Evaluation of the Hydrophilic/Hydrophobic Balance of 13X Zeolite by Adsorption of Water, Methanol, and Cyclohexane as Pure Vapors or as Mixtures.

Adsorption isotherms of pure vapors and vapor mixtures of water, methanol, and cyclohexane were studied using a synthesized 13X zeolite (FAU topology), by means of a DVS gravimetric vapor analyzer. These results were validated by GCMC calculations. The surface chemistry of the adsorbent was characterized by the thermodesorption of ammonia, and its textural properties were studied using nitrogen physisorption. The 13X zeolite was found to be strongly acidic (BrØnsted acid sites, Si/Al = 1.3) and its specific surface area around 1100 m2·g-1. Water was found to be able to diffuse within both the supercages and the sodalite cavities of the FAU structure, whereas methanol and cyclohexane were confined in the supercages only. The water/methanol sorption selectivity of the 13X zeolite was demonstrated by co-adsorption measurements. The composition of the water/methanol adsorbed phase could be calculated by assuming IAST hypotheses. This model failed in the case of the water/cyclohexane co-adsorption system, which is in line with the non-miscibility of the components in the adsorbed state. The sorption isotherms could be successfully simulated, confirming the robustness of the forcefields used. The 13X zeolite confirmed its a priori expected hydrophilic nature, which is useful for the selective adsorption of water in a methanol-water vapor mixture.

Alginate ester: New moisture-scavenging excipients for direct compressible pharmaceutical tableting.

The objective of this work is to evaluate methyl ester alginates and alginic acid (AA) as moisture-scavenging excipients for the formulation of aspirin tablets obtained by direct compression. The tablets were stored at accelerated conditions (40 °C/75 % RH) and assessed for changes in tensile strength, mass, thickness and disintegration time. While moisture caused a reduction in the hardness of MCC and AA tablets, hardness of the tablets made from methylated materials was virtually unaffected. The physical stability of alginate ester tablets was found to be related to their increased plastic deformation leading to extended interparticle contact with less impact on tablet porosity. Finally, the combination of higher moisture affinity and lower water dissociation exhibited by alginates esters resulted in tablets with the lowest aspirin degradation. These findings suggest that excipients with high water retention can act as moisture-scavengers without losing their functional properties and reducing the degradation of moisture-sensitive drugs.

Mesoporous organosilicas with thiol functionalised pores: multifunctional dendrimers as sacrificial building block and template.

The synthesis of multifunctional poly(amidoamine) (PAMAM)-based dendrimers containing a cleavable disulfide linker within each arm of the dendrimer, together with condensable triethoxysilyl groups on the periphery of the dendrimer, is described. The dendrimers were mixed with 1,4-bis(triethoxysilyl)benzene and subsequently transformed into silsesquioxane gels or periodic mesoporous organosilicas (PMOs) to generate materials with dendrimers covalently embedded within the interior of the silsesquioxane networks. Subsequent treatment of the gels with dithiothreitol enabled the core of the dendrimers to be selectively cleaved at the disulfide site, thus generating thiol functions localised within the pores. The effect of different dendrimer generations on the reactivity of the pendant thiol functions was probed by impregnation with gold salts, which were reduced to obtain gold nanoparticles within the pore networks of the gels and PMOs. The gels yielded polydisperse gold nanoparticles (2 to 70 nm) with dimensions modulated by the generation of the dendrimer, together with well-defined gold/thiolate clusters with Au⋯S distances of 2.3 Å. Such clusters were also observed in the PMO system, together with monodispersed gold nanoparticles with diameters comparable to that of the organised pores in the PMO. The role of surface functionalisation in controlling the formation of gold clusters and/or nanoparticles is discussed.

Periodic Mesoporous Organosilica Nanoparticles for CO2 Adsorption at Standard Temperature and Pressure.

(1) Background: Due to human activities, greenhouse gas (GHG) concentrations in the atmosphere are constantly rising, causing the greenhouse effect. Among GHGs, carbon dioxide (CO2) is responsible for about two-thirds of the total energy imbalance which is the origin of the increase in the Earth's temperature. (2) Methods: In this field, we describe the development of periodic mesoporous organosilica nanoparticles (PMO NPs) used to capture and store CO2 present in the atmosphere. Several types of PMO NP (bis(triethoxysilyl)ethane (BTEE) as matrix, co-condensed with trialkoxysilylated aminopyridine (py) and trialkoxysilylated bipyridine (Etbipy and iPrbipy)) were synthesized by means of the sol-gel procedure, then characterized with different techniques (DLS, TEM, FTIR, BET). A systematic evaluation of CO2 adsorption was carried out at 298 K and 273 K, at low pressure. (3) Results: The best values of CO2 adsorption were obtained with 6% bipyridine: 1.045 mmol·g-1 at 298 K and 2.26 mmol·g-1 at 273 K. (4) Conclusions: The synthetized BTEE/aminopyridine or bipyridine PMO NPs showed significant results and could be promising for carbon capture and storage (CCS) application.

