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The characterization of acid sites on solid catalysts is a key to understanding reaction mechanisms at the molecular level.

International audience; The direct synthesis of Dimethyl carbonate (DMC) from methanol and CO 2 is a green process which allows CO 2 valorization. Among efficient catalysts, ceria, zirconia and cerium-zirconium mixed oxides are often reported as the most active catalysts. In a recent report, we discovered that ceriumzirconium mixed oxides prepared by Flame Spray Pyrolysis (FSP) show greater catalytic activities than those prepared by precipitation, although both exhibit very similar surface area and bulk features. The objective of this study was to find out the origins of the superior catalytic activities obtained by flame spray pyrolysis synthesis method by a deeper analysis of bulk and surface properties. We have opted to focus on mixed ceria-zirconia of equimolar composition (Ce 0.5 Zr 0.5 O 2) as it exhibits maximum catalytic activity for both synthesis methods. Combining bulk and surface characterization as well as surface adsorption measurements using probe molecules, we propose that flame spray pyrolysis enables a surface enrichment in cerium oxide still in interaction with zirconium oxide that leads to a high concentration of adsorbed methanol at the surface, which might explain the greater activity of the catalysts prepared using this method. Beyond the application of DMC synthesis, we can anticipate that Flame Spray Pyrolysis synthesis should generate relative high surface area mixed oxides with different catalytic performances with respect to mixed oxides prepared at lower temperature owing their metastable nature.

RMN+ECI2D:ING+FWI:AGH:YMO:CLO:DFA:JEC; International audience; Herein, we report the molecular-level structuration of two full photosystems into conjugated porous organic polymers. The strategy of heterogenization gives rise to photosystems which are still fully active after 4 days of continuous illumination. Those materials catalyse the carbon dioxide photoreduction driven by visible light to produce up to three grams of formate per gram of catalyst. The covalent tethering of the two active sites into a singleframework is shown to play a key role in the visible light activation of the catalyst. The unprecedented long-term efficiency arises from an optimal photoinduced electron transfer from the light harvesting moiety to the catalytic site as anticipated by quantum mechanical calculations and evidenced by in-situ ultrafast time-resolved spectroscopy.

Heterogenization of molecular catalysts via their immobilization within extended structures often results in a lowering of their catalytic properties due to a change in their coordination sphere. Metal–organic polyhedra (MOP) are an emerging class of well-defined hybrid compounds with a high number of accessible metal sites organized around an inner cavity, making them appealing candidates for catalytic applications. Here, we demonstrate a design strategy that enhances the catalytic properties of dirhodium paddlewheels heterogenized within MOP (Rh-MOP) and their three-dimensional assembled supramolecular structures, which proved to be very efficient catalysts for the selective photochemical reduction of carbon dioxide to formic acid. Surprisingly, the catalytic activity per Rh atom is higher in the supramolecular structures than in its molecular sub-unit Rh-MOP or in the Rh-metal–organic framework (Rh-MOF) and yields turnover frequencies of up to 60 h–1 and production rates of approx. 76 mmole formic acid per gram of the catalyst per hour, unprecedented in heterogeneous photocatalysis. The enhanced catalytic activity is investigated by X-ray photoelectron spectroscopy and electrochemical characterization, showing that self-assembly into supramolecular polymers increases the electron density on the active site, making the overall reaction thermodynamically more favorable. The catalyst can be recycled without loss of activity and with no change of its molecular structure as shown by pair distribution function analysis. These results demonstrate the high potential of MOP as catalysts for the photoreduction of CO2 and open a new perspective for the electronic design of discrete molecular architectures with accessible metal sites for the production of solar fuels.

Heterogenization of molecular catalysts via their immobilization within extended structures often results in a lowering of their catalytic properties due to a change in their coordination sphere. Metal-organic polyhedra (MOP) are an emerging class of well-defined hybrid compounds with a high number of accessible metal sites organized around an inner cavity, making them appealing candidates for catalytic applications. Here, we demonstrate a design strategy that enhances the catalytic properties of dirhodium paddlewheels heterogenized within MOP (Rh-MOP) and their three-dimensional assembled supramolecular structures, which proved to be very efficient catalysts for the selective photochemical reduction of carbon dioxide to formic acid. Surprisingly, the catalytic activity per Rh atom is higher in the supramolecular structures than in its molecular sub-unit Rh-MOP or in the Rh-metal-organic framework (Rh-MOF) and yields turnover frequencies of up to 60 h

The multiscale porosity of hierarchical zeolite materials is analyzed through advanced adsorption-based characterization in conjunction with additional techniques including electron tomography.

