Silica Nanoboxes as New Nano-structured Materials: Their Secondary Synthesis from Alumina-Rich Zeolites

Abstract

Novel silica nanoboxes were prepared by controlled dealumination of Na-X and Ca-A type zeolites using ammonium hexafluorosilicate (AHFS). The silica-richer the parent zeolite, the smaller the average pore size produced and the narrower the pore size distribution obtained. This was due to the specific reactivity of the extracting agent with the zeolite framework aluminum atoms. High temperature calcination of the dealuminated X-zeolite (ammonium form) resulted in mesoporous materials exhibiting an ink-bottle shape, a quite high surface area (330 m 2 /g, no micropores), an average pore diameter of 4.5 nm with a quite narrow pore size distribution (±1.0 nm) and finally, a pore opening diameter of 3.9 nm. The latter was determined by using the nitrogen sorption isotherms (BET technique) and related pore volume data. The sorption behavior also suggested the interconnecting character of the newly created nanoboxes. The periodicity of these nanoboxes throughout the mesoporous material was clearly shown by X-ray powder diffraction at very small angles. These materials, herein called monomodal nanoboxes because of the absence of micropores in the structure, were also thermally stable. Incorporation of orthosilicate into the obtained silica nanoboxes, in accordance with the recently developed technique for pore size engineering in zeolites, led to materials with smaller pore openings but having almost the same textural properties. Solid superacidic materials were prepared by incorporating a liquid superacid (triflic acid or trifluoromethanesulfonic acid) into the silica nanoboxes using the wet impregnation technique. The maximum triflic acid loading which did not significantly affect the mesoporous framework of the materials was 24 wt%. As a reference, the maximum loading of less acidic sulfuric acid was slightly lower. All this showed the high chemical stability of the silica nanoboxes for supporting very acidic species. Temperature-programmed desorption using a combined DTA/TGA system allowed the identification of the bound phases and some liquid phase of the loaded triflic acid.

Silica nanoboxes from alumina rich zeolites: thermal and chemical stability of the monomodal and bimodal materials

“…[1]. In particular, the (m)Al-nanoboxes and the (b)Al-nanoboxes which were the monomodal and the bimodal materials, were obtained by secondary synthesis from the NaX using preferably the following procedures.…”

“…The ammonium forms, namely (m)NH 4 -deal X and (b)NH 4 -deal X respectively, were obtained by ionexchange with ammonium ions [1]. Subsequent calcination at 600°C resulted in (m)H-deal X and (b)H-deal X samples, respectively.…”

“…Some of the techniques used to characterize the materials comprising the atomic absorption spectroscopy (AAS) for the determination of the Si/Al ratio, X-ray powder diffraction (in particular at small angle), BET for the determination of textural properties, thermogravimetric (TGA) and differential thermal (DTA) analyses performed in Ar flow, were already described in detail in the previous work [1]. In particular with the technique of X-ray diffraction at small angles, great cares were taken in order to eliminate eventual optical artefacts.…”

“…Novel mesoporous materials, silica nanoboxes [1], were synthesized by controlled dealumination of alumina-rich zeolites (X and A types). In contrast with the synthetic MCM-41 materials [2] which show relatively low thermal and chemical stability [3], the new silica nanoboxes could withstand a temperature of at least 700°C or the loading of triflic acid -a superacidic compound -up to 20-25 wt without undergoing significant structural collapse [1].…”

“…Silica nanoboxes were obtained by pore enlargement of zeolite materials using ammonium hexafluorosilicate (AHFS) in buffered solution which ''selectively'' removed some zeolite walls in the way that the newly created nanometer-sized cavities exhibited a quite narrow pore size distribution (monomodal Al-nanoboxes) [1]. However, if some zeolite ''clusters'' were left in these cavities (bimodal Al-nanoboxes), the material underwent a rapid pore closure upon activation at high temperature, resulting in a dramatic decrease in surface area and pore volume.…”