Marlon T. Conato

Organic-Free Synthesis of a Highly Siliceous Faujasite Zeolite with Spatially Biased Q4(nAl) Si Speciation

We report the most siliceous FAU-type zeolite, HOU-3, prepared via a one-step organic-free synthesis route. Computational studies indicate that it is thermodynamically feasible to synthesize FAU with SAR=2-7, though kinetic factors seemingly impose a more restricted upper limit for HOU-3 (SAR≈3). Our findings suggest that a slow rate of crystallization and/or low concentration of Na+ ions in HOU-3 growth mixtures facilitate Si incorporation into the framework. Interestingly, Q4 (nAl) Si speciation measured by solid-state NMR can only be modeled with a few combinations of Al positioning at tetrahedral sites in the crystal unit cell, indicating the distribution of Si(-O-Si)4-n (-O-Al)n species is spatially biased as opposed to being random. Achieving higher SAR is desirable for improved zeolite (hydro)thermal stability and enhanced catalytic performance, which we demonstrate in benchmark tests that show HOU-3 is superior to commercial zeolite Y.

Synthesis Strategies for Ultrastable Zeolite GIS Polymorphs as Sorbents for Selective Separations.

Designing zeolites with tunable physicochemical properties can substantially impact their performance in commercial applications, such as adsorption, separations, catalysis, and drug delivery. Zeolite synthesis typically requires an organic structure-directing agent to produce crystals with specific pore topology. Attempts to remove organics from syntheses to achieve commercially viable methods of preparing zeolites often lead to the formation of impurities. Herein, we present organic-free syntheses of two polymorphs of the small-pore zeolite P (GIS), P1 and P2. Using a combination of adsorption measurements and density functional theory calculations, we show that GIS polymorphs are selective adsorbents for H2 O relative to other light gases (e.g., H2 , N2 , CO2 ). Our findings refute prior theoretical studies postulating that GIS-type zeolites are excellent materials for CO2 separation/sequestration. We also show that P2 is significantly more thermally stable than P1, which broadens the operating conditions for GIS-type zeolites in commercial applications and opens new avenues for exploring their potential use in processes such as catalysis.

Facile Fabrication of a Potential Slow-Release Fertilizer Based on Oxalate-Phosphate-Amine Metal-Organic Frameworks (OPA-MOFs)

This work demonstrates a simple, reproducible and scalable method of producing a potential slow-release fertilizer material. In this study, oxalate-phosphate-amine metal organic frameworks (OPA-MOFs) powder was synthesized from the hydrothermal treatment of ferric chloride (FeCl3•6H2O), orthophosphoric acid (H3PO4), oxalic acid dihydrate (H2C2O4•2H2O), and a common fertilizer, urea (CO(NH2)2). Being a structure directing agent (SDA)-type of MOF, the material is expected to slowly release urea via cation exchange, and eventually trigger the collapse of the framework, thus resulting to the subsequent release of the phosphates and iron-oxalate complexes. Elemental analysis revealed that the synthesized samples contains a promising amount of incorporated nitrogen and phosphorus. In this particular study, increasing in the amount of urea during the synthesis however revealed minimal change in the %N in the final product which tells us that maximum loading has already been achieved. P and N release experiments shall still be done both in vitro and in actual soil samples to monitor the release delivery kinetics and efficiency of the OPA-MOFs for fertilizer release applications.

Synthesis and characterization of zinc adeninate metal-organic frameworks (bioMOF1) as potential anti-inflammatory drug delivery material

Zn8(ad)4(BPDC)6O•2Me2NH2 (bioMOF1), a porous metal–organic framework with zinc-adeninate secondary building units (SBUs), interconnected via biphenyldicarboxylate linkers, shows great potential for drug delivery applications due to its non-toxic and biocompatible components (zinc and adenine). In this study, bioMOF1 crystals synthesized solvothermally at 130°C for 24 hours, were characterized thoroughly and loaded with a known anti-inflammatory drug, nimesulide (NIM). The crystalline nature of the material was confirmed using powder x-ray diffraction crystallography (PXRD) along with morphology assessment using focused-ion beam/field emission scanning electron microscopy (FIB/FESEM). NIM was introduced to the crystals via solvent exchange accompanied with vigorous stirring and quantified using thermogravimetric analysis (TGA) with loading saturation of ∼30% attained during the 2nd to 3rd day of drug immersion. Drug release in phosphate buffer saline and in deionized water was done to monitor the kinetic of drug release in vitro. The drug release showed a controlled discharge profile which slowed down at the 24th and 48th hour of release. Drug release in buffer showed a faster release of drug from the material, which means that the presence of cations in the solution could further trigger the release of drug. Slow drug release was observed for all of the set-ups with maximum % drug release of 24.47%, and 16.14% for the bioMOF1 in buffer and bioMOF1 in water respectively for the span of 48 hours.Zn8(ad)4(BPDC)6O•2Me2NH2 (bioMOF1), a porous metal–organic framework with zinc-adeninate secondary building units (SBUs), interconnected via biphenyldicarboxylate linkers, shows great potential for drug delivery applications due to its non-toxic and biocompatible components (zinc and adenine). In this study, bioMOF1 crystals synthesized solvothermally at 130°C for 24 hours, were characterized thoroughly and loaded with a known anti-inflammatory drug, nimesulide (NIM). The crystalline nature of the material was confirmed using powder x-ray diffraction crystallography (PXRD) along with morphology assessment using focused-ion beam/field emission scanning electron microscopy (FIB/FESEM). NIM was introduced to the crystals via solvent exchange accompanied with vigorous stirring and quantified using thermogravimetric analysis (TGA) with loading saturation of ∼30% attained during the 2nd to 3rd day of drug immersion. Drug release in phosphate buffer saline and in deionized water was done to monitor the kinetic o...