovering undetonated explosive residues following detonation events is well-known; however, the morphology and chemical identity of these condensed phase postblast particles remains undetermined. An understanding of the postblast explosive particle morphology would provide vital information during forensic examinations, allowing rapid initial indication of the explosive material to be microscopically determined prior to any chemical analyses and thereby saving time and resources at the crucial stage of an investigation. In this study, condensed phase particles collected from around the detonations of aluminized ammonium nitrate and RDX-based explosive charges were collected in a novel manner utilizing SEM stubs. By incorporating the use of a focused ion beam during analysis, for the first time it is possible to determine that such particles have characteristic shapes, sizes, and internal structures depending on the explosive and the distance from the detonation at which the particles are recovered. Spheroidal particles (10-210 µm) with microsurface features recovered following inorganic charge detonations were dissimilar to the irregularly shaped particles (5-100 µm) recovered following organic charge firings. Confirmatory analysis to conclude that the particles were indeed explosive included HPLC-MS, Raman spectroscopy, and mega-electron volt-secondary ionization mass spectrometry. These results may impact not only forensic investigations but also the theoretical constructs that govern detonation theory by indicating the potential mechanisms by which these particles survive and how they vary between the different explosive types.

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.

Titanium arsenide films from the atmospheric pressure chemical vapour deposition of tetrakisdimethylamidotitanium and tert-butylarsine.

Thin films of titanium arsenide have been deposited from the atmospheric pressure chemical vapour deposition (APCVD) of [Ti(NMe(2))(4)] and (t)BuAsH(2) at substrate temperatures between 350-550 °C. Highly reflective, silver coloured films were obtained which showed borderline metallic-semiconductor resistivities. The titanium arsenide films were analyzed by scanning electron microscopy (SEM), Raman spectroscopy, wavelength dispersive analysis of X-rays (WDX), powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The films showed variable titanium to arsenic ratios but at substrate temperatures of 500 and 550 °C films with a 1 : 1 ratio of Ti : As, consistent with the composition TiAs, were deposited. Powder XRD showed that all of the films were crystalline and consistent with the formation of TiAs. Both nitrogen and carbon contamination of the films were negligible.

The reaction of tin(IV) iodide with phosphines: formation of new halotin anions.

The reaction of SnI(4) with each of a primary, secondary and tertiary phosphine has been investigated and in none of the cases are simple adducts formed. With Cy(3)P, [Cy(3)PI](+) salts of both [SnI(3)](-) (1) and [SnI(5)](-) (2) are isolated arising from reactions involving both reduction at tin and halogen transfer. With the secondary and primary amines Ph(2)PH and CyPH(2), respectively, additional HI elimination reactions occur and the salts [Ph(2)PH(2)](+)(6)[Sn(3)I(12)](6-) (3), [Ph(2)PH(2)](+)(2)[SnI(6)](2-) (4) and [CyPH(3)](+)(2)[SnI(4)](2-) (5) have been isolated. Compounds 1-5 have been characterised crystallographically.

Tungsten imido complexes as precursors to tungsten carbonitride thin films.

Thin films of tungsten carbonitride have been formed on glass by low-pressure chemical vapour deposition (LP)CVD at 550 degrees C from four closely related precursors: [W(mu-N(t)Bu)(N(t)Bu)Cl(2)(H(2)N(t)Bu)](2), [W(N(t)Bu)(2)Cl(2)(TMEDA)] (TMEDA = N,N,N',N'-tetramethylethylenediamine), [W(N(t)Bu)(2)Cl(2)(py)(2)] (py = pyridine) and [W(N(t)Bu)(2)Cl(N{SiMe(3)}(2))]. The grey mirror-like films were grown with a nitrogen or ammonia bleed gas. In all cases the chlorine content of the deposited films was less than 1 at% and the oxygen content of the films was lower for those grown using ammonia. Surprisingly, the use of ammonia did not significantly change the carbon content of the resulting films. Despite the coordination environment around the metal being essentially the same and the materials having a comparable volatility, some differences in film quality were observed. The films were uniform, adhesive, abrasion resistant, conformal and hard, being resistant to scratching with a steel scalpel. X-Ray powder diffraction patterns of all the films showed the formation of beta-WN(x)C(y). As a comparison the aerosol-assisted chemical vapour deposition (AA)CVD of [W(mu-N(t)Bu)(N(t)Bu)Cl(2)(H(2)N(t)Bu)](2) was investigated and amorphous tungsten carbonitride films were deposited.

The effect of oxygen-containing reagents on the crystal morphology and orientation in tungsten oxide thin films deposited via atmospheric pressure chemical vapour deposition (APCVD) on glass substrates.

Thin films of monoclinic WO3 and WO(3-x) have been synthesized by atmospheric pressure chemical vapour deposition from WCl6 and three oxygen containing precursors; water, ethanol and ethanoic anhydride. A wide variation in the colour, crystal morphology and preferred orientation of the films was observed, depending on the chosen oxygen source. In particular contrast were the films formed from WCl6 and ethanol, which were blue and had needle-like crystallites, and those formed from WCl6 and water, which were yellow and had hexagonal shaped crystallites. Studies were also undertaken to form films from WCl6, ethanol and water simultaneously, in which the ratio of ethanol to water was varied, and this led to films in which the crystal morphology and orientation could be controlled.

The reaction of GeCl4 with primary and secondary phosphines.

Reaction of GeCl4 and CyPH2 leads to a range of products from which crystals of [CyPH3]+[GeCl3]- have been obtained. The major intermediate in this reaction, Cy(H)PGeCl3, can be obtained as the dominant product only when an excess of GeCl4 is used in the preparation. Similarly, crystals of [Ph2PH2]+[GeCl3]- have been obtained from reaction of Ph2PH and GeCl4(1 : 1). The structures of both primary and secondary phosphonium cations are reported. Aerosol-assisted and low-pressure chemical vapour deposition experiments using Cy(H)PGeCl3 as precursor lead to the deposition of thin films containing both germanium and phosphorus, contaminated with large amounts of oxygen. GeP has been identified as components of the film from bandgap measurements.