Genesis and Stability of Hydronium Ions in Zeolite Channels

Meng Wang, Nicholas R. Jaegers, Mal Soon Lee, Chuan Wan, Jian Zhi Hu, Hui Shi, Donghai Mei, Sarah D. Burton, Donald M. Camaioni, Oliver Y. Gutiérrez, Vassiliki Alexandra Glezakou, Roger Rousseau, Yong Wang, Johannes A. Lercher

Research output: Contribution to journalArticle

Abstract

The catalytic sites of acidic zeolite are profoundly altered by the presence of water changing the nature of the Brønsted acid site. High-resolution solid-state NMR spectroscopy shows water interacting with zeolite Brønsted acid sites, converting them to hydrated hydronium ions over a wide range of temperature and thermodynamic activity of water. A signal at 9 ppm was observed at loadings of 2-9 water molecules per Brønsted acid site and is assigned to hydrated hydronium ions on the basis of the evolution of the signal with increasing water content, chemical shift calculations, and the direct comparison with HClO 4 in water. The intensity of 1 H- 29 Si cross-polarization signal first increased and then decreased with increasing water chemical potential. This indicates that hydrogen bonds between water molecules and the tetrahedrally coordinated aluminum in the zeolite lattice weaken with the formation of hydronium ion-water clusters and increase the mobility of protons. DFT-based ab initio molecular dynamics studies at multiple temperatures and water concentrations agree well with this interpretation. Above 140 °C, however, fast proton exchange between bridging hydroxyl groups and water occurs even in the presence of only one water molecule per acid site.

Original languageEnglish
Pages (from-to)3444-3455
Number of pages12
JournalJournal of the American Chemical Society
Volume141
Issue number8
DOIs
Publication statusPublished - Feb 27 2019

Fingerprint

Zeolites
Water
Ions
Acids
Molecules
Protons
hydronium ion
Chemical potential
Temperature
Chemical shift
Aluminum
Discrete Fourier transforms
Molecular Dynamics Simulation
Hydroxyl Radical
Water content
Nuclear magnetic resonance spectroscopy
Thermodynamics
Molecular dynamics
Ion exchange
Hydrogen bonds

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Wang, M., Jaegers, N. R., Lee, M. S., Wan, C., Hu, J. Z., Shi, H., ... Lercher, J. A. (2019). Genesis and Stability of Hydronium Ions in Zeolite Channels. Journal of the American Chemical Society, 141(8), 3444-3455. https://doi.org/10.1021/jacs.8b07969

Genesis and Stability of Hydronium Ions in Zeolite Channels. / Wang, Meng; Jaegers, Nicholas R.; Lee, Mal Soon; Wan, Chuan; Hu, Jian Zhi; Shi, Hui; Mei, Donghai; Burton, Sarah D.; Camaioni, Donald M.; Gutiérrez, Oliver Y.; Glezakou, Vassiliki Alexandra; Rousseau, Roger; Wang, Yong; Lercher, Johannes A.

In: Journal of the American Chemical Society, Vol. 141, No. 8, 27.02.2019, p. 3444-3455.

Research output: Contribution to journalArticle

Wang, M, Jaegers, NR, Lee, MS, Wan, C, Hu, JZ, Shi, H, Mei, D, Burton, SD, Camaioni, DM, Gutiérrez, OY, Glezakou, VA, Rousseau, R, Wang, Y & Lercher, JA 2019, 'Genesis and Stability of Hydronium Ions in Zeolite Channels', Journal of the American Chemical Society, vol. 141, no. 8, pp. 3444-3455. https://doi.org/10.1021/jacs.8b07969
Wang, Meng ; Jaegers, Nicholas R. ; Lee, Mal Soon ; Wan, Chuan ; Hu, Jian Zhi ; Shi, Hui ; Mei, Donghai ; Burton, Sarah D. ; Camaioni, Donald M. ; Gutiérrez, Oliver Y. ; Glezakou, Vassiliki Alexandra ; Rousseau, Roger ; Wang, Yong ; Lercher, Johannes A. / Genesis and Stability of Hydronium Ions in Zeolite Channels. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 8. pp. 3444-3455.
@article{84c719dc21cf4b9089568583bb96081f,
title = "Genesis and Stability of Hydronium Ions in Zeolite Channels",
abstract = "The catalytic sites of acidic zeolite are profoundly altered by the presence of water changing the nature of the Br{\o}nsted acid site. High-resolution solid-state NMR spectroscopy shows water interacting with zeolite Br{\o}nsted acid sites, converting them to hydrated hydronium ions over a wide range of temperature and thermodynamic activity of water. A signal at 9 ppm was observed at loadings of 2-9 water molecules per Br{\o}nsted acid site and is assigned to hydrated hydronium ions on the basis of the evolution of the signal with increasing water content, chemical shift calculations, and the direct comparison with HClO 4 in water. The intensity of 1 H- 29 Si cross-polarization signal first increased and then decreased with increasing water chemical potential. This indicates that hydrogen bonds between water molecules and the tetrahedrally coordinated aluminum in the zeolite lattice weaken with the formation of hydronium ion-water clusters and increase the mobility of protons. DFT-based ab initio molecular dynamics studies at multiple temperatures and water concentrations agree well with this interpretation. Above 140 °C, however, fast proton exchange between bridging hydroxyl groups and water occurs even in the presence of only one water molecule per acid site.",
author = "Meng Wang and Jaegers, {Nicholas R.} and Lee, {Mal Soon} and Chuan Wan and Hu, {Jian Zhi} and Hui Shi and Donghai Mei and Burton, {Sarah D.} and Camaioni, {Donald M.} and Guti{\'e}rrez, {Oliver Y.} and Glezakou, {Vassiliki Alexandra} and Roger Rousseau and Yong Wang and Lercher, {Johannes A.}",
year = "2019",
month = "2",
day = "27",
doi = "10.1021/jacs.8b07969",
language = "English",
volume = "141",
pages = "3444--3455",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "8",

