Cerium and cerium oxide: A brief introduction
Abstract A short introduction on the history and main properties of cerium and cerium oxide is here provided. The main applications of cerium oxide, reported and discussed in this book, are also briefly summarized, with some final considerations on the future perspectives and the market outlooks of this outstanding oxide.
A Solar Photothermocatalytic approach for the CO2 conversion: Investigation of different synergisms on CoO-CuO/Brookite TiO2-CeO2 catalysts
Abstract The photoactive features of the least common polymorph of TiO2, i.e. brookite, were combined with the thermocatalytic redox ones of cerium oxide, focusing on the effects of the addition of small amounts of Co-Cu oxides for the solar CO2 conversion. By considering the characterization data, a surface segregation of the hosted metal oxides on the TiO2-CeO2 composite was evidenced, and their presence increased the amount of oxygen vacancies and improved the charge carriers separation. The bimetallic oxides-based sample was the most performing one in the photocatalytic carbon dioxide reduction at room temperature. The formation of carbon monoxide and methane was 5 and 0.5 μmol g−1h−1, …
Combined effect of noble metals (Pd, Au) and support properties on HDS activity of Co/SiO2 catalysts
Abstract Cobalt-based catalysts supported on different types of SiO 2 are studied in the hydrodesulfurization of thiophene. Amorphous silica and siliceous MCM-41 and HMS, characterized by different texture and surface acidity are used as carriers. The effects due to the modification of the support by impregnation with palladium precursor and to the co-impregnation of cobalt and gold are considered. The catalysts are characterized by N 2 physisorption (BET), XRD, TPR and XPS techniques. The use as supports of the ordered mesoporous silica with higher surface area with respect to amorphous silica, produces a better dispersion of the cobalt oxides particles. Moreover, the addition of palladium…
Prediction of ionic liquid's heat capacity by means of their in silico principal properties
The in silico principal properties (PPs) of ionic liquids (ILs), derived by means of the VolSurf+ approach, were used to develop a Partial Least Squares (PLS) model able to find a quantitative correlation among IL descriptors (accounting for both cationic and anionic structural features) and heat capacity values, providing affordable predictions validated by experimental Cp measurements for an external set of ILs. In silico predictions allowed the selection of a limited number of structurally different ILs with similar Cp values, providing the possibility to select an optimal IL according to efficiency, as well as to environmental and economic sustainability. The present general procedure, …
Photocatalytic H2 production over inverse opal TiO2 catalysts
Abstract The influence of BiVO4 and CuO on the chemico-physical properties of TiO2-based systems is reported. The performances of these systems were investigated in the photocatalytic H2 production both under UV and solar light irradiation. The characterization data pointed out that the obtained TiO2 samples have highly porous inverse opal structures with interconnected macropores. Inverse opal TiO2 exhibited higher activity in the H2 production than the commercial TiO2 due to the peculiar porosity that allows photons to enter inside the photocatalyst. A further improvement in terms of photoactivity was verified by addition of increasing amounts of BiVO4. On the contrary a small CuO content…
A solar photothermo-catalytic combined process for the VOCs combustion and the subsequent CO2 valorization using noble metal-free catalysts
We here investigated a solar photothermo-catalytic combined process where the toluene (as volatile organic compound model) was first oxidized to CO2 which was subsequently converted into solar fuels in a second reactor. For this aim two noble-metal free catalytic systems were used, namely MnOx-ZrO2, which gave the best results for the toluene removal, and brookite TiO2-CeO2 mixed oxides which were the most efficient in the subsequent CO2 conversion. This latter reaction was further improved by the addition of small amounts of copper-based materials on brookite-ceria, acting as co-catalysts. The key point for both the examined reactions was the synergism between the thermocatalytic and the p…
A comparison between photocatalytic and catalytic oxidation of 2-Propanol over Au/TiO2-CeO2 catalysts
