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H-D Exchange of Simple Aromatics as a Measure of Brønsted-Acid Site Strengths in Solids

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Abstract

The relative Brønsted-acid strengths of H-[Al]ZSM-5, H-[Fe]ZSM-5, H-[B]ZSM-5, silicalite, P-SPP, tungstated zirconia, ZrO2, and γ-Al2O3 were studied using H-D exchange with toluene and chlorobenzene. Temperature programmed desorption (TPD) of toluene-h8 and chlorobenzene-h5 from the deuterated forms of H-[Al]ZSM-5, H-[Fe]ZSM-5, and P-SPP demonstrated that the temperature at which H-D exchange rates become significant change with the proton affinity of the aromatic molecule and the strength of the Brønsted sites. The steady-state, gas-phase reaction between D2O and the aromatic molecules were consistent with the TPD results and allowed the Brønsted-acid site strengths to be ordered as follows: H-[Al]ZSM-5 > H-[Fe]ZSM-5 > tungstated zirconia > P-SPP > H-[B]ZSM-5. H-D exchange was also observed at high temperatures with ZrO2 and γ-Al2O3 but it appears that the reaction mechanism with these Lewis acids is different because reaction with toluene and chlorobenzene occur at nearly the same temperature. It is suggested that the H-D exchange reaction with simple aromatic molecules is a useful way to probe Brønsted acidity in solids.

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Acknowledgements

We acknowledge support from the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0001004.

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Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of Pennsylvania, Philadelphia, PA, 19104, USA

    Cong Wang, Xinyu Mao & Raymond J. Gorte

  2. Catalysis Center for Energy Innovation (CCEI), University of Delaware, Newark, DE, 19716, USA

    Cong Wang, Sha Li, Stavros Caratzoulas & Raymond J. Gorte

  3. Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, PA, 19104, USA

    Raymond J. Gorte

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  1. Cong Wang
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  2. Sha Li
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Correspondence to Raymond J. Gorte.

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Wang, C., Li, S., Mao, X. et al. H-D Exchange of Simple Aromatics as a Measure of Brønsted-Acid Site Strengths in Solids. Catal Lett 148, 3548–3556 (2018). https://doi.org/10.1007/s10562-018-2563-5

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