Surendar R. Venna

Highly Permeable Zeolite Imidazolate Framework-8 Membranes for CO2/CH4 Separation

ZIF-8 membranes, a type of zeolite imidazolate framework, were synthesized by secondary seeded growth on tubular alpha-Al(2)O(3) porous supports. The presence of small, highly crystalline, microporous crystals with narrow particle size distribution led to continuous thin membranes. The synthesized novel ZIF-8 membranes displayed unprecedented high CO(2) permeances and relatively high separation indexes for equimolar mixtures of CO(2) and CH(4).

Structural Evolution of Zeolitic Imidazolate Framework-8

We report the structural evolution of zeolitic imidazolate framework-8 (ZIF-8) as a function of time at room temperature. We have identified the different stages of ZIF-8 formation (nucleation, crystallization, growth, and stationary periods) and elucidated its kinetics of transformation. We hypothesize that the observed semicrystalline-to-crystalline transformation may take place via solution- and solid-mediated mechanisms, as suggested by the observed phase transformation evolution and Avramis kinetics, respectively. A fundamental understanding of ZIF-8 structural evolution as demonstrated in this study should facilitate the preparation of functional metal-organic framework phases with controlled crystal size and extent of crystallinity.

Fabrication of MMMs with improved gas separation properties using externally-functionalized MOF particles

Mixed matrix membranes (MMM) have the potential to overcome the limitations of traditional polymeric membranes for gas separation by improving both the permeability and selectivity. The most difficult challenge is accessing defect free and optimized MMM membranes. Defects are generally due to incompatible interfaces between the polymer and the filler particle. Herein, we present a new approach to modify and optimize the surface of UiO-66-NH2 based MOF particles to improve its interaction with Matrimid® polymer. A series of surface modified UiO-66-NH2 particles were synthesized and characterized using 1H NMR spectroscopy, mass spectrometry, XPS, and powder X-ray diffraction. MMMs containing surface optimized MOF particles exhibit improved thermal and mechanical properties. Most importantly, the MMMs show significantly enhanced gas separation properties; CO2 permeability was increased by ∼200% and CO2/N2 ideal selectivity was increased by ∼25%. These results confirm the success of the proposed technique to mitigate defective MOF/Matrimid® interfaces.

Amino-functionalized SAPO-34 membranes for CO2/CH4 and CO2/N2 separation.

SAPO-34 seeds and membranes were functionalized with several organic amino cations, such as ethylenediamine, hexylamine, and octylamine. The successful incorporation of the amino groups in the SAPO-34 framework was confirmed by Fourier transform infrared (FTIR) and X-ray photoemission (XPS) spectroscopies. The resultant SAPO-34 membranes were evaluated for the separation of CO2/CH4 and CO2/N2 gas mixtures. CO2/CH4 selectivities as high as 245, with CO2 permeances of ∼5 × 10(-7) mol m(-2) s(-1) Pa(-1) at 295K and 138 kPa, were observed for an optimum ethylenediamine-functionalized membrane, which corresponded to a ∼40% increase in the separation index, as compared to the nonfunctionalized SAPO-34 membrane. Similarly, the CO2/N2 separation performance was highly improved with the incorporation of ethylenediamine. CO2/N2 selectivities as high as 39, with CO2 permeances of ∼2.1 × 10(-7) mol m(-2) s(-1) Pa(-1) at 295K and 138 kPa, were observed for an optimum ethylenediamine-functionalized membrane, which corresponded to a ∼167% increase in the separation index, as compared to the nonfunctionalized SAPO-34 membrane.

Synthesis of SAPO-34 Crystals in the Presence of Crystal Growth Inhibitors

Microporous SAPO-34 molecular sieves were synthesized employing polyethylene glycol, polyoxyethylene lauryl ether, and methylene blue as crystal growth inhibitors. The synthesized SAPO-34 crystals displayed BET surface areas up to 700 m2/g, high CO2/CH4 adsorption ratios, and small crystal size in the approximately 0.6-0.9 microm range with narrow particle size distribution. The enhanced CO2/CH4 adsorption capacities were related to the high N/H ratios observed in the phases prepared in the presence of crystal growth inhibitors. The synthesized SAPO-34 crystals may find potential applications to prepare membranes for CO2 purification.

