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Stimulated Raman scattering in transparent glass-ceramics (TGCs) based on bulk nucleating phase Ba2NaNb5O15 were investigated with the aim to explore the influence of micro- and nanoscale structural transformations on Raman gain. Nanostructured TGCs were synthesized, starting with 8BaO·15Na2O·27Nb2O5·50SiO2 (BaNaNS) glass, by proper nucleation and crystallization heat treatments. TGCs are composed of nanocrystals that are 10–15 nm in size, uniformly distributed in the residual glass matrix, with a crystallinity degree ranging from 30 up to 50% for samples subjected to different heat treatments. A significant Raman gain improvement for both BaNaNS glass and TGCs with respect to SiO2 glass is demonstrated, which can be clearly related to the nanostructuring process. These findings show that the nonlinear optical functionalities of TGC materials can be modulated by controlling the structural transformations at the nanoscale rather than microscale.

CeO2 slow redox kinetics as well as low oxygen exchange ability limit its application as a catalyst in solar thermochemical two-step cycles. In this study, Ce0.75Zr0.25O2 catalysts doped with potassium or transition metals (Cu, Mn, Fe), as well as co-doped materials were synthesized. Samples were investigated by X-ray diffraction (XRD), N2 sorption (BET), as well as by electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) to gain insight into surface and bulk features, which were connected to redox properties assessed both in a thermogravimetric (TG) balance and in a fixed bed reactor. Obtained results revealed that doping as well as co-doping with non-reducible K cations promoted the increase of both surface and bulk oxygen vacancies. Accordingly, K-doped and Fe-K co-doped materials show the best redox performances evidencing the highest reduction degree, the largest H2 amounts and the fastest kinetics, thus emerging as very interesting materials for solar thermochemical splitting cycles.

Flame retardance of epoxy resins is usually imparted using suitable additives and/or properly modified curing agents. Herein, via a two-step green synthetic procedure, the chemical modification of the epoxy matrix with reactive silicon and phosphorus precursors is explored to obtain nanocomposites with intrinsic flame-retardant features. Nanoscale phase separation occurs in the first step, forming an inverse micelle system in which polar nanodomains act as nanoreactors for the hydrolysis of silanes (Si precursors), giving rise to silica lamellar nanocrystals (SLNCs). In the second step, inside the silica nanodomains, the formation of stable Si–O–P bonds occurs because the reactivity of phosphoric acid (P precursor) with the oxirane rings of the polymer chain is balanced by its tendency to diffuse into polar nanodomains. Intriguingly, the use of phosphoric acid alone in epoxy composite manufacturing leads to a wormlike morphology of the network, whereas its addition in the presence of silanes results in the formation of SLNCs with a thinner interlayer distance. The morphology of the hybrid Si/P–epoxy nanocomposites, comprising organic and inorganic co-continuous phases, can confer, through a prevalent mechanism in the condensed phase, interesting flame-retardant performances, namely, the absence of dripping during vertical burning tests, the formation of a large amount of coherent char after combustion, and a remarkable reduction (up to 27.7%) in the peak of heat release rate. The above characteristics make these nanostructured hybrid materials very promising for the manufacturing of epoxy systems with enhanced fire behavior (e.g., coatings, sealants, matrices for reinforced composites), even containing a low amount of specific flame retardants and thus keeping good viscoelastic properties.

Since the advent of photocatalytic technology, scientists have been searching for semiconductor materials with high efficiency in solar energy utilization and conversion to chemical energy. Recently, the development of quantum dot (QD) photocatalysts has attracted much attention because of their unique characteristics: small size, quantum effects, strong surface activity, and wide photoresponse range. Among ternary chalcogenide semiconductors, CuInS2 QDs are increasingly examined in the field of photocatalysis due to their high absorption coefficients, good matching of the absorption range with sunlight spectrum, long lifetimes of photogenerated electron-hole pairs and environmental sustainability. In this review paper, the structural and electronic properties, synthesis methods and various photocatalytic applications of CuInS2 QDs are systematically expounded. The current research status on the photocatalytic properties of materials based on CuInS2 QD is discussed combined with the existing modification approaches for the enhancement of their performances. Future challenges and new development opportunities of CuInS2 QDs in the field of photocatalysis are then prospected.

The catalytic and electro-optical properties of TiO2-based materials depend on the defectivity of their electronic structures and in turn on the synthesis conditions. It is however less clear how t...

