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Title: Direct Observation of the Orientational Anisotropy of Buried Hydroxyl Groups inside Muscovite Mica

Abstract

Muscovite mica (001) is a widely-used model surface for controlling molecular assembly and a common substrate for environmental adsorption processes. The mica (001) surface displays near trigonal symmetry, but many molecular adsorbates — including water — exhibit unequal probabilities of alignment along its three nominally equivalent lattice directions. Buried hydroxyl groups within the muscovite structure are speculated to be responsible, but direct evidence is lacking. Here we utilize vibrational sum frequency generation spectroscopy (vSFG) to characterize the orientation and hydrogen-bonding environment of near-surface hydroxyls inside mica. Multiple distinct peaks are detected in the O-H stretch region, which we attribute to Si/Al substitution in the SiO4 tetrahedron and K+ ion adsorption above the hydroxyls based on density functional theory simulations. Our findings demonstrate that vSFG can identify the absolute orientation of –OH groups and hence the surface termination at a mica surface, providing a means to investigate how –OH groups influence molecular adsorption and better understand mica stacking-sequences and physical behavior.

Authors:
ORCiD logo [1];  [2];  [1];  [3];  [1]; ORCiD logo [1];  [2];  [1]; ORCiD logo [4]; ORCiD logo [3];  [5]
  1. Physical Sciences Division, Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
  2. Physical Sciences Division, Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; School of Chemical and Biological Engineering, Washington State University, Pullman, Washington 99364, United States
  3. Physical Sciences Division, Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Department of Materials Science and Engineering, University of Washington, Seattle, Washington 98195, United States
  4. Physical Sciences Division, Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Department of Chemical Engineering, University of Washington, Seattle, Washington 98195, United States
  5. Physical Sciences Division, Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1502396
Report Number(s):
PNNL-SA-140259
Journal ID: ISSN 0002-7863
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 5; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Tuladhar, Aashish, Chase, Zizwe A., Baer, Marcel D., Legg, Benjamin A., Tao, Jinhui, Zhang, Shuai, Winkelman, Austin D., Wang, Zheming, Mundy, Christopher J., De Yoreo, James J., and Wang, Hong-fei. Direct Observation of the Orientational Anisotropy of Buried Hydroxyl Groups inside Muscovite Mica. United States: N. p., 2019. Web. doi:10.1021/jacs.8b12483.
Tuladhar, Aashish, Chase, Zizwe A., Baer, Marcel D., Legg, Benjamin A., Tao, Jinhui, Zhang, Shuai, Winkelman, Austin D., Wang, Zheming, Mundy, Christopher J., De Yoreo, James J., & Wang, Hong-fei. Direct Observation of the Orientational Anisotropy of Buried Hydroxyl Groups inside Muscovite Mica. United States. doi:10.1021/jacs.8b12483.
Tuladhar, Aashish, Chase, Zizwe A., Baer, Marcel D., Legg, Benjamin A., Tao, Jinhui, Zhang, Shuai, Winkelman, Austin D., Wang, Zheming, Mundy, Christopher J., De Yoreo, James J., and Wang, Hong-fei. Mon . "Direct Observation of the Orientational Anisotropy of Buried Hydroxyl Groups inside Muscovite Mica". United States. doi:10.1021/jacs.8b12483.
@article{osti_1502396,
title = {Direct Observation of the Orientational Anisotropy of Buried Hydroxyl Groups inside Muscovite Mica},
author = {Tuladhar, Aashish and Chase, Zizwe A. and Baer, Marcel D. and Legg, Benjamin A. and Tao, Jinhui and Zhang, Shuai and Winkelman, Austin D. and Wang, Zheming and Mundy, Christopher J. and De Yoreo, James J. and Wang, Hong-fei},
abstractNote = {Muscovite mica (001) is a widely-used model surface for controlling molecular assembly and a common substrate for environmental adsorption processes. The mica (001) surface displays near trigonal symmetry, but many molecular adsorbates — including water — exhibit unequal probabilities of alignment along its three nominally equivalent lattice directions. Buried hydroxyl groups within the muscovite structure are speculated to be responsible, but direct evidence is lacking. Here we utilize vibrational sum frequency generation spectroscopy (vSFG) to characterize the orientation and hydrogen-bonding environment of near-surface hydroxyls inside mica. Multiple distinct peaks are detected in the O-H stretch region, which we attribute to Si/Al substitution in the SiO4 tetrahedron and K+ ion adsorption above the hydroxyls based on density functional theory simulations. Our findings demonstrate that vSFG can identify the absolute orientation of –OH groups and hence the surface termination at a mica surface, providing a means to investigate how –OH groups influence molecular adsorption and better understand mica stacking-sequences and physical behavior.},
doi = {10.1021/jacs.8b12483},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 5,
volume = 141,
place = {United States},
year = {2019},
month = {1}
}