Separation of 2,3-Butanediol from Fermentation Broth via Cyclic and Simulated Moving Bed Adsorption Over Nano-MFI Zeolites.

The biomass-based platform molecule 2,3-butanediol (2,3-BDO) has a wide range of applications in production of sustainable fuels, chemicals, synthetic rubber, and others. However, the selective separation of 2,3-BDO from multicomponent fermentation broths presents challenges due to its low concentration, high solubility in water, high boiling point, and presence of many other species. Here, we demonstrate remarkably selective enrichment and recovery of 2,3-BDO from a corn stover hydrolysate fermentation broth by a pure-silica nano-MFI-type zeolite adsorbent.

Catalytic Upgrading of a Mixed Hydroxy Acid Feedstock Derived from Kraft Black Liquor.

Lignocellulosic feedstocks are widely studied for sustainable liquid fuel and chemical production. The pulp and paper industry generates large amounts of kraft black liquor (BL) from which a high volume of hydroxy acids (HAs) can be separated for further catalytic processing. Here, we explore the catalytic upgrading of HAs, including the conversion of (1) a model HA, gluconic acid; (2) a model mixture of HAs, and (3) a real mixture of HAs derived from kraft BL on M/NbO (M = Pd, Pt, Rh, and Ru).

Structural and Adsorption Properties of ZIF-8-7 Hybrid Materials Synthesized by Acid Gas-Assisted and Routes.

The tuning of micropore environments in zeolitic imidazolate frameworks (ZIFs) by mixed-linker synthesis has the potential for enabling new molecular separation properties. However, synthesis of mixed-linker (hybrid) ZIFs is often challenging due to the disparate chemical properties of the different linkers. Here, we elucidate the structure and properties of an unconventional ZIF-8-7 hybrid material synthesized via a controlled-acid-gas-assisted degradation and reconstruction (solvent-assisted crystal redemption, SACRed) strategy.

Recovery of 2,3-Butanediol from Fermentation Broth by Zeolitic Imidazolate Frameworks.

The efficient separation of the 2,3-butanediol (2,3-BDO) intermediate from fermentation broth is an important issue in the production of biofuels from biomass-derived intermediates. Two zeolitic imidazolate frameworks ZIF-8 and ZIF-71 were investigated for the adsorption of 2,3-butanediol (2,3-BDO) from fermentation broth via liquid breakthrough adsorption measurements. While both ZIF materials initially show high separation performance, ZIF-71 retains robust separation performance even after aging in ethanol for two years, whereas the capacity of ZIF-8 decreases significantly.

Hierarchical ZIF-8 Materials via Acid Gas-Induced Defect Sites: Synthesis, Characterization, and Functional Properties.

Microporous metal-organic frameworks (MOFs) have been widely studied for molecular separation and catalysis. The uniform micropores of MOFs (<2 nm) can introduce diffusion limitations and render the interiors of the crystal inaccessible to target molecules. The introduction of hierarchical porosity (interconnected micro and mesopores) can enhance intra-crystalline diffusion while maintaining the separation/catalytic selectivity.

Single-Walled Zeolitic Nanotubes: Advantaged Supports for Poly(ethylenimine) in CO Separation from Simulated Air and Flue Gas.

Previous research has demonstrated that amine polymers rich in primary and secondary amines supported on mesoporous substrates are effective, selective sorbent materials for removal of CO from simulated flue gas and air. Common substrates used include mesoporous alumina and silica (such as SBA-15 and MCM-41). Conventional microporous materials are generally less effective, since the pores are too small to support low volatility amines.

Kinetic Model of Acid Gas Induced Defect Propagation in Zeolitic Imidazolate Frameworks.

Understanding the degradation of nanoporous materials under exposure to common acid gas contaminants (e.g., SO, CO, NO, and HS) is essential to elongate their lifetime and thus enable their practical applications in separations and catalysis.

High-Performance Zeolitic Hollow-Fiber Membranes by a Viscosity-Confined Dry Gel Conversion Process for Gas Separation.

Zeolite membranes show great potential for gas and hydrocarbon separations, but high manufacturing cost has been one of the main hurdles in their industrial application. Here we demonstrate a method termed viscosity-confined dry gel conversion (VCDGC) for zeolite hollow fiber membrane fabrication. We demonstrate in detail the VCDGC synthesis of small-pore CHA zeolite membranes.

Single-walled zeolitic nanotubes.