Solid acids are the green alternative for heterogeneous acid catalysis, in particular for industrial processes exploiting biomass. Niobium–phosphorus oxides are valid candidates owing to their specific acidic properties and tolerance to water, on the other hand their synthesis often involves hazardous precursors and complex multistep procedures. We have recently employed Nb2Cl10 and POCl3 to synthesize Nb–P–Si mixed oxides with SiO2 content equal to 95 and 92.5 mol% and Nb/P molar ratios equal to 1 and 2, which showed remarkable catalytic activity and water stability in different biorefinery reactions. Here we propose a more sustainable hydrolytic sol–gel route to obtain these materials, starting from ammonium niobium oxalate hydrate and phosphoric acid. The one-pot procedure occurs in water at room temperature, with safe, available and inexpensive precursors, and does not require any catalyst, additive or organic solvent resulting in an energy-efficient protocol. The structural characterisation of the gel-derived solids, performed by FTIR, Raman and 29Si–31P solid state NMR spectroscopies, demonstrates that the designed procedure affords homogeneous samples at the microscopic level with good reproducibility, thus it represents a viable green route for the development of efficient biomass conversion catalytic cycles. Preliminary acid site characterisation and flow reactor experiments in gas-phase ethanol conversion to ethylene demonstrate that these catalytic materials are strongly acidic.

Metal oxide-organic hybrid semiconductors exhibit specific properties depending not only on their composition but also on the synthesis procedure, and particularly on the functionalization method, determining the interaction between the two components. Surface adsorption is the most common way to prepare organic-modified metal oxides. Here a simple sol-gel route is described as an alternative, finely controlled strategy to synthesize titanium oxide-based materials containing organic molecules coordinated to the metal. The effect of the molecular structure of the ligands on the surface properties of the hybrids is studied using three enediols able to form charge transfer complexes: catechol, dopamine, and ascorbic acid. For each system, the process conditions driving the transition from the sol to chemical, physical, or particulate gels are explored. The structural, optical, and photoelectrochemical characterization of the amorphous hybrid materials shows analogies and differences related to the organic component. In particular, electron paramagnetic resonance (EPR) spectroscopy at room temperature reveals the presence of organic radical species with different evolution and stability, and photocurrent measurements prove the effective photosensitization of TiO

Metal oxide-organic hybrid semiconductors exhibit specific properties depending not only on their composition but also on the synthesis procedure, and particularly on the functionalization method, determining the interaction between the two components. Surface adsorption is the most common way to prepare organic-modified metal oxides. Here a simple sol–gel route is described as an alternative, finely controlled strategy to synthesize titanium oxide-based materials containing organic molecules coordinated to the metal. The effect of the molecular structure of the ligands on the surface properties of the hybrids is studied using three enediols able to form charge transfer complexes: catechol, dopamine, and ascorbic acid. For each system, the process conditions driving the transition from the sol to chemical, physical, or particulate gels are explored. The structural, optical, and photoelectrochemical characterization of the amorphous hybrid materials shows analogies and differences related to the organic component. In particular, electron paramagnetic resonance (EPR) spectroscopy at room temperature reveals the presence of organic radical species with different evolution and stability, and photocurrent measurements prove the effective photosensitization of TiO2 in the visible range induced by interfacial ligand-to-metal charge transfer.

Amorphous catalytic materials belonging to the Nb2O5–P2O5–SiO2 system were prepared through an original sustainable sol-gel procedure, and characterized by surface area, porosity and acidity measurements. Their acid properties have been investigated by FT-IR spectroscopy of adsorbed pyridine, ammonia titration and TPR, as well as by titration with 2-phenylethylamine from organic solution. They present Lewis acidity attributed to niobium surface cationic centers, and Brønsted acidity sufficiently strong to protonate pyridine. The total acidity depends on the niobium content. The conversion of ethanol was investigated by vapor phase Temperature Programmed Reaction, steady-state catalytic experiments and static In Situ FTIR experiments. The samples are active in converting ethanol to ethylene with 100% selectivity at low conversion (523–573 K), but also produce acetaldehyde by dehydrogenation at higher temperature and conversion. They show an unusually poor activity for the production of diethylether also at low ethanol conversion. Ethoxy groups act as reaction surface intermediates.

