Simultaneous monitoring of acidity and intercalation for layered transition metal oxides in liquid media.

Layered transition metal oxides have a potential as catalysts for biomass conversions or as adsorbents. A better understanding of their properties is thus necessary, notably in liquid phase, where these materials have the specificity to intercalate molecules within their interlayers. To discriminate between potential catalysts or adsorbents, it is desirable to study the surface properties in the conditions of intercalation. The intercalation behaviour and acidity of four different acidic layered materials: pure tungstate phases H2W2O7, H2WO4 and mixed oxides HNbWO6 and HNbMoO6 have thus been investigated directly in liquid phase. Besides Powder X-ray diffraction, Raman spectroscopy provided valuable informations first during the preliminary protonation step and second by monitoring both the intercalation of liquid organic bases and the accessible acidity. N-alkylamines such as butylamine and octylamine were found unsuitable to discriminate the layered solids while pyridine was more selective. Pyridine did not intercalate in H2W2O7, highlighting also the lower acidity of this solid, but gave rise to new Raman features for H2WO4, HNbMoO6 and HNbWO6. Lewis and Brønsted acid sites could be discriminated from the perturbation of the inorganic layers and related to surface sites. Therefore, the characterization by Raman spectroscopy in conditions of liquid intercalation proves to efficiently evaluate layered materials.

Operando Reactor-Cell with Simultaneous Transmission FTIR and Raman Characterization (IRRaman) for the Study of Gas-Phase Reactions with Solid Catalysts.

Raman and transmission FTIR spectroscopic techniques have been coupled in a new homemade reactor-cell designed in a joint CSIC-LCS collaboration. The setup is easily adapted to any FTIR and fiber-coupled Raman spectrometers and gas analysis techniques. It allows for simultaneous operando FTIR and Raman spectroscopic measurement, which provide complementary characterization of adsorbed species, reaction intermediates, and structural properties of the catalyst. This system was validated with the study of vanadium-based catalysts during propane oxydehydrogenation (ODH). The combined use of both spectroscopies with gas analysis techniques to measure the activity contributes to the understanding of propane ODH and the identification of the role of different oxygen species bound to vanadium sites. For example, the simultaneous characterization of the catalyst under the same conditions by IR and Raman confirms that the V═O mode has the same frequency in both spectroscopies and that bridging oxygen sites (V-O-V, V-O-Zr) present higher activity than terminal V═O bonds. These results demonstrate the high potential of the new simultaneous transmission IR-Raman operando rig to correlate the activity and the structure of catalysts, thus assisting the rational design of catalytic processes.

Tuning Cellular Biological Functions Through the Controlled Release of NO from a Porous Ti-MOF.

Materials for the controlled release of nitric oxide (NO) are of interest for therapeutic applications. However, to date, many suffer from toxicity and stability issues, as well as poor performance. Herein, we propose a new NO adsorption/release mechanism through the formation of nitrites on the skeleton of a titanium-based metal-organic framework (MOF) that we named MIP-177, featuring a suitable set of properties for such an application: (i) high NO storage capacity (3 µmol mg-1solid ), (ii) excellent biocompatibility at therapeutic relevant concentrations (no cytotoxicity at 90 µg mL-1 for wound healing) due to its high stability in biological media (<9 % degradation in 72 hours) and (iii) slow NO release in biological media (≈2 hours for 90 % release). The prospective application of MIP-177 is demonstrated through NO-driven control of mitochondrial respiration in cells and stimulation of cell migration, paving the way for the design of new NO delivery systems for wound healing therapy.

Low Dimensional Magnetic Lattice and Room Temperature Magneto(di)electric Effect in Polyanion Ruddlesden-Popper Iron Oxides.

We have shown a new design strategy which exploits different oxyanions in a Ruddlesden-Popper (RP)-type phase to modulate the local crystal structure and magnetic lattice. Material (Sr4Fe2(SO4)0.5O6.5) with the larger voluminous oxyanion (SO4, S-O distance = 1.49 Å) as separating blocks between magnetic FeO layers shows a two-dimensional magnetic lattice. A three-dimensional magnetic lattice and spin reorientation transition is observed for the Sr4Fe2(CO3)O6, having CO3 (C-O distance = 1.25 Å), a smaller oxyanion, as a separating layer. Using mixed oxyanions (SO4 and CO3) in the central perovskite block of the RP3 phase, we have demonstrated a facile strategy to modulate the local crystal structure. The modulated displacement of the magnetic cations, which can break the local centrosymmetry, is suggested to originate the magnetodielectric effect near the magnetic ordering temperatures (higher than room temperature). Further, all CO3 containing samples show magnetodielectric coupling below room temperature due to the spin reorientation transition. The room temperature magnetodielectric effect coupled to the targeted local modulation of the crystal structure by oxyanions (in the absence of second-order Jahn-Teller active "distortion centers") opens a new door to the design of new multifunctional materials with the possibility for the room temperature application.

