“Chimie douce”: A land of opportunities for the designed construction of functional inorganic and hybrid organic-inorganic nanomaterials

Abstract“Chimie douce” based strategies allow, through the deep knowledge of materials chemistry and processing, the birth of the molecular engineering of nanomaterials. This feature article will highlight some of the main research accomplishments we have performed during the last years. We describe successively the design and properties of: sol–gel derived hybrids, Nano Building Blocks (NBBs) based hybrid materials, nanostructured porous materials proceeds as thin films and ultra-thin films, aerosol processed mesoporous powders and finally hierarchically structured materials. The importance of the control of the hybrid interfaces via the use of modern tools as DOSY NMR, SAXS, WAXS, Ellipsometry that are very useful to evaluate in situ the hybrid interfaces and the self-assembly processes is emphasized. Some examples of the optical, photocatalytic, electrochemical and mechanical properties of the resulting inorganic or hybrid nanomaterials are also presented

High yield synstheses of reactive fluoride K1 x(Y, LN)xF1+2x nanoparticules

International audienc

Block-copolymer-templated synthesis of electroactive RuO₂-based mesoporous thin films

International audienc

Ti8O8(OOCR)16, a new family of titanium-oxo clusters: Potential NBUs for reticular chemistry

The reactions of titanium alkoxides with a large excess of different carboxylic acids under nonhydrolytic conditions leads to the reproducible formation of well-defined nano-building units (NBUs) with the formula [Ti 8O8(OOCR)16] [R = C6H5, C(CH3)3, CH3]. The structures of these titanium-oxo-carboxylate clusters have been determined by crossingdifferent characterization techniques and methodologies (single-crystal X-ray diffraction, 13C and 1H NMR spectroscopy, and FTIR spectroscopy). These NBUs are obtained in high yields and, since all the alkoxo ligands have been removed by using solvothermal-synthesis conditions, they present better stability upon hydrolysis than the often reported alkoxo-carboxylate-titanium- oxo clusters [TinO2n-x/2-y/2(OR) x(OOCR)y] (n ⥠2; x ⥠1; y ⥠1). In addition, the solubility and transferability of these clusters in common solvents can be tuned by selecting the nature of the organic ligand. Moreover, we also report for the first time, a robust post-modification of the carboxylate ligands by transesterification reactions on the titanium-oxo clusters. These reactions keep the integrity of the octameric titanium-oxo core intact, while completely exchanging the organic shell of the cluster. This family of [Ti8O8(OOCR)16] clusters, which present 16 points of extension, a symmetric shape, and the ability to be post-modified with conservation of the core structure, can therefore be considered as interesting NBUs to form new metal-organic frameworks

The Active State of Supported Ruthenium Oxide Nanoparticles during Carbon Dioxide Methanation

Ruthenium catalysts supported on TiO2 have been shown to have competitive activity and selectivity for the methanation of CO2. In particular, a catalyst using preformed RuO2 nanoparticles deposited on a TiO2 support showed competitive performances in a previous study. In this work, ambient-pressure X-ray photoelectron spectroscopy was employed to determine the chemical state of this catalyst under reaction conditions. The active state of ruthenium was found to be the metallic one. Surface adsorbates were monitored in the steady state, and CHx species were found to be favored over adsorbed carbon monoxide at increasing temperatures