Controlled Covalent Functionalization of ZIF-90 for Selective CO2 Capture & Separation.

Mixed Matrix Membranes (MMM) with enhanced selectivity and permeability are preferred for gas separations. The porous metal-organic frameworks (MOFs) materials incorporated in them play a crucial part in improving the performance of MMM. In this study, Zeolitic imidazolate frameworks (ZIF-90) are selected to fabricate Polyetherimide (PEI) MMMs owing to their lucrative structural and chemical properties. This work reports new controlled post-synthetic modifications of ZIF-90 (50-PSM-ZIF-90) with ethanolamine to control the diffusion and uptake of CO2. Physical and chemical properties of ZIF-90, such as stability and presence of aldehyde functionality in the imidazolate linker, allow for easy modulation of the ZIF-90 pores and window size to tune the gas transport properties across ZIF-90-based membranes. Effects of these materials were investigated on the performance of MMMs and compared with pure PEI membranes. Performance of the MMMs was evaluated in terms of permeability of different gases and selective separation of CO2 and H2 gas. Results presented that the permeability of all membranes was in the following order, i.e., P(H2) > P(CO2) > P(O2) > P(CH4) > P(C2H6) > P(C3H8) > P(N2), demonstrating that kinetic gas diffusion is the predominant gas transport mode in these membranes. Among all the membranes, permeability of pure PEI membrane was highest for all gases due to the uniform porous morphology. The pure PEI membrane showed highest permeability of H2, which is 486.5 Barrer, followed by 49 Barrer for O2, 29 Barrer for N2, 142 Barrer for CO2, 41 Barrer for CH4, 40 Barrer for C2H6 and 39.6 Barrer for C3H8. Results also confirm the superiority of controlled PSM-ZIF-90-PEI membrane over the pure PEI and ZIF-90-PEI membranes in CO2 and H2 separation performance. The 50-PSM-ZIF-90 PEI membrane exhibited a 20% increase in CO2 separation from methane and a 26% increase over nitrogen compared to the ZIF-90-PEI membrane. The 50-PSM-ZIF-90 PEI membrane showed 15% more H2/O2 separation and 9% more H2/CH4 separation than ZIF-90 PEI membrane. Overall, this study represents the role of controlled PSM in enhancing the property of new materials like ZIF and its application in MMMs fabrication to develop a promising approach for the CO2 capture and separation.

ZIF-95 as a filler for enhanced gas separation performance of polysulfone membrane.

Metal-organic frameworks (MOFs) are found to be promising porous crystalline materials for application in gas separation. Considering that mixed matrix membranes usually increase the gas separation performance of a polymer by increasing selectivity, permeability, or both (i.e., perm-selectivity), the zeolitic imidazole framework-95 (ZIF-95) MOF was dispersed for the first time in polysulfone (PSF) polymer to form mixed matrix membranes (MMMs), namely, ZIF-95/PSF. The fabricated ZIF-95/PSF membranes were examined for the separation of various gases. The characterization of solvothermally synthesized ZIF-95 was carried out using different analyses such as powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), porosity measurements, etc. ZIF-95 was mixed with PSF at 8%, 16%, 24%, and 32% weight percent to form different loading MMMs. SEM analysis of membranes revealed good compatibility/adhesion between the MOF and polymer. The permeability of He, H2, O2, CO2, N2, and CH4 were measured for the pure and composite membranes. The ideal selectivity of different gas pairs were calculated and compared with reported mixed matrix membranes. The maximum increases in permeabilities were observed in 32% loaded membrane; nevertheless, these performance/permeability increases were at the expense of a slight decrease of selectivity. In the optimally loaded membrane (i.e., 24 wt% loaded membrane), the permeability of H2, O2, and CO2 increased by 80.2%, 78.0%, and 67.2%, respectively, as compared to the pure membrane. Moreover, the selectivity of H2/CH4, O2/N2, and H2/CO2 gas pairs also increased by 16%, 15%, and 8% in the 24% loaded membrane, respectively.

Highly Efficient Permeation and Separation of Gases with Metal-Organic Frameworks Confined in Polymeric Nanochannels.

