Although zeolites and related materials combine nanoporosity with high thermal stability, they are difficult to modify or derivatize in a systematic way. A highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield. It has interconnected [Cu2(O2CR)4] units (where R is an aromatic ring), which create a three-dimensional system of channels with a pore size of 1 nanometer and an accessible porosity of about 40 percent in the solid. Unlike zeolites, the channel linings can be chemically functionalized; for example, the aqua ligands can be replaced by pyridines. Thermal gravimetric analysis and high-temperature single-crystal diffractometry indicate that the framework is stable up to 240 degreesC.

http://science.sciencemag.org/content/sci/283/5405/1148.full.pdf

A chemically functionalizable nanoporous material (Cu3(TMA)2(H2O)3)n

/pdf/chemical-strategies-to-design-textured-materials-from-cb2un3cizv.pdf

Chemical strategies to design textured materials: from microporous and mesoporous oxides to nanonetworks and hierarchical structures.

The Hydrothermal Synthesis of Zeolites: History and Development from the Earliest Days to the Present Time

Silicate mesoporous materials have received widespread interest because of their potential applications as supports for catalysis, separation, selective adsorption, novel functional materials, and use as hosts to confine guest molecules, due to their extremely high surface areas combined with large and uniform pore sizes. Over time a constant demand has developed for larger pores with well-defined pore structures. Silicate materials, with well-defined pore sizes of about 2.0–10.0 nm, surpass the pore-size constraint ( 700 m2 g−1) and narrow pore size distributions. Instead of using small organic molecules as templating compounds, as in the case of zeolites, long chain surfactant molecules were employed as the structure-directing agent during the synthesis of these highly ordered materials. The structure, composition, and pore size of these materials can be tailored during synthesis by variation of the reactant stoichiometry, the nature of the surfactant molecule, the auxiliary chemicals, the reaction conditions, or by post-synthesis functionalization techniques. This review focuses mainly on a concise overview of silicate mesoporous materials together with their applications. Perusal of the review will enable researchers to obtain succinct information about microporous and mesoporous materials.

https://www.mdpi.com/1996-1944/5/12/2874/pdf

A Review: Fundamental Aspects of Silicate Mesoporous Materials

The hydrothermal synthesis of zeolites: precursors, intermediates and reaction mechanism

A novel class of crystalline, microporous, aluminophosphate phases has been discovered that represents the first family of framework oxide molecular sieves synthesized without silica. The new family of aluminophosphate materials (AlPO/sub 4/-n)/sup 3/ currently includes about 20, three-dimensional framework structures, of which at least 14 are microporous and 6 are two-dimensional layer-type materials. The aluminophosphate materials have interesting properties for potential use in adsorptive and catalytic applications, due to both their unique surface selectivity characteristics and novel structures.

Aluminophosphate molecular sieves: a new class of microporous crystalline inorganic solids

Donnees sur une nouvelle classe de tamis moleculaires, qui peuvent etre utilises comme catalyseurs, supports de catalyseurs, adsorbants ou echangeurs d'ions et qui correspondent a une formule generale 0-0,3R•(Si x Al y P z )O 2 avec R=reste d'ammonium quaternaire ou une amine organique

Silicoaluminophosphate molecular sieves: another new class of microporous crystalline inorganic solids

The role of organic molecules in molecular sieve synthesis

New generations of crystalline microporous molecular sieve oxides have been discovered based on the novel aluminophosphate family by incorporating one or more of an additional thirteen elements from the Periodic Table into the AIPO4 framework. Elements incorporated include Li, Be, B, Mg, Si, Ga, Ge, As, Ti, Hn, Fe, Co, and Zn, spanning monovalent through pentavalent framework cationic species. The new materials comprise more than two dozen structures and two hundred compositions, including multi-element frameworks containing combinations of up to six framework cations. Pore sizes range from 0.3nm to 0.8nm encompassing small, intermediate and large pore structures. The new molecular sieves are synthesized by hydrothermal crystallization of reactive aluminophosphate gels containing the additional framework elements and an organic template. Proof of framework incorportion includes the formation of novel structures, the enhancement of catalytic activity, elemental analysis, and various spectroscopic evidence. The Bronsted acidity observed ranges from weakly to strongly acidic. This landmark discovery of new generations of molecular sieve materials represents a remarkable diversity in crystal structure and crystal chemistry, and offers a nearly unlimited number of design parameters to tailor adsorptive and catalytic properties.

/pdf/aluminophosphate-molecular-sieves-and-the-periodic-table-51ma4ewpzg.pdf

Aluminophosphate Molecular Sieves and the Periodic Table

Titanium-containing molecular sieves are disclosed having use as molecular sieves and as catalyst compositions in hydrocarbon conversion and other processes.

Brent M. T. Lok

Papers

Aluminophosphate molecular sieves: a new class of microporous crystalline inorganic solids

Silicoaluminophosphate molecular sieves: another new class of microporous crystalline inorganic solids

The role of organic molecules in molecular sieve synthesis

Aluminophosphate Molecular Sieves and the Periodic Table

Titanium-containing molecular sieves