}

TY - JOUR

T1 - Genesis and Stability of Hydronium Ions in Zeolite Channels

AU - Wang, Meng

AU - Jaegers, Nicholas R.

AU - Lee, Mal Soon

AU - Wan, Chuan

AU - Hu, Jian Zhi

AU - Shi, Hui

AU - Mei, Donghai

AU - Burton, Sarah D.

AU - Camaioni, Donald M.

AU - Gutiérrez, Oliver Y.

AU - Glezakou, Vassiliki Alexandra

AU - Rousseau, Roger

AU - Wang, Yong

AU - Lercher, Johannes A.

PY - 2019/2/27

Y1 - 2019/2/27

N2 - The catalytic sites of acidic zeolite are profoundly altered by the presence of water changing the nature of the Brønsted acid site. High-resolution solid-state NMR spectroscopy shows water interacting with zeolite Brønsted acid sites, converting them to hydrated hydronium ions over a wide range of temperature and thermodynamic activity of water. A signal at 9 ppm was observed at loadings of 2-9 water molecules per Brønsted acid site and is assigned to hydrated hydronium ions on the basis of the evolution of the signal with increasing water content, chemical shift calculations, and the direct comparison with HClO 4 in water. The intensity of 1 H- 29 Si cross-polarization signal first increased and then decreased with increasing water chemical potential. This indicates that hydrogen bonds between water molecules and the tetrahedrally coordinated aluminum in the zeolite lattice weaken with the formation of hydronium ion-water clusters and increase the mobility of protons. DFT-based ab initio molecular dynamics studies at multiple temperatures and water concentrations agree well with this interpretation. Above 140 °C, however, fast proton exchange between bridging hydroxyl groups and water occurs even in the presence of only one water molecule per acid site.

AB - The catalytic sites of acidic zeolite are profoundly altered by the presence of water changing the nature of the Brønsted acid site. High-resolution solid-state NMR spectroscopy shows water interacting with zeolite Brønsted acid sites, converting them to hydrated hydronium ions over a wide range of temperature and thermodynamic activity of water. A signal at 9 ppm was observed at loadings of 2-9 water molecules per Brønsted acid site and is assigned to hydrated hydronium ions on the basis of the evolution of the signal with increasing water content, chemical shift calculations, and the direct comparison with HClO 4 in water. The intensity of 1 H- 29 Si cross-polarization signal first increased and then decreased with increasing water chemical potential. This indicates that hydrogen bonds between water molecules and the tetrahedrally coordinated aluminum in the zeolite lattice weaken with the formation of hydronium ion-water clusters and increase the mobility of protons. DFT-based ab initio molecular dynamics studies at multiple temperatures and water concentrations agree well with this interpretation. Above 140 °C, however, fast proton exchange between bridging hydroxyl groups and water occurs even in the presence of only one water molecule per acid site.

UR - http://www.scopus.com/inward/record.url?scp=85062283678&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85062283678&partnerID=8YFLogxK

U2 - 10.1021/jacs.8b07969

DO - 10.1021/jacs.8b07969

M3 - Article

C2 - 30698436

AN - SCOPUS:85062283678

VL - 141

SP - 3444

EP - 3455

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 8

ER -