David Farrusseng

• French National Centre for Scientific Research

Technological innovations allowing the capture of volatile organic compounds (VOCs), in particular aromatic compounds (BTEX), continue to be sought. Activated carbon (AC) is a widely-used adsorbent, but upon moderate temperature...

Sigma-catenated polynitrogen derivatives are scarce. Among polyazanes, the synthesis of derivatives of cyclotriazane (general formula N3H3) remains a challenge due to their very high reactivity. While several methods toward protected...

Crown rot is an economically important postharvest disease of 'Cavendish' banana fruit caused by a complex of phytopathogenic fungi including Colletotrichum musae. The sustained release of bioactive compounds, such as thymol, encapsulated in porous materials has been studied for applications in postharvest fruit treatments. The release concentratio...

Here we report the synthesis of series of bipyridine-based porous polymers as macroligands for molecular copper complexes. The resulting Cu@N-POP solids efficiently catalyze the dehydrogenative N-N coupling of di-p-tolylamine into...

Monoterpenes are the most prevalent compounds found in essential oils. They exhibit inhibitory actions against phytopathogenic postharvest fungi. Direct application limits their effectiveness due to their instability, high volatility, hydrophobicity and susceptibility to degradation. Encapsulation systems using metal–organic frameworks (MOFs) have...

The oxidative coupling of methane (OCM), which offers a direct route for converting methane into higher-value ethylene. Despite the development of selective catalyst formulations, kinetic and reactor design studies have been hampered by a lack of data for truly isothermal, relevant. Because of exothermicity issues, the temperature of a fixed-bed re...

This study presents the development of a dynamic multiscale model to simulate the adsorption and desorption processes in a fixed bed for medical air drying. The model includes equations of mass balance, thermodynamics, hydrodynamics, and adsorption/desorption kinetics. The temperature-dependent Toth–Aranovich–Donohue equation is used to approximate...

The synthesis of dimethyl carbonate (DMC) from carbon dioxide and methanol was studied over a ceria- zirconia mixed metal oxide. When using oxygen-18 labeled ceria-zirconia, no oxygen-18 labeled DMC or water was observed. On the other hand, using oxygen-18 labeled methanol led almost exclusively to the formation of double labeled DMC, CH318O (C16O)...

A static volumetric method measured the equilibrium adsorption isotherms of water vapor on commercial activated carbon, alumina and hopcalite adsorbents. A type II isotherm represents water vapor adsorption on alumina and hopcalite, whereas a type V isotherm characterizes activated carbon. A method based on the sensitivity analysis of parameters is...

An operando IR study was carried out to investigate the loss of selectivity to higher hydrocarbons observed over cobalt-based Fischer-Tropsch catalysts when CO is replaced with CO2. Our data unambiguously show that the structure and oxidation state of the surface of metallic cobalt remains the same whether CO2 or CO are cofed with H2. The selectivi...

Using a prototypical family of hierarchical zeolites, we show how adsorption-based characterization can be extended to provide morphological and topological assessment beyond state-of-the-art tools. The well-controlled materials under study consist...

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 gene...

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...

The direct synthesis of Dimethyl carbonate (DMC) from methanol and CO2 is a green process which allows CO2 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 cerium-zirconium mixed oxides prepared by Flame Spray Pyrolysis...

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 crysta...

Metal-Organic Frameworks (MOFs) thanks to their Type V water adsorption isotherm (“S-Shape”) and large water capacity are considered as potential breakthourgh adsorbents for heat-pump applications. In particular Al(OH)-fumarate could enable efficient regeneration at lower temperature than silica-gel which would allow to adress the conversion of was...

Several major refining catalytic processes show a strong dependence of overall performances upon catalyst formulation and structure. This observation is particularly true in naphtha catalytic reforming for which product distribution is sensitive to slight changes in active phase formulation. This review presents different issues encountered in naph...

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 th...

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...

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 proper...

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 gr...

Poröse organische Polymere wurden als Photosysteme eingesetzt, die über mehrere Tage eine konstante Produktionsrate in der Reduktion von CO2 zu Formiat liefern. Der Photoaktivierungspfad beinhaltet einen ultraschnellen elektronischen Energietransfer vom Photosensibilisator zum Katalysator, wie durch zeitauflösende Spektroskopie und quantenmechanisc...

Silver metal nanoparticles are among the most widely studied nanoparticles. They are widely used heterogeneous catalysts used for many purposes such as antisepsis, hydrogenation and carboxylation, but also for trapping xenon in nuclear test and detection facilities. The catalytic activity and adsorption capacity of silver nanoparticles, which depen...

