Introduction
In 1989 Kuznicki synthesized new titanium based mate-
rials [1]. Chapman in 1990 synthesised microporous
titanosilicate used as molecular sieves [2]. The ETS-10
is a newly formed titano-silicate the structure of which
was resolved thanks to the XRD, EDS, HREM and
mass NMR [3]. The structure contains TiO
6
octahedra,
two oxygen atoms being shared by neighboring TiO
6
units forming a Ti–O–Ti chain, while the other four ox-
ygen atoms are shared with neighboring tetrahedral
SiO
4
groups [3, 4]. A set of periodically placed chains
develops that way in an orthogonal direction. The super-
imposition of layer of this type gives rise to a tridimen-
sional structure of 12 membered ring channels. Only
few zeolitic structures have such an open structure, the
more important ones being zeolite Y (FAU) and zeo-
lite Beta (BEA). Each titanium atom in this structure is
associated with two negative charges that are neutral-
ized by cations not being part of the structure. The den-
sity of cations is roughly similar to that of a zeolite with
Si/Al=2.5. Due to the long interconnecting pores in the
structure and the high density of the extraframework
cations, the ETS-10 is a potentially good catalyst. In ad-
dition, aluminium can be substituted at tetrahedral posi-
tions replacing silicon and hence Broensted acid sites
can be introducted [5, 6]. In ETS-10, the disposition of
the layers composed of Ti–O–Ti chains in an orthogonal
way is not regular leading to defects in the structure. The
disorder can be modelled by the combination of two
polymorphic structures that are due to different se-
quences. The polymorph A corresponds to a sequence
ABCD and has a monoclinic symmetry with C2/c space
group, while the other corresponds to a sequence ABAB
and has a tetragonal symmetry with space group P41 or
P43 [7]. Eldewik et al. have investigated the incorpora-
tion of Co
2+
ions into ETS-10 [8]. Neither the physico-
chemical nor the catalytic properties of ETS-10 are well
characterized. Anyway it is not clear how they could be
influenced by the disorder. Anderson et al. used a com-
bination of atomic force microscopy, high-resolution
electron microscopy and modelling to elucidate the de-
tails of the mechanism of crystal growth in framework
of ETS-10 and other materials [9]. Kim et al. reported
studies on the crystallization of ETS-10 using various
compositional systems in presence of organics and in
the absence of seeds [10, 11]. Picquart et al. studied the
chemical-physical behaviour of sol–gel zirconia [12].
Naik et al. synthesized a sodium zirconium phosphate,
potential ceramic matrix for fixation of high level nu-
clear waste [13].
Experimental
The synthesis procedure for ETS-10 molecular sieves is
identical to that proposed by Pavel et al. [14]. Two
batches are separately prepared, the one being alkaline
and the other acidic. For the alkaline batch the ingredi-
ents are added in the following order: sodium silicate
(Merck; 8% Na
2
O, 27% SiO
2
, 65% H
2
O), sodium hy-
droxide (Carlo Erba; 50 mass%) and potassium fluoride
(Merck; 40 mass%). For acidic batch the components
are added in the following order: distilled water, hydro-
chloric acid (Carlo Erba; 37 mass%), titanium tetrachlo-
ride (Merck; 50 mass%) and zirconium tetrachloride in
1388–6150/$20.00 Akadémiai Kiadó, Budapest, Hungary
© 2005 Akadémiai Kiadó, Budapest Springer, Dordrecht, The Netherlands
Journal of Thermal Analysis and Calorimetry, Vol. 80 (2005) 585–590
INFLUENCE OF ZIRCONIUM ON THE CRYSTALLIZATION OF ETS-10
MOLECULAR SIEVE
D. Vuono
1*
, C. C. Pavel
2
, P. De Luca
1
, J. B. Nagy
3
and A. Nastro
1
1
Dipartimento di Pianificazione Territoriale, University of Calabria, via P. Bucci, C.A.P. 87036, Arcavacata di Rende (CS), Italy
2
Department of Chemical Technology and Materials Chemistry, Faculty of Chemistry, ‘Al. I. Cuza’ University of Iasi, Bd. Carol I,
6600 Iasi, Romania
3
Laboratoire de R.M.N., Facultés Universitaires Notre-Dame de la Paix, 5000 Namur, Belgium
The ETS-10 is a newly formed titano-silicate the structure of which was resolved thanks to the XRD, EDS, HREM and mass NMR.
The ETS-10 is a potentially good catalyst. The aim of this research is to study the physicochemical properties of ET(Zr)S-10 ob-
tained from a gel containing different amounts of Zr. The analyses used are XRD, thermal analysis (TG-DSC), SEM, and
29
Si NMR.
Keywords: DSC, ETS-10, initial gels, TG, zirconium
* Author for correspondence: danyvuono@yahoo.it