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Ciriminna R.,CNR Institute of Nanostructured Materials | Fidalgo A.,University of Lisbon | Pandarus V.,PARC Inc. | Beland F.,PARC Inc. | And 2 more authors.
Chemical Reviews | Year: 2013

Environmental and clean energy concerns were responsible for another impetus on the search for new sol-gel materials. For example, recent results with doped sol-gels of long-lasting photobioreactors and biofuel cells, which can advantageously exploit solar radiation to convert polluting carbon dioxide into useful biofuels and electricity,18 constitute a significant advance toward the practical chemical exploitation of solar energy. First, there is a need for a perspective and unified view on the actual development of the science and technology behind these advanced materials, especially in light of the fast growth in scientific publications addressing disparate new applications in fields as diverse as catalysis for fine chemicals and healthcare. Second, there is a strong contemporary research interest in clean energy and environmental issues.


Detty M.R.,State University of New York at Buffalo | Ciriminna R.,CNR Institute of Nanostructured Materials | Bright F.V.,State University of New York at Buffalo | Pagliaro M.,CNR Institute of Nanostructured Materials
Accounts of Chemical Research | Year: 2014

Biofouling on ships and boats, characterized by aquatic bacteria and small organisms attaching to the hull, is an important global issue, since over 80000 tons of antifouling paint is used annually. This biofilm, which can form in as little as 48 hours depending on water temperature, increases drag on watercraft, which greatly reduces their fuel efficiency. In addition, biofouling can lead to microbially induced corrosion (MIC) due to H2S formed by the bacteria, especially sulfate-reducing bacteria.When the International Maritime Organization (IMO) international convention banned the use of effective but environmentally damaging coatings containing tributyl tin in 2008, the development of clean and effective antifouling systems became more important than ever. New nonbiocidal coatings are now in high demand. Scientists have developed new polymers, materials, and biocides, including new elastomeric coatings that they have obtained by improving the original silicone (polydimethylsiloxane) formulation patented in 1975. However, the high cost of silicones, especially of fluoropolymer-modified silicones, has generally prevented their large-scale diffusion. In 2009, traditional antifouling coatings using cuprous oxide formulated in copolymer paints still represented 95% of the global market volume of anti-fouling paints.The sol-gel nanochemistry approach to functional materials has emerged as an attractive candidate for creating low fouling surfaces due to the unique structure and properties of silica-based coatings and of hybrid inorganic-organic silicas in particular. Sol-gel formulations easily bind to all types of surfaces, such as steel, fiberglass, aluminum, and wood. In addition, they can cure at room temperature and form thin glassy coatings that are markedly different from thick silicone elastomeric foul-releasing coatings. Good to excellent performance against biofouling, low cure temperatures, enhanced and prolonged chemical and physical stability, ease of application, and the waterborne nature of sol-gel coatings all support the diffusion of these paints to efficiently reduce the accumulation of fouling layers on valued surfaces immersed in marine or fluvial waters. Furthermore, sol-gel glassy coatings are transparent and can be effectively applied to optical devices, windows, and solar panels used in lake, fluvial, or marine environments.Sol-gel technology is eminently versatile, and the first generation sol-gel paints have already shown good performance. Even so, vast opportunities still exist for chemists to develop novel sol-gel derived coatings to both prevent biofouling and enhance the hydrodynamic properties of boat and ship hulls. Moreover, researchers have prepared and applied multifunctional sol-gel coatings providing protection against both biofouling and corrosion. They have tested these in the marine environment with good preliminary results.In this Account, we discuss some of our new strategies for the controlled functionalization of surfaces for the development of efficient antifouling and foul-releasing systems and summarize the main achievements with biocidal and nonbiocidal sol-gel coatings. We conclude by giving insight into the marine coatings and sol-gel products markets, providing arguments to justify our conclusion that the sol-gel coatings technology is now a mature platform for the development of economically viable and environmentally friendly antifouling and foul-release formulations of enhanced performance. © 2014 American Chemical Society.


