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Title: Importance of interlayer H bonding structure to the stability of layered minerals

Layered (oxy) hydroxide minerals often possess out-of-plane hydrogen atoms that form hydrogen bonding networks which stabilize the layered structure. However, less is known about how the ordering of these bonds affects the structural stability and solubility of these minerals. Here, we report a new strategy that uses the focused electron beam to probe the effect of differences in hydrogen bonding networks on mineral solubility. In this regard, the dissolution behavior of boehmite (γ-AlOOH) and gibbsite (γ-Al(OH)3) were compared and contrasted in real time via liquid cell electron microscopy. Under identical such conditions, 2D-nanosheets of boehmite (γ-AlOOH) exfoliated from the bulk and then rapidly dissolved, whereas gibbsite was stable. Further, substitution of only 1% Fe(III) for Al(III) in the structure of boehmite inhibited delamination and dissolution. Factors such as pH, radiolytic species, and knock on damage were systematically studied and eliminated as proximal causes for boehmite dissolution. Instead, the creation of electron/hole pairs was considered to be the mechanism that drove dissolution. The widely disparate behaviors of boehmite, gibbsite, and Fe-doped boehmite are discussed in the context of differences in the OH bond strengths, hydrogen bonding networks, and the presence or absence of electron/hole recombination centers.
Authors:
 [1] ;  [2] ;  [3] ;  [1] ;  [1] ;  [2] ;  [2] ;  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environment Directorate
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). National Security Directorate
Publication Date:
Report Number(s):
PNNL-SA-126728
Journal ID: ISSN 2045-2322; PII: 13452
Grant/Contract Number:
AC05-76RL01830
Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org:
USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); PNNL Laboratory Directed Research and Development (LDRD) Program
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES; geochemistry; imaging techniques
OSTI Identifier:
1430728

Conroy, Michele, Soltis, Jennifer A., Wittman, Rick S., Smith, Frances N., Chatterjee, Sayandev, Zhang, Xin, Ilton, Eugene S., and Buck, Edgar C.. Importance of interlayer H bonding structure to the stability of layered minerals. United States: N. p., Web. doi:10.1038/S41598-017-13452-7.
Conroy, Michele, Soltis, Jennifer A., Wittman, Rick S., Smith, Frances N., Chatterjee, Sayandev, Zhang, Xin, Ilton, Eugene S., & Buck, Edgar C.. Importance of interlayer H bonding structure to the stability of layered minerals. United States. doi:10.1038/S41598-017-13452-7.
Conroy, Michele, Soltis, Jennifer A., Wittman, Rick S., Smith, Frances N., Chatterjee, Sayandev, Zhang, Xin, Ilton, Eugene S., and Buck, Edgar C.. 2017. "Importance of interlayer H bonding structure to the stability of layered minerals". United States. doi:10.1038/S41598-017-13452-7. https://www.osti.gov/servlets/purl/1430728.
@article{osti_1430728,
title = {Importance of interlayer H bonding structure to the stability of layered minerals},
author = {Conroy, Michele and Soltis, Jennifer A. and Wittman, Rick S. and Smith, Frances N. and Chatterjee, Sayandev and Zhang, Xin and Ilton, Eugene S. and Buck, Edgar C.},
abstractNote = {Layered (oxy) hydroxide minerals often possess out-of-plane hydrogen atoms that form hydrogen bonding networks which stabilize the layered structure. However, less is known about how the ordering of these bonds affects the structural stability and solubility of these minerals. Here, we report a new strategy that uses the focused electron beam to probe the effect of differences in hydrogen bonding networks on mineral solubility. In this regard, the dissolution behavior of boehmite (γ-AlOOH) and gibbsite (γ-Al(OH)3) were compared and contrasted in real time via liquid cell electron microscopy. Under identical such conditions, 2D-nanosheets of boehmite (γ-AlOOH) exfoliated from the bulk and then rapidly dissolved, whereas gibbsite was stable. Further, substitution of only 1% Fe(III) for Al(III) in the structure of boehmite inhibited delamination and dissolution. Factors such as pH, radiolytic species, and knock on damage were systematically studied and eliminated as proximal causes for boehmite dissolution. Instead, the creation of electron/hole pairs was considered to be the mechanism that drove dissolution. The widely disparate behaviors of boehmite, gibbsite, and Fe-doped boehmite are discussed in the context of differences in the OH bond strengths, hydrogen bonding networks, and the presence or absence of electron/hole recombination centers.},
doi = {10.1038/S41598-017-13452-7},
journal = {Scientific Reports},
number = ,
volume = 7,
place = {United States},
year = {2017},
month = {10}
}

Works referenced in this record:

Liquid Exfoliation of Layered Materials
journal, June 2013
  • Nicolosi, V.; Chhowalla, M.; Kanatzidis, M. G.
  • Science, Vol. 340, Issue 6139, p. 1226419
  • DOI: 10.1126/science.1226419

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976

Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials
journal, February 2011