Abstract Photocatalytic and catalytic oxidation of 2-propanol, representative of volatile organic compounds (VOC’s), were compared over mixed TiO 2 –CeO 2 -based catalysts. The effect of different amounts of CeO 2 and the presence of gold (1 wt%) on TiO 2 was investigated. In the photocatalytic oxidation CeO 2 had a negative effect on the performance towards the alcohol conversion of both TiO 2 –CeO 2 and Au/TiO 2 –CeO 2 catalysts, being Au/TiO 2 the most active system. On the contrary mixed TiO 2 –CeO 2 and Au/TiO 2 –CeO 2 samples showed a higher catalytic oxidation efficiency for 2-propanol conversion compared to the single oxides. In this case Au/CeO 2 catalyst had the best performance. …
Photocatalytic and photothermocatalytic applications of cerium oxide-based materials
Abstract Cerium dioxide (CeO2) presents unique properties as the special electronic and optical properties of the 4f electrons, the capacity to form nonstoichiometric oxygen-deficient CeO2 − x oxides, the high oxygen mobility, and the reversible transformation between Ce4 + and Ce3 + that make it interesting for photocatalytic applications. CeO2 is a wide bandgap semiconductor (3.0–3.4 eV), but different approaches as combination with oxides, deposition of noble metals, doping with metal and nonmetal species, and the formation of surface defects have been adopted to extend its absorption towards the visible region with the aim to improve its photocatalytic performance. Cerium oxide-based ma…
Catalytic applications of TiO2
Abstract The use of TiO2 as heterogeneous catalyst and/or active support for metals or other oxides is here reported. Many reactions of industrial relevance involve, in fact, titania-based catalysts, among them, NOx abatement, Fischer–Tropsch and water–gas shift, Deacon and Claus processes, hydrodesulfurizations and hydrogenations, selective reductions and selective oxidations. This chapter aims to discuss the main applications of TiO2, in its different forms, as effective support or catalyst for thermocatalytic and photo-thermocatalytic reactions, focusing on the role of its structural and physicochemical properties on the catalytic performance (activity, selectivity, stability).
A multivariate insight into ionic liquids toxicities
A multivariate insight into Ionic Liquids' (ILs) toxicity, a broad term highly dependent on the biological systems adopted as “sensors”, addressed four main groups of toxicities: aquatic toxicity, toxicity towards fungi and bacteria, cytotoxicity towards IPC-81 rat cell lines and acetylcholinesterase enzyme inhibition. This approach, summarizing toxicity information available from a huge amount of scattered literature data, allowed derivation of aquatic toxicity scores for 104 ILs and bacteria and fungi toxicity scores for 87 ILs as well as identification of a correlation between aquatic ecotoxicity and the response of IPC-81 rat cell lines. Further evidence on the effects of cation structu…
Effect of the addition of different doping agents on visible light activity of porous TiO2 photocatalysts
Abstract The influence of the addition of different doping agents (N, W and Hf) on the macroporous TiO2 photoactivity toward the Rhodamine B degradation and ethanol photo-oxidation was evaluated. The samples were characterized by XRD, XPS, SEM, TEM, N2 adsorption-desorption, UV–vis Diffuse Reflectance and Photoluminescence spectroscopies to study also the changes in the physico-chemical properties due to the presence of dopants. The photonic effect and the high ordered porous structure of the macroporous TiO2 that lead to increase the path length of the light, were the key factors that allow to enhance the catalytic activity towards the dye and VOC degradation under visible and solar light …
Exploring the photothermo-catalytic performance of brookite tio2-ceo2 composites
The thermocatalytic, photocatalytic and photothermo-catalytic oxidation of some volatile organic compounds (VOCs), 2-propanol, ethanol and toluene, was investigated over brookite TiO2-CeO2 composites. The multi-catalytic approach based on the synergistic effect between solar photocatalysis and thermocatalysis led to the considerable decrease in the conversion temperatures of the organic compounds. In particular, in the photothermo-catalytic runs, for the most active samples (TiO2-3 wt% CeO2 and TiO2-5 wt% CeO2), the temperature at which 90% of VOC conversion occurred was about 60 °
Efficient H2 production by photocatalytic water splitting under UV or solar light over variously modified TiO2-based catalysts
Abstract This paper focused for the first time on the comparison between three different approach to modify the chemico-physical properties of TiO2-based photocatalysts and their effect in the H2 production by photocatalytic water splitting both under UV and solar light irradiation, under the same experimental conditions. The application of pulsed laser irradiation to aqueous TiO2 suspensions (first approach) induced structural transformations both on the bulk and on the surface of TiO2, boosting the H2 production, under UV light irradiation, of almost three times (20.9 mmol/gcat·h) compared to bare TiO2 (7.7 mmol/gcat·h). The second strategy was based on a templating method to obtain TiO2 …