Tetrahedral chain ordering and low dimensional magnetic lattice in a new brownmillerite Sr2ScFeO5.

We report the synthesis, structure and physical properties of a hitherto unreported brownmillerite compound Sr2ScFeO5. We have shown a new ordering sequence of the interlayer iron tetrahedral chains. Reduced dimensionality of the magnetic lattice and the frustration in the two dimensional iron tetrahedral chains originate complex magnetic and magneto-dielectric effects. Our study highlights a novel approach to tailor the magnetic lattice in bulk oxides.

A MOF-assisted phosphine free bifunctional iron complex for the hydrogenation of carbon dioxide, sodium bicarbonate and carbonate to formate.

The hydrogenation of carbon dioxide into formic acid (FA) with Earth-abundant metals is a vibrant research area because FA is an attractive molecule for hydrogen storage. We report a cyclopentadienyl iron tricarbonyl complex that provides up to 3000 turnover number for carbon dioxide hydrogenation when combined with a catalytic amount of the chromium dicarboxylate MOF MIL-53(Cr). To date, this is the highest turnover number reported in the presence of a phosphine-free iron complex.

Toward an Understanding of the Microstructure and Interfacial Properties of PIMs/ZIF-8 Mixed Matrix Membranes.

A study integrating advanced experimental and modeling tools was undertaken to characterize the microstructural and interfacial properties of mixed matrix membranes (MMMs) composed of the zeolitic imidazolate framework ZIF-8 nanoparticles (NPs) and two polymers of intrinsic microporosity (PIM-1 and PIM-EA-TB). Analysis probed both the initial ZIF-8/PIM-1 colloidal suspensions and the final hybrid membranes. By combination of dynamic light scattering (DLS) and transmission electron microscopy (TEM) analytical and imaging techniques with small-angle X-ray scattering (SAXS), the colloidal suspensions were shown to consist mainly of two distinct kinds of particles, namely, polymer aggregates of about 200 nm in diameter and densely packed ZIF-8-NP aggregates of a few 100 nm in diameter with a 3 nm thick polymer top-layer. Such aggregates are likely to impart the granular texture of ZIF-8/PIMs MMMs as shown by SEM-XEDS analysis. At the molecular scale, modeling studies showed that the surface coverage of ZIF-8 NPs by both polymers appears not to be optimal with the presence of microvoids at the interfaces that indicates only a moderate compatibility between the polymer and ZIF-8. This study shows that the microstructure of MMMs results from a complex interplay between the ZIF-8/PIM compatibility, solvent, surface chemistry of the ZIF-8 NPs, and the physicochemical properties of the polymers such as molecular structure and rigidity.

Azine-Linked Covalent Organic Framework (COF)-Based Mixed-Matrix Membranes for CO2 /CH4 Separation.

Mixed-matrix membranes (MMMs) comprising Matrimid and a microporous azine-linked covalent organic frameworks (ACOF-1) were prepared and tested in the separation of CO2 from an equimolar CO2 /CH4 mixture. The COF-based MMMs show a more than doubling of the CO2 permeability upon 16 wt % ACOF-1 loading together with a slight increase in selectivity compared to the bare polymer. These results show the potential of COFs in the preparation of MMMs.

Metal Organic Framework Crystals in Mixed-Matrix Membranes: Impact of the Filler Morphology on the Gas Separation Performance.

Mixed-matrix membranes (MMMs) comprising NH2-MIL-53(Al) and Matrimid® or 6FDA-DAM have been investigated. The MOF loading has been varied between 5 and 20 wt%, while NH2-MIL-53(Al) with three different morphologies: nanoparticles, nanorods and microneedles have been dispersed in Matrimid®. The synthesized membranes have been tested in the separation of CO2 from CH4 in an equimolar mixture. At 3 bar and 298 K for 8 wt% MOF loading, incorporation of NH2-MIL-53(Al) nanoparticles leads to the largest improvement compared to nanorods and microneedles. The incorporation of the best performing filler, i.e. NH2-MIL-53(Al) nanoparticles, to the highly permeable 6FDA-DAM has a larger effect, and the CO2 permeability increased up to 85 % with slightly lower selectivities for 20 wt% MOF loading. Specifically, these membranes have a permeability of 660 Barrer with CO2/CH4 separation factor of 28, leading to a performance very close to the Robeson limit of 2008. Furthermore, a new non-destructive technique based on Raman spectroscopy mapping is introduced to assess the homogeneity of the filler dispersion in the polymer matrix. The MOF contribution can be calculated by modelling the spectra. The determined homogeneity of the MOF filler distribution in the polymer is confirmed by FIB-SEM analysis.

