Renewing Interest in Zeolites as Adsorbents for Capture of Cationic Dyes from Aqueous and Ethanolic Solutions: A Simulation-Based Insight into the Efficiency of Dye Adsorption in View of Wastewater Treatment and Valorization of Post-Sorption Materials.

The impact of solvents on the efficiency of cationic dye adsorption from a solution onto protonated Faujasite-type zeolite (FAU-Y) was investigated in the prospect of supporting potential applications in wastewater treatment or in the preparation of building blocks for optical devices. The adsorption isotherms were experimentally determined for methylene blue (MB) and auramine O (AO) from single-component solutions in water and in ethanol. The limiting dye uptake (saturation capacity) was evaluated for each adsorption system, and it decreased in the order of MB-water > AO-water > AO-ethanol > MB-ethanol. The mutual distances and orientations of the adsorbed dye species, and their interactions with the oxygen sites of the FAU-Y framework, with the solvent molecules, and among themselves were inferred from Monte Carlo simulations and subsequently utilized to rationalize the observed differences in the saturation capacity. The dye-solvent competition and the propensity of the dyes to form compact pi-stacked dimers were shown to play an important role in establishing a non-uniform distribution of the adsorbed species throughout the porous space. The two effects appeared particularly strong in the case of the MB-water system. The necessity of including solvent effects in modeling studies is emphasized.

Expanding the horizons of porphyrin metal-organic frameworks via catecholate coordination: exploring structural diversity, material stability and redox properties.

Porphyrin based Metal-Organic Frameworks (MOFs) have generated high interest because of their unique combination of light absorption, electron transfer and guest adsorption/desorption properties. In this study, we expand the range of available MOF materials by focusing on the seldom studied porphyrin ligand H10TcatPP, functionalized with tetracatecholate coordinating groups. A systematic evaluation of its reactivity with M(iii) cations (Al, Fe, and In) led to the synthesis and isolation of three novel MOF phases. Through a comprehensive characterization approach involving single crystal and powder synchrotron X-ray diffraction (XRD) in combination with the local information gained from spectroscopic techniques, we elucidated the structural features of the solids, which are all based on different inorganic secondary building units (SBUs). All the synthesized MOFs demonstrate an accessible porosity, with one of them presenting mesopores and the highest reported surface area to date for a porphyrin catecholate MOF (>2000 m2 g-1). Eventually, the redox activity of these solids was investigated in a half-cell vs. Li with the aim of evaluating their potential as electrode positive materials for electrochemical energy storage. One of the solids displayed reversibility during cycling at a rather high potential (∼3.4 V vs. Li+/Li), confirming the interest of redox active phenolate ligands for applications involving electron transfer. Our findings expand the library of porphyrin-based MOFs and highlight the potential of phenolate ligands for advancing the field of MOFs for energy storage materials.

Methanol diffusion and dynamics in zeolite H-ZSM-5 probed by quasi-elastic neutron scattering and classical molecular dynamics simulations.

Zeolite ZSM-5 is a key catalyst in commercially relevant processes including the widely studied methanol to hydrocarbon reaction, and molecular diffusion in zeolite pores is known to be a crucial factor in controlling catalytic reactions. Here, we present critical analyses of recent quasi-elastic neutron scattering (QENS) data and complementary molecular dynamics (MD) simulations. The QENS experiments show that the nature of methanol diffusion dynamics in ZSM-5 pores is dependent both on the Si/Al ratio (11, 25, 36, 40 and 140), which determines the Brønsted acid site density of the zeolite, and that the nature of the type of motion observed may vary qualitatively over a relatively small temperature range. At 373 K, on increasing the ratio from 11 to 140, the observed mobile methanol fraction increases and the nature of methanol dynamics changes from rotational (in ZSM-5 with Si/Al of 11) to translational diffusion. The latter is either confined localized diffusion within a pore in zeolites with ratios up to 40 or non-localized, longer-range diffusion in zeolite samples with the ratio of 140. The complementary MD simulations conducted over long time scales (1 ns), which are longer than those measured in the present study by QENS (≈1-440 ps), at 373 K predict the occurrence of long-range translational diffusion of methanol in ZSM-5, independent of the Si/Al ratios (15, 47, 95, 191 and siliceous MFI). The rate of diffusion increases slightly by increasing the ratio from 15 to 95 and thereafter does not depend on zeolite composition. Discrepancies in the observed mobile methanol fraction between the MD simulations (100% methanol mobility in ZSM-5 pores across all Si/Al ratios) and QENS experiments (for example, ≈80% immobile methanol in ZSM-5 with Si/Al of 11) are attributed to the differences in time resolutions of the techniques. This perspective provides comprehensive information on the effect of acid site density on methanol dynamics in ZSM-5 pores and highlights the complementarity of QENS and MD, and their advantages and limitations. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.

PySHS: Python Open Source Software for Second Harmonic Scattering.

The PySHS package is a new python open source software tool which simulates the second harmonic scattering (SHS) of different kinds of colloidal nano-objects in various experimental configurations. This package is able to compute polarizations resolved at a fixed scattered angle or angular distribution for different polarization configurations. This article presents the model implemented in the PySHS software and gives some computational examples. A comparison between computational results and experimental data concerning molecular dye intercalated inside liposomes membrane is presented to illustrate the possibilities with PySHS.

A Switch in the Hydrophobic/Hydrophilic Gas-Adsorption Character of Prussian Blue Analogues: An Affinity Control for Smart Gas Sorption.

Porous coordination polymers are molecule-based materials presenting a high degree of tunability, which offer many advantages for targeted applications over conventional inorganic materials. This work demonstrates that the hydrophilic/hydrophobic character of Prussian blue analogues having a lipophilic feature may be tuned to optimize the gas adsorption properties. The role of the coordinatively unsaturated metal sites is emphasized through a combination of theoretical and experimental study of water, ethanol, and n-hexane adsorption.

Prussian Blue Analogues for the Separation of Hydrocarbons in Humid Conditions.

The relative affinity of a series of Prussian Blue analogues presenting various chemical compositions for the adsorption of different gases, such as water vapor and hydrocarbons, was studied. The ability of Co[CoIII(CN)6]0.66·5.2H2O for the separation of hydrocarbons in a humid atmosphere was demonstrated.