SSCI-VIDE+ING+CDA:YSC:DFA; International audience; The direct synthesis of dimethyl carbonate from methanol and CO2 is particularly attractive as it provides a green alternative to other routes while allowing CO2 conversion. Although the evaluation of catalyst formulations figures prominently in the literature, one can hardly identify which formulations are the most active. One of the reasons is that there is no standard testing protocol. Initial water content in the reactive mixture is critical as it can drag down thermodynamic equilibrium. This study aims to rank catalyst activities and to identify the most active catalysts using a systematic protocol for the measurement of the true catalytic activity. Based on an assessment of critical parameters, a protocol for the measurement of the activity in the liquid phase, taking care to the limitation induced by thermodynamic equilibrium, was developed. Special attention was paid to the quantitative assessment of critical experimental parameters. Following the protocol, a screening of various pure and mixed oxides of about 60 different solids was carried out. Finally, an optimization study was carried out on Zr-Ce mixed oxides produced by different synthesis methods, leading to the discovery of the catalyst which, to the best of our knowledge, is the most active reported so far.

Conventional solid oxide fuel cells (SOFCs) could suffer from carbon deposition when fueled with hydrocarbons. For comparison, a new type of SOFC with porous electrolyte can resist carbon deposition because it allows oxygen molecules to transport from the cathode to the anode. As the transport of O2 to the anode lowers the fuel cell performance and causes the risk of explosion, the rate of O2 transport must be well controlled to ensure efficient and safe operation. Following our previous model, this paper focuses on electrolyte porosity optimization under various inlet methane mole fractions, inlet oxygen mole fractions and inlet gas flow rates. Furthermore, a new design with a partial porous electrolyte is proposed and numerically evaluated. The new design significantly improves the electrochemical performance compared with all-porous one. A conversion rate >90% from methane to syngas is achieved at the 0.33 inlet CH4 mole fraction with the new design. The results enhance the understanding of all porous solid oxide fuel cells and the mechanism underlying, inspiring novel designs of solid oxide fuel cells.

International audience; Bridging the gap between kinetic model conception and catalyst design is targeted in catalytic naphtha reforming process development. New catalysts are continuously optimised in order to achieve higher selectivity in C5+ products. An adequate description of catalytic transformations by the kinetic models would therefore provide clues for catalyst design and accelerate the time to market implementation of process simulators. This study investigates the influence of site density and location on n-heptane reforming selectivity. It identifies the nature of the limiting steps for the different reforming pathways on a broad range of catalyst formulations. A common lumped model using power law kinetics is developed to describe already published experimental observations on the set of selected catalysts. Linear free energy relationships are used in order to handle a reduced number of statistically relevant adjustable parameters. The dependence between reference rate constants and active phase formulation is then unravelled. Unexpected results indicate that chlorine content and repartition at the crystallite scale affects the hydrogenolysis activity. Within the range of tested formulations, this study suggests that hydroisomerisation reactions are limited by acid sites transformations whereas the aromatisation pathways seem to proceed through a metal/acid bi-functional scheme. The further elaboration of a kinetic model that is able to predict the effect of an industrial catalyst active phase formulation change in full naphtha cut reforming lies beyond the scope of this article.

A simple kinetic model based on the zeolite acid strength, the number of Brønsted acid sites, and the catalyst efficiency was developed for the cracking of n-hexane. A series of HY zeolites with a mesopore volume from 0.04 to 0.32 cm3/g was synthesized and characterized by various physical-chemical methods and tested for n-hexane cracking. The generation of mesoporosity influenced several other important parameters, such as acidity and extra-framework aluminum. Zero-length column diffusion measurements for mesitylene showed a large decrease in the characteristic diffusion time upon the introduction of mesoporosity, which changed only slightly with a further increase in mesoporosity. Similar n-hexane physisorption enthalpies were measured for all samples. The highest initial activity for n-hexane cracking per catalyst volume was observed for the sample with an intermediate mesopore volume of 0.15 cm3/g. The three mesoporous H-USY zeolites showed the same value of the intrinsic rate constant and the same activation energy. The difference in initial activity of the mesoporous zeolites was caused by the difference in the number of Brønsted acid sites. The increase in initial activity for the mesoporous zeolites compared to a microporous zeolite was caused by an increase in the acid strength.

fff; International audience; The design of efficient separation and catalytic processes in nanoporous adsorbents requires to finely tune gas adsorption in their porosity. Here, using a large set of Si-rich zeolites (Silicalite-1, Beta, Chabazite, ITQ-13), we report on an experimental study of vapor adsorption in zeolites showing the pivotal role of the hydroxyl concentration. By studying the adsorption of water and methanol in zeolites assisted with in situ IR and 29 Si NMR measurements, we find that adsorption switches from non-wetting to wetting as the hydroxyl surface density reaches the same critical value ~2.5 OH/nm2. While this hydroxyl concentration-induced crossover is well-known for water, we extend here the concept of a critical concentration by showing that a consistent picture arises when different polar substrates are considered. In particular, by establishing a generic behavior between the two protic substrates (H2O, MeOH), we pave the way for the rational design of hydrophobic adsorbents

