Self-Organization of 1-Propanol at H-ZSM-5 Brønsted Acid Sites

Sungmin Kim; Mal Soon Lee; Donald M. Camaioni; Oliver Y. Gutiérrez; Vassiliki Alexandra Glezakou; Niranjan Govind; Thomas Huthwelker; Ruixue Zhao; Roger Rousseau; John L. Fulton; Johannes A. Lercher

doi:10.1021/jacsau.3c00259

Self-Organization of 1-Propanol at H-ZSM-5 Brønsted Acid Sites

Sungmin Kim
, Mal Soon Lee
, Donald M. Camaioni
, Oliver Y. Gutiérrez
, Vassiliki Alexandra Glezakou
, Niranjan Govind
, Thomas Huthwelker
, Ruixue Zhao
, Roger Rousseau
, John L. Fulton
, Johannes A. Lercher

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

In situ Al K-edge X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS) spectroscopy in conjunction with ab initio molecular dynamics (AIMD) simulations show that adsorption of 1-propanol alters the structure of the Brønsted acid site through changes in the associated aluminum-oxygen tetrahedron in zeolite H-MFI. The decreasing intensity of the pre-edge signal of the in situ Al K-edge XANES spectra with increasing 1-propanol coverage shows that Al T-sites become more symmetric as the sorbed alcohol molecules form monomers, dimers, and trimers. The adsorption of monomeric 1-propanol on Brønsted acid sites reduces the distortion of the associated Al T-site, shortens the Al-O distance, and causes the formation of a Zundel-like structure. With dimeric and trimeric alcohol clusters, the zeolite proton is fully transferred to the alcohols and the aluminum-oxygen tetrahedron becomes fully symmetric. The subtle changes in Al-K-edge XANES in the presence of sorbate structures, with the use of theory, are used to probe the local zeolite structures and provide a basis to predict the population and chemical state of the sorbed species.

Original language	English
Pages (from-to)	2487-2497
Number of pages	11
Journal	JACS Au
Volume	3
Issue number	9
DOIs	https://doi.org/10.1021/jacsau.3c00259
State	Published - Sep 25 2023
Externally published	Yes

Funding

This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, and Geosciences & Biosciences (FWP 47319). PNNL is a multiprogram national laboratory operated for DOE by Battelle under Contract DE-AC05-76RL01830. Computational Resources were provided by user proposals at the Molecular Sciences Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences Laboratory, a US Department of Energy (DOE) national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL, and the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkley National Laboratory (LBNL).

Keywords

AIMD simulation
MD-EXAFS
TD-DFT XANES
adsorption on H-MFI
in situ Al K-edge XAS
quantitative XANES analysis

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10.1021/jacsau.3c00259

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title = "Self-Organization of 1-Propanol at H-ZSM-5 Br{\o}nsted Acid Sites",

abstract = "In situ Al K-edge X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS) spectroscopy in conjunction with ab initio molecular dynamics (AIMD) simulations show that adsorption of 1-propanol alters the structure of the Br{\o}nsted acid site through changes in the associated aluminum-oxygen tetrahedron in zeolite H-MFI. The decreasing intensity of the pre-edge signal of the in situ Al K-edge XANES spectra with increasing 1-propanol coverage shows that Al T-sites become more symmetric as the sorbed alcohol molecules form monomers, dimers, and trimers. The adsorption of monomeric 1-propanol on Br{\o}nsted acid sites reduces the distortion of the associated Al T-site, shortens the Al-O distance, and causes the formation of a Zundel-like structure. With dimeric and trimeric alcohol clusters, the zeolite proton is fully transferred to the alcohols and the aluminum-oxygen tetrahedron becomes fully symmetric. The subtle changes in Al-K-edge XANES in the presence of sorbate structures, with the use of theory, are used to probe the local zeolite structures and provide a basis to predict the population and chemical state of the sorbed species.",

keywords = "AIMD simulation, MD-EXAFS, TD-DFT XANES, adsorption on H-MFI, in situ Al K-edge XAS, quantitative XANES analysis",

