Selective Carbon Deposition on γ-Alumina Acid Sites: toward the Design of Catalyst Supports with Improved Hydrothermal Stability in Aqueous Media.

γ-Alumina, a widely used industrial catalyst support, undergoes irreversible transformation into various aluminum hydroxides under hydrothermal (HT) conditions, resulting in strong modification of its intrinsic properties. Most of the strategies that have been proposed to prevent or at least minimize its transformation into oxy-hydroxides consist in covering the alumina surface with a hydrophobic carbon layer, making it less sensitive to modifications induced by water. However, such methods necessitate high carbon contents, which significantly modifies structural and chemical properties of alumina. Here, we propose a new method based on a series of adsorption/pyrolysis cycles using sorbitol molecules previously adsorbed on specific hydration sites of the (110) faces of γ-alumina crystals. These sites, which are responsible for the dissolution of γ-alumina crystals in water, are thus selectively protected by carbon clusters, with the rest of the surface being totally exposed and accessible to adsorbates. Under HT conditions (10 h in water at 200 °C), the formation of hydroxides is almost totally suppressed by covering less than 25% of the surface with only 7 wt % carbon, which is far below the amount necessary to achieve similar results with more conventional carbon deposition methods.

Hydrogenation Size-Selective Pt/Hollow Beta Catalysts.

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.

The mechanism of the initial step of germanosilicate formation in solution: a first-principles molecular dynamics study.

The condensation reactions between Ge(OH)4 and Si(OH)4 units in solution are studied to understand the mechanism and stable species during the initial steps of the formation process of Ge containing zeolites under basic conditions. The free energy of formation of (OH)3Ge-O-Ge-(OH)2O(-), (OH)3Si-O-Si-(OH)2O(-), (OH)3Ge-O-Si-(OH)2O(-) and (OH)3Si-O-Ge-(OH)2O(-) dimers is calculated with ab initio molecular dynamics and thermodynamic integration, including an explicit description of the water solvent molecules. Calculations show that the attack of the conjugated base (Ge(OH)3O(-) and Si(OH)3O(-)) proceeds with a smaller barrier at the Ge center. In addition, the formation of the pure germanate dimer is more favorable than that of the germano-silicate structure. These results explain the experimental observation of Ge-Ge and Si-Ge dimer species in solutions, with a few Si-Si ones.

Durable PROX catalyst based on gold nanoparticles and hydrophobic silica.

3 nm gold nanoparticles obtained by direct chemical reduction of AuPPh3Cl in the presence of hydrophobic silica are highly active and selective over a prolonged period of time in the low temperature oxidation of CO in the presence of hydrogen.

Synthesis, characterization and optical properties of an amino-functionalized gold thiolate cluster: Au10(SPh-pNH2)10.

Research interest in ultra small gold thiolate clusters has been rising in recent years for the challenges they offer to bring together properties of nanoscience and well-defined materials from molecular chemistry. Here, a new atomically well-defined Au10 gold nanocluster surrounded by ten 4-aminothiophenolate ligands is reported. Its synthesis followed the similar conditions reported for the elaboration of Au144(SR)60, but because the reactivity of thiophenol ligands is different from alkanethiol derivates, smaller Au10 clusters were formed. Different techniques, such as ESI-MS, elemental analysis, XRD, TGA, XPS and UV-vis-NIR experiments, have been carried out to determine the Au10(SPh-pNH2)10 formula. Photoemission experiment has been done and reveals that the Au10 clusters are weakly luminescent as opposed to the amino-based ultra-small gold clusters. This observation points out that the emission of gold thiolate clusters is highly dependent on both the structure of the gold core and the type of the ligands at the surface. In addition, ultra-small amino-functionalized clusters offer the opportunity for extended work on self-assembling networks or deposition on substrates for nanotechnologies or catalytic applications.

Size-selective hydrogenation at the subnanometer scale over platinum nanoparticles encapsulated in silicalite-1 single crystal hollow shells.

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.

Quasi all-silica zeolite obtained by isomorphous degermanation of an as-made germanium-containing precursor.

