ZnO/PDA/Mesoporous Cellular Foam Functionalized Thin-Film Nanocomposite Membrane towards Enhanced Nanofiltration Performance.

Thin-film nanocomposite (TFN) membranes are the third-generation membranes being explored for nanofiltration applications. Incorporating nanofillers in the dense selective polyamide (PA) layer improves the permeability-selectivity trade-off. The mesoporous cellular foam composite Zn-PDA-MCF-5 was used as a hydrophilic filler in this study to prepare TFN membranes. Incorporating the nanomaterial onto the TFN-2 membrane resulted in a decrease in the water contact angle and suppression of the membrane surface roughness. The pure water permeability of 6.40 LMH bar-1 at the optimal loading ratio of 0.25 wt.% obtained was higher than the TFN-0 (4.20 LMH bar-1). The optimal TFN-2 demonstrated a high rejection of small-sized organics (>95% rejection for 2,4-dichlorophenol over five cycles) and salts-Na2SO4 (≈95%) > MgCl2 (≈88%) > NaCl (86%) through size sieving and Donnan exclusion mechanisms. Furthermore, the flux recovery ratio for TFN-2 increased from 78.9 to 94.2% when challenged with a model protein foulant (bovine serum albumin), indicating improved anti-fouling abilities. Overall, these findings provided a concrete step forward in fabricating TFN membranes that are highly suitable for wastewater treatment and desalination applications.

Carbon dioxide adsorption and activation on ionic liquid decorated Au(111) surface: A DFT study.

We use first principle approaches to study the adsorption and catalytic activation mechanism of CO2 on ionic liquids (ILs, [CnMIm]+[Cl]- (n = 0-6)) attached to a Au(111) surface. The adsorption of CO2 at this liquid-solid model interface occurs via either (i) parallel π-stacking mode or (ii) CO2 oxygen lone pair (lp)···π interaction. These CO2 physisorption modes, which depend on the CO2 landing angle at this interface, are identified as an efficient way to activate CO2 and its further conversion into value-added products. For illustration, we discuss the conversion of CO2 into formic acid where the ILs@Au(111) decorated interface allows reduction of the activation energy for the CO2 + H2 → HCOOH reaction. In sum, our electrode/electrolyte based interface model provides valuable information to design novel heterogeneous catalysts for CO2 conversion. Indeed, our work establishes that a suitable interface material is enough to activate CO2.

Sodium ion intercalation and multi redox behavior of a Keggin type polyoxometalate during [PMo10V2O40]5- to [PMo10V2O40]27- as a cathode material for Na-ion rechargeable batteries.

Recently, the development of cathode materials for Na-ion batteries has gained much attention due to the abundance, low cost, and easy availability of resources. Apart from the usual metal oxides, multi-electron redox materials grabbed attention due to their high energy density and practical capacity with long cycle life. Polyoxometalates (POMs) are inorganic clusters of higher valent metals, and act as electron sponges with multi-electron redox properties. Herein we report a Keggin-type polyoxometalate [PMo10V2O40]5- with Na+ and H+ counter cations as a cathode material for Na-ion batteries. Further the formation of POM is evidenced by PXRD, FT-IR, flame photometry and XPS studies. In Na-POM, Na+ ions in the intercluster cavities provide a better pathway and easy diffusion during the charge/discharge process, and contribute to better electrochemical properties than H-POM. The DFT studies further explore the detailed mechanistic pathway of Na+ ions around the clusters in the normal and super-reduced states. Na-POM enables better cycling stability and capacity retention with a specific discharge capacity of 123 mA h g-1 at 0.1C rate at room temperature.

Selection of a suitable ZIF-8/ionic liquid (IL) based composite for selective CO2 capture: the role of anions at the interface.

The effective capture of CO2 from the atmosphere is much needed to reduce its environmental impact. The design and development of CO2 capturing materials is getting much attention. A zeolitic imidazolate framework (ZIF) can replace many of the conventional materials in gas separation due to its stability and high performance. Here, we analyzed the effect of encapsulation of ionic liquids (ILs) into the pores of ZIF-8 for selective CO2 capture and separation. The [BMIM]+ cation with a series of anions was selected to study suitable carbon capture materials using density functional theory (DFT) approaches. Our calculations suggest that the nitrogen containing anions are not well adsorbed on the ZIF-8 surface but their gas separation performance is not affected by these interfacial interactions. This is confirmed from the CO2/N2 and CO2/CH4 selectivity of these composites, calculated using grand canonical Monte Carlo (GCMC) simulations. A suitable force field for the composites was identified by comparing the available force fields with the experiments. The IL@ZIF-8 composite shows better CO2 selectivity compared to pristine ZIF-8. Fluorinated hydrophobic anions (such as [BF4]-, [PF6]- and [Tf2N]-) in the composites show better CO2 adsorption and significant CO2 selectivity than pristine ZIF-8, especially at low pressure. The nature of the anion plays an important role in CO2 separation, rather than its stability at the pores of ZIF-8. Close scrutiny of the results reveal that the CO2 selectivity of these composite materials depends on the anion of the IL and thus through the selection of a suitable anion we can significantly enhance the CO2 selectivity for different flue gas mixtures. Our molecular level design shows that the selection of suitable anions in IL based composites is very important in identifying potential carbon capture materials for industrial applications.

Density Functional Theory Studies on Zeolitic Imidazolate Framework-8 and Ionic Liquid-Based Composite Materials.

The identification of suitable density functional methods for predicting the properties of nanoporous composite materials is highly significant in the field of chemical and material sciences. The stability of the composite materials depends on the nature of bonding and dispersive interaction at the interface. Thus, we have studied the effect of dispersion correction in the incorporation of hydrophobic and hydrophilic ionic liquids (ILs) into zeolitic imidazolate framework-8 (ZIF-8) nanostructures using the density functional theory (DFT)-based approaches. These structures were analyzed employing selected methods (Becke-Lee-Yang-Parr and Perdew-Burke-Ernzerhof) with dispersion correction (D2 or D3) and different basis sets (such as double-zeta valence polarized (DZVP), triple-zeta valence polarized (TZVP), and triple-zeta valence doubly polarized (TZV2P)) for the understanding of microscopic features of IL@ZIF-8 nanopores. It is found that the result obtained from DFT-D2/TZVP is more reliable for the prediction of the experimental crystal structure as well as stability and spectral information of the complexes. Furthermore, the microscopic analysis of geometries reveals that ILs are highly dispersed and stabilized at the nanopores of ZIF-8, particularly the ZIF-8 structure is highly preferable for the hydrophobic group in ILs. It is found that fluorine-containing anions are highly dispersed on the ZIF-8 surface compared to the nonfluorinated anion (i.e., [BMIM]+[Cl]-). This is confirmed from the adsorption energies (E ads), charge transfer, electron density analyses, and IR spectral analysis. These findings can provide more insights into the stability of composite materials, which are suitable for applications of catalytic conversion at the confined state, gas storage, and separation techniques.