Tuning the properties of the UiO-66 metal organic framework by Ce substitution.

Crystallisation of a mixed-metal form of the porous framework UiO-66 in which Zr is partially replaced by Ce produces a ligand-defective material, that contains some Ce(III) as well as a majority of Ce(IV). Infrared spectroscopy shows enhanced binding of methanol in the substituted material that leads to catalytic decomposition of the alcohol, which may be due to a combination of defects and redox activity.

Isomorphous substitution in a flexible metal-organic framework: mixed-metal, mixed-valent MIL-53 type materials.

Mixed-metal iron-vanadium analogues of the 1,4-benzenedicarboxylate (BDC) metal-organic framework MIL-53 have been synthesized solvothermally in N,N'-dimethylformamide (DMF) from metal chlorides using initial Fe:V ratios of 2:1 and 1:1. At 200 °C and short reaction time (1 h), materials (Fe,V)(II/III)BDC(DMF(1-x)F(x)) crystallize directly, whereas the use of longer reaction times (3 days) at 170 °C yields phases of composition [(Fe,V)(III)0.5(Fe,V)0.5(II)(BDC)(OH,F)](0.5-)·0.5DMA(+) (DMA = dimethylammonium). The identity of the materials is confirmed using high-resolution powder X-ray diffraction, with refined unit cell parameters compared to known pure iron analogues of the same phases. The oxidation states of iron and vanadium in all samples are verified using X-ray absorption near edge structure (XANES) spectroscopy at the metal K-edges. This shows that in the two sets of materials each of the vanadium and the iron centers are present in both +2 and +3 oxidation states. The local environment and oxidation state of iron is confirmed by (57)Fe Mössbauer spectrometry. Infrared and Raman spectroscopies as a function of temperature allowed the conditions for removal of extra-framework species to be identified, and the evolution of µ2-hydroxyls to be monitored. Thus calcination of the mixed-valent, mixed-metal phases [(Fe,V)(III)0.5(Fe,V)0.5(II)(BDC)(OH,F)](0.5-)·0.5DMA(+) yields single-phase MIL-53-type materials, (Fe,V)(III)(BDC)(OH,F). The iron-rich, mixed-metal MIL-53 shows structural flexibility that is distinct from either the pure Fe material or the pure V material, with a thermally induced pore opening upon heating that is reversible upon cooling. In contrast, the material with a Fe:V content of 1:1 shows an irreversible expansion upon heating, akin to the pure vanadium analogue, suggesting the presence of some domains of vanadium-rich regions that can be permanently oxidized to V(IV).

Tuning the breathing behaviour of MIL-53 by cation mixing.

A mixed cation MIL-53(Cr-Fe) MOF has been obtained by direct synthesis. Multiple experimental techniques have demonstrated the presence of a genuine mixed phase, leading to a breathing behaviour different from either of the single cation analogues.

Well-studied Cu-BTC still serves surprises: evidence for facile Cu2+/Cu+ interchange.

Cu-BTC (also known as HKUST-1) is a well-characterized metal-organic framework material produced in an industrial scale and widely studied for a number of potential applications by the scientific community. The co-existence of Cu(+) and Cu(2+) entities has already been observed in this material, but the presence of Cu(+) ions was attributed to oxide impurities. The results presented here clearly demonstrate that Cu(+) ions can be present in high concentrations inside the hybrid structure. Furthermore, switching between the two copper oxidation states can be induced by redox treatments, using vacuum and/or reducing gases at different sample temperatures.

An evaluation of UiO-66 for gas-based applications.

In addition to its high thermal stability, repetitive hydration/dehydration tests have revealed that the porous zirconium terephthalate UiO-66 switches reversibly between its dehydroxylated and hydroxylated versions. The structure of its dehydroxylated form has thus been elucidated by coupling molecular simulations and X-ray powder diffraction data. Infrared measurements have shown that relatively weak acid sites are available while microcalorimetry combined with Monte Carlo simulations emphasize moderate interactions between the UiO-66 surface and a wide range of guest molecules including CH(4), CO, and CO(2). These properties, in conjunction with its significant adsorption capacity, make UiO-66 of interest for its further evaluation for CO(2) recovery in industrial applications. This global approach suggests a strategy for the evaluation of metal-organic frameworks for gas-based applications.

