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

Journal Article · · JACS Au
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [3];  [4]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [5]
  1. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Institute for Integrated Catalysis and Physical Science Division
  2. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Institute for Integrated Catalysis and Physical Science Division; Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
  3. Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  4. Technische Univ. Munchen, Garching (Germany)
  5. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Institute for Integrated Catalysis and Physical Science Division; Technische Univ. Munchen, Garching (Germany)

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.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-76RL01830; FWP 47319
OSTI ID:
1997434
Alternate ID(s):
OSTI ID: 2246647
Report Number(s):
PNNL-SA-179083
Journal Information:
JACS Au, Vol. 3, Issue 9; ISSN 2691-3704
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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