International audience; Nano-zeolites and hierarchical zeolites have shown enhanced transport properties that are generally attributed to a shorter diffusion path length (L). However, the concomitant increase in the external surface of these types of zeolites may also affect overall transport as the interfaces may act as diffusion barriers. Recently, hollow zeolite crystals have been presented as an alternative zeolite morphology. They possess a large inner cavity and an overall size and shape similar to those of plain microporous zeolite. In contrast to classic hierarchical zeolite materials, the inner cavity of the hollow zeolite induces a shortened diffusion path length with no effect on external surface area. In this work, we have studied the impact of diffusion path length on transport properties by comparing the characteristic time of transport of hydrocarbons in plain zeolite crystals and their hollow counterparts, using zero-length column (ZLC) measurements. Our results show that hollow morphology doubles or quadruples the transport speed for Silicalite-1 and Beta zeolites, respectively. Compared to other reports focusing on nanosized or hierarchical zeolites, this study is free of any bias due to major modifications in external surface area, because hollow and plain zeolites have very similar crystal dimensions.

SSCI-VIDE+ING+OSA:VPT:DFA:FMO; International audience; The synthesis of 19 carefully selected Pt/γ‐Al2O3−Cl formulations was followed by high‐throughput catalytic testing in order to unravel the effect of an active phase formulation change on n ‐heptane reforming performances. Pt/γ‐Al2O3−Cl catalysts were prepared with different Pt (0.3–1 %wt) and Cl (0.1–1.4 %wt) contents and using two γ‐Al2O3 supports so that both sites concentrations and sites locations at the crystallite surface vary among the catalyst pool. Catalytic tests were conducted in mild conditions for a comparison of catalysts in kinetic regime. Results show that Pt and Cl concentrations control the competition between hydroisomerisation, hydrogenolysis and hydrocracking pathways. Aromatisation, on the contrary, is poorly affected by formulation changes. Non‐monotonous trends linking Pt/Cl ratio to isomerisation selectivity are found for both γ‐Al2O3 supports. This study provides new insights for the description of bi‐functional transformations in catalytic naphtha reforming.

SSCI-VIDE+ING+YKH:DFA; International audience; We report herein the upscaled synthesis and shaping of UiO66-COOH for NH3 air purification. The synthesis of the zirconium-based MOF was carried out in a batch reactor in an aqueous suspension with a yield of 89% and a space-time yield of 350 kg/day/m3. Neither toxic chemicals nor organic solvents were used, allowing this MOF to be employed in individual or collective air purification devices. Freeze-granulation and extrusion shaping techniques were investigated. The NH3 air purification performances of UiO66-COOH in bead, tablet and extrudate forms were compared to those of commercial carbon based materials (type K adsorbents from3M and Norit). Testing conditions were chosen to reflect current standards for ammonia concentration (600–1200 ppm) and velocity. In addition, the breakthrough measurements were carried out at three different relative humidity levels (0%, 40%, and 70%). Pellets and extrudates of UiO66-COOH outperformed commercial benchmark adsorbents in all conditions, especially in dry conditions, for which the commercial adsorbents suffered impaired ammonia uptake and shortened service life. Extrudates of UiO66-COOH also withstood attrition after intensive shaking.

SSCI-VIDE+ING+DLP:CTH:ATU:DFA:FRM; International audience; The steam reforming of methane was studied over Rh and Ni-based catalysts exposed to naphthalene, which was used as a representative of polyaromatic tars found in biomass-derived biogas. In particular, two Ni-based samples in which part of the metal was encapsulated within silicalite-1 nanoboxes were tested. The reforming reaction was carried at 700, 800 and 900 degrees C using a model feed and high space velocities to limit methane full conversion and better evidence any deactivation. A strong decrease of methane conversion was observed in the presence of 1400 ppm of naphthalene, stressing the marked deleterious effect of this molecule in the present conditions. The effect of naphthalene was partly reversible, especially at higher temperatures. The silicalite-1 membrane could not prevent the deactivation of embedded nickel particles, probably because naphthalene (kinetic diameter = 0.62 nm) could diffuse throughout the MFI-type (pore diameter ca. 0.56 nm) porous layer at the high reaction temperatures used. The effect of 5 ppm of the bulkier pyrene (kinetic diameter = 0.74 nm) was investigated at 700 degrees C and also led to a rapid deactivation of the Ni@silicalite-1, likely because pyrene was cracked into naphthalene, which could then enter the silicalite-1 nanoboxes. The poisoning effect of toluene on the Ni-based catalysts was minor in comparison to that induced by the polyaromatics. A marked sintering of the embedded Ni was also observed. (C) 2016 Elsevier B.V. All rights reserved.

