Flame-spray pyrolysis preparation of perovskites for methane catalytic combustion

A flame spray pyrolysis apparatus was set-up and optimised for the preparation of perovskitic mixed metal oxides in nanoparticle-size powder form. LaCoO3 was chosen as test catalyst, aiming at correlating crystallinity, surface area, particle size, catalytic activity and durability with some fundamental operating parameters of the apparatus. In particular, feeding rate of precursors solution, flow rate of the O2/CH4 mixture for the igniter and flow rate and linear velocity of the main dispersing-oxidising oxygen have been thoroughly analysed. The activity of the prepared samples was tested for the catalytic flameless combustion of methane, a reaction requiring a proper combination of activity and thermal stability of the catalyst. Provided a crystalline perovskitic phase forms, activity increases with increasing surface area of the powder. By contrast, the higher the initial sintering of catalyst particles within the flame, the higher is thermal stability. Tuning up of operating parameters allows to properly address the desired catalyst properties

Low temperature/uv-assisted composites as gas sensors for medical applications

The sensing of gas molecules is of fundamental importance for environmental monitoring, control of chemical processes, medical applications, and so on [1]. Furthermore, recent success in non-invasive medical diagnostics, based on human breath analysis, is pushing forward the development of extremely sensitive gas sensors for ppb detection of specific analytes (e.g. acetone) in a complex gas mixture [1,2]. In recent years, graphene-based gas sensors have attracted much attention and different structures have been developed showing high sensing performances and room temperature working conditions [2]. However, they still suffer from several problems, which could be overcome by covering the graphene surface with metal oxide semiconductors. Furthermore, studies regarding the detection of Volatile Organic Compounds (VOCs) are still at the beginning [3]. Hence, the present work will be aimed at: i) optimizing the synthetic routes of ad hoc composite VOCs sensing materials (based on graphene oxide/SnO2 hybrids); ii) engineering the gas sensor device; and iii) evaluating the sensing performances at both high and mild temperatures (also exploiting the UV light) towards gaseous ethanol, acetone and ethylbenzene. Starting from pure graphite, graphene oxide (GO) powder was synthesized by adopting the Hummer\u2019s modified method, in which the synthetic route was deeply investigated, and several parameters (such as H2O2 concentration) were modulated. Once optimized this step, SnO2 were grown on its surface by hydrothermal method, varying the starting salt precursor/GO weight ratio between 4 and 32. For comparison, pure commercial and home-made SnO2 were also tested. Several physico-chemical analyses were performed to characterize all the as-prepared nanopowders. Subsequently, a homogeneous film was deposited by spraying technique onto Pt-Interdigitated Electrodes (Pt-IDEs). Then, gaseous ethanol (Figure 1) and acetone were sensed, obtaining very promising results for both pure and hybrid materials at 350\ub0C, and at lower temperatures (150\ub0C to 30\ub0C, by exploiting the UV light) for the graphene-based samples

Multilayer WO3/BiVO4 Photoanodes for Solar-Driven Water Splitting Prepared by RF-Plasma Sputtering

A series of WO3, BiVO4 and WO3/BiVO4 heterojunction coatings were deposited on fluorine-doped tin oxide (FTO), by means of reactive radio frequency (RF) plasma (co)sputtering, and tested as photoanodes for water splitting under simulatedAM1.5 G solar light in a three-electrode photoelectrochemical (PEC) cell in a 0.5 M NaSO4 electrolyte solution. The PEC performance and time stability of the heterojunction increases with an increase of the WO3 innermost layer up to 1000 nm. A two-step calcination treatment (600 \ub0C after WO3 deposition followed by 400 \ub0C after BiVO4 deposition) led to a most performing photoanode under back-side irradiation, generating a photocurrent density of 1.7 mA cm-2 at 1.4 V vs. SCE (i.e., two-fold and five-fold higher than that generated by individual WO3 and BiVO4 photoanodes, respectively). The incident photon to current efficiency (IPCE) measurements reveal the presence of two activity regions over the heterojunction with respect to WO3 alone: The PEC efficiency increases due to improved charge carrier separation above 450 nm (i.e., below the WO3 excitation energy), while it decreases below 450 nm (i.e., when both semiconductors are excited) due to electron\u2013hole recombination at the interface of the two semiconductors

