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Title: Variations in proton transfer pathways and energetics on pristine and defect-rich quartz surfaces in water: Insights into the bimodal acidities of quartz

Journal Article · · Journal of Colloid and Interface Science
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [3];  [4]; ORCiD logo [1]; ORCiD logo [1]
  1. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Columbia Univ., New York, NY (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  4. Argonne National Laboratory (ANL), Argonne, IL (United States)
+ Show Author Affiliations

Hypothesis: Understanding the mechanisms of proton transfer on quartz surfaces in water is critical for a range of processes in geochemical, environmental, and materials sciences. The wide range of surface acidities ( >9 p K a units) found on the ubiquitous mineral quartz is caused by the structural variations of surface silanol groups. Molecular scale simulations provide essential tools for elucidating the origin of site-specific surface acidities. Simulations: We used density -functional tight -binding -based molecular dynamics combined with rare -event metadynamics simulations to probe the mechanisms of deprotonation reactions from ten representative surface silanol groups found on both pristine and defect -rich quartz (1 01) surfaces with Si vacancies. Findings: The results show that deprotonation is a highly dynamic process where both the surface hydroxyls and bridging oxygen atoms serve as the proton acceptors, in addition to water. Deprotonation of embedded silanols through intrasurface proton transfer exhibited lower p K a values with less H -bond participation and higher energy barriers, suggesting a new mechanism to explain the bimodal acidity observed on quartz surface. Defect sites, recently shown to comprise a significant portion of the quartz (101) surface, diversify the coordination and local H -bonding environments of the surface silanols, changing both the deprotonation pathways and energetics, leading to a wider range of p K a values (2.4 to 11.5) than that observed on pristine quartz surface (10.4 and 12.1).

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC05-00OR22725; AC02-05CH11231; AC02-06CH11357
OSTI ID:
2345310
Alternate ID(s):
OSTI ID: 2500780
Journal Information:
Journal of Colloid and Interface Science, Vol. 666; ISSN 0021-9797
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
quartz
proton transfer
interface
acidity constant
molecular dynamics
metadynamics