Zirconium-Based Metal Organic Frameworks for the Capture of Carbon Dioxide and Ethanol Vapour. A Comparative Study.

This paper reports on the comparison of three zirconium-based metal organic frameworks (MOFs) for the capture of carbon dioxide and ethanol vapour at ambient conditions. In terms of efficiency, two parameters were evaluated by experimental and modeling means, namely the nature of the ligands and the size of the cavities. We demonstrated that amongst three Zr-based MOFs, MIP-202 has the highest affinity for CO2 (-50 kJ·mol-1 at low coverage against around -20 kJ·mol-1 for MOF-801 and Muc Zr MOF), which could be related to the presence of amino functions borne by its aspartic acid ligands as well as the presence of extra-framework anions. On the other side, regardless of the ligand size, these three materials were able to adsorb similar amounts of carbon dioxide at 1 atm (between 2 and 2.5 µmol·m-2 at 298 K). These experimental findings were consistent with modeling studies, despite chemisorption effects, which could not be taken into consideration by classical Monte Carlo simulations. Ethanol adsorption confirmed these results, higher enthalpies being found at low coverage for the three materials because of stronger van der Waals interactions. Two distinct sorption processes were proposed in the case of MIP-202 to explain the shape of the enthalpic profiles.

Efficient Removal of Chromium(VI) Anionic Species and Dye Anions from Water Using MOF-808 Materials Synthesized with the Assistance of Formic Acid.

This study presents a simple approach to prepare MOF-808, an ultra-stable Zr-MOF constructed from 6-connected zirconium clusters and 1,3,5-benzene tricarboxylic acid, with tailored particle sizes. Varying the amount of formic acid as a modulator in the range of 200-500 equivalents results in MOF-808 materials with a crystal size from 40 nm to approximately 1000 nm. Apart from the high specific surface area, a combination of a fraction of mesopore and plenty of acidic centers on the Zr-clusters induces a better interaction with the ionic pollutants such as K2Cr2O7 and anionic dyes. MOF-808 shows uptakes of up to 141.2, 642.0, and 731.0 mg/g for K2Cr2O7, sunset yellow, and quinoline yellow, respectively, in aqueous solutions at ambient conditions. The uptakes for the ionic dyes are significantly higher than those of other MOFs reported from the literature. Moreover, the adsorption capacity of MOF-808 remains stable after four cycles. Our results demonstrate that MOF-808 is a promising ideal platform for removing oxometallates and anionic dyes from water.

Quaternary Ammonium-Based Ionosilica Hydrogels as Draw Solutes in Forward Osmosis.

In the last few years, forward osmosis (FO) has attracted increasing interest as a sustainable technique for water desalination and wastewater treatment. However, FO remains as an immature process principally due to the lack of efficient and easily recyclable draw solutes. In this work, we report that ionosilica hydrogels based on quaternary ammonium halide ionosilica are efficient draw solutes in FO. Fluidic ionosilica hydrogels were obtained via hydrolysis-polycondensation reactions of a trisilylated quaternary ammonium precursor in slightly acidic water/ethanol solvent mixtures. The liquid-to-gel transition of the precursor and the kinetics of the formation of hydrogels were monitored by liquid NMR measurements. The formed hydrogels were shown to generate osmotic pressure up to 10.0 atm, indicating the potential of these hydrogels as efficient draw solutes in FO. Our results suggest that iodide anions are the osmotically active species in the system. Regeneration of the hydrogels via ultrafiltration (UF) was successfully achieved, allowing the development of a closed FO-UF process. However, the osmotic performances of the ionosilica hydrogels irreversibly decreased along the successive FO-UF cycles, probably due to anion exchange processes.

Proton Conductive Zr-Phosphonate UPG-1-Aminoacid Insertion as Proton Carrier Stabilizer.

Proton exchange membrane fuel cells (PEMFCs) are an attractive green technology for energy generation. The poor stability and performances under working conditions of the current electrolytes are their major drawbacks. Metal-Organic Frameworks (MOFs) have recently emerged as an alternative to overcome these issues. Here, we propose a robust Zr-phosphonate MOF (UPG-1) bearing labile protons able to act a priori as an efficient electrolyte in PEMFCs. Further, in an attempt to further enhance the stability and conductivity of UPG-1, a proton carrier (the amino acid Lysine, Lys) was successfully encapsulated within its porosity. The behaviors of both solids as an electrolyte were investigated by a complete experimental (impedance spectroscopy, water sorption) and computational approach (MonteCarlo, water sorption). Compared with the pristine UPG-1, the newly prepared Lys@UPG-1 composite showed similar proton conductivity but a higher stability, which allows a better cyclability. This improved cyclability is mainly related to the different hydrophobic-hydrophilic balance of the Lys@UPG-1 and UPG-1 and the steric protection of the reactive sites of the MOF by the Lys.

