Sara Morandi

Photoreduction of mesoporous In2O3: mechanistic model and utility in gas sensing.

A model is proposed for the drop in electronic resistance of n-type semiconducting indium oxide (In(2)O(3)) upon illumination with light (350 nm, 3.5 eV) as well as for the (light-enhanced) sensitivity of In(2)O(3) to oxidizing gases. Essential features of the model are photoreduction and a rate-limiting oxygen-diffusion step. Ordered, mesoporous In(2)O(3) with a high specific surface area serves as a versatile system for experimental studies. Analytical techniques comprise conductivity measurements under a controlled atmosphere (synthetic air, pure N(2)) and temperature-resolved in-situ Fourier transform infrared (FTIR) spectroscopy. IR measurements reveal that oxygen vacancies form a donor level 0.18 eV below the conduction band.

Nano and micro-TiO2 for the photodegradation of ethanol: experimental data and kinetic modelling

With TiO2-photocatalysis being an effective alternative to other more expensive Advanced Oxidation Processes (AOPs), the possibility of using micro-sized TiO2 materials rather than the well-known nano-sized powders is an important goal in terms of both handling safety and cost saving. In this work the photodegradation of ethanol, used as a model VOC (Volatile Organic Compound) molecule, was investigated, comparing the efficiency of both commercial nano- and micro- sized TiO2 samples. In all cases the same degradation pathway was observed, namely, a consecutive first-order reaction with acetaldehyde as an intermediate product and CO2 and water as the final products. All photocatalysts were characterized by means of XRD, TEM, IR, BET and XPS analysis. A kinetic model was also developed considering the collected experimental data and a regression of both adsorption and kinetic constants was made using MATLAB software. The optimized parameters were used for simulating the experimental data using an ode15s algorithm.

Effect of water and ammonia on surface species formed during NOx storage–reduction cycles over Pt–K/Al2O3 and Pt–Ba/Al2O3 catalysts

The effect of water, in the temperature range 25-350 °C, and ammonia at RT on two different surface species formed on Pt-K/Al2O3 and Pt-Ba/Al2O3 NSR catalysts during NO(x) storage-reduction cycles was investigated. The surface species involved are nitrates, formed during the NO(x) storage step, and isocyanates, which are found to be intermediates in N2 production during reduction by CO. FT-IR experiments demonstrate that the dissociative chemisorption of water and ammonia causes the transformation of the bidentate nitrates and linearly bonded NCO(-) species into more symmetric species that we call ionic species. In the case of water, the effect on nitrates is observable at all the temperatures studied; however, the extent of the transformation decreases upon increasing temperature, consistent with the decreased extent of dissociatively adsorbed water. It was possible to hypothesize that the dissociative chemisorption of water and ammonia takes place in a competitive way on surface sites able to give bidentate nitrates and linearly bonded NCO(-) that are dislocated, remaining on the surface as ionic species.

Electrical and spectroscopic analysis in nanostructured SnO2: “Long-term” resistance drift is due to in-diffusion

A model for conductance in n-type non-degenerate semiconductors is proposed and applied to polycrystalline SnO2 used as a gas sensor. Particular attention is devoted to the fundamental mechanism of Schottky barrier formation due to surface states in nanostructured grains. Electrical and absorption infra-red spectroscopic analysis constitutes strong evidence for oxygen diffusion into the tin oxide grains. The model is then extended to include oxygen in- and out-diffusion. Thus, it is possible to explain the “long-term” resistance drift in oxygen for fully depleted grained samples in terms of tunneling through the double barrier.

Copper NPs decorated titania: A novel synthesis by high energy US with a study of the photocatalytic activity under visible light

The most important drawback of the use of TiO2 as photocatalyst is its lack of activity under visible light. To overcome this problem, the surface modification of commercial micro-sized TiO2 by means of high-energy ultrasound (US), employing CuCl2 as precursor molecule to obtain both metallic copper as well as copper oxides species at the TiO2 surface, is here. We have prepared samples with different copper content, in order to evaluate its impact on the photocatalytic performances of the semiconductor, and studied in particular the photodegradation in the gas phase of some volatile organic molecules (VOCs), namely acetone and acetaldehyde. We used a LED lamp in order to have only the contribution of the visible wavelengths to the TiO2 activation (typical LED lights have no emission in the UV region). We employed several techniques (i.e., HR-TEM, XRD, FT-IR and UV-Vis) in order to characterize the prepared samples, thus evidencing different sample morphologies as a function of the various copper content, with a coherent correlation between them and the photocatalytic results. Firstly, we demonstrated the possibility to use US to modify the TiO2, even when it is commercial and micro-sized as well; secondly, by avoiding completely the UV irradiation, we confirmed that pure TiO2 is not activated by visible light. On the other hand, we showed that copper metal and metal oxides nanoparticles strongly and positively affect its photocatalytic activity.