Factors that control zeolite L crystal size.

Time-series hydrothermal syntheses from two organic-cation-free gels with different compositions were employed to study the factors that control the final size of zeolite L crystals. The first gel had a starting K/Al ratio of 10, whereas in the second one it was three times lower. The relatively simple chemical composition of the starting gels and the combination of complementary characterization methods allowed us to track down the different stages of transformation of the initial amorphous gels into zeolite crystals and the factors that control the nucleation and growth processes. The role of the starting mixture components in the formation of the primary amorphous particles was explored. It was found that the profoundly different reaction kinetics in the two systems are caused by the difference in diffusion rates, which in turn are controlled by the extent of the polymerization reactions at room temperature during mixing of the starting components prior to hydrothermal treatment. As a consequence, nucleation is fast and ubiquitous in the first system with higher water content and K/Al ratio, whereas it is slow and sporadic in the second system with lower water content and K/Al ratio. Ultimately, these differences in the kinetics lead to the formation of two distinctly different patterns of crystal-size distribution, with a large number of small nanocrystals in the first sample and fewer large crystals in the second sample. The new findings put zeolite crystal growth on a rational basis that would enable the control of zeolite crystal size in similar organic-template-free systems.

Explanation of the adsorption of polar vapors in the highly flexible metal organic framework MIL-53(Cr).

A comparison of the adsorption of water, methanol, and ethanol polar vapors by the flexible porous chromium(III) terephthalate MIL-53(Cr) was investigated by complementary techniques including adsorption gravimetry, ex situ X-ray powder diffraction, microcalorimetry, thermal analysis, IR spectroscopy, and molecular modeling. The breathing steps observed during adsorption strongly depend on the nature of the vapor. With water, a significant contraction of the framework is observed. For the alcohols, the initial contraction is followed by an expansion of the framework. A combination of IR analysis, X-ray diffraction, and computer modeling leads to the molecular localization of the guest molecules and to the identification of the specific guest-guest and host-guest interactions. The enthalpies of adsorption, measured by microcalorimetry, show that the strength of the interactions decreases from ethanol to water. Differential scanning calorimetry experiments on an EtOH/H(2)O mixture suggest a selective adsorption of ethanol over water.

Functionalization in flexible porous solids: effects on the pore opening and the host-guest interactions.

The synthesis on the gram scale and characterization of a series of flexible functionalized iron terephthalate MIL-53(Fe) type solids are reported. Chemical groups of various polarities, hydrophilicities, and acidities (-Cl, -Br, -CF(3), -CH(3), -NH(2), -OH, -CO(2)H) were introduced through the aromatic linker, to systematically modify the pore surface. X-ray powder diffraction (XRPD), molecular simulations, thermogravimetric analyses, and in situ IR and (57)Fe Mössbauer spectrometries indicate some similarities with the pristine MIL-53(Fe) solid, with the adoption of the narrow pore form for all solids in both the hydrated and dry forms. Combined XRPD and computational structure determinations allow concluding that the geometry of the pore opening is predominantly correlated with the intraframework interactions rather than the steric hindrance of the substituent. Only (MIL-53(Fe)-(CF(3))(2)) exhibits a nitrogen accessible porosity (S(BET) approximately 100 m(2) g(-1)). The adsorption of some liquids leads to pore openings showing some very specific behaviors depending on the guest-MIL-53(Fe) framework interactions, which can be related to the energy difference between the narrow and large pore forms evaluated by molecular simulation.

Co-adsorption and separation of CO2-CH4 mixtures in the highly flexible MIL-53(Cr) MOF.

The present study attempts to understand the use of the flexible porous chromium terephthalate Cr(OH)(O(2)C-C(6)H(4)-CO(2)) denoted MIL-53(Cr) (MIL = Material from Institut Lavoisier) for the separation of mixtures of CO(2) and CH(4) at ambient temperature. The coadsorption of CO(2) and CH(4) was studied by a variety of different techniques. In situ synchrotron X-ray Powder Diffraction allowed study of the breathing of the solid upon adsorption of the gas mixtures and simultaneously measured Raman spectra yielded an estimation of the adsorbed quantities of CO(2) and CH(4), as well as a quantification of the fraction of the narrow pore (NP) and the large pore (LP) form of MIL-53. Quantitative coadsorption data were then measured by gravimetry and by breakthrough curves. In addition, computer simulation was performed to calculate the composition of the adsorbed phase in comparison with experimental equilibrium isotherms and breakthrough results. The body of results shows that the coadsorption of CO(2) and CH(4) leads to a similar breathing of MIL-53(Cr) as with pure CO(2). The breathing is mainly controlled by the partial pressure of CO(2), but increasing the CH(4) content progressively decreases the transformation of LP to NP. CH(4) seems to be excluded from the NP form, which is filled exclusively by CO(2) molecules. The consequences in terms of CO(2)/CH(4) selectivity and the possible use of MIL-53(Cr) in a PSA process are discussed.

