Effect of Ligand Aromaticity on Cyclohexane and Benzene Sorption in IRMOFs: A Computational Study.

A series of four isoreticular MOFs (IRMOF-1, -10, -14, and -16) were selected for a computational investigation of the effect of ligand aromaticity on the adsorption capacity of an aromatic VOC (benzene) compared to its nonaromatic analog (cyclohexane). The affinity of the adsorbates was evaluated by calculating Henry's constants and adsorption enthalpies. It has been evidenced that while KH values decrease with ligand elongation (IRMOF-10 and -16), inserting a pyrene core into the MOF structure (IRMOF-14) increases both the cyclohexane and benzene adsorption efficiency by ∼290 and 54%, respectively. To elucidate host-guest interactions, we sought to locate preferential adsorption sites in MOF structures for the two VOCs studied by using the GCMC method. It appears that benzene interacts with the metal center (Zn4O clusters) and most of the ligand while cyclohexane tends to localize preferentially only near the Zn4O clusters. Coadsorption isotherms (equimolar mixture of benzene and cyclohexane) demonstrated the preferential adsorption of cyclohexane due to the stronger affinity for the MOF structure. On the other hand, for other isoreticular structures, the ligand elongation leads to a shift of the adsorption curve of cyclohexane caused by pore size increase and therefore less interactions with the walls. This phenomenon is counterbalanced in the case of IRMOF-14 due to stronger interactions between the cyclohexane and pyrene groups. The present results thus open perspectives in the design of promising MOF candidates for high-performing separation and sorption/detection of hydrocarbon VOCs.

Mesoporous SiC-Based Photocatalytic Membranes and Coatings for Water Treatment.

Photocatalytically active silicon carbide (SiC)-based mesoporous layers (pore sizes between 5 and 30 nm) were synthesized from preceramic polymers (polymer-derived ceramic route) on the surface and inside the pores of conventional macroporous α-alumina supports. The hybrid membrane system obtained, coupling the separation and photocatalytical properties of SiC thin films, was characterized by different static and dynamic techniques, including gas and liquid permeation measurements. The photocatalytic activity was evaluated by considering the degradation efficiency of a model organic pollutant (methylene blue, MB) under UV light irradiation in both diffusion and permeation modes using SiC-coated macroporous supports. Specific degradation rates of 1.58 × 10-8 mol s-1 m-2 and 7.5 × 10-9 mol s-1 m-2 were obtained in diffusion and permeation modes, respectively. The performance of the new SiC/α-Al2O3 materials compares favorably to conventional TiO2-based photocatalytic membranes, taking advantage of the attractive physicochemical properties of SiC. The developed synthesis strategy yielded original photocatalytic SiC/α-Al2O3 composites with the possibility to couple the ultrafiltration SiC membrane top-layer with the SiC-functionalized (photocatalytic) macroporous support. Such SiC-based materials and their rational associations on porous supports offer promising potential for the development of efficient photocatalytic membrane reactors and contactors for the continuous treatment of polluted waters.

Thermochemical Activity of Single- and Dual-Phase Oxide Compounds Based on Ceria, Ferrites, and Perovskites for Two-Step Synthetic Fuel Production.

This study focuses on the generation of solar thermochemical fuel (hydrogen, syngas) from CO2 and H2O molecules via two-step thermochemical cycles involving intermediate oxygen-carrier redox materials. Different classes of redox-active compounds based on ferrite, fluorite, and perovskite oxide structures are investigated, including their synthesis and characterization associated with experimental performance assessment in two-step redox cycles. Their redox activity is investigated by focusing on their ability to perform the splitting of CO2 during thermochemical cycles while quantifying fuel yields, production rates, and performance stability. The shaping of materials as reticulated foam structures is then evaluated to highlight the effect of morphology on reactivity. A series of single-phase materials including spinel ferrite, fluorite, and perovskite formulations are first investigated and compared to state-of-the-art materials. NiFe2O4 foam exhibits a CO2-splitting activity similar to its powder analog after reduction at 1400 °C, surpassing the performance of ceria but with much slower oxidation kinetics. On the other hand, although identified as high-performing materials in other studies, Ce0.9Fe0.1O2, Ca0.5Ce0.5MnO3, Ce0.2Sr1.8MnO4, and Sm0.6Ca0.4Mn0.8Al0.2O3 are not found to be attractive candidates in this work (compared with La0.5Sr0.5Mn0.9Mg0.1O3). In the second part, characterizations and performance evaluation of dual-phase materials (ceria/ferrite and ceria/perovskite composites) are performed and compared to single-phase materials to assess a potential synergistic effect on fuel production. The ceria/ferrite composite does not provide any enhanced redox activity. In contrast, ceria/perovskite dual-phase compounds in the form of powders and foams are found to enhance the CO2-splitting performance compared to ceria.