Role of pulping process as synergistic treatment on performance of agro-based activated carbons.

To recommend the beneficial effect of the pulping process on enhancing agro-wastes as precursors for the production of high-performance activated carbons (ACs), different pulping methods (alkali, sulfite and neutral sulfite) were applied on two available Egyptian agriculture by-products (rice straw and sugar cane bagasse), using the one-step pyrolysis method and H3PO4 activating agent. The adsorption performance of the different prepared ACs was evaluated in terms of Iodine Numbers and their sorption properties for removing the methylene blue (MB) from aqueous solutions. The corresponding sorption processes were also analysed using Lagergren first order, pseudo-second order and intraparticle diffusion models. Data revealed that the applied pulping conditions were effective for removing the non-cellulosic constituents of agro-residues. This was demonstrated by the hydrogen/carbon and oxygen/carbon ratios, thermal stability and IR-measurements of the final pulps. These data were effective on the particular sorption properties of RS and SCB-based ACs. Interestingly, the pulping process is a profound modification of the SCB-based fibres, on which it induced a clear increase of the specific surface areas of the corresponding ACs even though they had an impact on the sorption of MB and iodine. These values are superior to the reported data on agro-based ACs with H3PO4 activators. Pulping processes therefore play a dual role in the sorption properties of ACs. The first important role is the impact on the specific surface areas and the second impact is a profound modification of the surface chemistry of the ACs. Therefore, SCB-based ACs can be seen as an economical breakthrough product, and an alternative to the high-cost commercial ACs for the purification of industrial wastewaters.

Comparison of the benzene sorption properties of metal organic frameworks: influence of the textural properties.

The adsorption of benzene by CuBTC and MIL101(Cr) is investigated. The differences between both materials are discussed in terms of porous volume and affinities, determined by calculating Henry's constants and by measuring the adsorption enthalpies. If MIL101(Cr) adsorbs higher quantities of benzene, CuBTC develops stronger interaction, interesting for VOC remediation.

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.

Sorption pH dependance of strontium/calcium by sodium nonatitanate.

Sodium nonatitanate powder is a layered material containing some potential exchangeable sodium ions between layers. In this work, sorption mechanism of this material has been studied and modeled at the solid-liquid interface. In particular, the ion-exchange mechanism is up to now not entirely known and especially the role of the pH on sorption properties. To investigate this latter, the solid is first equilibrated with inert acidic and base (nitric acid and triethylamine) for which the co-ions nitrate and triethylammonium do not penetrate the solid. The exchange between proton or divalent ions (strontium or calcium), and the sodium initially located in the sodium nonatitanate, is characterized through capillary ionic chromatography and conductivity experiments. To understand and explain the sorption properties, we modeled the equilibrium constant of different exchange reactions as a function of the solution pH. The equilibrium constants of the strontium/sodium and the calcium/sodium exchange have been obtained. We have shown the important role of the pH on the sorption rate of the strontium and moreover the hydrolysis rate of the sodium nonatitanate is calculated. We found that one eighth of sodium is spontaneously hydrolysed in aqueous phase whereas seven-eighths are exchanged by different divalent cations (strontium or calcium). Strontium and calcium exhibit similar exchange curves and competition with the proton adsorbed is modeled with global equilibrium constant. The prediction is in agreement with the conductivity experiments and the global extraction isotherms.

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.

Tailoring the hydrophilic/lipophilic balance of clickable mesoporous organosilicas by the copper-catalyzed azide-alkyne cycloaddition click-functionalization.

We have designed and synthesized a clickable bridged silsesquioxane material featuring pendant alkyne chains as an aggregate of golf-ball-like nanoparticles, as evidenced by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and small- and wide-angle X-ray scattering (SWAXS). Using the copper-catalyzed azide-alkyne cycloaddition reaction with a range of organic azides of variable characteristics, we transformed this parent bridged silsesquioxane into new materials with tunable hydrophilic/lipophilic balance in high conversions while preserving the original morphology. N2, cyclohexane, and water sorption experiments were used to quantify the affinity of these materials toward the sorbates through the determination of their Henry's constants. This resulted in the following hydrophilic scale: M-OH > M-PEG > M-C6 > M-Ph > M-F > M-C16, which was mostly confirmed by SWAXS measurements.