Formaldehyde sensing mechanism of SnO2 nanowires grown on-chip by sputtering techniques

Tin dioxide nanowires have been grown by thermal oxidation of sputtered thin films by means of a VLS method. A tin sputtered layer catalyzed by gold nanoparticles acts as a material seed for the localized growth of NWs directly on gas sensor devices, avoiding the manipulation and transport of the nanowires to the electrodes. XRD and HRTEM analysis show that the nanowires crystallize in a rutile structure with a [100] preferential growth direction, and are single-crystalline with diameters lower than 50 nm. The response of nanowires to formaldehyde has been compared to thin film based sensors. A sensitivity of 0.10 ppm−1 is reported, twofold the sensitivity of the thin film, and short response and recovery times are measured (6 times shorter than thin films). The sensing mechanism proposed for the SnO2 NWs under formaldehyde exposure is explained by means of conduction measurements and FT-IR analysis. Oxygen species chemisorbed on the surface of each SnO2 nanowire produce a band bending, which generates a potential barrier (of 0.74 ± 0.02 eV at 300 °C) between the point contact of different nanowires. As evidenced by IR spectroscopy at 300 °C, electrons in the conduction band and in mono-ionized oxygen vacancies (at 0.33 eV below the bottom of the conduction band) are responsible for gas detection.

Micro-sized TiO2 as photoactive catalyst coated on industrial porcelain grès tiles to photodegrade drugs in water

Pharmaceutical compounds and their metabolites raise worrying questions because of their continuous release and lack of efficient removal by conventional wastewater treatments; therefore, they are being detected in groundwater, surface water and drinking water in increasing concentrations. Paracetamol and aspirin are two of the most commonly used drugs employed as fever reducer, analgesic and anti-inflammatory. They and their metabolites are very often found in river water, so their degradation is necessary in order to render water suitable for human consumption. The present work is focused on the comparison of the photocatalytic performance of industrial active grés porcelain tiles covered with a commercial micro-sized TiO2 by industrial process using either conventional spray deposition or innovative digital printing methods. The photodegradation of two commonly used drugs, namely aspirin and paracetamol, was investigated both individually and as a mixture, in both deionized and tap water. The results reveal the full conversion of the drugs and the significant role of the photocatalytic tiles in the mineralization processes leading to harmless inorganic species. In particular, the digitally printed tiles exhibited better photodegradation performance for both drugs compared to the spray deposited tiles. No deactivation was observed on both photocatalytic tiles.

Aspirin and paracetamol removal using a commercial micro-sized TiO2 catalyst in deionized and tap water

Micro-sized TiO2 catalyst was employed to degrade pharmaceutical compounds, i.e. aspirin and paracetamol, two of the most widely used drugs, purchasable without prescription. Their active agents, acetylsalicylic acid and acetaminophen, are characterized by different substituent groups, linked to the aromatic ring, which affect both the photodegradation and mineralization processes. The experimental conditions highlight the relationship between the nature of the pristine molecules, their degradation mechanisms, their mutual interference and the water’s role. The research started from model systems with a single pollutant to the mixture of them and finally by moving from deionized water to tap water.

FTIR and Transient Reactivity Experiments of the Reduction by H2, CO and HCs of NOx Stored Over Pt–Ba/Al2O3 LNTs

The reduction of NOx stored over a Pt–Ba/Al2O3 Lean NOx Trap is analysed when H2, CO or heptane are used as reductants. In all cases, the reduction proceeds via a Pt-catalyzed process involving the formation of intermediate species like ammonia and isocyanates in the case of H2 and CO, respectively. No specific intermediates have been observed when heptane is used as reductant. It is claimed that the role of the reductant is to keep Pt in a reduced state; this favours nitrate decomposition and reduction over the Pt sites. The effect of water on the reaction is also investigated.

A New Frontier of Photocatalysis Employing Micro-Sized TiO2: Air/Water Pollution Abatement and Self-Cleaning/ Antibacterial Applications

This chapter presents the use of a commercial micro-sized TiO2 powder as an alternative to the traditional nano-powders as semiconductors in photocatalytic processes. Results of the photocatalytic efficiency towards the photodegradation of the traditional pollutant molecules both in gas phase (nitrogen oxides (NOx) and volatile organic compounds (VOCs)) and in water phase (phenol) are presented and compared to the results obtained with two nano-sized reference powders. Micro-sized TiO2 is also industrially coated at the surfaces of porcelain grés tiles (Active Clean Air and Antibacterial CeramicTM). The possibility to have a photocatalytic material, strongly stuck at the surface of a vitrified tile, increases the use of photocatalysis in real conditions: no problem of filtration of the semiconductor from the liquid medium after use and no risks of leakage of nanoparticles in the atmosphere. Tests were performed using reactors equipped with UV-A lamps and with suitable analytical systems, depending on the final purpose. Characterization data from both powders and coated tiles are put in correlation with the photocatalytic results to understand the semiconductor action during the photocatalytic process. Polluting molecules were chosen in order to cover all the common aspects of environmental pollution: NOx and some VOCs represent the model molecules to test the efficiency of the micro-sized TiO2 (degradation from the pristine molecule to CO2 or inorganic salts) in gas phase. As for the water pollution, phenol was chosen as common pollutant in worldwide rivers. Moreover, tests on self-cleaning and antibacterial properties are also report‐ ed. The positive results of micro-sized TiO2 both in powder and coated onto the surface of porcelain grés tiles open the way to new photocatalytic products that do