Rediscovery of the Importance of Inorganic Synthesis Parameters in the Search for New Zeolites.

Abstract

Zeolites and related crystalline microporous materials with cavities and channels of molecular dimensions are of major importance for applications ranging from ion-exchange to adsorption and to catalysis. Because their unique shape-selective properties are closely related to the size, shape, and dimensionality of the intracrystalline channels and cavities, much interest has been devoted to the discovery of novel zeolitic materials over the last several decades. As a result, a dramatic expansion in the structural domain of crystalline microporous materials, as well as in their compositional range, has been achieved. This is largely due to the development of innovative synthetic strategies, for example, organic structure-directing agent (OSDA) design, introduction of heteroatoms like Ge in OSDA-mediated zeolite synthesis, topotactic transformation of two-dimensional layered zeolite precursors, assembly-disassembly-organization-reassembly method, etc. However, although many of these methodologies are quite successful in finding unprecedented zeolite structures, the resulting materials tend to be (hydro)thermally unstable and are often commercially impractical from a manufacturing perspective because of the high cost of the OSDA and/or heteroatom employed. Therefore, we focused on inorganic synthesis parameters as the key phase selectivity factor that has received relatively little attention in the search for new industrially relevant zeolites. This Account describes our recent efforts to find previously undiscovered aluminosilicate zeolites by boosting the roles of inorganic structure-directing agents (ISDAs) in the presence of OSDAs. They include the multiple inorganic cation and excess fluoride approaches, which aim to promote a synergistic cooperation between ISDAs and/or OSDAs and thus to hold a rational design concept, although the latter is not friendly to the practical zeolite manufacturing process due to the toxicity of fluoride. Using these two approaches, we were able to synthesize not only the second generation (PST-29) and four higher generations (PST-20 (RHO-G5), PST-25 (RHO-G6), PST-26 (RHO-G7), and PST-28 (RHO-G8)) of the RHO family of embedded isoreticular zeolites but also three other novel zeolite structures (EU-12, PST-21, and PST-22). We also explored the synthesis of a number of heteroatom-containing aluminophosphate (AlPO4) molecular sieves with different framework structures and unusually high framework charge density through the cooperative structure direction of alkali metal and small OSDA cations or under wholly inorganic conditions. Although we need to clarify the nature and extent of interactions between the inorganic cations and framework components in synthesis mixtures, we believe that our synthetic concepts, shedding new light on the importance of inorganic synthesis parameters, will open a door for achieving many other novel zeolite structures and compositions.