Epoxy resins show a combination of thermal stability, good mechanical performance, and durability, which make these materials suitable for many applications in the Aerospace industry. Different types of curing agents can be utilized for curing epoxy systems. The use of aliphatic amines as curing agent is preferable over the toxic aromatic ones, though their incorporation increases the flammability of the resin. Recently, we have developed different hybrid strategies, where the sol-gel technique has been exploited in combination with two DOPO-based flame retardants and other synergists or the use of humic acid and ammonium polyphosphate to achieve non-dripping V-0 classification in UL 94 vertical flame spread tests, with low phosphorous loadings (e.g., 1-2 wt%). These strategies improved the flame retardancy of the epoxy matrix, without any detrimental impact on the mechanical and thermal properties of the composites. Finally, the formation of a hybrid silica-epoxy network accounted for the establishment of tailored interphases, due to a better dispersion of more polar additives in the hydrophobic resin.

In this work, two acidic Nb P Si mixed oxide gel-derived materials characterized by Nb/P molar ratios equal to 2 (5Nb2.5P) and 1 (2.5NbP) were investigated for their surface and bulk properties in relation with the catalytic performances in the fructose dehydration reaction. The structural characteristics of the studied samples and the changes occurring after water treatment and after reaction were investigated by 29Si and 31P solid state nuclear magnetic resonance (MAS-NMR) and X-ray photoelectron (XPS) spectroscopies, while the characterization of their acidic properties was performed by base (2-phenylethylamine) adsorption in liquid phase. MAS-NMR showed that the phosphorus remains firmly anchored into the siloxane matrix after exposure to cold water for 5Nb2.5P sample and XPS confirmed the homogeneity of the sample composition. Both samples exhibited good intrinsic acidity and maintained significant effective acidity in polar-protic liquids; 2.5NbP manifested a double amount of acid sites compared to 5Nb2.5P, when 2-phenylethylamine is used as probe. Fructose dehydration to 5-(hydroxymethyl)furfural (HMF) on the two gel-derived catalysts was performed in water and in water-isopropanol solution under mild conditions (130 °C) working in a recirculation reaction line comprising a tubular catalytic reactor. In water-isopropanol solution, the samples displayed good performances, as expected thanks to the lively effective acidity. Around 45–50% fructose conversion was attained on both samples, with selectivity to HMF equal to about 50% on 2.5NbP gel-derived catalyst. Recycling tests showed satisfactorily stable activity during three consecutive runs.

The functional properties of metal oxide semiconductors depend on intrinsic and extrinsic defects. The population of intrinsic defects is strongly affected by the synthesis method and subsequent treatments of the material, while extrinsic defects can originate from suitable doping. Stoichiometric ZrO2 is a nonreducible oxide with a large band gap. Therefore, controlling and modulating its defect profile to induce energy states in the band gap is the sole possibility to make it a photocatalyst responsive to visible light. We report a method, based on low temperature sol−gel synthesis coupled with treatments performed in mild conditions, to obtain undoped visible light-responsive ZrO2−x. The electronic structure of these materials is interpreted in relation to their oxygen vacancy defect population. On the basis of a wide set of experimental measurements (X-ray photoelectron, steady-state and time-resolved photoluminescence, electron paramagnetic resonance, and UV−visible diffuse reflectance spectroscopy) and supported by density functional theory calculations, we demonstrate, for the first time, the predominance of positively charged F-center oxygen vacancies that do not give rise to Zr3+ species.

The transformation of γ-valerolactone (GVL) into levulinic acid (LA) requires the use of bifunctional catalysts allowing the hydrogenation and lactonization steps to occur. The aim of this study is to clarify the role played by both redox (Ru) and acid (Nb) sites of the ruthenium-niobium-silicon mixed oxides catalysts, synthesized by sol-gel route, when this reaction is performed in mild conditions. The catalytic performances of the materials are related to an in-depth morphologic and structural characterization, demonstrating that the interaction between the two metals and their relative amount and dispersion are crucial in determining their activity. The results confirm the hydrogenation-dehydration consecutive reaction network and evidence the possibility to selectively produce either GVL or the intermediate γ-hydroxypentanoic acid by an accurate choice of the catalyst composition.

