No abstract

Manipulating interfacial thermal transport is important for many technologies including nanoelectronics, solid-state lighting, energy generation and nanocomposites. Here, we demonstrate the use of a strongly bonding organic nanomolecular monolayer (NML) at model metal/dielectric interfaces to obtain up to a fourfold increase in the interfacial thermal conductance, to values as high as 430 MW m(-2) K(-1) in the copper-silica system. We also show that the approach of using an NML can be implemented to tune the interfacial thermal conductance in other materials systems. Molecular dynamics simulations indicate that the remarkable enhancement we observe is due to strong NML-dielectric and NML-metal bonds that facilitate efficient heat transfer through the NML. Our results underscore the importance of interfacial bond strength as a means to describe and control interfacial thermal transport in a variety of materials systems.

Phosphonic acids are increasingly being used for controlling surface and interface properties in hybrid or composite materials, (opto)electronic devices and in the synthesis of nanomaterials. In this perspective article, a concise survey of phosphonate coupling molecules is first presented, including details on their coordination chemistry, their use in the surface modification of inorganic substrates with self-assembled monolayers, and the analytical techniques available to characterize their environment in nanomaterials. Then, some of their recent applications in the development of organic electronic devices, photovoltaic cells, biomaterials, biosensors, supported catalysts and sorbents, corrosion inhibitors, and nanostructured composite materials, are presented. In the last part of the article, a brief overview of recent progress in the use of phosphonate ligands for the preparation of molecular nanomaterials like metal organic frameworks and functionalized polyoxometalates is given.

Over the past decade, there has been an increasing number of reports on low-temperature preparations of oxides and organic−inorganic hybrids (including sol−gel, solvothermal synthesis, and atomic layer deposition) that take place in nonaqueous media and involve no water as a reactant. This growing interest lies on the ability of these nonhydrolytic routes (in organic solvents, unusual media, condensed phase or under vapor deposition conditions) to reach a higher control over composition, morphology, and structure. An overview of the main results is proposed here, which emphasizes the molecular approach (molecular precursors used, nonhydrolytic reactions involved), the ability to design oxide-based materials with a high degree of homogeneity (mixed oxides, organically modified silicates and ceramics, polysiloxane resins, polymer nanocomposites, etc.) and specific nanostructures (nanoparticles, mesocrystals, nanoporous materials, nanocomposites, nanolayers).

High-field 17O MAS NMR was used to investigate the binding of self-assembled monolayers of 17O-enriched phosphonic acids deposited on a titania anatase support. The spectra were recorded at two different magnetic fields (9.4 and 17.6 T), to improve the reliability of the simulations of the different resonances. The spectra recorded at 17.6 T offer an excellent resolution between the different oxygen sites, PO, P−O−H, and P−O−Ti, thus greatly facilitating their quantification. The data reported here give direct evidence of the extensive formation of Ti−O−P bonds in the surface modification of titania by phosphonic acids. The presence of residual PO and P−O−H sites indicates the presence of several different binding modes in phosphonic acid monolayers. The chemical shift of P−O−Ti sites is consistent with bridging (as opposed to chelating) modes.

Oxides and mixed oxides have a tremendous importance in the field of heterogeneous catalysis, serving either as catalysts or as supports for active species. The performance of a catalyst depends directly on its composition, texture, structure and surface properties, which have to be precisely controlled and adapted to each application. In this context, the sol-gel process is a unique tool for the preparation and understanding of catalytic materials, owing to its exceptional versatility. In the last 10 years, the non-hydrolytic sol-gel (NHSG) or non-aqueous sol-gel process based on nonhydrolytic condensations in nonaqueous media has established itself as a simple and powerful method for the design of a wide range of oxide, mixed oxide and hybrid materials with controlled composition, morphology, texture and structure. NHSG proved particularly interesting for the preparation of catalytic materials, notably mesoporous xerogels, single site catalysts and highly crystalline nanoparticles. This critical review addresses the application of NHSG to the preparation of heterogeneous catalysts, emphasizing the specificities of this process, and giving a comprehensive overview of the literature (251 references).

The selective surface modification by phosphonic acids of SiO 2 -TiO 2 supports at the micrometer and molecular scale was investigated. Under aqueous conditions, phosphonic acids bind to TiO 2 and not to SiO 2 surfaces. A micropatterned support was prepared by electron beam microlithography and selectivity, of the surface modification was evidenced using scanning Auger electron spectroscopy (SAES). The second support was a mesoporous SiO 2 -TiO 2 mixed oxide (10 mol % Ti) epoxidation catalyst prepared by sol-gel processing. Selectivity was deduced from the decrease of the catalytic activity upon modification and from chemical analysis; bonding modes to the surface were investigated using solid-state 29 Si and 31 P MAS NMR. The possibility to introduce different organic groups by successive treatments with a phosphonic acid and a silylating agent was illustrated in the case of the mixed oxide.

No abstract