David Farrusseng

French National Centre for Scientific Research, Lutetia Parisorum, Île-de-France, France

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Publications (125)386.94 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: A set of 15 metal–organic frameworks (MIL-53, MIL-68, MIL-125, UiO-66, ZIF) exhibiting different pore size, morphology, and surface chemistry is used to unravel the numerous behaviors of water adsorption at room temperature in this class of materials. Outstanding “S”-shaped (type V) adsorption isotherms are observed for MIL-68 type solids. We show that the underlying mechanism of water adsorption can be rationalized using a simple set of three parameters: the Henry constant (i.e. the slope of the adsorption pressure in the low pressure range), the pressure at which pore filling occurs, and the maximum water adsorption capacity. While the Henry constant and pore filling pressure mostly depend on the affinity of water for the surface chemistry and on pore size, respectively, these two parameters are correlated as they both reflect different aspects of the hydrophobicity–hydrophilicity of the material. For a given type of porous structure, the functionalization of the material by hydrophilic moieties such as hydrogen bonding groups (amine or aldehyde) systematically leads to an increase in the Henry constant concomitantly with a decrease in the pore filling pressure. As for the adsorption mechanism, we show that, for a given temperature, there is a critical diameter (Dc 20 Å for water at room temperature) above which pore filling occurs through irreversible capillary condensation accompanied by capillary hysteresis loops. Below this critical diameter, pore filling is continuous and reversible unless the material exhibits some adsorption-induced flexibility.
    New Journal of Chemistry 06/2014; 38(7). · 2.97 Impact Factor
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    ABSTRACT: Two cobalt imidazolate metal–organic frameworks were evaluated as a bactericidal material against the growt h of the Gram-negative bacteria Pseudomonas putida and Escherichia coli. Under the most unfavourable conditions, within the exponential growth phase and in the culture media for both microorganisms, the growth inhibition reached over 50% for concentrations of biocidal material in the 5–10 mg L�-1 range. The release of metal gives excellent durability with the antibacterial effect persisting after 3 months. Both cobalt-based materials can be prepared with simple, cheap and easily accessible commercial ligands, leading to a more affordable possible future application as antimicrobial materials.
    Chemosphere 06/2014; 113:188-192. · 3.14 Impact Factor
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    ABSTRACT: This review article presents the fundamental and practical aspects of water adsorption in Metal-Organic Frameworks (MOFs). The state of the art of MOF stability in water, a crucial issue to many applications in which MOFs are promising candidates, is discussed here. Stability in both gaseous (such as humid gases) and aqueous media is considered. By considering a non-exhaustive yet representative set of MOFs, the different mechanisms of water adsorption in this class of materials are presented: reversible and continuous pore filling, irreversible and discontinuous pore filling through capillary condensation, and irreversibility arising from the flexibility and possible structural modifications of the host material. Water adsorption properties of more than 60 MOF samples are reported. The applications of MOFs as materials for heat-pumps and adsorbent-based chillers and proton conductors are also reviewed. Some directions for future work are suggested as concluding remarks.
    Chemical Society Reviews 05/2014; · 24.89 Impact Factor
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    ABSTRACT: The hydrogen uptake in hybrid sorbents consisting of n-alkane solvents confined in mesoporous silica aerogel is measured at different temperatures from 273 to 313 K and pressures up to 40 bar. An apparent “oversolubility” effect is observed as the H2 uptake in the hybrid sorbents is much larger than that in bulk solvents. The H2 uptake in the hybrid sorbents is found to increase with increasing temperature, which suggests that the flexibility and conformation of n-alkane molecules confined in the aerogel play a crucial role; high-entropy (disordered) alkane configurations lead to the creation of numerous cavities which make it possible to solubilize a larger number of H2 molecules. This departs from adsorption-driven solubility effects for which the number of solubilized molecules decreases with increasing temperature. For a given temperature and pressure, it is found that the number of solubilized H2 molecules per unit volume increases with decreasing alkane chain length. Such an effect, which is observed for both the bulk alkanes and the alkanes confined in the silica aerogel, can be rationalized by considering the number density of CHx (x = 2 or 3) groups; for a given temperature, the latter number density decreases with decreasing alkane chain length so that the free volume available to solubilize H2 molecules increases.
    The Journal of Physical Chemistry C. 05/2014; 118(20):10720–10727.
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    ABSTRACT: Recently, the use of mixtures of organic-building-block linkers has given chemists an additional degree of freedom for engineering metal-organic frameworks (MOFs) with specific properties; however, the poor characterization of the chemical complexity of such MixMOF structures by conventional techniques hinders the verification of rational design. Herein, we describe the application of a technique known as photothermal induced resonance to individual MixMOF microcrystals to elucidate their chemical composition with nanoscale resolution. Results show that MixMOFs isoreticular to In-MIL-68, obtained either directly from solution or by postsynthetic linker exchange, are homogeneous down to approximately 100 nm. Additionally, we report a novel in situ process that enables the engineering of anisotropic domains in MOF crystals with submicron linker-concentration gradients.