Diclofenac (DCF), a non-steroidal anti-inflammatory drug, is considered one of the most widespread emerging contaminants. Its incidence in water can favor the growth of drug-resistant bacteria and harm aquatic organisms endangering both the human health and the ecosystem. Advanced oxidation processes (AOPs) based on the action of reactive oxygen species are very effective technologies for the removal of this contaminant from water. In this context, ZnO is one of the most studied semiconductors for photocatalytic water treatment. In this work, the photocatalytic activity of fluorine-doped ZnO nano- and meso-crystals synthesized by a hydrothermal approach is reported, exploring the role of a low F atomic concentration (0.25, 0.5 and 1 at. %) on the degradation of DCF in comparison with bare ZnO. All doped samples show high rates of DCF degradation and mineralization, which were realized primarily thanks to their high efficiency in the generation of hydroxyl radicals ( OH). The property-structure-function relationships of the materials are investigated by complementary techniques, such as SEM, XRD, EPR, UV–vis DRS and PL, with the aim to evaluate the role of fluorine in determining their morphological, electronic and optical properties.

Sol-Gel chemistry is a “bottom-up” synthesis route that starting from simple molecules allows to obtain films, particles (also nano), fibers, gels and bulk materials both glassy than crystalline. Silicatic materials are generally obtained from the following Si precursors: tetramethoxysilane (TMOS) or tetraethoxysilane (TEOS). The chemistry is based on the very well-known hydrolysis and polycondensation reactions. In alkaline environment monodisperse silica particles may be easily obtained with sizes from a few nanometers till micron (“Stöber” method). The above reminded reactions occur at room temperature allowing matching their formation with polymer chemistry. In the “in situ” strategy, nanoparticles are produced in the presence of a monomer before polymerization is promoted. In this communication a series of innovative self-responsive materials for aeronautical applications produced by the research group using the Sol-Gel chemistry will be shown.

Endocrine Disrupting Compounds (EDCs) comprise a class of natural or synthetic molecules and groups of substances which are considered as emerging contaminants due to their toxicity and danger for the ecosystems, including human health. Nowadays, the presence of EDCs in water and wastewater has become a global problem, which is challenging the scientific community to address the development and application of effective strategies for their removal from the environment. Particularly, catalytic and photocatalytic degradation processes employing nanostructured materials based on metal oxides, mainly acting through the generation of reactive oxygen species, are widely explored to eradicate EDCs from water. In this review, we report the recent advances described by the major publications in recent years and focused on the degradation processes of several classes of EDCs, such as plastic components and additives, agricultural chemicals, pharmaceuticals, and personal care products, which were realized by using novel metal oxide-based nanomaterials. A variety of doped, hybrid, composite and heterostructured semiconductors were reported, whose performances are influenced by their chemical, structural as well as morphological features. Along with photocatalysis, alternative heterogeneous advanced oxidation processes are in development, and their combination may be a promising way toward industrial scale application.

Hydrogen production by photocatalytic water splitting is one of the most promising sustainable routes to store solar energy in the form of chemical bonds. To obtain significant H

Hydrogen production by photocatalytic water splitting is one of the most promising sustainable routes to store solar energy in the form of chemical bonds. To obtain significant H2 evolution rates (HERs) a variety of defective TiO2 catalysts were synthesized by means of procedures generally requiring highly energy-consuming treatments, e.g. hydrogenation. Even if a complete understanding of the relationship between defects, electronic structure and catalytic active sites is far from being achieved, the band gap narrowing and Ti3+-self-doping have been considered essential to date. In most reports a metal co-catalyst (commonly Pt) and a sacrificial electron donor (such as methanol) are used to improve HERs. Here we report the synthesis of TiO2/C bulk heterostructures, obtained from a hybrid TiO2-based gel by simple heat treatments at 400 °C under different atmospheres. The electronic structure and properties of the grey or black gel-derived powders are deeply inspected by a combination of classical and less conventional techniques, in order to identify the origin of their photoresponsivity. The defective sites of these heterostructures, namely oxygen vacancies, graphitic carbon and unpaired electrons localized on the C matrix, result in a remarkable visible light activity in spite of the lack of band gap narrowing or Ti3+-self doping. The materials provide HER values ranging from about 0.15 to 0.40 mmol h−1 gcat−1, under both UV- and visible-light irradiation, employing glycerol as sacrificial agent and without any co-catalyst.