Zhang N.,Fuzhou University | Ciriminna R.,CNR Institute of Nanostructured Materials | Pagliaro M.,CNR Institute of Nanostructured Materials | Xu Y.-J.,Fuzhou University
Chemical Society Reviews | Year: 2014

Low cost and easily made bismuth tungstate (Bi2WO6) could be one of the key technologies to make chemicals and fuels from biomass, atmospheric carbon dioxide and water at low cost using solar radiation as an energy source. Its narrow band gap (2.8 eV) enables ideal visible light (λ > 400 nm) absorption. Yet, it is the material's shape, namely the superstructure morphology wisely created via a nanochemistry approach, which leads to better electron-hole separation and much higher photoactivity. Recent results coupled to the versatile photochemistry of this readily available semiconductor suggest that the practical application of nanochemistry-derived Bi2WO6 nanostructures for the synthesis of value-added fine chemicals and fuel production is possible. We describe progress in this important field of chemical research from a nanochemistry viewpoint, and identify opportunities for further progress. This journal is © the Partner Organisations 2014.


Yang M.-Q.,Fuzhou University | Zhang N.,Fuzhou University | Pagliaro M.,CNR Institute of Nanostructured Materials | Xu Y.-J.,Fuzhou University
Chemical Society Reviews | Year: 2014

Tremendous interest is devoted to fabricating numerous graphene (GR)-semiconductor composites toward improved conversion of solar energy, resulting from the observation that the photogenerated electrons from semiconductors (e.g., TiO2, CdS) can be readily accepted or shuttled in the two-dimensional (2D) GR sheet. Yet although the hunt is on for GR-semiconductor composite based photoredox applications that aim to exploit the remarkable electronic conductivity of GR, the work necessary to find out how it could best be harnessed to improve the photocatalytic performance of semiconductors remains scanty. In this review, we highlight a few problems associated with improving the photocatalytic performance of semiconductors via methodological coupling with GR. In particular, we address strategies for harnessing the structure and electronic conductivity of GR via strengthening the interfacial contact, optimizing the electronic conductivity of GR, and spatially optimizing the interfacial charge carrier transfer efficiency. Additionally, we provide a brief overview of assembly methods for fabricating GR-semiconductor composites with controllable film infrastructure to meet the requirements of practical photocatalytic applications. Finally, we propose that, only with the principle of designing and understanding GR-semiconductor composites from a system-level consideration, we might get better at imparting the power of GR with unique and transformative properties into the composite system. © The Royal Society of Chemistry 2014.


Brucale M.,CNR Institute of Nanostructured Materials | Schuler B.,University of Zürich | Samori B.,University of Bologna
Chemical Reviews | Year: 2014

Single-molecule techniques have started to provide important new types of information on the structural and dynamic behavior of intrinsically disordered proteins (IDPs). All single-molecule experiments are by definition able to avoid ensemble averaging since they give information on the smallest possible subensembles of a population. Two of the key strengths of the approaches are their ability to resolve structural and dynamic heterogeneity and to provide quantitative information that can be used for testing physical models. The single-molecule fluorescence approaches available, ranging from Förster Resonance Energy Transfer (FRET) to Positron Emission Topography (PET) and (FCS), can provide information on intra and intermolecular distances and, even more importantly, distance distributions, dynamics on time scales from nanoseconds to seconds, and changes in molecular size or dimensions. Combination of single-molecule fluorescence and ionic current measurements in single-ion channels was developed to monitor structural changes in single channels.


Cavallini M.,CNR Institute of Nanostructured Materials
Physical Chemistry Chemical Physics | Year: 2012

Spin crossover compounds are a class of functional materials able to switch their spin state upon external stimuli. They were proposed as potential candidates for several technological applications that require highly controlled thin films and patterns. Here we present a critical overview of the most important approaches for thin film growth and patterning of spin-crossover compounds, giving special attention to Fe(ii) based molecules, which are the most studied materials. We present both conventional approaches to thin film growth (Langmuir-Blodgett, constructive chemical approach, spin coating, drop casting and vacuum sublimation) and patterning (combined top-down/bottom-up method, soft and unconventional lithography). We critically discuss the application of thin film growth and fabrication techniques highlighting the most critical aspects and the perspectives opened by the recent progress. This journal is © 2012 the Owner Societies.