Modulated excitation extended X-ray absorption fine structure spectroscopy

The sensitivity of extended X-ray absorption fine structure spectroscopy (EXAFS) for minute structural changes can be enhanced by combination with the modulated excitation approach and making use of phase sensitive analysis. A modulated EXAFS experiment of a reversible periodic Pd to PdO partial oxidation has been simulated in order to understand the effect of the phase sensitive analysis on the shape and meaning of the resulting phase-resolved EXAFS spectra. In particular, the simulation comprises either a synchronous or a delayed sinusoidal variation of the EXAFS parameters, i.e. coordination number (N), interatomic distance (R) and Debye\u2013Waller factor (s2 ), of first Pd\u2013Pd, first Pd\u2013O, and second Pd\u2013(O)\u2013Pd coordination shells. The effect of these variations on the resulting phase-resolved Fourier transform EXAFS spectra is discussed. The results of the simulation are validated by an in situ EXAFS experiment at the Pd K-edge over 1.6 wt% Pd/Al2O3 undergoing reversible partial oxidation in a H2 vs. O2 modulation at 573 K. It is shown that phase sensitive detection (PSD) is able to separate the minor contribution at ca. 2.8 \uc5 corresponding to the growth of the Pd\u2013(O)\u2013Pd shell that is otherwise hidden under the static signal of the Pd\u2013Pd shell of reduced Pd particles. The fitting of the phase-resolved EXAFS spectra suggests that the fast H2 to O2 switch leads the partial oxidation of the Pd surface with the formation of a PdO shell covering a metallic Pd core. Therefore, the dynamics of the full system can be described with greater detail than in conventional EXAFS. The intention of this work is to provide the tools and therefore a solid guidance to qualitatively and quantitatively understand the nature of the shape of phase-resolved FT-EXAFS spectra that may prove helpful in the analysis of a wide range of functional materials

Solvent nature effect in preparation of perovskites by flame pyrolysis: 2 : Alcohols and alcohols plus propionic acid mixtures

The effect of either pure alcohols or alcohols + propionic acid mixtures as solvents for the preparation by flame pyrolysis of a standard LaCoO3 catalyst, to be employed for the catalytic flameless combustion of methane, has been investigated. All the catalysts proved very active for the mentioned reaction. Low-MW pure alcohols showed however less suitable than alcohols-propionic acid mixtures, leading to lower perovskite phase purity, less particle size homogeneity and lower specific surface area. The high volatility of the solvent seems to be the major cause, together with the improper behaviour of nitrates (forced by solubility reasons) as perovskite metals precursors. However, the addition of propionic acid to the alcohols allowed to use the acetates as precursors and hence to obtain high perovskitic phase purity, high SSA and Uniform particle size. Moreover, the increase of combustion enthalpy of the solvent, through the addition of higher-MW alcohols, leading to progressively higher flame temperature, strongly improved the thermal resistance of the catalyst, without lowering catalytic performance

Solvent nature effect in preparation of perovskites by flame pyrolysis: 1: carboxylic acids

The effect of a series of carboxylic acids (C(2)-C(8)), as solvents for the preparation by flame spray pyrolysis of LaCoO(3) catalyst for the flameless combustion of methane, has been investigated. Acetic acid showed to be unsatisfactory from several points of view: low phase purity of the catalyst, higher amount of unburnt carbonaceous residua, lower catalytic activity and low thermal stability. By increasing the carbon chain length of the solvent, the consequent increase of flame temperature led to an increase of crystal phase purity and of particle size and to a decrease of specific surface area of the catalyst. Catalytic activity showed only marginally affected by the last parameter, phase purity seeming more important. Thermal resistance showed directly related to flame temperature, i.e. to the combustion enthalpy of the solvent, but a relatively high amount of residual organic matter can negatively affect this property

In situ attenuated total reflection infrared spectroscopy study of the photocatalytic steam reforming of methanol on Pt/TiO2