Catalytic and photothermo-catalytic applications of TiO2-CoOx composites
Objective: The necessity to have green and sustainable industrial processes has promoted new technologies for air and water purification together with the research of new energy sources. In this contest, the TiO2-based photocatalysis can be considered a promising route for both environmental applications aIn this work, we have investigated the photocatalytic performance of TiO2-CoOx composites on both photooxidation and photoreduction reactions. Specifically, we have compared the performance of the composites in the thermo-catalytic, photo-catalytic and photothermal-catalytic oxidation of ethanol chosen as model volatile organic compound (VOC) and in the photocatalytic hydrogen production …
Visible light photocatalytic activity of macro-mesoporous TiO2-CeO2inverse opals
Macro-mesoporous TiO2 inverse opal materials were synthesized and they were tested as photocatalysts under visible light irradiation. The influence of cerium oxide addition towards the Rhodamine B (RhB) photodegradation activity was evaluated. Structural, textural, spectral and surface properties of the TiO2-CeO2 inverse opal nanocomposites were studied by XRD, XPS, SEM, TEM, N2 adsorption-desorption, Diffuse Reflectance UV–vis and Photoluminescence spectroscopies. Compared to commercial TiO2 anatase, the macro-mesoporous TiO2 inverse opal exhibited six times higher kinetic rate constant in the RhB degradation under visible light irradiation. The good photocatalytic activity was related to …
Selective aqueous oxidation of aromatic alcohols under solar light in the presence of TiO2 modified with different metal species
AbstractA set of metals modified TiO2 photocatalysts were prepared starting from titanium tetraisopropoxyde and different metal precursors to study the influence of the addition of the various foreign agents on the physico-chemical and photocatalytic properties of the catalysts. The powders were characterized by X-ray diffraction, Raman spectroscopy, specific surface area measurements, scanning electron microscopy, energy dispersive X-ray spectroscopy, UV–Vis diffuse reflectance spectroscopy, photoluminescence, temperature programmed desorption after CO2 adsorption. The photocatalytic activity was evaluated using as probe reactions the partial oxidation of three aromatic alcohols: benzyl al…
Effect of the Al/Si atomic ratio on surface and structural properties of sol-gel prepared aluminosilicates
Abstract A series of aluminosilicates with an Al/Si ratio ranging from 0 to ∞ (0 for pure silica and ∞ for pure alumina) was prepared by sol–gel process and characterized by surface and structure techniques. Aluminum tri sec butoxide and tetramethylorthosilicate were used as precursors for the sol–gel synthesis. The acidic properties of the oxides were studied by determination of the zero point charges, through mass titration method, and, for selected samples, by FT-IR spectroscopy of adsorbed pyridine used as a probe for both Bronsted and Lewis acidity. A dependence of the acidity on the Al/Si atomic ratio was found. According to the X-ray diffraction patterns, all the oxides have an amorp…
Cyclocarbonylation reactions of allylphenols and allylnaphthols catalyzed by Pd/C- 1,4-bis(diphenylphosphine)butane
Palladium/activated carbon (Pd/C) in the presence of 1,4-bis(diphenylphosphino)butane is an efficient heterogeneous catalyst for cyclocarbonylation reactions of 2-allyl phenols affording five-, six-, and seven-membered ring lactones. Various examples of cyclocarbonylation are reported and the regioselectivity is compared with the homogeneous system. Both commercial Pd/C and Pd/C prepared from activated carbons obtained from vegetable and polymeric wastes are investigated.
Au/TiO2-CeO2 Catalysts for Photocatalytic Water Splitting and VOCs Oxidation Reactions
Photocatalytic water splitting for H2 production and photocatalytic oxidation of 2-propanol, an example of volatile organic compounds, were investigated over TiO2 catalysts loaded with gold and/or ceria. In the water splitting reaction the presence of gold only slightly affected the performance of TiO2 whereas the presence of CeO2 had a more remarkable positive effect. In the 2-propanol oxidation Au/TiO2 was the most active sample in terms of alcohol conversion whereas Au/TiO2-CeO2 exhibited the highest CO2 yield. On the basis of characterization experiments (X-Ray Diffraction (XRD), Energy Dispersive X-ray Analysis EDX, surface area measurements, Diffuse Reflectance Spectroscopy (DRS) and …