We report the synthesis and structure of single-walled aluminosilicate nanotubes with microporous zeolitic walls. This quasi-one-dimensional zeolite is assembled by a bolaform structure-directing agent (SDA) containing a central biphenyl group connected by C alkyl chains to quinuclidinium end groups. High-resolution electron microscopy and diffraction, along with other supporting methods, revealed a unique wall structure that is a hybrid of characteristic building layers from two zeolite structure types, beta and MFI.

Origins of Acid-Gas Stability Behavior in Zeolitic Imidazolate Frameworks: The Unique High Stability of ZIF-71.

Zeolitic imidazolate frameworks (ZIFs) are promising materials for industrial process separations, but recent literature reports have highlighted their vulnerability to acid gases (e.g., SO, CO, NO, HS), often present in practical applications.

Similarities in Recalcitrant Structures of Industrial Non-Kraft and Kraft Lignin.

This work compares the structure of industrially isolated lignin samples from kraft pulping and three alternative processes: butanol organosolv, supercritical water hydrolysis, and sulfur dioxide/ethanol/water fractionation. Kraft processes are known to produce highly condensed lignin, with reduced potential for catalytic depolymerization, whereas the alternative processes have been hypothesized to impact the lignin less. The structural properties most relevant to catalytic depolymerization are characterized by elemental analysis, quantitative C and 2 D HQSC NMR spectroscopy, gel permeation chromatography, and thermogravimetric analysis.

All-Nanoporous Hybrid Membranes: Incorporating Zeolite Nanoparticles and Nanosheets with Zeolitic Imidazolate Framework Matrices.

Metal-organic framework (MOF) membranes have attractive molecular separation properties but require challenging thin-film deposition techniques on expensive/specialty supports to obtain high performance relative to conventional polymer membranes. We demonstrate and analyze in detail the new concept of all-nanoporous hybrid membranes (ANHMs), which combines two or more nanoporous materials of different morphologies into a single membrane without the use of any polymeric materials. This allows access to a previously inaccessible region of very high permeability and selectivity properties, a feature that enables ANHMs to show high performance even when fabricated with simple coating and solvent evaporation methods on low-cost supports.

Continuous Zeolite MFI Membranes Fabricated from 2D MFI Nanosheets on Ceramic Hollow Fibers.

High-quality 2D MFI nanosheet coatings were prepared on α-alumina hollow fiber supports by vacuum filtration and then transformed into molecular sieving membranes by two sequential hydrothermal treatments. This processing method eliminates the need for specially engineered silica-based support materials that have so far been necessary to allow the formation of functional membranes from 2D MFI nanosheets. The sequential steps enhance adhesion of the membrane on the fiber support, fill in nanoscale gaps between the 2D nanosheets, and preserve the desirable (0k0) out-of-plane orientation without the need of any support engineering or modification.

All-Nanoporous Hybrid Membranes: Redefining Upper Limits on Molecular Separation Properties.

New membrane-based molecular separation processes are an essential part of the strategy for sustainable chemical production. A large literature on "hybrid" or "mixed-matrix" membranes exists, in which nanoparticles of a higher-performance porous material are dispersed in a polymeric matrix to boost performance. We demonstrate that the hybrid membrane concept can be redefined to achieve much higher performance if the membrane matrix and the dispersed phase are both nanoporous crystalline materials, with no polymeric phase.

Ion-Exchanged SAPO-34 Membranes for Krypton-Xenon Separation: Control of Permeation Properties and Fabrication of Hollow Fiber Membranes.

Separation of radioisotope Kr from Xe is of importance in used nuclear fuel reprocessing. Membrane separation based on zeolite molecular sieves such as chabazite SAPO-34 is an attractive alternative to energy-intensive cryogenic distillation. We report the synthesis of SAPO-34 membranes with considerably enhanced performance via thickness reduction based upon control of a steam-assisted vapor-solid conversion technique followed by ion exchange with alkali metal cations.

Recovery of Acid-Gas-Degraded Zeolitic Imidazolate Frameworks by Solvent-Assisted Crystal Redemption (SACRed).

The acid stability of zeolitic imidazolate frameworks (ZIFs) is an important issue hindering their application. Acid-gas damage of ZIFs has been considered irreversible. However, we demonstrate a methodology called solvent-assisted crystal redemption (SACRed) to reverse acid-gas damage to ZIFs with a high degree of structural and functional recovery.