    Angewandte Chemie International Edition 02/2014; · 11.34 Impact Factor
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    ABSTRACT: Highly controlled "ship-in-a-bottle" platinum nanoparticles in silicalite-1 hollow single crystals have been prepared. This catalyst is highly active for toluene hydrogenation but shows no activity for the hydrogenation of 1,3,5-trimethylbenzene.
    Chemical Communications 01/2014; · 6.38 Impact Factor
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    ABSTRACT: We report an original and scalable synthesis pathway to produce encapsulated gold nanoparticles. Precise control of the gold particles is achieved in the range of 1-10 nm through the impregnation of silicalite-1 with a controlled concentration of gold solution, followed by dissolution-recrystallization of the zeolite.
    Chemical Communications 08/2013; · 6.38 Impact Factor
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    ABSTRACT: We report two new microporous mixed-metals triazolate based MOFs made from zinc and nickel salts combined with either 1,2,4-triazole or 3,5-diamino-1,2,4-triazole. Their structures, refined from X-ray powder diffraction, their CO2 adsorption and photoluminescent properties show a direct correlation with the structure of their parent organic ligand.
    CrystEngComm 07/2013; · 3.88 Impact Factor
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    ABSTRACT: Hierarchical zeolitic imidazolate framework-8 nanocrystals catalyze esterification of glycerol with oleic acid at low temperature and become hierarchical upon local transformation of the framework
    ChemCatChem 07/2013; · 5.18 Impact Factor
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    ABSTRACT: The number and strength of adsorption sites for Xe in silver-modified zeolites are estimated from isotherm measurements at various temperatures over a broad range of pressure (from 1 ppm to atmospheric pressure). Fully and partially exchanged silver zeolites were synthesized starting from Na-ZSM-5(25), Na-ZSM-5(40), Na-Beta, NaX, and NaY. We have discovered that silver-modified zeolites may present one or two distinct adsorption sites depending on the nature of the material and silver loadings. The strongest adsorption sites are characterized by isosteric heat of adsorption in the order of −40 to −50 kJ·mol–1. For Pentasil-type zeolites, we observe a linear 2:1 correlation between the total amount of silver and the number of strong sites. The highest concentration of strong sites is found for fully silver exchanged ZSM-5 (5.7 × 10–4 mol/g), which presents the largest silver content for Pentasil-type zeolite. The equilibrium constant of Ag-ZSM-5 at low pressure is about 50 times larger than that of AgX. Qualitative correlations were established between Xe adsorption isotherms and Xe NMR signals. We show that Xe NMR could be used as a quantitative method for the characterization of the strength and of the number of strong Xe adsorption sites on silver-exchanged zeolites. The numbers of strong adsorption sites responsible for the Xe adsorption at 10–1000 ppm can be determined by the length of the plateau observed at low Xe uptake. In practice, our findings give guidelines for the discovery and optimization of silver-loaded zeolites for the capture of Xe at ppm levels. It appears that the amount of silver is a key parameter. Silver-modified ZSM-5 shows adsorption capacities 2–3 orders of magnitude larger than currently applied adsorbents for atmospheric Xe capture.
    The Journal of Physical Chemistry C. 07/2013; 117(29):15122–15129.
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    ABSTRACT: Three molecular mechanisms for gas uptake in a solvent confined in mesopores are identified. On the one hand, CO2 uptake is an adsorption-driven phenomenon that arises from the strong interaction between the gas molecules and the pore surface. On the other hand, H2 uptake is a confinement-induced enhanced solubility in which solubility is favored in the regions of low solvent density formed by the layering of the solvent. In partially filled pores, adsorption at the gas/liquid solvent interface is a third mechanism that leads to large gas uptakes. This study, which sheds light on previously reported yet unclear oversolubility in pores, provides a guide to design hybrid porous catalysts consisting of a solvent confined in a porous solid.
    Journal of Physical Chemistry Letters 06/2013; 4(14):2274–2278. · 6.59 Impact Factor
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    ABSTRACT: A novel concept that employs dual chamber SOFC technology with a porous electrolyte, which allows the controlled distribution of gaseous O2 at the anode side, was successfully designed using an all porous structure. The oxidative reforming of hydrocarbon streams can consequently operate in a similar fashion to single chamber SOFCs, but within a safer, better controlled process.
    Energy & Environmental Science 06/2013; 6(7):2119-2123. · 11.65 Impact Factor
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    L. Baumes, C. Mirodatos, D. Farrusseng