Electron tomography in transmission electron microscopy provides valuable three-dimensional structural, morphological and chemical information of condensed matter at nanoscale. Current image acquisitions require at least tens of minutes, which prohibits the analysis of nano-objects evolving rapidly such as under dynamic environmental conditions. Reducing the acquisition duration to tens of seconds or less permits to follow in 3D the same object during its evolution under varying temperatures and pressures. We report Operando Electron nanotomography using image series acquired in less than 230 seconds instead of typically 15 min in the best cases so far. The in situ calcination of silica zeolites encaging silver nanoparticles, a catalytic nanosystem of potential interest for, e.g., nuclear waste treatments or selective heterogeneous catalysis, was successfully studied. Kinetic environmental Operando 3D electron microscopy becomes possible, as well as real time observation of beam sensitive samples (polymers, biological objects) without prior preparation, which reduces their contrast and reactivity.

SSCI-VIDE+ING+DLP:ATU:DFA:FRM; International audience; Undesired metal nanoparticles located outside zeolite nanoboxes (hollow zeolites) can be formed during the preparation of zeolite-embedded metal nanoparticles. The present work demonstrates that it is possible to use citric acid to selectively leach outmost of the external Ni nanoparticles from a Ni@silicalite-1 material. The leached sample exhibited an improved selectivity in the hydrogenation of toluene as compared to that of the bulkier mesitylene. (C) 2017 Elsevier B.V. All rights reserved.

Metal-Organic Frameworks (MOFs), thanks to their type V water adsorption isotherms ("S-Shape") and large water capacities, are considered as potential breakthrough adsorbents for heat-pump applications. In particular, Al(OH)-fumarate could enable efficient regeneration at a lower temperature than silica-gel which would allow us to address the conversion of waste heat at low temperature such as found in data centers. Despite its greater adsorption capacity features, heat and mass transport limitations could jeopardize the potential performance of Al(OH)-fumarate. Heat and mass transport depend on the size of the bodies (mm range), their packing and on the pore structures, i.e. macro-mesopore volumes and sizes. This paper describes the cost-efficient and scalable synthesis and shaping processes of Al(OH)-fumarate beads of various sizes appropriate for use in water Adsorption Heat-Pumps (AHPs). The objective was to study transport limitations (i.e. mass and heat) in practical e beads which meet mechanical stability requirements. Dynamic data at the grain scale was obtained by the Large Temperature Jump method while dynamic data at the adsorber scale was obtained on a heat exchanger filled with more than 1 kg of Al(OH)-fumarate beads. Whereas the binder content had little impact on mass and heat transfer in this study, we found that Knudsen diffusion in mesopores of the grain may be the main limiting factor at the grain scale. At the adsorber scale, heat-transfer within the bed packing as well as to the heat exchanger is likely responsible for the slow adsorption and desorption kinetics which have been observed for very low desorption temperature. Finally, the dynamic aspects of the observed water adsorption isotherm shift with temperature are discussed in light of reported reversible structure modification upon temperature triggered water adsorption-desorption.

SSCI-VIDE+ING+OSA:DFA; International audience; Several major refining catalytic processes show a strong dependence of overall performances upon catalyst formulations and their structure. This observation is particularly true in naphtha catalytic reforming for which the product distribution is sensitive to slight changes in active phase formulations. This review presents different issues encountered in naphtha reforming that are related to active phase formulation changes. Two research and development approaches are usually proposed. (i) Rationalise the development of new catalytic formulations in order to increase selectivity towads valuable products. (ii) Design simulators that would guide operation in order to maintain process performances. Current limitations to a faster process development come from the disjunction between kinetic modelling and catalyst optimisation. This critical review is not an extensive analysis of existing naphtha reforming kinetic modelling methodologies or advances in catalytic behaviour elucidation. Rather, it proposes an original and pragmatic process development approach aimed at merging catalyst development with kinetic modelling through the identification of “effective” and “measurable” catalytic descriptors. The specificities of the structure–property relationships of naphtha reforming catalysts are reviewed and taken into account in order to list potential catalytic descriptors for this process. A focus is made on a current bottleneck faced in the description of the active phase which lies in understanding the role of the proximity and the interaction between acid and metallic sites in the balance between different bi-functional pathways. A variety of experimental approaches that can be used to measure these naphtha reforming active phase catalytic descriptors are presented and compared.