Biodegradable ethylene-bis(propyl)disulfide-based periodic mesoporous organosilica nanorods and nanospheres for efficient in-vitro drug delivery.

Periodic mesoporous organosilica nanorods and nanospheres are synthesized from 1,4-bis(triethoxysilyl)ethylene and bis(3-ethoxysilylpropyl)disulfide. The nanosystems present the long-range order of the hexagonal nanostructure. They are degraded in simulated physiological conditions. The loading and release of doxorubicin with these nanosystems are both pH dependent. These nanoparticles are endocytosed by breast cancer cells and are very efficient for doxorubicin delivery in these cells.

Silylated melamine and cyanuric acid as precursors for imprinted and hybrid silica materials with molecular recognition properties.

Two monotrialkoxysilylated compounds that consist of complementary fragments of melamine (M) and cyanuric acid (CA) have been synthesised. The molecular recognition properties of the M and CA fragments through complementary hydrogen bonds (DAD and ADA; D=donor, A=acceptor) are the key factor used to direct the formation of hybrid silica materials by using a sol-gel process. These materials were synthesised following two methods: First, an organo-bridged silsesquioxane was obtained by the hydrolysis of the two complementary monotrialkoxysilylated melamine and cyanuric acid derivatives, with fluoride ions as a catalyst. The hydrogen-bonding interactions between the two organic fragments are responsible for the formation of the bridging unit. The transcription of the assembly into the hybrid material was characterised and evidenced by solid-state NMR (29Si, 13C) and FTIR spectroscopic experiments. Second, the molecular recognition was exploited to synthesise an imprinted hybrid silica. This material was prepared by co-condensation of tetraethyl orthosilicate (TEOS) with the monosilylated cyanuric acid derivative (CA) templated by nonsilylated melamine. The melamine template was completely removed by treating the solid material with hydrochloric acid. The reintroduction of the template was performed by treating the resulting material with an aqueous suspension of melamine. These steps were monitored and analysed by several techniques, such as solid-state NMR (29Si, 13C) and FTIR spectroscopic analysis and nitrogen adsorption-desorption isotherms.

Hydrocarbon adsorption in the flexible metal organic frameworks MIL-53(Al, Cr).

A general study of the adsorption of n-alkanes in the flexible metal organic framework (MOF) MIL-53 is presented. The roles of the length of the alkyl chain (n = 1-9), the nature of the metal (Al, Cr), and temperature were investigated. The shape of the adsorption curves is driven by the alkyl chain length of the n-alkanes. While traditional type-I isotherms are observed for short alkanes (n = 1, 2), adsorbates with longer chains induce clear substeps in the isotherm curves whose positions depend on the chain length. Such substeps are due to a breathing phenomenon, as proven by ex situ X-ray diffraction analysis. They strongly depend on the amount of adsorbate in the pores and on the nature of the metal (Al, Cr), which, for a given alkane, leads to a strong change in the substep positions despite the similar characteristics of the two metals. The adsorption kinetics are highly sensitive to small variations in temperature. Their detailed analysis in different regions of the isotherms shows in some cases the existence of distinct diffusion regimes and/or conformations within the flexible phases.

A macrothermodynamic approach to the limit of reversible capillary condensation.

The threshold of reversible capillary condensation is a well-defined thermodynamic property, as evidenced by corresponding states treatment of literature and experimental data on the lowest closure point of the hysteresis loop in capillary condensation-evaporation cycles for several adsorbates. The nonhysteretical filling of small mesopores presents the properties of a first-order phase transition, confirming that the limit of condensation reversibility does not coincide with the pore critical point. The enthalpy of reversible capillary condensation can be calculated by a Clausius-Clapeyron approach and is consistently larger than the condensation heat in unconfined conditions. Calorimetric data on the capillary condensation of tert-butyl alcohol in MCM-41 silica confirm a 20% increase of condensation heat in small mesopores. This enthalpic advantage makes easier the overcoming of the adhesion forces by the capillary forces and justifies the disappearing of the hysteresis loop.

New evidence of confinement effects in mesoporous materials and the definition of confined Pitzer acentric factors.

In the present work, the corresponding states principle is proposed as a new approach to clarify the comparison between adsorption-desorption isotherms obtained on porous solids. The applicability of this principle at the capillary critical point in adsorption-desorption isotherms is demonstrated. Deviations of the Clausius-Clapeyron curves in reduced coordinates are interpreted in terms of polarizability, and those are perfectly correlated using analogous Pitzer acentric factors in confined environments. New acentric factors are proposed to take confinement effects in mesoporous materials into account. Enthalpic excesses during capillary condensation could be predicted, and those are supported by calorimetric experiments.