RÉSUMÉ
Among the several classes of chemical reactions, the green oxidation of organic compounds has emerged as an important topic in nanocatalysis. Nonetheless, examples of truly green oxidations remain scarce due to the low activity and selectivity of reported catalysts. In this paper, we present an approach based on the optimization of both the support material and the active phase to achieve superior catalytic performances towards green oxidations. Specifically, our catalysts consisted of ultrasmall Au NPs deposited onto MnO2 nanoflowers. They displayed hierarchical morphology, large specific surface areas, ultrasmall and uniform Au NPs sizes, no agglomeration, strong metal-support interactions, oxygen vacancies, and Auδ+ species at their surface. These features led to improved performances towards the green oxidations of CO, benzene, toluene, o-xylene, glucose, and fructose relative to the pristine MnO2 nanoflowers, commercial MnO2 decorated with Au NPs, and other reported catalysts. We believe that the catalytic activities, stabilities, and mild/green reaction conditions described herein for both gas and liquid phase oxidations due to the optimization of both the support and active phase may inspire the development of novel catalytic systems for a wealth of sustainable transformations.
RÉSUMÉ
Single crystals of the potassium salt K3(H2O)4[H2SiVW11O40](H2O)8+x of the vanadium monosubstituted alpha-Keggin dodecatunsgstosilicate were grown from an aqueous solution and analyzed by EDS, XRD, vibration and electronic spectroscopy, and 1H, 51V, and 29Si solid-state NMR spectroscopy. Results indicate the formation of a nanoporous-like compound of hexagonal symmetry (space group P62) with large, water-filled channels running along the c axis. A uniform distribution of vanadium over the 12 metal sites of the alpha-Keggin anion is observed by XRD. Two different neighborhoods were characterized by 51V NMR in a 2:1 ratio (deltaiso=-546.3 and -536.2 ppm), in accordance with a difference in the number of potassium ions in the second coordination shell of vanadium.