MICROSCOPIE+ING+LBU:DFA:ATU; International audience; The present work examines the different parameters that affect desilication of nanometric Beta zeolite crystals in alkaline solutions. The influences of different synthesis parameters such as the nature of the zeolite (size of the crystals, composition), the alkalinity, the temperature and the amount of added Al species on the morphology and properties of hollow structures are discussed. Addition of sodium aluminate to the alkaline solution protects the surface from desilication and favors dissolution at the center of the crystals, leading to the formation of hollow structures. The size, morphology and crystallinity of those structures depend mainly on zeolite composition, treatment temperature and alkalinity of the solution. If hollow structures are totally amorphous when desilication is carried out under stirring, their crystallinity and thermal stability are significantly improved in the presence of tetraethyammonium (TEA+) cations.

Oversolubility effects refer to a large increase of the solubility of gases in liquids confined in nanoporous solids with respect to the value predicted by Henry's law. This review presents the state of the art of oversolubility by discussing the molecular mechanisms responsible for such effects and the conditions for their observation. Both experimental and theoretical approaches are reviewed, in a non-exhaustive fashion, with special emphasis on results that have helped to unravel the oversolubility phenomenon. Different porous materials including metal-organic frameworks (MOF), ordered porous silicas, and zeolites are considered in combination with various nanoconfined liquids and gases relevant to practical applications in energy and environmental science. Depending on the gas/liquid/solid system considered, oversolubility is shown to pertain either to adsorption (increased concentration at solid/gas and liquid/gas interfaces) or to confinement-induced solubility increase. We also critically discuss when oversolubility effects are expected to lead to improved performance in catalysis or environmental applications such as for air purification.

The molecular-level structuration of two full photosystems into conjugated porous organic polymers is reported. The strategy of heterogenization gives rise to photosystems which are still fully active after 4 days of continuous illumination. Those materials catalyze the carbon dioxide photoreduction driven by visible light to produce up to three grams of formate per gram of catalyst. The covalent tethering of the two active sites into a single framework is shown to play a key role in the visible light activation of the catalyst. The unprecedented long-term efficiency arises from an optimal photoinduced electron transfer from the light harvesting moiety to the catalytic site as anticipated by quantum mechanical calculations and evidenced by in situ ultrafast time-resolved spectroscopy.

Silver nanoparticles are currently one of the most studied nanostructured nanomaterials. Because nanoparticle size and dispersion act together in determining a material&rsquo, s physical and chemical properties, there is a continuous quest to develop size-controlled synthesis methods. Nonetheless, the instability of the nanometer-sized particles, which is caused by their tendency to aggregate irreversibly into larger particles, remains a recurrent problem. The use of confining scaffolds, such as the regular system of cages in a crystalline zeolite-type material, is often reported in the literature as an efficient solution to overcome particle migration at the surface. Silver nanoparticles encapsulated in ZSM-5 (Ag@ZSM-5) represent a new generation of adsorbent for Xe enrichment from the atmosphere that is currently being developed at the pilot scale in a Temperature Swing Adsorption (TSA) process. In this study, we have found that the presence of Cl-containing compounds in the air (VOCs) leads to a poisoning of the active silver phase by the formation of silver chloride. By a careful study of process parameters, we have found that most of the chlorine can be removed by heat treatment above 573 K so that the adsorption properties of silver are regenerated. That said, when applying 573 K temperature regeneration at the pilot scale, we observe a very minor but observable decay of xenon adsorption capacity that continues cycle after cycle. The mechanism of capacity decay is discussed in terms of (i) the residual presence of Cl at the surface of silver nanoparticles, (ii) the aggregation of silver nanoparticles into larger particles (sintering mechanism), and (iii) the acceleration of silver particle migration to the surface and sintering.

SSCI-VIDE+ING+CDA:DFA; International audience; In this work we provide a detailed study on grafting reactions of various dialkylphosphonate-based ILs. A special attention has been devoted to a comprehensive investigation on how the nature of the anion, and the organic spacer composition (hydrophilic or hydrophobic groups) could impact on the grafting densities and bonding modes of phosphonate-based ILs anchored to  alumina (-Al2O3) powders. For the first time, the bonding of phosphonate-based ILs with only surface hexacoordinated aluminum nuclei was established using both solid-state 31P-27Al D HMQC and 31P NMR experiments. It has been demonstrated that the grafting of dialkylphosphonate-based ILs is competing with a hydrolysis and/or precipitation process which could be attactively hindered by changing the anion nature: bis(trifluoromethane) sulfonylimide anion instead of bromide. In additon, independently of the chosen spacer, similar reaction conditions led to equivalent grafting densities with different bonding modes configuration. The CO2 physisorption analysis on both pure ILs and grafted ILs on alumina powders confirmed that the initial sorption properties of ILs do not change upon grafting, thus confirming the attractive potential of as-grafted ILs for the preparation of hybrid materials in a form of selective adsorbers or membranes for CO2 separation applications.