Silver nanoparticles are currently one of the most studied nanostructured nanomaterials. Because nanoparticle size and dispersion act together in determining a material’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...

In this work we provide a detailed study on grafting reactions of various dialkylphosphonate-based ILs. 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 the grafting densities and bonding modes of phosphonate-based I...

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 experi...

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 pollutants, etc. Yet, the design of efficient technologies in this field is hampered by the lack of robust strategies to predict the gas selectivity of optima...

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 h...

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...

Hollow zeolite single crystals represent a new class of materials that have received considerable attention over the last decade. Besides facilitating the transport of molecules in zeolite crystals, the cavity present in hollow crystals offers many possibilities for encapsulating active species and constitutes a closed space that can be used as a n...

Streamlining the xylene separation process on faujasites is a promising way to design innovative adsorbents for this appli-cation. 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...

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 cataly...

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 s...

We report herein the upscaled synthesis and shaping of UiO66-COOH for NH3 air purification. The synthesis of the zir-conium-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 ind...

The Cover Feature illustrates the relation between the Hammett parameter (σ) of substituents and the activity (TOF) of rhodium catalysts heterogenized inside molecularly defined porous structures, as shown in the background. In their Communication, F. M. Wisser et al. demonstrate how, like in a famous word game, porous solids such as metal‐organic...

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 a material having the same properties to the one obtained previously by solvothermal method in DMF route. This method...

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 sp...

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...

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...

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...

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...

Here we present 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, an...

Porous metal-organic frameworks (MOFs) are attracting great attention from industry, thanks to their myriad potential applications in areas such as catalysis and gas storage. Zr-MOFs (also known as UiO-type MOFs) are especially promising, owing to their large surface areas, high chemical versatility and remarkable hydrothermal, chemical and thermal...

Zeolites are crystalline microporous materials with open frameworks built of corner-sharing TO4 tetrahedra, where T is generally Si or Al. The flexibility of the T-O-T linkage allows a large variety of zeolite structures to be prepared by simply changing synthesis conditions, for example, the composition of the gel, the nature of the structure dire...

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....

Photoacoustic Fourier transform infrared spectroscopy makes it possible to determine the organic composition of mixed-linker metal-organic frameworks. The sound produced upon IR irradiation enables the discrimination of azido and amino linkers in three different MOF platforms with a sensitivity two orders of magnitude higher than using classic IR a...

This study addresses the modeling of exchange isotherms for faujasite-type zeolites X and Y with K+, Cs+, Ca2+ and Ba2+ cations based on a large experimental dataset obtained under operating conditions of 0.5 N total normality and an exchange temperature of 80°C. The isotherm models are based on the mass action law. Ideal solution phase is assumed....

Four different Metal-Organic Framework powders (UiO-66, UiO-66-NH2, UiO-67, HKUST-1) were shaped into tablets. The effect of the applied pressure on porous properties, mechanical resistance and tablets bulk density is reported. We observe a linear relationship between densification and tensile strength for all four studied MOFs, with a slope being...

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. Re...

For the first time, a systematic, consistent domain exploration has been conducted on mono- and bi-cationic exchanged X and Y faujasites for xylene separation using a combinatorial approach. In total, a large, diverse library of 68 faujasites exchanged with alkali cations (Na⁺, K⁺, Cs⁺) and alkali earth cations (Ca²⁺, Ba²⁺) was prepared and tested...

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 out most of the external Ni nanoparticles from a Ni@silicalite-1 material. The leached sample exhibi...

Multi hollow silicalite-1 single crystals (MH) were prepared for the first time by an original synthesis pathway using tetrabutylphosphonium hydroxide (TBPOH) as a mild desilicating agent. This new generation of hierarchical zeolite allowed the encapsulation of NPs featuring an enhanced confinement of the metallic guest and a thin wall thickness. T...

It is known that Fischer‐Tropsch synthesis [1] is one of the best processes to convert syngas emitted from combusted of fossil fuels like coal and natural gas into liquid gas/ liquid fuels and other petro chemicals. Moreover, iron based catalysts are known to be efficient and active components of Fischer‐Tropsch catalyst. Encapsulating iron nanopar...

Gasification of carbon can be achieved, in the presence of metal catalysts supported on solid carbon materials, at high temperature in oxidative environments. Indeed, oxygen adsorbs and dissociates on the metal surface then interacts with the carbon at the interface with the metal leading to the formation of carbon dioxide; concurrently carbon is c...

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 70...

We use density functional theory, newly parameterized molecular dynamics simulations, and last generation (15) N dynamic nuclear polarization surface enhanced solid-state NMR spectroscopy (DNP SENS) to understand graft-host interactions and effects imposed by the metal-organic framework (MOF) host on peptide conformations in a peptide-functionalize...

