Zeolites rigidity

Omstein [276] developed a model for a rigidly organized gel as a cubic lattice, where the lattice elements consist of the polyacrylamide chains and the intersections of the lattice elements represent the cross-links. Figure 7 shows the polymer chains arranged in a cubic lattice as in Omstein s model and several other uniform pore models for comparison. This model predicted r, the pore size, to be proportional to I/Vt, where T is the concentration of total monomer in the gel, and he found that for a 7.5% T gel the pore size was 5 nm. Although this may be more appropriate for regular media, such as zeolites, this model gives the same functional dependence on T as some other, more complex models. 

Because the size of the interlayers can be easily varied by incorporation of complex moieties of different sizes, these clays (montmorillonite, hectorite) may nevertheless compete as catalyst supports with zeolites which have a rigid, predetermined cavity size. 

Monte Carlo simulations and energy minimization procedures of the non-bonding interactions between rigid molecules and fixed zeolite framework provide a reasonable structural picture of DPP occluded in acidic ZSM-5. Molecular simulations carried out for DPB provide evidence of DPB sorption into the void space of zeolites and the preferred locations lay in straight channels in the vicinity of the intersection with the zigzag channel in interaction with H+ cation (figure 1). 

For rigid Si-F bonds, the 19F CSA is characterized by a span, Q = Sn - S33, of about 80 ppm [150]. This parameter describes the total static linewidth of 19F NMR of rigid Si-F bonds in zeolites. Line narrowing (reduced span values) is observed, when the fluoride ion carries out motional jumps between two or more Si sites. 

Shape selectivity and orbital confinement effects are direct results of the physical dimensions of the available space in microscopic vessels and are independent of the chemical composition of nano-vessels. However, the chemical composition in many cases cannot be ignored because in contrast to traditional solution chemistry where reactions occur primarily in a dynamic solvent cage, the majority of reactions in nano-vessels occur in close proximity to a rigid surface of the container (vessel) and can be influenced by the chemical and physical properties of the vessel walls. Consequently, we begin this review with a brief examination of both the shape (structure) and chemical compositions of a unique set of nano-vessels, the zeolites, and then we will move on to examine how the outcome of photochemical reactions can be influenced and controlled in these nanospace environments. 

Solid surfaces nature of the surface of colloidal silica, clays, zeolites, silica gels, porous Vycor glasses, alumina rigidity, polarity and modification of surfaces... 

It is known that the flexibility of the zeolite framework arises from the flexibility of the Si-O-Si joints linking rigid Si04 tetrahedra. This feature allows for... 

Glassy polymers with much higher glass transition temperatures and more rigid polymer chains than rubbery polymers have been extensively used as the continuous polymer matrices in the zeolite/polymer mixed-matrix membranes. Typical glassy polymers in the mixed-matrix membranes include cellulose acetate, polysul-fone, polyethersulfone, polyimides, polyetherimides, polyvinyl alcohol, Nafion , poly(4-methyl-2-pentyne), etc. 

The zeolite Si/Al—O framework is rigid, but the cations are not an integral part of this framework and are often called exchangeable cations they are fairly mobile and readily replaced by other cations (hence their use as cation exchange materials). 

Assumptions How valid are common assumptions such as maintaining a rigid zeolite framework Is the imposition of rigidity less serious for some systems than others ... 

Xenon has been considered as the diffusing species in simulations of microporous frameworks other than faujasite (10-12, 21). Pickett et al. (10) considered the silicalite framework, the all-silica polymorph of ZSM-5. Once again, the framework was assumed to be rigid and a 6-12 Lennard-Jones potential was used to describe the interactions between Xe and zeolite oxygen atoms and interactions between Xe atoms. The potential parameters were slightly different from those used by Yashonath for migration of Xe in NaY zeolite (13). In total, 32 Xe atoms were distributed randomly over 8 unit cells of silicalite at the beginning of the simulations and calculations were made for a run time of 300 ps at temperatures from 77 to 450 K. At 298 K, the diffusion coefficient was calculated to be 1.86 X 10 9 m2/s. This... 

June et al. (12) used TST as an alternative method to investigate Xe diffusion in silicalite. Interactions between the zeolite oxygen atoms and the Xe atoms were modeled with a 6-12 Lennard-Jones function, with potential parameters similar to those used in previous MD simulations (11). Simulations were performed with both a rigid and a flexible zeolite lattice, and those that included flexibility of the zeolite framework employed a harmonic term to describe the motion of the zeolite atoms, with a force constant and bond length data taken from previous simulations (26). 

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