Whereas the synthesis principles of supported metal catalysts are well documented in the open literature, impregnation protocols on shaped bodies represent sensitive industrial know-how and are, therefore, rarely found. We investigated various synthesis parameters for both wetness (WI) and dry (DI) impregnations to prepare Pd/&gamma, &ndash, Al2O3 alumina beads. Two kinds of catalysts were achieved: homogeneously dispersed catalysts with no metal gradient across the beads and eggshell catalysts. A combination of optical images, Castaing microprobe analysis, elemental analysis, and TEM made it possible to discriminate between catalysts according to their metal loading, location across the bead diameter, and metal dispersion. Regardless of the macropore structure of the alumina beads, we found that volatile solvents (acetone) were preferred for preparing homogeneous catalysts by WI, whereas the use of a viscous aqueous solution (water/glycerol) in DI resulted in an eggshell-type catalyst. The atomic layer deposition (ALD) method was also investigated as a physical vapor phase deposition method for preparing eggshell catalysts. Representative-shaped catalysts were tested for CO oxidation as a model reaction in order to highlight the differences between catalysts with a homogeneous metal distribution (no metal gradient) and eggshell-type.

SSCI-VIDE+ING+DFA; International audience; Experiment and molecular simulation are used to investigate adsorption in heterogeneous porous media consisting of hierarchical solids (combining different porosity scales) or composite solids (such as silver nanoparticles adsorbed at the external surface of zeolite). It is shown that adsorption in such heterogeneous materials can be written as a linear combination of the adsorption isotherms in its different domains (i.e. porosity scales for the hierarchical sample and constituents for the composite sample). In the case of the composite material, we also show that the linear combination can be used with weighing parameters obtained for a different adsorbate. Such a superimposition principle, which is validated using well-characterized experimental samples, is of interest for characterization purpose as well as industrial applications as they can be used to determine accurately the amount of phases in a given sample (volume corresponding to a given porosity scale or constituent). In contrast, significant departure between the experimental adsorption isotherm and the linear combination can be used to detect coupling effects between the different domains or restrained access to a given domain type. Such a characterization strategy of complex heterogeneous media is complementary to other experiments, such as those probing capillary hysteresis shapes, scanning curves and subloops, which allow determining the distribution of domains within the framework of the independent domain theory. (C) 2016 Elsevier Inc. All rights reserved.

The development of gas separation processes dealing with very low concentration ranges is a rapidly growing domain with key applications such as trace detection, air purification from harmful pollu...

SSCI-VIDE+ING+FRM:DFA:ATU; International audience; The aim of the present work is to synthesize a zeolite‐based catalyst with a hollow morphology and highly dispersed metal nanoparticles (NPs) encapsulated inside the zeolite micropores. For this purpose, we have studied a treatment using tetraalkylammonium (TAA) bromides for the selective removal of a large Pt particle from the outer surface of a hollow Beta zeolite. TEM analysis reveals that we succeeded in the synthesis of a hollow beta zeolite single crystal with encapsulated particles, with a high dispersion of 50–60 %. The molecular‐sieve‐type mechanism of the obtained catalysts was evaluated in the model reaction of toluene and mesitylene catalytic hydrogenation. Thanks to the high dispersion. a 10‐fold activity enhancement has been obtained with respect to hollow beta zeolites with encapsulated NPs recently described in the literature.

Hollow Y zeolite single crystals have been obtained from a conventional NaY zeolite following a three-step process involving a severe dealumination of the zeolite with silicon tetrachloride (step #1), followed by an acid washing under mild conditions (step #2) and finally a selective dissolution of the crystals core in the presence of protective Al species (step #3). Crystals are characterized by the presence of a regular internal cavity with 0.1–0.2 nm thick microporous walls. They contain a relatively low framework Al content but significant amounts of extraframework Al oxide species mainly located on the external surface of the crystals. Hollow crystals have been mixed with a Pt-supported alumina binder and used as catalysts in the hydroisomerization of n-hexadecane. Compared to the corresponding bulk crystals obtained after step #2, their higher activity has been attributed to a better efficiency, directly resulting from the presence of the cavity.