SiC Foams for the Photocatalytic Degradation of Methylene Blue under Visible Light Irradiation.

SiC foams were synthesized by impregnating preceramic polymer into polyurethane foam templates, resulting in a photo-catalytically active material for the degradation of methylene blue. The crystalline structure, electronic properties, and photocatalytic performance of the SiC foams were characterized using a series of experimental techniques, including X-ray diffraction, electron microscopy, energy dispersive X-ray spectroscopy, N2 physisorption measurements, UV-visible spectroscopy, and methylene blue photodegradation tests. The original polyurethane template's microporous structure was maintained during the formation of the SiC foam, while additional mesopores were introduced by the porogen moieties added to the preceramic polymers. The prepared SiC-based photocatalyst showed attractive photocatalytic activity under visible light irradiation. This structured and reactive material offers good potential for application as a catalytic contactor or membrane reactor for the semi-continuous treatment of contaminated waste waters in ambient conditions.

A Palladium-Based MOF for the Preferential Sorption of Benzene.

Selective sorption of volatile aromatic compounds is a challenging issue for their total abatement. Despite the well-known affinity of palladium toward rich π systems, studies dedicated to volatile organic compound (VOC) capture with Pd(II)-based metal-organic frameworks (MOFs) are still very scarce. Intending to shed more light on this complex topic, this work compares the adsorption properties of two isostructural MOFs [Cu(2-pymo)2]n and [Pd(2-pymo)2]n and their selectivity for the sorption of linear, cyclic, or aromatic VOCs. The combination of both experimental and computational investigations highlights an increasing aromatic affinity over saturated hydrocarbons when palladium is chosen as a metal center (nBenzene/nn-hexane = 1.8 at 0.5 p/p0) in the MOF instead of copper (nBenzene/nn-hexane = 0.7 at 0.5 p/p0). Furthermore, [Pd(2-pymo)2]n clearly exhibits preferential adsorption of benzene over toluene (nBenzene/nToluene = 1.7 at 0.5 p/p0), due to the steric hindrance effects of the latter. The present results clearly underline the attractiveness of Pd-based MOFs for the design of selective aromatic adsorbents. Moreover, they also highlight the [Pd(2-pymo)2]n MOF as a relevant candidate for the selective capture of benzene, by a synergistic combination of both charge interactions and steric hindrance effects.

Gas Adsorption in Zeolite and Thin Zeolite Layers: Molecular Simulation, Experiment, and Adsorption Potential Theory.

Molecular simulations and experiments are used to investigate methane adsorption in bulk and thin layers of MFI zeolite (silicalite-1). After comparing the theoretical adsorption data obtained using Grand Canonical Monte Carlo simulations for bulk MFI at various temperatures against experiments, zeolite layers with different crystalline orientations and levels of surface flexibility are considered. The data obtained for such prototypical systems allow us to rationalize both the qualitative and quantitative impact of external surface in nanoporous solids. In particular, due to strong confinement in zeolite pores, methane is found to adsorb at low pressures in the core of the zeolite while external surface adsorption occurs at pressures where the internal porosity of zeolite is saturated. Using Polanyi's adsorption potential theory, which is derived here from Hill's general scheme for adsorption, we provide a simple thermodynamic formalism to predict consistently adsorption both in the internal porosity and at the external surface of nanoporous solids. While this seminal theory has been already applied for gases in nanoporous solids, its extension to describe both surface and volume adsorption is important to provide a general rational framework for fluid adsorption in finely divided materials. We also discuss the applicability of this formalism for gas adsorption data under supercritical conditions.

Fe-Nanoporous Carbon Derived from MIL-53(Fe): A Heterogeneous Catalyst for Mineralization of Organic Pollutants.

Catalytic electrodes were prepared via carbonization of MIL-53(Fe) on the surface of porous carbon felt electrodes (CF) for use in wastewater treatment by the heterogeneous electro-Fenton (EF) process. The best results were obtained when the carbon felt was pretreated with nitric acid, enhancing the affinity of the MIL-53(Fe) for the surface. Following a series of optimization experiments, carbonization conditions of 800 °C for 5 h were used to form Fe-nanoporous carbon (MOFs@CF). The as-prepared electrodes were used as both cathode and heterogeneous catalyst in the EF process for the mineralization of exemplar dye Acid Orange 7 (AO7). Total organic carbon (TOC) removal of 46.1% was obtained within 8 h of electrolysis at around neutral pH (6.5) and the electrode retained over 80% of its original efficiency over five treatment cycles.

