Stern Layer Structure and Energetics at Mica-Water Interfaces

Bourg, Ian C.; Lee, Sang Soo; Fenter, Paul; Tournassat, Christophe

doi:10.1021/acs.jpcc.7b01828

Title: Stern Layer Structure and Energetics at Mica-Water Interfaces

Journal Article · Tue Apr 11 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b01828· OSTI ID:1364386

Bourg, Ian C. ^[1]; Lee, Sang Soo ^[2]; Fenter, Paul ^[2]; Tournassat, Christophe ^[3]

Princeton Univ., NJ (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. d'Orleans (France)

The screening of surface charge by dissolved ions at solid liquid interfaces in the region of interfacial fluid known as the electrical double layer (EDL)-plays a recurrent role in surface science, from ion adsorption to colloidal mechanics to the transport properties of nanoporous media. A persistent unknown in theories of EDL-related phenomena is the structure of the Stern layer, the near-surface portion of the EDL where water molecules and adsorbed ions form specific short-range interactions with surface atoms. Here, we describe a set of synchrotron X-ray reflectivity (XRR) experiments and molecular dynamics (MD) simulations carried out under identical conditions for a range of 0.1 M alkali chloride (Li-, Na-, K-, Rb-, or CsCl) solutions on the basal surface of muscovite mica, a mineral isostructural to phyllosilicate clay minerals and one of the most widely studied reference surfaces in interfacial science. Our XRR and MD simulation results provide a remarkably consistent view of the structure and energetics of the Stern layer, with some discrepancy on the fraction of the minor outer-sphere component of Rb and on the adsorption energetics of Li. The results of both techniques, along with surface complexation model calculations, provide insight into the sensitivity of water structure and ion adsorption to surface topography and the type of adsorbed counterion.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1364386

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 17; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 102 works

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Electrokinetic flow of an aqueous electrolyte in amorphous silica nanotubes Daub, Christopher D.; Cann, Natalie M.; Bratko, D. Physical Chemistry Chemical Physics, Vol. 20, Issue 44 https://doi.org/10.1039/c8cp03791d	journal	January 2018
From Atoms to Pre-salt Reservoirs: Multiscale Simulations of the Low-Salinity Enhanced Oil Recovery Mechanisms da Silva, Gabriela Dias; de Freitas Martins, Ernane; Salvador, Michele Aparecida Polytechnica, Vol. 2, Issue 1-2 https://doi.org/10.1007/s41050-019-00014-1	journal	November 2019
Role of hydration energy and co-ions association on monovalent and divalent cations adsorption at mica-aqueous interface Adapa, Sai; Malani, Ateeque Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-30549-9	journal	August 2018
Anion Layering and Steric Hydration Repulsion on Positively Charged Surfaces in Aqueous Electrolytes Hu, Qingyun; Weber, Christian; Cheng, Hsiu-Wei ChemPhysChem, Vol. 18, Issue 21 https://doi.org/10.1002/cphc.201700865	journal	October 2017
Cationic Hofmeister Series of Wettability Alteration in Mica–Water–Alkane Systems Bera, B.; Kumar, N.; Duits, M. H. G. Langmuir, Vol. 34, Issue 45 https://doi.org/10.1021/acs.langmuir.8b03297	journal	October 2018
Ion-Specific and pH-Dependent Hydration of Mica–Electrolyte Interfaces van Lin, Simone R.; Grotz, Kara K.; Siretanu, Igor Langmuir, Vol. 35, Issue 17 https://doi.org/10.1021/acs.langmuir.9b00520	journal	April 2019
Structure, Dynamics, and Stability of Water Molecules during Interfacial Interaction with Clay Minerals: Strong Dependence on Surface Charges Li, Qinyi; Li, Xiong; Yang, Sen ACS Omega, Vol. 4, Issue 3 https://doi.org/10.1021/acsomega.9b00401	journal	March 2019
Ion Distribution and Hydration Structure at Solid–Liquid Interface between NaCl Crystal and Its Solution Liu, Feng; Sun, Deyan ACS Omega, Vol. 4, Issue 20 https://doi.org/10.1021/acsomega.9b02620	journal	November 2019

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