Ge-containing ITQ-22 zeolites have been almost completely degermanated under strong acidic conditions without modifications of the framework topology. Simultaneous to Ge extraction, the framework was partially dissolved; mesopores were formed but the structure was maintained through the re-incorporation of some of silicon species at vacant sites. The presence of many defects in the degermanated framework enabled the incorporation of tetrahedral aluminum, opening the way to the preparation of new and stable acid catalysts with original topologies.

Ultimate size control of encapsulated gold nanoparticles.

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.

Functionalized gold magic clusters: Au25(SPhNH2)17.

New Au(25) nanoclusters stabilized by heterotopic 4-aminothiophenolate ligands (HSPhNH(2)) have been isolated with a yield of ~70%. The nanoclusters formula determined by ESI-MS is Au(25)(SPhNH(2))(17), with the 18(th) position occupied by an amine or DMF molecules to close their electronic shell.

Aerobic methylcyclohexane-promoted epoxidation of stilbene over gold nanoparticles supported on Gd-doped titania.

Aerobic partial oxidations of alkanes and alkenes are important processes of the petrochemical industry. The radical mechanisms involved can be catalyzed by soluble salts of transition metals (Co, Cu, Mn...). We show here that the model methylcyclohexane/stilbene co-oxidation reaction can be efficiently catalyzed at lower temperature by supported gold nanoparticles. The support has little influence on gold intrinsic activity but more on the apparent reaction rates which are a combination of catalytic activity and diffusion limitations. These are here minimized by using gadolinium-doped titania nanocrystallites as support for gold nanoparticles. This material is obtained by mild hydrolysis of a new Gd(4)TiO(O(i)Pr)(14) bimetallic oxoalkoxide. It leads to enhanced wettability of the < 3 nm gold particles in the tert-butyl hydroperoxide (TBHP)-initiated epoxidation of stilbene in methylcyclohexane; Au/TiO(2):Gd(3+) is in turn as active as the state-of-the-art hydrophobic Au/SiO(2) catalyst. The rate-determining step of this reaction is identified as the gold-catalyzed homolytic decomposition of TBHP generating radicals and initiating the methylcyclohexane-mediated epoxidation of stilbene, yielding a methylcyclohexan-1-ol/trans-stilbene oxide mixture. Methylcyclohexan-1-ol can also be obtained in the absence of the alkene in the gold-catalyzed solvent-free autoxidation of methylcyclohexane, evidencing the catalytic potential of gold nanoparticles for low temperature C-H activation.

A theoretical study of cohesion, structural deformation, inclusion, and dynamics in porous hydrogen-bonded molecular networks.

Molecules with multiple sites of hydrogen bonding attached to suitable cores tend to crystallize as open networks. The resulting crystals can have the following unusual properties: They can include significant amounts of guest molecules; the guests are typically located in channels and can be exchanged without loss of crystallinity; and the geometry of the networks can change in response to new guests. We have found that DFT calculations can provide accurate simulations of the unusual structure and properties of such materials, represented by crystals of prototypic tetrapyridinone 1. These calculations have yielded three key insights that cannot be obtained directly from experiments. (1) The hypothetical porous network obtained by removing guests from crystals of compound 1 is highly flexible, and its deformations are inherently anisotropic, leading to lengthening or shortening of the channels along the c axis and no significant changes along the a and b axes. (2) Quantitative analysis of the total cohesive energy has revealed that hydrogen bonding within the network makes a dominant contribution, along with interactions of guests with the network. (3) Differences in the overall stability of crystals of compound 1 as the guests are varied do not arise primarily from significant changes in the cohesive energy of the network itself; instead, differences in guest-guest interactions play a key role, resulting from the nature of the guests and constraints imposed by the surrounding network. These insights, together with the results of ab initio molecular dynamics, help explain how hydrogen-bonded networks can be robust yet permit molecular movement that underlies the exchange of guests and adaptive porosity. These insights promise to be of general value to scientists studying ordered molecular materials in which strong directional interactions are prominent.