High-Performance Nanowire Hydrogen Sensors by Exploiting the Synergistic Effect of Pd Nanoparticles and Metal-Organic Framework Membranes.

Herein, we report the fabrication of hydrogen gas sensors with enhanced sensitivity and excellent selectivity. The sensor device is based on the strategic combination of ZnO nanowires (NWs) decorated with palladium nanoparticles (Pd NPs) and a molecular sieve metal-organic framework (MOF) nanomembrane (ZIF-8). The Pd NPs permit the sensors to reach maximal signal responses, whereas the ZIF-8 overcoat enables for an excellent selectivity. Three steps were employed for the fabrication: (i) coating of a miniaturized sensor with vapor-grown ZnO NWs, (ii) decoration of these NWs with Pd NPs by atomic layer deposition, and (iii) partial solvothermal conversion of the tuned NWs surface to ZIF-8 nanomembrane. The microstructure and composition investigations of the ZIF-8/Pd/ZnO nanostructured materials confirmed the presence of both metallic Pd NPs and uniform ZIF-8 thin membrane layer. The integration of these nanomaterials within a miniaturized sensor device enabled the assessment of their performance for H2 detection at concentrations as low as 10 ppm in the presence of various gases such as C6H6, C7H8, C2H5OH, and CH3COCH3. Remarkably high-response signals of 3.2, 4.7, and 6.7 ( Ra/ Rg) have been measured for H2 detection at only 10, 30, and 50 ppm, whereas no noticeable response toward other tested gases was detected, thus confirming the excellent H2 selectivity obtained with such a sensor design. The results obtained showed that the performance of gas sensors toward H2 gas can be greatly increased by both the addition of Pd NPs and the use of ZIF-8 coating, acting as a molecular sieve membrane. Furthermore, the presented strategy could be extended toward the sensing of other species by a judicious choice of both the metallic NPs and MOF materials with tuned properties for specific molecule detection, thus opening a new avenue for the preparation of highly selective sensing devices.

Exploring the Gas-Permeation Properties of Proton-Conducting Membranes Based on Protic Imidazolium Ionic Liquids: Application in Natural Gas Processing.

This experimental study explores the potential of supported ionic liquid membranes (SILMs) based on protic imidazolium ionic liquids (ILs) and randomly nanoporous polybenzimidazole (PBI) supports for CH4/N2 separation. In particular, three classes of SILMs have been prepared by the infiltration of porous PBI membranes with different protic moieties: 1-H-3-methylimidazolium bis (trifluoromethane sulfonyl)imide; 1-H-3-vinylimidazolium bis(trifluoromethane sulfonyl)imide followed by in situ ultraviolet (UV) polymerization to poly[1-(3H-imidazolium)ethylene] bis(trifluoromethanesulfonyl)imide. The polymerization process has been monitored by Fourier transform infrared (FTIR) spectroscopy and the concentration of the protic entities in the SILMs has been evaluated by thermogravimetric analysis (TGA). Single gas permeability values of N2 and CH4 at 313 K, 333 K and 363 K were obtained from a series of experiments conducted in a batch gas permeance system. The results obtained were assessed in terms of the preferential cavity formation and favorable solvation of methane in the apolar domains of the protic ionic network. The most attractive behavior exhibited poly[1-(3H-imidazolium)ethylene]bis(trifluoromethanesulfonyl)imide polymeric ionic liquid (PIL) cross-linked with 1% divinylbenzene supported membranes, showing stable performance when increasing the upstream pressure. The CH4/N2 permselectivity value of 2.1 with CH4 permeability of 156 Barrer at 363 K suggests that the transport mechanism of the as-prepared SILMs is solubility-dominated.

Environmental mineralization of caffeine micro-pollutant by Fe-MFI zeolites.

Environmentally emerging micro-pollutant, caffeine, was mineralized (i.e., full degradation) by the isomorphic incorporation of Fe into silicalite-1 (mordenite framework inverted (MFI) structure zeolite) through a microwave synthesis method. The Fe incorporation conferred mesopore formation that facilitated caffeine access and transport to the MFI zeolite structure. Increasing the Fe content favored the formation of Fe(O)4 sites within the MFI structure. The catalytic activity for the degradation of caffeine increased as a function of Fe(O)4 sites via a Fenton-like heterogeneous reaction, otherwise not attainable using Fe-free pure MFI zeolites. Caffeine degradation reached 96% (TOC based) for zeolites containing 2.33% of Fe.

Hierarchical Porous Polybenzimidazole Microsieves: An Efficient Architecture for Anhydrous Proton Transport via Polyionic Liquids.