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    ABSTRACT: We have developed a generic two-step post-functionalisation technique for transforming amino-functionalised MOFs into their isocyanate analogues. The first part of the synthetic pathway consists in the conversion of the amino moieties into azido groups. Next, the thermal activation of these azido groups leads to nitrene species that can react with carbon monoxide to yield the desired products. As a proof of concept, this method was applied to the highly stable Al-MIL-53-NH2 and to the acid-sensitive In-MIL-68-NH2. The resulting nitrene species were highly reactive, with side reactions dominating initially. This issue was overcome through the use of a mixed-linker strategy applied during the MOF synthesis that decreased the nitrene radical density within the pore, thereby permitting In-MIL-68-NH2 to be converted into its isocyanate analogue with 100% selectivity. To illustrate the potential of this method for grafting a wide library of potentially active organic groups inside MOFs, amines were condensed onto isocyanato MOFs to form urea analogues.
    Dalton Transactions 04/2013; · 3.81 Impact Factor
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    ABSTRACT: The one-pot post-functionalization allows anchoring a molecular nickel complex into a mesoporous metal-organic framework (Ni@(Fe)MIL-101). It is generating a very active and reusable catalyst for the liquid-phase ethylene dimerization to selectively form 1-butene. Higher selectivity for 1-butene is found using the Ni@(Fe)MIL-101 catalyst than reported for molecular nickel diimino complexes.
    Journal of the American Chemical Society 03/2013; · 10.68 Impact Factor
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    ABSTRACT: Selective synthesis of monoglycerides by esterification of glycerol with fatty acids is a difficult reaction because of immiscibility of reagents and the formation of di- and tri-glyceride by-products. In this work a heterogeneous catalytic process was conceived in which the reactant mixture was homogenized using tert-butanol solvent. Candidate catalysts were screened in the reaction of oleic acid with glycerol. While under such reaction conditions zeolites were rather inactive, metal–organic frameworks and, especially, tin–organic frameworks were found promising. A tin–organic framework (Sn–EOF) was most active and achieved ≥98 % monoglyceride selectivity at 40 % conversion in catalyzing esterification of oleic acid with glycerol at a low reaction temperature of 150 °C. Leaching of tin from Sn–EOF catalyst was suppressed by limiting the amount of oleic acid in the starting mixture. Characterization of the acid sites of Sn–EOF by pyridine-chemisorption and FTIR revealed Lewis acidity to be responsible for the catalytic activity.
    Catalysis Letters 02/2013; 143(4):356. · 2.24 Impact Factor
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    ABSTRACT: a b s t r a c t The establishment of periodic trends is a powerful approach for rational design of heterogeneous cata-lysts. It deals with measuring or computing a physico-chemical descriptor of a solid which is correlated to the activity in a specific catalytic reaction. In this work, the metal–carbon bond energy (E MC), calcu-lated in the M 2 C carbide phases was calculated as a bulk descriptor to predict the catalytic activity of metal supported catalysts for the selective hydrogenation of styrene. A set of different metals (Cu, Pt, Pd, Ir, Co, Ni, Ru and Rh) supported on silica were prepared and characterized. Experimental TOFs were measured in a semi-batch reactor. The TOF follows the order Pd > Rh > Ru, Pt, Ir > Ni > Co > Cu which dif-fers from the well established hydrogenation of ethylene. We show that the metal–carbon bond energy (E MC) calculated by DFT from the corresponding M 2 C carbide bulk structure correlates the TOF of styrene hydrogenation over the 8 metal catalysts according to a double volcano curve. The predictive model indicates Pd is the most active monometallic phase and suggests quantitative guidelines for the rational design of very active catalyst compositions.
    Journal of Catalysis 01/2013; 307:352. · 5.79 Impact Factor
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    ABSTRACT: We have developed an original synthetic pathway for the conversion of a MIL-68(In)-NH(2) metal-organic framework into its corresponding isocyanate (-NCO) derivative. This two-step soft post-modification technique leads to highly porous isostructural materials.
    Dalton Transactions 10/2012; · 3.81 Impact Factor
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    ABSTRACT: Hydrogen uptake at 298 K and 30 bar in hybrid sorbents consisting of n-hexane confined in MIL-101 is found to be 22 times larger than in sole n-hexane. The enhanced solubility in MIL-101, found to be 3 times larger than in mesoporous silica of similar pore size, highlights the key roles played by surface chemistry and accessible surface area.
    Journal of the American Chemical Society 10/2012; 134(42):17369-71. · 10.68 Impact Factor
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    ABSTRACT: Absolute ethylene/ethane separation is achieved by ethane exclusion on silver-exchanged zeolite A adsorbent. This molecular sieving type separation is attributed to the pore size of the adsorbent, which falls between ethylene and ethane kinetic diameters.
    Journal of the American Chemical Society 08/2012; 134(36):14635-7. · 10.68 Impact Factor

Publication Stats

490 Citations
386.94 Total Impact Points

Institutions

  • 1999–2014
    • French National Centre for Scientific Research
      • Institut de recherches sur la catalyse et l`environment de Lyon (IRCELYON)
      Lutetia Parisorum, Île-de-France, France
  • 2003–2013
    • Claude Bernard University Lyon 1
      • Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON)
      Villeurbanne, Rhône-Alpes, France
  • 2011–2012
    • University of Lyon
      Lyons, Rhône-Alpes, France
  • 2008
    • Université Lumiere Lyon 2
      Rhône-Alpes, France
  • 2001–2007
    • Max Planck Institute for Coal Research
      Mülheim-on-Ruhr, North Rhine-Westphalia, Germany
  • 2005
    • Delft University of Technology
      Delft, South Holland, Netherlands
  • 2004
    • University of Amsterdam
      Amsterdamo, North Holland, Netherlands