author = "Sungmin Kim and Lee, \{Mal Soon\} and Camaioni, \{Donald M.\} and Guti{\'e}rrez, \{Oliver Y.\} and Glezakou, \{Vassiliki Alexandra\} and Niranjan Govind and Thomas Huthwelker and Ruixue Zhao and Roger Rousseau and Fulton, \{John L.\} and Lercher, \{Johannes A.\}",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. Published by American Chemical Society.",

year = "2023",

month = sep,

day = "25",

doi = "10.1021/jacsau.3c00259",

language = "English",

volume = "3",

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journal = "JACS Au",

issn = "2691-3704",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Self-Organization of 1-Propanol at H-ZSM-5 Brønsted Acid Sites

AU - Kim, Sungmin

AU - Lee, Mal Soon

AU - Camaioni, Donald M.

AU - Gutiérrez, Oliver Y.

AU - Glezakou, Vassiliki Alexandra

AU - Govind, Niranjan

AU - Huthwelker, Thomas

AU - Zhao, Ruixue

AU - Rousseau, Roger

AU - Fulton, John L.

AU - Lercher, Johannes A.

PY - 2023/9/25

Y1 - 2023/9/25

N2 - In situ Al K-edge X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS) spectroscopy in conjunction with ab initio molecular dynamics (AIMD) simulations show that adsorption of 1-propanol alters the structure of the Brønsted acid site through changes in the associated aluminum-oxygen tetrahedron in zeolite H-MFI. The decreasing intensity of the pre-edge signal of the in situ Al K-edge XANES spectra with increasing 1-propanol coverage shows that Al T-sites become more symmetric as the sorbed alcohol molecules form monomers, dimers, and trimers. The adsorption of monomeric 1-propanol on Brønsted acid sites reduces the distortion of the associated Al T-site, shortens the Al-O distance, and causes the formation of a Zundel-like structure. With dimeric and trimeric alcohol clusters, the zeolite proton is fully transferred to the alcohols and the aluminum-oxygen tetrahedron becomes fully symmetric. The subtle changes in Al-K-edge XANES in the presence of sorbate structures, with the use of theory, are used to probe the local zeolite structures and provide a basis to predict the population and chemical state of the sorbed species.

AB - In situ Al K-edge X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS) spectroscopy in conjunction with ab initio molecular dynamics (AIMD) simulations show that adsorption of 1-propanol alters the structure of the Brønsted acid site through changes in the associated aluminum-oxygen tetrahedron in zeolite H-MFI. The decreasing intensity of the pre-edge signal of the in situ Al K-edge XANES spectra with increasing 1-propanol coverage shows that Al T-sites become more symmetric as the sorbed alcohol molecules form monomers, dimers, and trimers. The adsorption of monomeric 1-propanol on Brønsted acid sites reduces the distortion of the associated Al T-site, shortens the Al-O distance, and causes the formation of a Zundel-like structure. With dimeric and trimeric alcohol clusters, the zeolite proton is fully transferred to the alcohols and the aluminum-oxygen tetrahedron becomes fully symmetric. The subtle changes in Al-K-edge XANES in the presence of sorbate structures, with the use of theory, are used to probe the local zeolite structures and provide a basis to predict the population and chemical state of the sorbed species.

KW - AIMD simulation

KW - MD-EXAFS

KW - TD-DFT XANES

KW - adsorption on H-MFI

KW - in situ Al K-edge XAS

KW - quantitative XANES analysis

UR - https://www.scopus.com/pages/publications/85171892246

U2 - 10.1021/jacsau.3c00259

DO - 10.1021/jacsau.3c00259

M3 - Article

AN - SCOPUS:85171892246

SN - 2691-3704

VL - 3

SP - 2487

EP - 2497

JO - JACS Au

JF - JACS Au

IS - 9

ER -

Self-Organization of 1-Propanol at H-ZSM-5 Brønsted Acid Sites

Abstract

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Keywords

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