Interactions on External MOF Surfaces: Desorption of Water and Ethanol from CuBDC Nanosheets.

The external surfaces of metal-organic framework (MOF) materials are difficult to experimentally isolate due to the high porosities of these materials. MOF surface surrogates in the form of copper benzenedicarboxylate (CuBDC) nanosheets were synthesized using a bottom-up approach, and the surface interactions of water and ethanol were investigated by temperature-programmed desorption (TPD). A method of analysis of diffusion-influenced TPD was developed to measure the desorption properties of these porous materials.

Structural and Mechanistic Differences in Mixed-Linker Zeolitic Imidazolate Framework Synthesis by Solvent Assisted Linker Exchange and de Novo Routes.

Mixed-linker zeolitic imidazolate frameworks (ZIFs) are a subclass of metal-organic frameworks (MOFs) amenable to significant property tuning by altering the functional groups on the imidazolate linkers. Solvent assisted linker exchange (SALE) and de novo synthesis of mixed-linker ZIFs have been demonstrated, but the differences in structural properties-most importantly the linker distributions-and synthesis mechanisms of these two different types of hybrid ZIFs are unknown. In this work, a combination of H NMR combined rotation and multiple pulse spectroscopy (CRAMPS), water adsorption, and nitrogen measurements reveal distinct differences in linker mixing between SALE and de novo ZIF-8-90 hybrids.

ZIF-8 Membranes via Interfacial Microfluidic Processing in Polymeric Hollow Fibers: Efficient Propylene Separation at Elevated Pressures.

Propylene/propane (C3H6/C3H8) separations are performed on a large scale by energy-intensive distillation processes. Membranes based on metal-organic framework (MOF) molecular sieves, such as zeolitic imidazolate framework-8 (ZIF-8), offer the potential to perform these separations at considerably lower cost. However, the fabrication of scalable ZIF-8 membranes with high performance at elevated pressures and temperatures is challenging.

One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters.

Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor.

Engineering Porous Organic Cage Crystals with Increased Acid Gas Resistance.

Both known and new CC3-based porous organic cages are prepared and exposed to acidic SO2 in vapor and liquid conditions. Distinct differences in the stability of the CC3 cages exist depending on the chirality of the diamine linkers used. The acid catalyzed CC3 degradation mechanism is probed via in situ IR and a degradation pathway is proposed and supported with computational results.

Structure Elucidation of Mixed-Linker Zeolitic Imidazolate Frameworks by Solid-State (1)H CRAMPS NMR Spectroscopy and Computational Modeling.

Mixed-linker zeolitic imidazolate frameworks (ZIFs) are nanoporous materials that exhibit continuous and controllable tunability of properties like effective pore size, hydrophobicity, and organophilicity. The structure of mixed-linker ZIFs has been studied on macroscopic scales using gravimetric and spectroscopic techniques. However, it has so far not been possible to obtain information on unit-cell-level linker distribution, an understanding of which is key to predicting and controlling their adsorption and diffusion properties.

Temperature and Loading-Dependent Diffusion of Light Hydrocarbons in ZIF-8 as Predicted Through Fully Flexible Molecular Simulations.

Accurate and efficient predictions of hydrocarbon diffusivities in zeolitic imidazolate frameworks (ZIFs) are challenging, due to the small pore size of materials such as ZIF-8 and the wide range of diffusion time scales of hydrocarbon molecules in ZIFs. Here we have computationally measured the hopping rates of 15 different molecules (kinetic diameters of 2.66-5.

Highly tunable molecular sieving and adsorption properties of mixed-linker zeolitic imidazolate frameworks.

Nanoporous zeolitic imidazolate frameworks (ZIFs) form structural topologies equivalent to zeolites. ZIFs containing only one type of imidazole linker show separation capability for limited molecular pairs. We show that the effective pore size, hydrophilicity, and organophilicity of ZIFs can be continuously and drastically tuned using mixed-linker ZIFs containing two types of linkers, allowing their use as a more general molecular separation platform.

Silylated mesoporous silica membranes on polymeric hollow fiber supports: synthesis and permeation properties.

We report the synthesis and organic/water separation properties of mesoporous silica membranes, supported on low-cost and scalable polymeric (polyamide-imide) hollow fibers, and modified by trimethylsilylation with hexamethyldisilazane. Thin (∼1 μm) defect-free membranes are prepared, with high room-temperature gas permeances (e.g.