This work demonstrates the confinement of porous metal-organic framework (HKUST-1) on the surface and walls of track-etched nanochannel in polyethylene terephthalate (np-PET) membrane using a liquid-phase epitaxy (LPE) technique. The composite membrane (HKUST-1/np-PET) exhibits defect-free MOF growth continuity, strong attachment of MOF to the support, and a high degree of flexibility. The high flexibility and the strong confinement of the MOF in composite membrane results from (i) the flexible np-PET support, (ii) coordination attachment between HKUST-1 and the support, and (iii) the growth of HKUST-1 crystal in nanoconfined geometries. The MOF has a preferred growth orientation with a window size of 3.5 Å, resulting in a clear cut-off of CO2 from natural gas and olefins. The experimental results and DFT calculations show that the restricted diffusion of gases only takes place through the nanoporous MOF confined in the np-PET substrate. This research thereby provides a new perspective to grow other porous MOFs in artificially prepared nanochannels for the realization of continuous, flexible, and defect-free membranes for various applications.

Novel Porous Organic Polymer for the Concurrent and Selective Removal of Hydrogen Sulfide and Carbon Dioxide from Natural Gas Streams.

Natural gas sweetening currently requires multistep, complex separation processes to remove the acid gas contaminants, carbon dioxide and hydrogen sulfide. In addition to being widely recognized as energy inefficient and cost-intensive, the effectiveness of this conventional process also suffers considerably because of limitations of the sorbent materials it employs. Herein, we report a new porous organic polymer, termed KFUPM-5, that is demonstrated to be effective in the concurrent separation of both hydrogen sulfide and carbon dioxide from a mixed gas stream at ambient conditions. To understand the ability of KFUPM-5 to selectively capture these gas molecules, we performed both pure-component thermodynamic and mixed gas kinetic adsorption studies and correlated these results with theoretical molecular simulations. Our results show that the underlying polar backbone of KFUPM-5 provides favorable adsorption sites for the selective capture of these gas molecules. The outcome of this work lends credence to the prospect that, for the first time, porous organic polymers can serve as sorbents for industrial natural gas sweetening processes.

A green sorbent for CO2 capture: α-cyclodextrin-based carbonate in DMSO solution.

Cyclodextrin (α-CD)/KOH pellet dissolved in DMSO was utilized to capture CO2. KOH has a dual function of enhancing the nucleophilicity of the hydroxyl groups on the α-CD rims and acting as a desiccant. 13C NMR spectroscopy provided evidence for the chemisorption of CO2 through the formation of organic carbonate (RO-CO2 -·K+). This was supported by the spectral changes obtained using ex situ ATR-FTIR spectroscopy upon bubbling CO2. Activation of α-CD with NaH or bubbling with 13CO2 verified that chemisorption occurred solely via RO-CO2 -·K+ rather than inorganic bicarbonate. Volumetric gas uptake demonstrated a sorption capacity of 21.3 wt% (4.84 mmol g-1). To the best of our knowledge, this is the highest chemisorption value reported to date for CD-based sorbents. DFT calculations of the Gibbs free energies indicated that the formation of RO-CO2 -·K+ was more favoured at the primary carbinol rather than its secondary counterpart.

Tuning the Interplay between Selectivity and Permeability of ZIF-7 Mixed Matrix Membranes.

Nanoparticles of zeolitic imidazolate framework-7 (nZIF-7) were blended with poly(ether imide) (PEI) to fabricate a new mixed-matrix membrane (nZIF-7/PEI). nZIF-7 was chosen in order to demonstrate the power of postsynthetic modification (PSM) by linker exchange of benzimidazolate to benzotriazolate for tuning the permeability and selectivity properties of a resulting membrane (PSM-nZIF-7/PEI). These two new membranes were subjected to constant volume, variable pressure gas permeation measurements (H2, N2, O2, CH4, CO2, C2H6, and C3H8), in which unique gas separation behavior was observed when compared to the pure PEI membrane. Specifically, the nZIF-7/PEI membrane exhibited the highest selectivities for CO2/CH4, CO2/C2H6, and CO2/C3H8 gas pairs. Furthermore, PSM-nZIF-7/PEI membrane displayed the highest permeabilities, which resulted in H2/CH4, N2/CH4, and H2/CO2 permselectivities that are remarkably well-positioned on the Robeson upper bound curves, thus, indicating its potential applicability for use in practical gas purifications.

Quest for anionic MOF membranes: continuous sod-ZMOF membrane with CO2 adsorption-driven selectivity.

