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Detection of Brønsted acid sites in zeolite HY with high-field 17O-MAS-NMR techniques

Abstract

The acidity and unique porous structures of zeolites play an important role in controlling the activity and selectivity of many zeolite-based catalysts1,2. Although 27Al, 29Si and 1H NMR spectroscopy represent standard analytical tools with which to study these materials3,4, 17O-NMR investigations are much less routine, owing to the very low natural abundance of 17O (0.037%), its relatively low resonant frequency and its large quadrupole moment. 17O-NMR resonances from framework oxygen sites in a variety of zeolites have been detected5,6,7,8,9,10,11, but the 17O-NMR resonance from oxygen directly bound to the Brønsted acid site (Si–O(H)–Al) has remained elusive. Here we report the direct observation of this resonance in dehydrated zeolite HY, by using high magnetic-field strengths. 17O–1H double-resonance NMR experiments are used to prove unambiguously that the 17O signal arises from O nearby H atoms. A large quadrupolar coupling constant, the measure of the local distortion of this site, of 6.6 MHz is determined, which is similar to that obtained in ab initio calculations of zeolite HY-like clusters; this value drops to 5 MHz on acetone binding. The results presented in this paper open up methods for characterizing zeolite acidity and investigating H+-sorbent interactions.

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Figure 1: 17O-MAS-NMR spectra of 17O-enriched zeolite HY and a non-enriched sample of HY loaded with H217O.
Figure 2: 17O–1H REDOR NMR spectra of zeolite HY.
Figure 3: Detection of Brønsted acid sites in zeolite HY with high-field 17O-MAS-NMR techniques.
Figure 4

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Acknowledgements

We thank Martine Ziliox and Boris Itin for their help in obtaining the 14.1 and 17.6 T NMR data, respectively. Financial support was provided by the Department of Energy through grant DEFG0296ER14681. We thank the New York Structural Biology Center for access to their 17.6 T spectrometer.

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Correspondence to Clare P. Grey.

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Supplementary figures S1, S2, S3, S4 and S5 (PDF 154 kb)

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Peng, L., Liu, Y., Kim, N. et al. Detection of Brønsted acid sites in zeolite HY with high-field 17O-MAS-NMR techniques. Nature Mater 4, 216–219 (2005). https://doi.org/10.1038/nmat1332

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