Microporous crystalline materials (e.g. zeolites, aluminophosphates), also called molecular sieves, are widely used as catalysts, adsorbents, and membranes. Two factors largely determine the utility of such materials: their regular nanoscaled size of pores and cavities, and their structural rigidity and stability under quite harsh working conditions. However, the maximum pore size of these materials is about 0.8 nm. Extending the application of porous crystalline materials to encompass the control of molecules much larger than simple gases and small molecules, with potential interest for fine chemicals, pharmaceuticals, and nanotechnology requires stable materials with larger pores.
TECHNOLOGY OVERVIEW Silica nanoboxes are novel nano-structured materials obtained by secondary synthesis from zeolites and having the following physical-chemical properties:
• Nanometric pore size (4 nm [type I] or 12 nm [type II]);
• Nanocavities of well-defined shapes (ink-bottle) with 3 dimensions interconnection throughout the material mass (2 types: monomodal and bimodal silica nanoboxes);
• Thermally and hydrothermally resistant over 600 oC and in the presence of steam; Figure 1 : pore size distribution of monomodal silica nanoboxes (type IX) (nm)
• Chemically resistant to very acidic media; nanoboxes can withstand loading of triflic acid, a super acidic product, up to 20 wt % without significant structural losses;
• Nanocavities host a microporous zeolite-like component (bimodal silica nanobox).
Therefore, these silica nanoboxes can withstand quite harsh operating conditions (high temperature and high pressure). Being in solid form, they are environmentally friendly materials (green chemistry) because they can be easily recovered after use. They can be regenerated by chemical treatment or simple combustion.
Intellectual property of silica nanoboxes is protected under international patent applications for material structures, method of manufacturing and their applications.
EXPECTED COMMERCIAL APPLICATIONS Silica nanoboxes can be used as:
Selective adsorbents and ion-exchangers;
Materials for chromatographic separation by size exclusion or separation by selective adsorption (proteins, vitamins, etc);
Matrices (encapsulation) and supports for:
• catalytically active (even very aggressive) species (see nanocatalysts);
• chemically active (and even very aggressive) species, including acidic liquids and ionic liquids; and for use as chemical sensors;
• electronically and magnetically active species.
Filters for ultra filtration using pinhole-free membranes or as a mask component for the retention of chemicals and bacterial species.
In particular, when loaded with triflic acid, silica nanoboxes can be used as highly efficient nanocatalysts for the:
• Production of fine organic chemicals obtained by acido-catalysed reactions, which include oligomerization and polymerization.
• Production of intermediates for pharmaceutical and cosmetic industries as: nitration, halogenation, Friedel-Crafts acylation, alkylation, cyclization, Beckmann and Fries rearrangements, etc.
• In biotechnology: Production of olefins / aromatics from products of fermentation; production of biofuels.
Some promising applications are in the environmental protection sector. Silica nanoboxes can be used to provide a broad spectrum of removal of toxic heavy metal ions such as mercury and smaller ions (alkaline and rare-earth cations) from wastewaters and industrial liquid effluents. In such applications, the bimodal silica nanoboxes show a combination of components of different pore sizes, exhibiting combined adsorption and ion-exchange effects.
COMMERCIAL ROAD AND STRATEGY Tests have been conducted to demonstrate commercial potential of the silica nanoboxes. The commercial strategy is to conduct some tests with silica nanoboxes in industrial and commercial applications, jointly with industrial partners, to evaluate the potential advantages of these silica nanoboxes.
Commercialization of the silica nanoboxes could be done either by technology transfer or by licensing the rights to use these materials.
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