Relations between structure, acidity, and activity of WOx/TiO2: influence of the initial state of the support, titanium oxyhydroxide, or titanium oxide.

Two series of WO(x)/TiO(2) catalysts, containing W surface densities up to 4.4 W atoms/nm(2), were prepared by pore volume impregnation of two different supports, titanium oxyhydroxide (amorphous) or titanium oxide (crystallized, 100% anatase). The influence of W surface density and the nature of the support on the surface structure, development of the acidity, and catalytic performances were examined. The texture and structure of the catalysts were investigated by Brunauer-Emmett-Teller measurements, X-ray diffraction (XRD), and Raman and infrared spectroscopy. The catalytic activity was tested for 2-propanol dehydration and n-hexane isomerization. For catalysts obtained by impregnation of titanium oxide, XRD and Raman results showed that W was present as a surface phase. Infrared spectra indicated an increase in the degree of polymerization of W species with increasing W surface density. CO and lutidine adsorption, followed by infrared spectroscopy, showed an increase in the strength and abundance of Brønsted acid sites (measured after lutidine desorption at 573 K) with the W surface density above a threshold of 1.3 W atoms/nm(2). The development of Brønsted acidity correlated with the evolution of the infrared bands attributed to polymerized W species. A direct relationship was observed between the concentration of Brønsted acid sites and the catalytic activity for 2-propanol dehydration. Catalytic activity, for n-hexane isomerization, appears to be associated with the presence of highly condensed W species. The catalysts synthesized by impregnation of titanium oxyhydroxide exhibited a comparable behavior. Hence, for a given W surface density, the W surface structure, concentration of Brønsted acid sites, and catalytic performances were similar. Thus, no significant effect of the initial form of the support (titanium oxyhydroxide versus titanium oxide; 100% anatase) was evidenced.

A comparative study of the surface structure, acidity, and catalytic performance of tungstated zirconia prepared from crystalline zirconia or amorphous zirconium oxyhydroxide.

Tungstated zirconias prepared from W deposition on zirconium oxyhydroxide are reportedly active for alkane isomerization, whereas solids synthesized by impregnation of zirconia are inactive. The origin of the differences between the two preparations is not fully understood. The present paper examines the influence of W surface density and the nature of the support on the surface structure, development of the acidity, and catalytic performance of WO(x)()/ ZrO(2) catalysts. Two series of catalysts containing W surface densities up to 5.2 at. W/nm(2) were prepared by pore volume impregnation of two different supports: zirconium oxyhydroxide and predominantly tetragonal zirconia (65% tetragonal, 35% monoclinic). The texture and structure of the catalysts were investigated by BET measurements, X-ray diffraction, Raman and infrared spectroscopy. The catalytic activity was tested for 2-propanol dehydration and n-hexane isomerization. For catalysts obtained by impregnation of Zr oxyhydroxide, Raman results showed that W was present as a surface phase. Infrared spectra indicated an increase in the degree of polymerization of W species with increasing W surface density. The development of the acidity was monitored by lutidine adsorption and desorption at 523 K, followed by infrared spectroscopy. The results indicated the presence of a threshold of W surface density at 1.3 at. W/ nm(2) for the detection of these acid sites, followed by a progressive increase in their abundance with increasing W surface density. The development of Brønsted acidity correlated with the evolution of the infrared bands attributed to "extensively" polymerized W species. A direct relationship was observed between the abundance of Brønsted acid sites and the catalytic activity for 2-propanol dehydration. For n-hexane isomerization, compared to 2-propanol dehydration, a higher threshold of W surface densities (3.4 at. W/ nm(2)) for the development of activity was observed. The difference was attributed to stronger Brønsted acid sites required for n-hexane isomerization. The catalysts prepared by impregnation of zirconia exhibited comparable behavior. For a given W surface density, the crystalline composition of the support (tetragonal/monoclinic zirconia), the W surface structure, abundance of Brønsted acid sites, and catalytic performance were similar. Thus, in an apparent variance with some of the results reported in the literature with respect to the influence of preparation methods, no significant effect of the initial form of the support (Zr oxyhydroxide versus predominantly tetragonal zirconia) was evidenced.