The effect of Pt deposition on TiO2 and of Pt particle size on the photocatalytic steam reforming of methanol was studied by in situ attenuated total reflectance infrared spectroscopy (ATR-IR). Two 0.5 wt.% Pt/TiO2 samples were investigated, one possessing Pt nanoparticles of ca. 4 nm mean size, the other Pt clusters of ca. 1.3 nm mean size showing significantly different photoactivity in terms of both hydrogen production rate and selectivity to CO, CO2 and all other by-products. The presence of Pt nanoparticles strongly affected both the adsorption/desorption and the reactivity properties of the TiO2 surface. Moreover, the variation of the IR spectrum background upon UV\u2013vis irradiation proved that the photopromoted electrons can be trapped by the Pt particles with the consequent increase of electron-hole separation. Reducing the Pt size from nanoparticles to clusters increased the rate of methanol and water absorption and hindered the detrimental formation of irreversibly adsorbed CO on Pt. All of these aspects contribute to increase the photocatalytic performance of Pt cluster-decorated TiO2 with respect to Pt nanoparticles containing TiO2. Finally, prolonged exposure of all samples to methanol/water vapour in the dark led to the formation of unreactive formate which persisted also under UV\u2013vis irradiation. By contrast, this spectator species did not form when the sample was exposed to methanol/water vapour under UV\u2013vis irradiation

TiO2-based materials for photocatalytic hydrogen production

Hydrogen, the cleanest and most promising energy vector, can be produced by solar into chemical energy conversion, either by the photocatalytic direct splitting of water into H2 and O2, or, more efficiently, in the presence of sacrificial reagents, e.g., in the so-called photoreforming of organics. Efficient photocatalytic materials should not only be able to exploit solar radiation to produce electron-hole pairs, but also ensure enough charge separation to allow electron transfer reactions, leading to solar energy driven thermodynamically up-hill processes. Recent achievements of our research group in the development and testing of innovative TiO2-based photocatalytic materials are presented here, together with an overview on the mechanistic aspects of water photosplitting and photoreforming of organics. Photocatalytic materials were either i) obtained by surface modification of commercial photocatalysts, or produced ii) in powder form by different techniques, including traditional sol gel synthesis, aiming at engineering their electronic structure, and flame spray pyrolysis starting from organic solutions of the precursors, or iii) in integrated form, to produce photoelectrodes within devices, by radio frequency magnetron sputtering or by electrochemical growth of nanotube architectures, or photocatalytic membranes, by supersonic cluster beam deposition

Fabrication of Pt/Ti/TiO2 Photoelectrodes by RF-Magnetron Sputtering for Separate Hydrogen and Oxygen Production

Evolution of pure hydrogen and oxygen by photocatalytic water splitting was attained from the opposite sides of a composite Pt/Ti/TiO2 photoelectrode. The TiO2 films were prepared by radio frequency (RF)-Magnetron Sputtering at different deposition time ranging from 1 up to 8 h and then characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and ultraviolet-visible-near infrared (UV-vis-NIR) diffuse reflectance spectroscopy. The photocatalytic activity was evaluated by incident photon to current efficiency (IPCE) measurements and by photocatalytic water splitting measurements in a two-compartment cell. The highest H2 production rate was attained with the photoelectrode prepared by 6 h-long TiO2 deposition thanks to its high content in the rutile polymorph, which is active under visible light. By contrast, the photoactivity dropped for longer deposition time, because of the increased probability of electron-hole recombination due to the longer electron transfer path

Bismuth vanadate photoanodes for water splitting deposited by radio frequency plasma reactive co-sputtering

Photoactive bismuth vanadate (BiVO4) thin coatings were deposited on fluorine-doped tin oxide glass by plasma reactive sputtering from Bi2O3 and vanadium (V) radio frequency (RF) powered targets. The films were characterized by x-ray diffraction, scanning electron microscopy, energy dispersion spectroscopy, and UV-vis spectroscopy. The effects that the power density supplied to the Bi2O3 target, the post-annealing treatment, and the film thickness have on the structural features and on the photoelectrochemical (PEC) performances of the so obtained BiVO4 film-based photoelectrodes were investigated. Their PEC performance in water splitting was evaluated in a three-electrode cell by both incident photon to current efficiency (IPCE) and linear sweep voltammetry measurements under AM 1.5 G simulated solar light irradiation. A monoclinic phase of BiVO4, which is more photoactive than the tetragonal BiVO4 phase, was obtained by optimizing the power density supplied to the Bi2O3 target, i.e., by tuning the Bi:V:O atomic ratio. The best PEC performance was obtained for a stoichiometric 1:1 Bi:V atomic ratio, attained with 20 W power supplied at the Bi2O3 target and 300 W power supplied at the vanadium target, and an optimal 200 nm thickness of the BiVO4 film, with a 0.65 mA/cm2 photocurrent density attained at 1.23 V vs. standard calomel electrode, under simulated solar light. These results show the suitability of plasma reactive sputtering with two RF powered electrodes for the deposition of BiVO4 photoanodes for water splitting