The generation and stabilization of reactive oxygen species (ROS), including the superoxide radical anion (O2-), have a huge potential in environmental remediation and industrial chemical processes, but they still remain a challenge. Here, we elucidate the formation, stability and reactivity of superoxide radicals spontaneously produced on the surface of a hybrid TiO2-acetylacetonate material exposed to air. EPR spectra reveal an exceptional lifetime (up to three years, in air at room temperature) of the adsorbed O2-, which can also be easily regenerated after its decay. The performances of this material in the degradation of organic pollutants in aqueous solution without any light irradiation indicate a heterogeneous catalytic mechanism, mediated by superoxide radicals, with a synergistic homogeneous action of hydroxyl radicals (OH), which are released in solution, as detected by the EPR spin trapping method. The regeneration ability of the adsorbed superoxide radicals by simple exposure to air counteracts the partial instability in aqueous environment of the organic component of the hybrid structure allowing the catalyst reuse. These structural and functional features joined to the simple preparation route open a new perspective in the field of advanced oxidation processes for hybrid TiO2 materials.

The development of a simple, economic and low-temperature synthesis procedure for titanium oxide thin films is an important challenge, due to their diffusion and to the limitations imposed by high temperature annealing. The knowledge on the properties of amorphous TiO2 films, as well as on the effect of their functionalization by organic compounds, is still inadequate. Here we describe a hydrolytic sol-gel procedure to prepare TiO2-based hybrid (inorganic-organic) thin films containing four different complexing agents in their structure (acetylacetone, dibenzoylmethane, citric acid and diethanolamine). The process variables were explored in order to attain stable sols and to tune the features of the amorphous films resulting by drying at 80 °C. Their structural, morphological, optical and electrical properties were studied by SEM, AFM, XRD, ellipsometry, FT-IR and UV–vis-NIR spectroscopy and resistivity measurements. The effect of the organic component, precursors concentration, deposition parameters and annealing temperature was considered. Moreover, the modifications induced by the exposure of the hybrid films to UV light were deeply investigated. A short UV treatment has a strong impact on the microstructure and wettability of the films and promotes a striking increase in their electrical conductivity.

The surface and catalytic properties of oxide ternary materials consisting of niobium-phosphorus-silicon, Nb-P-Si, with Nb/P = 1 and general formula xNb2O5·xP2O5·(100–2x)·SiO2, with x = 2.5, 5, 7.5, and 10, and Si content ranging from 95 to 80 mol% are presented. Amorphous gel-derived samples were obtained, characterized by a very high degree of silicon cross-linking with presence of Si O Nb bridges, allowing phosphorus to be stably anchored to the matrix through Nb O P bonds. The morphology (surface area and porosity), the intrinsic acidity (density and average strength of the surface acid sites, by PEA-TPD in a TGA-DSC coupled instrument), and the nature of the acid sites were determined. The LAS/BAS ratio has been evaluated by FTIR of adsorbed pyridine in absence/presence of water to discover the differences between the intrinsic and effective nature of the acid sites. The amount of acid sites decreased with the Nb-content in the samples as well as the surface average acid strength. Both LAS and BAS are maintained in the presence of water, even if BAS are predominant in any case. The catalytic performances of the Nb-P-Si samples in the reaction of inulin hydrolysis were investigated in aqueous solution under mild conditions (below 100 °C).

The generation and stabilization of reactive oxygen species (ROS), including the superoxide radical anion (O

Thermochemical cycles received renewed interest as CO2 and H2O energy-upgrading processes using solar energy as source. The two-step cycles, based on self-reduction in a solar reactor at high temperature (above 1300–1400 °C) and re-oxidation by CO2 and/or H2O flow, are the most interesting due to their simplicity and high theoretical solar-to-fuel efficiency. In the two-step cycle, ceria has been recognized as the benchmark material but it suffers from high reduction temperature, low re-oxidation kinetics as well as low stability, thus hindering practical application. In this work, the redox properties of two Ce0.75Zr0.25O2 materials prepared by hydrothermal synthesis were compared with those of a co-precipitated sample with the same nominal composition used as reference. Samples were characterized by X-Ray Diffraction (XRD), N2 physisorption, Scanning Elecron Microscopy (SEM), X-Ray Photoelectron Spectroscopy (XPS), and Electron Paramagnetic Resonance (EPR); their self-reducibility and CO2 splitting activity were tested in a Thermogravimetric (TG) balance, while H2O splitting properties were studied in an ad-hoc fixed bed reactor on H2 pre-reduced samples. Characterization results and activity tests agreed that the Ce3+ fraction both on the surface and in the bulk of ceria-zirconia can be increased by hydrothermal synthesis, thus providing improved redox properties and higher splitting activity with respect to the co-precipitated sample. So, hydrothermal synthesis, providing a controlled nucleation and growth of crystallites, appears as a promising route for the preparation of ceria-based materials with tuned oxygen vacancies.

