Pillaring of layered zeolite precursors with ferrierite topology leading to unusual molecular sieves on the micro/mesoporous border

0506560 - ÚFCH JH 2020 RIV GB eng J - Journal Article
Roth, W. J. - Gil, B. - Mayoral, A. - Grzybek, J. - Korzeniowska, A. - Kubů, Martin - Makowski, W. - Čejka, Jiří - Olejniczak, Z. - Mazur, M.
Pillaring of layered zeolite precursors with ferrierite topology leading to unusual molecular sieves on the micro/mesoporous border.
Dalton Transactions. Roč. 47, č. 9 (2018), s. 3029-3037. ISSN 1477-9226. E-ISSN 1477-9234
R&D Projects: GA ČR GA17-01440S
Grant - others:GA MŠk(CZ) CZ.02.1.01/0.0/0.0/15_003/0000417
Institutional support: RVO:61388955
Keywords : quasi-equilibrated thermodesorption * fer-type zeolite * intercalation chemistry * topotactic condensation * n-nonane * silicate
OECD category: Physical chemistry
Impact factor: 4.052, year: 2018
Method of publishing: Limited access

Layered zeolite materials with FER layer topology can produce various condensed and expanded structures including zeolite frameworks, FER and CDO, their interlayer expanded forms (IEZ), and organic-intercalated and pillared derivatives. This work concerns pillaring of the surfactant-swollen derivative with a gallery height of ca. 2.5 nm between layers by treatment with tetraethylorthosilicate (TEOS) at room and elevated temperatures. The materials obtained at 100 degrees C and higher showed unusual properties including 2 nm pores on the micro/mesoporous border and disordered layer packing indicated by the absence of distinct low angle interlayer peaks at d-spacing >3 nm (similar to 3 degrees 2 theta Cu K alpha radiation) in the X-ray diffraction pattern (XRD). TEOS treatment at room temperature produced a pillared molecular sieve with the expected mesoporous characteristics, namely a pore size of around 3 nm and a high intensity low angle (001) peak at 2.3 degrees 2 theta, and a d-spacing of 3.8 nm, in the XRD. The characterization aiming to elucidate the nature of the obtained unusual products included gas adsorption isotherms, aberration corrected (Cs-corrected) Scanning Transmission Electron Microscopy (STEM) studies and Si-29 solid state NMR. BET surface area values decreased with the temperature of TEOS treatment from approximately 1200 m(2) g(-1) to similar to 900 and 600 m(2) g(-1), at room temperature, 100 degrees C, and 120 degrees C, respectively. The Si-29 solid state NMR revealed the presence of both Q(3) ((SiO)(3)SiOX, X = H or minus charge) and Q(4) ((SiO)(4)Si) centers giving separated signals up to the pillaring step. After pillaring at 100 degrees C and calcination, the nominal intensity ratios Q(4) : Q(3) were 2.17 and 2.61 but the signals were merged into one broad peak indicating the structural heterogeneity of Si-O coordination. The microscopy showed the presence of FER layers in the samples but the overall structure and composition were not well-defined. The observed unusual disorganization and possible partial degradation of layers during pillaring may result from the combination of high temperature, alkalinity (surfactant hydroxide) and siliceous composition of the layers. The obtained pillared products are of interest for the preparation of larger pore catalysts and sorbents or controlled drug delivery.
Permanent Link: http://hdl.handle.net/11104/0297793