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

Nanostructured materials: basic concepts and microstructure☆

The second edition of The Biomarker Guide is a fully updated and expanded version of this essential reference. Now in two volumes, it provides a comprehensive account of the role that biomarker technology plays both in petroleum exploration and in understanding Earth history and processes. Biomarkers and Isotopes in the Environment and Human History details the origins of biomarkers and introduces basic chemical principles relevant to their study. It discusses analytical techniques, and applications of biomarkers to environmental and archaeological problems. The Biomarker Guide is an invaluable resource for geologists, petroleum geochemists, biogeochemists, environmental scientists and archaeologists.

The Biomarker Guide

/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

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

A new polymorph of SiO2 (silicalite, refractive index 1.39, density 1.76 g cm−3) has a novel topologic type of tetrahedral framework. This encloses a three-dimensional system of intersecting channels defined by 10-rings wide enough to adsorb molecules up to 0.6 nm diameter. Silicalite is hydrophobic and organophilic, and selectively adsorbs organic molecules over water.

Silicalite, a new hydrophobic crystalline silica molecular sieve

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

A novel family of crystalline, microporous aluminophosphate compositions is synthesized by hydrothermal crystallization at elevated temperatures of aluminophosphate gels containing a molecular structure-forming template. The family comprises a number of distinct species, each with a unique crystal structure. Calcination removes volatile extraneous matter from the intracrystalline void space and yields microporous crystalline adsorbents with uniform pores, the dimensions of which vary, among the individual species, from about 3A to 10A in diameter. The compositions represent a new class of adsorbents of the molecular sieve type, and also exhibit properties somewhat analogous to zeolitic molecular sieves which render them useful as catalysts or catalyst bases in chemical reactions such as hydrocarbon conversions.

Crystalline metallophosphate compositions

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

Edith M. Flanigen

Papers

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

Silicalite, a new hydrophobic crystalline silica molecular sieve

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

Crystalline metallophosphate compositions

Aluminophosphate Molecular Sieves and the Periodic Table