SSCI-VIDE+ING+CPG:FRM:YSC:ATU:DFA; International audience; Pt/NaY zeolites with bulk and hollow morphologies have been used as model catalysts in the hydrogenation of cyclohexene as model reaction. In contrast to most hierarchical zeolites, the presence of a single internal cavity modifies only the mean diffusion length, without changing the external surface area and the crystal size. Differences in catalytic activities have been attributed to a shorter diffusion length in hollow crystals. The volume fraction of zeolite used in bulk crystals (ca. 0.63–0.70) matches well with the shell thickness in hollow crystals, leading to an efficiency factor value for the latter close to 1.

International audience; Streamlining the xylene separation process on faujasites is a promising way to design innovative adsorbents for this application. For this purpose, we present herein an original quantitative structure–property relationship (QSPR) approach. It deals with the development of a multi-linear predictive model correlating the separation properties with a set of structural descriptors for the adsorbents. The implementation of such an approach makes it necessary to (i) set an appropriate design of experiment (DOE), (ii) prepare an adsorbent database, (iii) test the adsorbent database for xylene separation and (iv) compute a set of relevant descriptors. The selected descriptors essentially characterize the nature of the confinement in the faujasite supercage, i.e., the size of the cations localized in adsorption sites II, as well as the occupancy ratio of both adsorption sites II and III. Two different statistical methods were applied to develop a structure–property relationship model linking experimental selectivity and the set of descriptors. A multiple linear regression model enables the prediction of para/meta-xylene selectivity with a correlation coefficient R2 of 0.78, while a linear discriminant analysis predicts the assignment of the adsorbents to four identified classes with a total prediction percentage of 76%.

SSCI-VIDE+ING+CPG:ATU:DFA; International audience; Highly crystalline hollow Y zeolite has been obtained by post-synthesis modification of conventional NaY crystals. The top-down transformation involves substantial dealumination of the zeolite framework by silicon tetrachloride followed by acid leaching and finally selective dissolution of the crystal core in the presence of protective aluminium species. The formation of internal cavities depends on the extent of dealumination of the zeolite as well as on the efficiency to remove extraframework Al species prior to realumination. Hollow Y zeolite crystals possess more or less regular internal cavities of ca. 0.8 μm diameter with external size and shape similar to those of the original NaY crystals. They differ from those recently reported in the literature by much higher Si/Al ratios, higher crystallinities and pure microporous shells of ca. 0.12 μm thickness. As a result of these differences, the family of hollow faujasites is significantly enlarged towards more siliceous and less defective materials. Their formation is most likely based on the presence of an Al-rich surface generated by NaAlO2 species during the last stage of the process, which protects the outer parts of the crystals from desilication.

SSCI-VIDE+CARE:CDFA+MBE:PVE; International audience; We report the supercell crystal structure of a ZIF-8 analog substituted imidazolate metal–organic framework (SIM-1) obtained by combining solid-state nuclear magnetic resonance and powder X-ray diffraction experiments with density functional theory calculations

SSCI-VIDE+ING+CPG:ATU:DFA; International audience; Hollow polycrystalline Y zeolite spheres have been obtained by combining zeolite crystallization and selective dissolution steps. Beta-Y core shell composites were first obtained by hydrothermal recrystallization of a synthesis mixture containing as-made Beta crystals in the presence of Y zeolite seeds. Under such conditions, Beta zeolite crystals served not only as cores but they also progressively dissolved and provided the necessary Si species for the formation of the shell. The proportion of Beta zeolite remaining in the composite strongly depended on the composition of the solution, in particular the amount of Al and the alkalinity. It could not be decreased below 45–50 wt. % without formation of contaminating phases, mainly zeolites with GME, GIS and LTA topologies. Successive additions of Al could significantly reduce the amount of Beta zeolite in the composite but to the detriment of faujasite crystal size. Hollow shells with less than 10 wt. % Beta have been obtained by selective removal of Beta zeolite from a composite containing 20 wt. % Beta and obtained after two successive recrystallizations in the presence of aluminum. These shells are built up from faujasite nanocrystals with a high silicon content, making them potentially interesting in diffusion-limited catalytic reactions.

SSCI-VIDE+ING+FWI:YMO:DFA:JEC; International audience; Herein, we report the synthesis of two bipyridine‐based porous polymers and their use as platforms for the heterogenization of pentamethylcyclopentadienylrhodium catalytic species. These highly stable heterogeneous catalysts demonstrate their efficiency in the transfer hydrogenation of α‐aryl ketones. Moreover, we show that their catalytic activity is similar to that of homogeneous analogues, highlighting the absence of diffusion limitations in the solids. We rationalize the differences in the measured activities by using the Hammett parameter as a descriptor of the electronic environment of the catalytic site in both homogeneous and heterogeneous systems.

