Rao, Yuxiang, Kemp, Thomas F., Trudeau, Michel, Smith, Mark E. and Antonelli, Dave M. (2008) O-17 and N-15 solid state NMR studies on ligand-assisted templating and oxygen coordination in the walls of mesoporous Nb, Ta and Ti oxides. Journal of the American Chemical Society, Vol.130 (No.46). pp. 15726-15731. doi:10.1021/ja8056387

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Abstract

A multinuclear solid state NMR approach is applied to four templated mesoporous oxides (silica, titania, niobia and tantala) to include N-15 and O-17 magic angle spinning (MAS) NMR and double resonance N-15-Nb-93, O-17 Rotational-Echo Adiabatic Passage Double Resonance (REAPDOR). The templated samples were ramped in steps of 20 degrees C for 2 days up to typically 110 degrees C where the samples were left for 2-4 days. N-15 MAS NMR shows that amines are the only species present in the TiO2, Nb2O5, and Ta2O5. In SiO2, amines are only present as a minor coordination (10 +/- 2%), but there are several strong ammonium N-15 resonances. The REAPDOR experiments show that the nitrogen interacts with niobium, confirming a ligand interaction between the Nb and N, as previously believed. In the case of silica, the amine is quaternized and there is apparently no interaction with the Si, suggesting a RNH3+ O--Si- hydrogen-bonding interaction with the walls. O-17 MAS NMR provides the clearest indication of the local wall structure. In the aged, templated samples in all cases only OM2 coordinations are present which is very different from the pure bulk oxides (apart from SiO2) and must be due to the effects of amine coordination at the metal centers. On removal of the template, these oxides behave differently, with Ta2O5 showing a mixture of OTa2 (85 +/- 5%) and OTa3 (15 +/- 5%) which is similar to the types of coordination found in the bulk oxide. The previously reported O-17 MAS NMR data from heat-treated mesoporous niobia shows only ONb2, which is very highly ordered. In contrast for titania, the OTi2 coordination is immediately lost on removal of the template to be replaced by a mixture of OTi3 (60 +/- 5%) and OTi4 (40 +/- 5%), with the OTi4 becoming dominant above 250 degrees C, very different behavior from the corresponding bulk oxide. In summary, this NMR study shows that the local oxygen coordination in amine-templated mesoporous transition metal oxides is present as OM2 which is relatively rare in bulk oxides. The data indicates that the template interaction is largely controlled by the N-M dative bond to the wall, suppressing higher oxygen coordination numbers. Qualitatively it appears that the strength of this interaction varies greatly in the different mesoporous oxides.

Item Type:	Journal Article
Subjects:	Q Science > QC Physics Q Science > QD Chemistry
Divisions:	Faculty of Science, Engineering and Medicine > Science > Physics
Library of Congress Subject Headings (LCSH):	Nuclear magnetic resonance spectroscopy, Mesoporous materials, Oxides
Journal or Publication Title:	Journal of the American Chemical Society
Publisher:	American Chemical Society
ISSN:	0002-7863
Official Date:	19 November 2008
Dates:	Date Event 19 November 2008 Published
Volume:	Vol.130
Number:	No.46
Number of Pages:	6
Page Range:	pp. 15726-15731
DOI:	10.1021/ja8056387
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
Funder:	Natural Sciences and Engineering Research Council Canada (NSERC), University of Warwick, Engineering and Physical Sciences Research Council (EPSRC), Johnson Matthey Plc.

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