title: Growth of boehmite particles in the presence of xylitol: morphology oriented by the nest effect of hydrogen bonding.
abstract: The ability to design nanoparticles size and shape through the addition of simple and commercially available organic molecules is of particular interest in the catalytic domain because huge amounts of very fine powders are needed. The origin of this effect is all the more difficult to elucidate because the involved interactions are weak. In this paper, we have investigated the shaping of boehmite AlO(OH) nanoparticles in the presence of polyols like xylitol (C(5) alditol) by a combined experimental and theoretical approach. Experimental techniques such as XRD, TEM, IEP measurements, adsorption isotherms measurements, and (13)C MAS NMR experiments demonstrate that the effect of xylitol has a thermodynamic origin and suggest weak interactions between xylitol and the surface. Furthermore, the strongest proportion of lateral faces ((100), (001), and (101)) that of basal face would be in agreement with a preferential adsorption upon lateral surfaces. These results were refined by a computational approach. DFT calculations of surface energies (taking into account temperature and solvation effects) and of NMR shielding constants corroborate that molecular adsorption mode is preferred over all adsorption modes involving exchanges with surface OH groups. The preferred adsorption on lateral surfaces is attributed to the nest effect induced by hydroxyl groups localized on the concavities of the (001) and (101) surfaces, able to stabilize the xylitol molecule by hydrogen-bonding, whereas the basal (010) surface is almost flat. This combined experimental and computational approach thus provides interesting rationalization for the morphology effects observed.
authors.affiliation: UPMC University Paris 06, UMR 7574 CNRS, Chimie de la Matière Condensée de Paris, 11 place Marcelin Berthelot, 75231 Paris Cedex 05, France.
authors.forename: David
authors.initials: D
authors.lastname: Chiche
authors.forename: Céline
authors.initials: C
authors.lastname: Chizallet
authors.forename: Olivier
authors.initials: O
authors.lastname: Durupthy
authors.forename: Corinne
authors.initials: C
authors.lastname: Chanéac
authors.forename: Renaud
authors.initials: R
authors.lastname: Revel
authors.forename: Pascal
authors.initials: P
authors.lastname: Raybaud
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Jolivet