Controlled interactions between anhydrous keggin-type heteropolyacids and silica support: Preparation and characterization of well-defined silica-supported polyoxometalate species

Grinenval, Eva; Rozanska, Xavier; Baudouin, Anne Christine; Berrier, Élise; Delbecq, Françoise; Sautet, Philippe; Basset, Jean-Marie; Lefèbvre, Frédéric

Controlled interactions between anhydrous keggin-type heteropolyacids and silica support: Preparation and characterization of well-defined silica-supported polyoxometalate species

Type

Article

Authors

Grinenval, Eva
Rozanska, Xavier
Baudouin, Anne Christine
Berrier, Élise
Delbecq, Françoise
Sautet, Philippe
Basset, Jean-Marie

Lefèbvre, Frédéric

KAUST Department

Chemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division

Online Publication Date

2010-10-20

Print Publication Date

2010-11-11

Date

2010-10-20

Abstract

Anhydrous Keggin-type phosphorus heteropolyacids were deposited on partially dehydroxylated silica by using the surface organometallic chemistry (SOMC) strategy. The resulting solids were characterized by a combination of physicochemical methods including IR, Raman, 1D and 2D 1H, and 31P MAS NMR, electron microscopy experiments and density functional theory (DFT) calculations. It is shown that the main surface species is [ - Si(OH...H+)]2[H+]1[PM 12O403-] where the polyoxometalate is linked to the support by proton interaction with two silanols. Two other minor species (10% each) are formed by coordination of the polyoxometalate to the surface via the interaction between all three protons with three silanol groups or via three covalent bonds formed by dehydroxylation of the above species. Comparison of the reactivity of these solids and of compounds prepared by a classical way shows that the samples prepared by the SOMC approach contain ca. 7 times more acid sites. © 2010 American Chemical Society.

Citation

Grinenval, E., Rozanska, X., Baudouin, A., Berrier, E., Delbecq, F., Sautet, P., … Lefebvre, F. (2010). Controlled Interactions between Anhydrous Keggin-Type Heteropolyacids and Silica Support: Preparation and Characterization of Well-Defined Silica-Supported Polyoxometalate Species. The Journal of Physical Chemistry C, 114(44), 19024–19034. doi:10.1021/jp107317s