Marta Stucchi

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.

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.

Ultrasound assisted synthesis of Ag-decorated TiO2 active in visible light

Titanium dioxide is the most popular photocatalyst to degrade organic pollutants in air, as well as in water. The principal drawback preventing its commercial application lies in its limited absorption of the visible light (400-700nm), while it is active under UV irradiation (≤387nm). Supporting noble metals in the form of nanoparticles on TiO2 increases its activity in the visible range. However, both the synthesis of noble metal nanoparticles and their deposition on TiO2 are multi-step processes that often require organic solvents. Here, we deposit Ag nanoparticles from AgNO3 on the surface of micrometric TiO2 with H2O as a solvent and under ultrasound irradiation at 30Wcm-2. Ultrasound increases the surface amount of Ag on TiO2 with heterogeneous size distribution of Ag nanoparticles, which are bigger and overlaid (1-20nm vs. 0.5-3nm) compared to the sample obtained in traditional conditions (TEM images). While this change in morphology had no effect on acetone photodegradation under UV light, the 5%, 10%, and 20% Ag-TiO2 degraded 17%, 20% and 24% acetone under visible light, respectively. The 10% by weight Ag-TiO2 sample obtained in absence of ultrasound only degraded 14% acetone in 6h, while the bare TiO2 was not active.

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

Micro-sized TiO2 catalyst in powder form and as coating on porcelain grès tile for the photodegradation of phenol as model pollutant for water phase

In presence of TiO2 and irradiation, phenol can be degraded by hydroxyl radicals or directly via photogenerated carriers, as occurs in photocalytic processes. In this work a commercial micro-sized TiO2 sample in powder form and industrially coated on porcelain grès tiles were tested in water remediation with phenol as model molecule. Firstly, we investigated the behaviour of the commercial micro-sized TiO2 comparing the results with reference nano-sized catalyst in the phenol photodegradation process, widely studied in the last decades. Following the phenol concentration as well as the main intermediates formation over time by HPLC analysis, and the mineralization by TOC analysis, we presented results about the photocatalytic behaviour in terms of adsorption, by-products formation, and reaction rate at different phenol starting concentrations. In particular, with the photocatalytic tiles, phenol photodegradation percentage is almost the same at 15 ad 25 ppm (78% and 73% respectively), and much lower at 50 ppm (46%) after 6 hours of test. Correspondence to: Claudia L. Bianchi, Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133 Milano, Italy, E-mail: claudia. bianchi@unimi.it Benedetta Sacchi, Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133 Milano, Italy, E-mail: benedetta.sacchi@unimi.it Giuseppina Cerrato, Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133 Milano, Italy, E-mail: giuseppina.cerrato@unito.it

NOx degradation in a continuous large-scale reactor using full-size industrial photocatalytic tiles

Many reactors were proposed to investigate the efficiency of photocatalytic materials in the degradation of NOx, but the operative conditions are often very far from reality: the parameters and the reactor set-up, which are good for laboratory tests, cannot verify the real efficiency of a photocatalytic material in a real context. To solve this issue, we experimented for the first time with a new kind of gas-flow reactor able to test photocatalytic building materials of large size, optimizing the reaction conditions in order to work both under artificial conditions of irradiation (UV-A lamp) and under direct sunshine.

Carbon-Supported Au Nanoparticles: Catalytic Activity Ruled Out by Carbon Support

The catalytic oxidation of glycerol produces high added value chemical products. Gold-based catalysts showed activity and selectivity depending on particle size and specific preparation method. Moreover, the support plays a fundamental role in modulating the stability of the catalytic system. However, the literature is still lacking of a precise disclosure of these important relationships. Herein, we synthesized two series of gold catalysts on different carbon supports (Vulcan-XC72R, X40S and Norit GSX), the first synthesized by solvated metal atom deposition (SMAD) and the second by Sol Immobilization technique (SOL). First of all, the specific physico-chemical properties of the supports and the synthesis procedure influenced the dispersion and the size of Au NPs making a direct comparison among the different carbon difficult. In particular, on Vulcan-XC72R, AuNPs showed narrow size and good dispersion, whereas on Norit GSX and X40S-Camel a notably wider size distribution has been revealed. XPS analyses showed Au exposure changed accordingly to the presence of oxygen species, lower O content corresponding to lower Au exposure. Unexpectedly however this does not correspond to a lower activity, being the lowest Au/C (%at), the Vulcan ones, the most active catalysts. Comparing SOL and SMAD prepared samples on the same carbon, the SOL ones always result more active.

Ultrasound to improve both synthesis and pollutants degradation based on metal nanoparticles supported on TiO 2

Sonochemistry is based on acoustic cavitation, which consist in the formation, growth, and implosive collapse of bubbles within a liquid. Collapsing bubbles generate localized hot spots, characterized by temperatures up to 5000 K and pressures up to 1800 atm. These extreme conditions allow producing a variety of nanostructured and amorphous materials, as well as they are advantageous for chemical processes. Ultrasound requires inexpensive equipment and fewer steps than conventional methods. Combining ultrasound and photocatalysis enhances the performance of the processes, reduces reaction time, avoids the use of extreme physical conditions and improves the photocatalytic materials properties increasing their activity. Here, we reported the positive effect of US in synthesizing Me-modified TiO2 (Me = Ag, Cu, Mn) for pollutants degradation in gas-phase; also, we proved the advantageous application of ultrasound for the photocatalytic removal of organic compounds in water. Ultrasound produced more efficient Me-doped TiO2, which showed higher activity in visible light. When combined with photocatalytic water treatment, the organic compounds degradation and mineralization increases.

Nano-MnO2 Decoration of TiO2 Microparticles to Promote Gaseous Ethanol Visible Photoremoval

TiO2-based photocatalysis under visible light is an attractive way to abate air pollutants. Moreover, developing photocatalytic materials on a large-scale requires safe and low-cost precursors. Both high-performance TiO2 nanopowders and visible-light active noble metals do not match these requirements. Here, we report the design of novel Mn-decorated micrometric TiO2 particles. Pigmentary TiO2 replaced unsafe nano-TiO2 and firmly supported MnOx particles. Mn replaced noble metals such as Au or Ag, opening the way for the development of lower cost catalysts. Varying Mn loading or pH during the impregnation affected the final activity, thus giving important information to optimize the synthesis. Photocatalytic activity screening occurred on the gas-phase degradation of ethanol as a reference molecule, both under ultraviolet (UV) (6 h) and Light Emitting Diode (LED) (24 h) irradiation. Mn-doped TiO2 reached a maximum ethanol degradation of 35% under visible light after 24 h for the sample containing 20% of Mn. Also, we found that an acidic pH increased both ethanol degradation and mineralization to CO2, while an alkaline pH drastically slowed down the reaction. A strict correlation between photocatalytic results and physico-chemical characterizations of the synthesized powders were drawn.

Gold Catalysts for the Selective Oxidation of Biomass Derived Products

Biomass constitutes a renewable source for new chemical platforms. Among other processes the catalytic ones represent a green alternative when active and selective catalysts can be developed. In this paper, applications of gold and gold‐based catalysts have been reviewed in the field of the selective oxidations. Indeed, from the discovery of the peculiarity of gold as catalytic material, the liquid phase oxidations have been differently viewed. Three important biomass‐derived molecules, namely glucose, hydroxymethyl furfural (HMF) and glycerol have been considered as precursors for products of industrial interest where gold catalysts have played an important role. This review starts from the research on monometallic gold catalysts which have been explored initially and then look at gold as modifier of other metal catalyst. This latter field is still in evolution and probably needs to be look at in the future.