Here, we report the structural characteristics, the surface properties, and the catalytic performances of a Nb–P–Si ternary oxide material (2.5Nb2O5·2.5P2O5·95SiO2, 2.5NbP) in two reactions of importance for biomass valorisation and green industrial production: hydrolysis of inulin and esterification of oleic acid with polyalcohol for biolubricant production. High dispersion of the Nb centers, ascertained by UV–vis–DRS, 29Si, 31P, and 1H solid-state NMR spectroscopy, is the key point for the successful activity of 2.5NbP. Intrinsic and effective acidities of the sample were studied by FT-IR of adsorbed pyridine in the absence and presence of water and by volumetric titrations of the acid sites in cyclohexane and in water, to enlighten the nature and amount of acid sites in different environments. For both studied reactions, 2.5NbP catalyst exhibits water-tolerant acidic sites, mainly Brønsted ones, giving higher activity and better stability in the reaction medium than well-known niobium oxophosphate catalyst, which is considered one of the best water-tolerant acid catalysts.

Factors tuning the functional performances of the various TiO2-based materials in the wide range of their possible applications are poorly understood. Here the electronic structure of TiO2-based materials characterized by Ti3+ self-doping, obtained by a sol–gel route wholly performed in air at room temperature, is reported. In the amorphous hybrid TiO2–acetylacetonate (HSGT) material the formation of the Ti(IV)–acac complex makes it photoresponsive to visible light and allows us to obtain by means of a simple annealing in air at 400 °C a very stable black Ti3+ self-doped anatase TiO2 nanomaterial (HSGT-400), characterized by an extraordinary high concentration of Ti atoms with oxidation states lower than IV (about 26%), which absorbs light in the entire visible range. The very high stability of HSGT-400 is mainly related to the process, which does not require the use of harsh conditions nor external reducing agents. The electronic structure of HSGT, owing to the presence of the Ti(IV)–acac complex, allows the stabilization of superoxide anion radicals on its surface for a very long time (months) at room temperature. The extraordinary low recombination rate of electron–hole pairs gives to HSGT unusual catalytic performances at room temperature allowing the complete removal of 2,4-dichlorophenol from water in about one hour without any light irradiation. Our results clearly highlight the connection among the production process of TiO2-based materials, their electronic structure and, finally, their functional behaviour., RSC Advances, 7 (4), ISSN:2046-2069

A series of TiO2-based hybrid inorganic–organic materials was synthesized by sol–gel and characterized by thermal and spectroscopic techniques. The xerogels have an amorphous structure, with part of Ti4+ ions stably coordinated to acetylacetonate ligands. Ligand-to metal charge transfer results in an extended light absorption in the visible range, with a significant reduction of the band gap compared to the reference TiO2. The hybrid structure is also related to the unusual presence of superoxide radical anions stably adsorbed on the materials surface. These properties make the studied materials active in the degradation of organic pollutants: their catalytic efficiency was tested in the removal of 2,4-dichlorophenol from water without light irradiation.

Hybrid sol–gel TiO2–acetylacetonate (HSGT) material has been synthesized via a sol–gel route. The as dried HSGT can be described as an amorphous polymeric network of titanium oxo-clusters on which surface part of Ti4+ ions are involved in strong complexation with acetylacetonate (acac) ligands. In this material a ligand-to-metal charge transfer (LMCT) is active giving light absorption in the visible region indicating a band gap of 2.5 eV, lower than crystalline TiO2. In the HSGT gel derived material the LMCT mechanism results much more active respect to ligands on crystalline nanoparticles. In presence of air, the acac ligands on the HSGT surface are able to generate and stabilize superoxide radical as resulting by EPR measurements. The ˙O2− radicals were stably adsorbed on the HSGT at room temperature for very long time. The presence of these free radicals makes HSGT material a useful catalyst in degradation of organic pollutants. Its catalytic activity has been tested in the oxidative degradation of phenanthrene resulting in a fast degradation rate in absence of any light irradiation.