We report the fabrication of the first continuous zeolite-like metal-organic framework (ZMOF) thin-film membrane. A pure phase sod-ZMOF, sodalite topology, membrane was grown and supported on a porous alumina substrate using a solvothermal crystallization method. The absence of pinhole defects in the film was confirmed and supported by the occurrence of quantifiable time-lags, for all studied gases, during constant volume/variable pressure permeation tests. For both pure and mixed gas feeds, the sod-ZMOF-1 membrane exhibits favorable permeation selectivity toward carbon dioxide over relevant industrial gases such as H2, N2, and CH4, and it is mainly governed by favorable CO2 adsorption.

Some new [(thione)2Au(diamine)]Cl3 complexes: synthesis, spectroscopic characterization, computational and in vitro cytotoxic studies.

Recent advances in oncology are focused on developing new complexes of gold(III) with various ligands that show augmented anti-proliferative potential and reduced toxicity as compared to cis-platin. In this study, new Au(III) complexes of the type [(thione)2Au(diamine)]Cl3 are reported, where thione=1,3-imidazolidine-2-thione (Imt), 1,3-Diazinane-2-thione (Diaz) and diamine=1,2-diaminoethane (en), 1,3-diaminopropane (pn) or 1,4-diaminobutane (bn). The solid state IR as well as (13)C and (15)N NMR data indicate that Au(III) center is bonded via sulfur of thiocarbonyl SC site of the thiones and also chelated by the diamines from the trans side of coordinated thiones. Spectroscopic data are evaluated by comparisons with calculated data from the built and optimized structure by GAUSSIAN 09 at the RB3LYP level with LanL2DZ bases set. These new Au(III) complexes based on mixed thione and diamine ligands are very similar to the square planar structure of tetracoordinate [Au(en)2]Cl3complex. In this study, cytotoxicity data for these gold(III) complexes against C6 glioma cell lines are also reported, and the results indicate some complexes have cytotoxicity comparable to cis-platin.

Synthesis, CP-MAS NMR Characterization, and Antibacterial Activities of Glycine and Histidine Complexes of Cd(SeCN) 2 and Hg(SeCN) 2.

The synthesis and characterization of cadmium and mercury complexes of selenocyanate of the type [(L)M(SeCN)2] are described, where L is L-Histidine (His) or L-Glycine (Gly) and M is Cd(2+) or Hg(2+). These complexes are obtained by the reaction of 1 equivalent of respective amino acids with metal diselenocyanate precursor in a mixture of solvents (methanol : water = 1 : 1). These synthesized compounds are characterized by analytical and various spectroscopic techniques such as elemental analysis (EA), IR, H,1 and C13 NMR in solution and in the solid state for C13 and N15. The in vitro antibacterial activities of these complexes have been investigated with standard type cultures of Escherichia coli (MTCC 443), Klebsiella pneumoniae (MTCC 109), Pseudomonas aeruginosa (MTCC 1688), Salmonella typhi (MTCC 733), and Staphylococcus aureus (MTCC 737).

Synthesis, characterization and anti proliferative effect of [Au(en)2]Cl3 and [Au(N-propyl-en)2]Cl3 on human cancer cell lines.

Two Au(III) complexes of the type [Au(en)2]Cl3 (2a) and [Au(N-pr-en)2]Cl3 (3a) were synthesized by reacting Auric acid (HAuCl(4)·3H2O) with 2 equiv. ethylenediamine (en) or N-alkyl substituted ethylenediamine ligands. This metallodrug was characterized by various analytical and spectroscopic techniques such as elemental analysis, UV-Vis, Far-IR, 1H NMR and solution 13C as well as solid 13C and 15N NMR. Potentiality of [Au(en)2]Cl3 and [Au(N-pr-en)2]Cl3 as an anti-cancer agent were investigated by measuring some relevant physicochemical and biochemical properties such as stability of Au-N bonds by vibrational stretching from Far IR as well as cytotoxicity and stomach cancer cell inhibiting effect, respectively. The solid-state 15N NMR chemical shift shows that the ligand is strongly bound to gold(III) centre via N atoms. The computational study of 2a shows that the gold coordination sphere adopts distorted square planar geometry with bidentate ethylenediamine ligands acting as a tetradentate chelate. While stable in the solution state, the in vitro biological studies performed with these compounds 2a in solution showed higher activity towards the inhibitory effects of the human cancer cell lines such as prostate cancer (PC-3) and gastric carcinoma (SGC-7901) than that of the N-substituted gold(III) complex (3a). Cytotoxicity of the new compounds has also been estimated in PC-3 and SGC-7901 cells.