5-(Ethoxymethyl)furfural (EMF) was produced from glucose in ethanol in a single reactor at 90 °C. The reaction proceeds via the isomerization of glucose to fructose with zeolite Sn-Beta, a Lewis acid catalyst. Fructose is converted to 5-(hydroxymethyl)furfural, which is then etherified to EMF using a Brønsted acid catalyst, Amberlyst 131. An EMF yield of 31% was achieved.

Zeolites are a class of crystalline oxides that have uniform and molecular-sized pores (3-12 A in diameter). Although natural zeolites were first discovered in 1756, significant commercial development did not begin until the 1950s when synthetic zeolites with high purity and controlled chemical composition became available. Since then, major commercial applications of zeolites have been limited to catalysis, adsorption, and ion exchange, all using zeolites in powder form. Although researchers have widely investigated zeolite thin films within the last 15 years, most of these studies were motivated by the potential application of these materials as separation membranes and membrane reactors. In the last decade, we have recognized and demonstrated that zeolite thin films can have new, diverse, and economically significant applications that others had not previously considered. In this Account, we highlight our work on the development of zeolite thin films as low-dielectric constant (low-k) insulators for future generation computer chips, environmentally benign corrosion-resistant coatings for aerospace alloys, and hydrophilic and microbiocidal coatings for gravity-independent water separation in space stations. Although these three applications might not seem directly related, they all rely on the ability to fine-tune important macroscopic properties of zeolites by changing their ratio of silicon to aluminum. For example, pure-silica zeolites (PSZs, Si/Al = infinity) are hydrophobic, acid stable, and have no ion exchange capacity, while low-silica zeolites (LSZs, Si/Al < 2) are hydrophilic, acid soluble, and have a high ion exchange capacity. These new thin films also take advantage of some unique properties of zeolites that have not been exploited before, such as a higher elastic modulus, hardness, and heat conductivity than those of amorphous porous silicas, and microbiocidal capabilities derived from their ion exchange capacities. Finally, we briefly discuss our more recent work on polycrystalline zeolite thin films as promising biocompatible coatings and environmentally benign wear-resistant and antifouling coatings. When zeolites are incorporated into polymer thin films in the form of nanocrystals, we also show that the resultant composite membranes can significantly improve the performance of reverse osmosis membranes for sea water desalination and proton exchange membrane fuel cells. These diverse applications of zeolites have the potential to initiate new industries while revolutionizing existing ones with a potential economic impact that could extend into the hundreds of billions of dollars. We have licensed several of these inventions to companies with millions of dollars invested in their commercial development. We expect that other related technologies will be licensed in the near future.

Following our previous works on pure-silica-zeolite (PSZ) MFI, in this study we explore PSZ MEL as a new option for low-k dielectric films. Our motivation has been to increase the microporosity of the spin-on films by moving to structures with a framework density (FD) lower than MFI. Nanoparticle PSZ MEL suspensions were synthesized by a two-stage method that allowed the yield of nanocrystals to be significantly enhanced, while the zeolite nanocrystals remain small. For the first time zeolite nanocrystals of about 50 nm were synthesized with a yield as high as 57%. Nanoparticle suspensions with different particle sizes and crystallinities were spun on silicon wafers to prepare continuous thin films. An ultralow-k value as low as 1.5 was obtained with MEL nanoparticle suspension of high relative crystallinity. The surface roughness of the PSZ MEL film with high relative crystallinity is greatly improved (R(rms) approximately 5.6 nm) compared to MFI films with high relative crystallinity (R(rms) approximately 12 nm).

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Cross-linked polybenzimidazole membranes were obtained by heating at 160 C, using 4,4 0diglycidyl(3,3 0 ,5,5 0 -tetramethylbiphenyl) epoxy resin (TMBP) as the cross-linker. The cross-linking reaction temperature was determined by DSC and the successful completion of the cross-linking reaction was shown by FTIR and solubility tests. The cross-linked membranes showed high proton conductivity and strong mechanical properties, as well as low swelling after immersion in 85% phosphoric acid at 90 C. For instance, the membrane with a cross-linker content weight percent of 20% (PBI-TMBP 20%) with a PA doping level of 4.1 exhibited a proton conductivity of 0.010 S cm À1 and a low swelling volume of 50%. Moreover, the cross-linked membranes showed excellent oxidative stability. The PBI-TMBP 20% cross-linked membrane tested in Fenton's reagent (3% H 2 O 2 solution, 4 ppm Fe 2+ , 70 C) kept its shape for more than 480 h and did not break. In particular, the proton conductivity of the PA-PBI-TMBP 20% membrane after Fenton's test (30% H 2 O 2 , 20 ppm Fe 2+ , 85 C) remained at a high level of 0.009 S cm À1 . This investigation proved that cross-linking is a very effective approach for improving the performance of proton exchange membranes.

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