Liquid-induced phase-separation micromolding (LIPSµM) has been successfully used for manufacturing hierarchical porous polybenzimidazole (HPBI) microsieves (42-46% porosity, 30-40 µm thick) with a specific pore architecture (pattern of macropores: ∼9 µm in size, perforated, dispersed in a porous matrix with a 50-100 nm pore size). Using these microsieves, proton-exchange membranes were fabricated by the infiltration of a 1H-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide liquid and divinylbenzene (as a cross-linker), followed by in situ UV polymerization. Our approach relies on the separation of the ion conducting function from the structural support function. Thus, the polymeric ionic liquid (PIL) moiety plays the role of a proton conductor, whereas the HPBI microsieve ensures the mechanical resistance of the system. The influence of the porous support architecture on both proton transport performance and mechanical strength has been specifically investigated by means of comparison with straight macroporous (36% porosity) and randomly nanoporous (68% porosity) PBI counterparts. The most attractive results were obtained with the poly[1-(3H-imidazolium)ethylene]bis(trifluoromethanesulfonyl)imide PIL cross-linked with 1% divinylbenzene supported on HPBI membranes with a 21-µm-thick skin layer, achieving conductivity values up to 85 mS cm-1 at 200 °C under anhydrous conditions and in the absence of mineral acids.

Design of Phosphonated Imidazolium-Based Ionic Liquids Grafted on γ-Alumina: Potential Model for Hybrid Membranes.

Imidazolium bromide-based ionic liquids bearing phosphonyl groups on the cationic part were synthesized and grafted on γ-alumina (γ-Al2O3) powders. These powders were prepared as companion samples of conventional mesoporous γ-alumina membranes, in order to favor a possible transfer of the results to supported membrane materials, which could be used for CO2 separation applications. Effective grafting was demonstrated using energy dispersive X-ray spectrometry (EDX), N2 adsorption measurements, fourier transform infrared spectroscopy (FTIR), and special attention was paid to (31)P and (13)C solid state nuclear magnetic resonance spectroscopy (NMR).

MOF-Based Membrane Encapsulated ZnO Nanowires for Enhanced Gas Sensor Selectivity.

Gas sensors are of a great interest for applications including toxic or explosive gases detection in both in-house and industrial environments, air quality monitoring, medical diagnostics, or control of food/cosmetic properties. In the area of semiconductor metal oxides (SMOs)-based sensors, a lot of effort has been devoted to improve the sensing characteristics. In this work, we report on a general methodology for improving the selectivity of SMOx nanowires sensors, based on the coverage of ZnO nanowires with a thin ZIF-8 molecular sieve membrane. The optimized ZnO@ZIF-8-based nanocomposite sensor shows markedly selective response to H2 in comparison with the pristine ZnO nanowires sensor, while showing the negligible sensing response to C7H8 and C6H6. This original MOF-membrane encapsulation strategy applied to nanowires sensor architecture pave the way for other complex 3D architectures and various types of applications requiring either gas or ion selectivity, such as biosensors, photo(catalysts), and electrodes.

Effect of gas adsorption on acoustic wave propagation in MFI zeolite membrane materials: experiment and molecular simulation.

The present study reports on the development of a characterization method of porous membrane materials which consists of considering their acoustic properties upon gas adsorption. Using acoustic microscopy experiments and atomistic molecular simulations for helium adsorbed in a silicalite-1 zeolite membrane layer, we showed that acoustic wave propagation could be used, in principle, for controlling the membranes operando. Molecular simulations, which were found to fit experimental data, showed that the compressional modulus of the composite system consisting of silicalite-1 with adsorbed He increases linearly with the He adsorbed amount while its shear modulus remains constant in a large range of applied pressures. These results suggest that the longitudinal and Rayleigh wave velocities (VL and VR) depend on the He adsorbed amount whereas the transverse wave velocity VT remains constant.

Iron Oxide Silica Derived from Sol-Gel Synthesis.

In this work we investigate the effect of iron oxide embedded in silica matrices as a function of Fe/Si molar ratio and sol pH. To achieve homogeneous dispersion of iron oxide particles, iron nitrate nonahydrate was dissolved in hydrogen peroxide and was mixed with tetraethyl orthosilicate and ethanol in a sol-gel synthesis method. Increasing the calcination temperature led to a reduction in surface area, although the average pore radius remained almost constant at about 10 Å, independent of the Fe/Si molar ratio or sol pH. Hence, the densification of the matrix was accompanied by similar reduction in pore volume. However, calcination at 700 °C resulted in samples with similar surface area though the iron oxide content increased from 5% to 50% Fe/Si molar ratio. As metal oxide particles have lower surface area than polymeric silica structures, these results strongly suggest that the iron oxides opposed the silica structure collapse. The effect of sol pH was found to be less significant than the Fe/Si molar ratio in the formation of molecular sieve structures derived from iron oxide silica.