Modular polymerized ionic liquid block copolymer membranes for CO2/N2 separation

The continuing discovery of broad classes of materials, such as ionic liquids, zeolites, metal–organic frameworks, and block copolymers, presents an enormous opportunity in developing materials for new applications. Polymerized ionic liquid block copolymers (PIL-BCPs) fall at the union of two already large sets of materials, and are an emerging class of materials useful in gas separation membranes, ion and electron conducting materials, and as mechanical actuators. A wide range of ionic liquid moieties can be used as pendant groups along the polymer backbone, potentially allowing for a wide variation in the resulting material properties; however in practice the range of ionic liquids explored is hindered by the need to optimize polymerization conditions for each new monomer. Here, we present a modular approach to PIL-BCP synthesis where a variety of olefin bearing cations are readily conjugated to polymers using thiol-Michael click chemistry. This approach allowed for the rapid development of a diverse material library including phase separated thin films, ion-gels, and liquid PIL-BCPs, with a reduced investment in synthetic time. Finally, we demonstrate that this approach identified PIL-BCPs with increased CO2 permeability relative to PILs, which could find use in carbon capture from flue gas.

Microwave assisted phase transformation of silicoaluminophosphate zeolite crystals

SAPO-34 zeolite displaying ∼0.5 µm crystal size with a narrow particle size distribution and preferential adsorption of CO2 over that of CH4 was prepared via phase transformation of SAPO-5 under microwave heating.

Continuous Flow Processing of ZIF-8 Membranes on Polymeric Porous Hollow Fiber Supports for CO2 Capture

We have utilized an environmentally friendly synthesis approach for the accelerated growth of a selective inorganic membrane on a polymeric hollow fiber support for postcombustion carbon capture. Specifically, continuous defect-free ZIF-8 thin films were grown and anchored using continuous flow synthesis on the outer surface of porous supports using water as solvent. These membranes demonstrated CO2 permeance of 22 GPU and the highest reported CO2/N2 selectivity of 52 for a continuous flow synthesized ZIF-8 membrane.

Separation of carbon dioxide from flue gas by mixed matrix membranes using dual phase microporous polymeric constituents

This study presents the fabrication of a new mixed matrix membrane using two microporous polymers: a polymer of intrinsic microporosity PIM-1 and a benzimidazole linked polymer, BILP-101, and their CO2 separation properties from post-combustion flue gas. 17, 30 and 40 wt% loadings of BILP-101 into PIM-1 were tested, resulting in mechanically stable films showing very good interfacial interaction due to the inherent H-bonding capability of the constituent materials. Gas transport studies showed that BILP-101/PIM-1 membranes exhibit high CO2 permeability (7200 Barrer) and selectivity over N2 (15). The selected hybrid membrane was further tested for CO2 separation using actual flue gas from a coal-fired power plant.

Rightsizing Nanochannels in Reduced Graphene Oxide Membranes by Solvating for Dye Desalination

Membranes with high water permeance, near-zero rejection to inorganic salts (such as NaCl and Na2SO4), and almost 100% rejection to organic dyes are of great interest for the dye desalination (the separation of dyes and salts) of textile wastewater. Herein, we prepared reduced graphene oxide membranes in a solvation state (S-rGO) with nanochannel sizes rightly between the salt ions and dye molecules. The S-rGO membrane rejects >99.0% of Direct Red 80 (DR 80) and has almost zero rejection for Na2SO4. By contrast, conventional GO or rGO membranes often have channel sizes smaller than divalent ions (such as SO42-) and thus high rejection for Na2SO4. More interestingly, high salinity in typical dye solutions decreases the channel size in the S-rGO membranes and thus increases the dye rejection, while the Na2SO4 rejection decreases because of the negatively charged surface on GO and the salt screening effect. The membranes also show pure water permeance as high as 80 L m-2 h-1 bar-1, which is about 8 times that of commercial NF 90 membrane and 2 times that of a commercial ultrafiltration membrane (with a molecular weight cutoff of 2000 Da), rendering their promise for practical dye desalination.