Framework stability

Ni [182], V [183], and A1 [184]. SU-M [185] is a mesoporous germanium oxide with crystalline pore walls, possessing one of the largest primitive cells and the lowest framework density of any inorganic material. The channels are defined by 30-rings. Structural and thermal information show that there exists a mismatch between framework stability and template decomposition. The latter requires temperatures higher than 450 °C, while the structure is preserved only until 300 °C. 

Several reaction mechanisms have been suggested to explain the framework stabilization of zeolites upon dea-lumination ... 

The silica freed from the collapsed framework migrates under steam towards the vacancies of the remaining framework and by filling them, increases framework stability. 

The ammonia is released and the protons remain in the zeolite, which then can be used as acidic catalysts. Applying this method, all extra-framework cations can be replaced by protons. Protonated zeolites with a low Si/Al ratio are not very stable. Their framework structure decomposes even upon moderate thermal treatment [8-10], A framework stabilization of Zeolite X or Y can be achieved by introducing rare earth (RE) cations in the Sodalite cages of these zeolites. Acidic sites are obtained by exchanging the zeolites with RE cations and subsequent heat treatment. During the heating, protons are formed due to the autoprotolysis of water molecules in the presence of the RE cations as follows ... 

Silicoaluminophosphates (SAPOs), along with their crystalline aluminum phosphate counterparts (ALPOs), first discovered by Union Carbide workers in the early 1970s [41, 42], derive their acidity through the substitution of framework phosphorous by silicon thereby creating the charge imbalance which, when compensated for by protons, creates acidic centers. SAPOs in general have seen limited use in bond-breaking applications primarily due to weaker acidity, framework stability, or technoeconomic reasons. Of the rich variety of structures available,... 

Zeolite framework stabilization effects uniformly all transition states and charged transient intermediates, and does not effect the neutral intermediates. Similar effect of the zeolite framework has been described by Corma et al. for another reaction. 

Reversible electrochemical lithium deintercalation from 2D and 3D materials is important for applications in lithium-ion batteries. New developments have been realized in two classes of materials that show exceptionally promising properties as cathode materials. The first includes mixed layered oxides exemplified by LijMn Nij, Co ]02, where the Mn remains inert to oxidation/reduction and acts as a framework stabilizer while the other elements carry the redox load. Another class that shows much potential is metal phosphates, which includes olivine-type LiFeP04, and the NASICON-related frameworks Li3M2(P04)3. 

E. de vos Burchart, PhD thesis. Delft University of Technology, The Netherlands, 1992. Studies on Zeolites Molecular Mechanics, Framework Stability, and Crystal Growth. 

The mesoporous materials discussed here comprise silicates and aluminosilicates that are formed from synthesis conditions comparable to zeolites. The main difference with the latter is the use of supra-molecular assemblies of surfactant molecules, e.g. alkyltrimethylammonium ions, as the structure directing agents. Due to the large dimensions of these spherical or cylindrical micelles, the framework of the silicates is not so well crystallized as in the case of zeolites. This causes lower framework stability as well as weaker Bronsted acidity. Upon calcination, large pores of uniform diameter (say 4-10 nm, depending on the surfactants used) become accessible. 

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