The luminescent MOF-based sensor shown on the Front Cover can detect endogenously produced hydrogen sulfide at the sub-micromolar level. This high sensitivity is reached thanks to a novel laser-pulse irradiation protocol developed during the luminescence study of three different MOF platforms. The reported laser-excited MOF system opens new perspec...

Hollow capsules with dimensions below 1 μm have recently attracted much attention due to their potential applications as catalysts as well as biomedical and pharmaceutical vectors for controlled drug delivery. Among them, hollow zeolites are particularly interesting because they possess (i) a crystalline structure, which greatly improves their hydr...

The development of new and efficient metal-organic framework (MOF)-based catalytic systems requires the combined skills of material scientists, organic chemists, and spectroscopy experts who should closely work together. The recent years show the trend toward the design of MOF catalyst for enzymes mimic such as chiral induction/separation and artif...

Rare gas capture and purification is a major challenge for energy, environment, and health applications. Of utmost importance for the nuclear industry, novel separation processes for Xe are urgently needed for spent nuclear fuel reprocessing and nuclear activity monitoring. The recovered, non-radioactive Xe is also of high economic value for lighti...

The substituted imidazolate-based MOF (SIM-1) forms easily a homogeneous layer at the surface of millimetric platinum-loaded alumina beads. This new core-shell SIM-1@Pt/Al2O3 catalyst shows fine molecular sieving effect for the Pt-catalyzed hydrogenation of carbon-carbon double bonds.

Metal–organic frameworks are appealing hybrid solids which attract continuously growing interest. Their advantageous application in sensing devices is demonstrated here. In particular, the use of a short-pulse laser excitation of luminescent metal-organic framework is reported for the first time to favor the ligand-based emission. The designed MOF-...

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 l...

Standard chemical and physical methods to control the size of supported metallic nanoparticles are generally not compatible with harsh conditions of applications (high temperature, presence of steam). Here we describe a generic process for synthesizing nanoalloys of controlled size and composition encapsulated in zeolite nanoboxes. The nanoboxes ac...

The sorption kinetics of isooctane at 150 °C over a series of silicalite-1 materials comprising small and large crystals and their corresponding hollow forms were followed by in situ diffuse reflectance FT-IR spectroscopy. The results suggest that sorption rate was mostly limited by surface effects in the case of small (i.e. 100 nm diameter) crysta...

Pt nanoparticles supported on ZSM-5 nanoshells have been prepared by a mild desilication method. The zeolite support is a ZSM-5 crystal with extremely thin walls (ca. 15 nm) that contain meso/microporous defects. The 2-3 nm diameter Pt nanoparticles are entrapped and highly dispersed in these ZSM-5 nanoshells. The particles are stable up to 750 °C...

This article provides a comprehensive review of the nature of catalytic sites in MOFs. In the last decade, a number of striking studies have reported outstanding catalytic activities of MOFs. In all cases, the authors were intrigued as it was unexpected from the ideal structure. We demonstrate here that (surface) defects are at the origin of the ca...

Most perovskite materials are stable at high temperatures making them interesting catalysts or catalyst supports to consider for high-temperature reactions, such as partial or total oxidation reactions, steam or dry reforming of hydrocarbons, and oxidative coupling of methane. These reactions are usually fast at high temperatures and often accompan...

SSCI-VIDE+ING+DFA:CDA:JEC

SSCI-VIDE+ING+JEC:JOB:DFA

SSCI-VIDE+ING+ALE:JEC:DFA

Oversolubility, which corresponds to large apparent gas solubilities in liquids confined in nanoporous solids, has been proposed as a means to develop novel adsorption, phase separation, or catalytic processes. We report a molecular simulation study to help design such hybrid adsorbents consisting of a solvent confined in host nanoporous materials....

MICROSCOPIE+ATARI:ING+FCA:MAO:CDA:FRM:DFA

SSCI-VIDE+ING+JEC:ALE:DFA

We present herein the first example of Metal-Organic Frameworks post-functionalized with peptides. Our microwave-assisted post-synthetic modification method yields enantiopure peptides anchored inside MOF cavities. Al-MIL-101-NH2, In-MIL-68-NH2 and Zr-UiO-66-NH2 were chosen as starting platforms. A single amino acid and various oligopeptides are gr...

John Wiley and Sons, Hoboken, 2014. 592 pp., hardcover, € 175.00.—ISBN 978-1119952893

Brevet : N° de publication WO 2016/151245 A1 / Déposant CNRS / N° de dépot 1552769 / Date de dépot 31 mars 2015 /

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. The superstructure of a substituted zeolitic imidazolate metal–organic framework was de...

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.

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