Scire S.,University of Catania | Liotta L.F.,CNR Institute of Nanostructured Materials
Applied Catalysis B: Environmental | Year: 2012

This review intends to describe and critically analyze the growing literature dealing with the use of supported gold catalysts in the catalytic deep oxidation of volatile organic compounds (VOC). Among the wide family of VOC, attention has been given to the oxidation of saturated (methane, ethane, propane, isobutane, n-hexane) and unsaturated (acetylene, ethylene, propene) aliphatic compounds, aromatic hydrocarbons (benzene, toluene, xylenes, naphthalene), alcohols (methanol, ethanol, n- and iso-propanol), aldehydes (formaldehyde), ketones (acetone), esters (ethylacetate). Moreover, the oxidation of chlorinated VOC (dichloromethane, o-dichlorobenzene, o-chlorobenzene), as well as of nitrogen- (trimethylamine) and sulphur-containing (dimethyldisulfide) compounds has been addressed.The reaction mechanism and the influence of different factors, such as the nature and the properties of the support, the Au particle size and shape, the electronic state of gold, the preparation method and the pretreatment conditions of catalysts, the nature and the concentration of the organic molecule, are discussed in detail. © 2012 Elsevier B.V..


Gentili D.,CNR Institute of Nanostructured Materials | Foschi G.,CNR Institute of Nanostructured Materials | Valle F.,CNR Institute of Nanostructured Materials | Cavallini M.,CNR Institute of Nanostructured Materials | Biscarini F.,CNR Institute of Nanostructured Materials
Chemical Society Reviews | Year: 2012

Dewetting is a spontaneous phenomenon where a thin film on a surface ruptures into an ensemble of separated objects, like droplets, stripes, and pillars. Spatial correlations with characteristic distance and object size emerge spontaneously across the whole dewetted area, leading to regular motifs with long-range order. Characteristic length scales depend on film thickness, which is a convenient and robust technological parameter. Dewetting is therefore an attractive paradigm for organizing a material into structures of well-defined micro- or nanometre-size, precisely positioned on a surface, thus avoiding lithographical processes. This tutorial review introduces the reader to the physical-chemical basis of dewetting, shows how the dewetting process can be applied to different functional materials with relevance in technological applications, and highlights the possible strategies to control the length scales of the dewetting process. © The Royal Society of Chemistry 2012.


Gentili D.,CNR Institute of Nanostructured Materials | Cavallini M.,CNR Institute of Nanostructured Materials
Coordination Chemistry Reviews | Year: 2013

Coordination compounds have been applied in many fields of technology, such as electronics, optics and optoelectronics, information storage, sensing and magnetism. These materials are designed to incorporate a variety of functional properties, and at the same time are gifted with functional groups that control their interactions and assembly in the solid state. In order to integrate coordination compounds in solid-state devices, the control of their assembly should not only be at the molecular level but also at different length scales since the precise positioning and size-control of the individual assembled structures are needed. In this direction, wet-lithographic techniques play a key role in the manufacture and application of micro- and nanostructures based on soluble coordination compounds. This review provides an overview of wet-lithographic methods applied to patterning of coordination compounds, highlighting some of the recent advances and the major criticisms. The first part is focused on probe-assisted methods while the second part is focused on stamp-assisted ones. Eventually, a section on the combination of wet and conventional lithographic methods is presented. © 2013 Elsevier B.V.


Ciriminna R.,CNR Institute of Nanostructured Materials | Pagliaro M.,CNR Institute of Nanostructured Materials
Chemical Society Reviews | Year: 2013

The sol-gel approach to encapsulate fragrance and aroma chemicals in porous silica-based materials has the potential to afford odorant and flavoured materials with novel and unique beneficial properties. Amorphous sol-gel SiO2 is non-toxic and safe, whereas the sol-gel entrapment of delicate chemicals in its inner pores results in pronounced chemical and physical stabilization of the entrapped actives, thereby broadening the practical utilization of chemically unstable essential oils. Reviewing progress in the fabrication of diverse odorant and flavoured sol-gels, we show how different synthetic strategies afford advanced materials suitable for practical application with important health and environmental benefits. © 2013 The Royal Society of Chemistry.

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