XPS+ING+FWI:LCS:YMO:DFA:JEC; International audience; Here we present a series of heterogeneous catalysts based on metal–organic frameworks and microporous polymers used as macroligands for heterogenized organometallic complexes. We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity. This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The rational design of heterogenized catalysts can thus be guided by molecular chemistry rules. The conception of highly efficient heterogeneous catalyst based on porous polymer support and driven by the Hammett parameter of bipyridine-chelating macroligand is demonstrated here for the Rh-catalyzed photoreduction of carbon dioxide with turnover frequencies up to 28 h–1, among the highest reported for heterogeneous photocatalytic formate production.

Zeolitic imidazolate framework ZIF-93 was synthesized from a stoichiometric mixture of metal–ligand in aqueous solutions at room temperature, yielding 80% of pure product. The characterization of the material confirmed the formation of a material having the same properties as the one obtained previously by a solvothermal method in the DMF route. This method is very promising for the efficient and environmentally friendly synthesis of ZIFs for CO2 capture application, proved by breakthrough experiments of binary CO2/N2 mixtures. EVRF thanks MINECO for his Ramon y Cajal fellowship RYC-2012-11427 and the following project MAT2016-81732-ERC and Generalitat Valenciana for the project PROMETEOII/2014/004.

SSCI-VIDE+ING+YKH:DFA; International audience; Air purification of ammonia, a toxic industrial chemicals (TICs), by adsorption process on Metal-Organic Framework solids is attracting high scientific and commercial interests. While active carbon based adsorbents required high level of relative humidity for achieving proper performance ammonia capture, zeolite performance degrades in presence of humidity. For MOFs, the presence of humidity has been shown to be MOF dependent, either beneficial or detrimental. It appears that the role of humidity is of key importance and that different ammonia adsorption mechanisms co-exist depending on the material's physico-chemical features. Based on a screening of various microporous adsorbents including carbons, zeolites and MOFs, we show that in the presence of humidity, the ammonia uptake mostly follows the Henry law of ammonia solubilization in water. At the exception of Copper based MOF, the ammonia capture is mostly correlated with the amount of “condensed water” in the micropore. We also generally observe a systematic higher uptake than the Henry law which can be attributed to the effect of confinement i. e surface-condensed phase interaction.

We present a Pt@Beta catalyst with a unique, well-controlled location of metal nanoparticles that allows more efficient use of this rare, expensive metal in catalysis. The zeolite crystal has an inner cavity, leaving a thin zeolite shell where the metal nanoparticles are encapsulated, thereby ensuring a relatively small diffusional path length and high selectivity. Hollow Beta is obtained by a controlled dissolution–recrystallization method. The location of the particles not only was revealed by electron tomography 3D reconstruction but was further confirmed by a model hydrogenation reaction of aromatics.

The all porous solid oxide fuel cell concept is proposed to solve the carbon deposition problem of solid oxide fuel cells. The transport of oxygen molecules from the cathode to the fuel side through the porous electrolyte can resist carbon deposition but could reduce the fuel cell performance. In this paper, a two-dimensional model for all porous solid oxide button cells is developed for the first time. After model validation with experimental data, the model is then extended for a tubular cell for parametric simulations. The effects of operating conditions and the electrolyte microstructure properties on carbon resistance and electrochemical performance of all porous solid oxide fuel cells are examined. The good carbon resistance of all porous solid oxide fuel cell is numerically demonstrated. It is found that the electrochemical performance and anode surface O/C ratio is significantly affected by anode inlet gas composition and flowrate. In addition, the anode supported all porous solid oxide fuel cell shows a great potential in terms of both power generation and coking resistance. The results of this study form a solid foundation to understand the mechanism and promising future of all porous solid oxide fuel cells.

A series of Rh and Ni-based catalysts were tested for the reforming of methane and phenanthrene using a feed composition similar in terms of main components to that of the producer gas obtained from wood gasification. The objective was to identify formulations that would enable reforming methane and tars without the need to purify the producer gas. Phenanthrene was chosen as a representative tar because this compound is produced in significant concentrations during low-temperature gasification of woody biomasses and its three-ring structure favors coke formation. The concentration of H2S used was set at the higher range of typical values, i.e. 200 ppm, to make these tests more challenging. At 900 °C, 200 ppm of H2S induced a significantly higher activity loss for methane reforming than that induced by 200 ppm of phenanthrene. The rate of methane consumption in the presence of both poisons varied linearly with the Rh metal surface area. The slight deviation observed at higher loading was in part due to heat and mass transport limitations. The rate of methane consumption per unit of metal surface area was about 5-fold higher on Rh than that on Ni. No information could be derived from the measure of apparent activation energies, due to changes in adsorption coverages of reactants and poisons with temperature. Incomplete conversion of polycyclic aromatic hydrocarbons, well-known coke precursors, was obtained at 875 °C and 850 °C.