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Concerted Metal Cation Desorption and Proton Transfer on Deprotonated Silica Surfaces

Journal Article · · Journal of Physical Chemistry Letters
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  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
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The adsorption equilibrium constants of monovalent and divalent cations to material surfaces in aqueous media are central to many technological, natural, and geochemical processes. Cation adsorption–desorption is often proposed to occur in concert with proton transfer on hydroxyl-covered mineral surfaces, but to date this cooperative effect has been inferred indirectly. This work applies density functional theory-based molecular dynamics simulations of explicit liquid water/mineral interfaces to calculate metal ion desorption free energies. Monodentate adsorption of Na+, Mg2+, and Cu2+ on partially deprotonated silica surfaces are considered. Na+ is predicted to be unbound, while Cu2+ exhibits binding free energies to surface SiO– groups that are larger than those of Mg2+. The predicted trends agree with competitive adsorption measurements on fumed silica surfaces. As desorption proceeds, Cu2+ dissociates one of the H2O molecules in its first solvation shell, turning into Cu2+(OH–)(H2O)3, while Mg remains Mg2+(H2O)6. The protonation state of the SiO– group at the initial binding site does not vary monotonically with cation desorption

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1473940
Alternate ID(s):
OSTI ID: 1575159
Report Number(s):
SAND--2018-10050J; 667842
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 18 Vol. 9; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (49)

Kinetics and thermodynamics of aluminum oxide nanopowder as adsorbent for Fe (III) from aqueous solution journal June 2015
Copper uptake by silica and iron oxide under high surface coverage conditions: surface charge and sorption equilibrium modeling journal December 2003
Bimodal Acidity at the Amorphous Silica/Water Interface journal November 2015
Adsorption of Singly Charged Ions at the Hydroxylated (0001) α-Quartz/Water Interface journal February 2016
Electrolytes at the Hydroxylated (0001) α-Quartz/Water Interface: Location and Structural Effects on Interfacial Silanols by DFT-Based MD journal June 2016
Quantifying the Mechanisms of Site-Specific Ion Exchange at an Inhomogeneously Charged Surface: Case of Cs + /K + on Hydrated Muscovite Mica journal March 2017
Sum-Frequency Vibrational Spectroscopy on Water Interfaces:  Polar Orientation of Water Molecules at Interfaces journal April 2006
Prediction of the p K a ’s of Aqueous Metal Ion +2 Complexes journal March 2015
XAFS Spectroscopy Study of Cu(II) Sorption on Amorphous SiO2and γ-Al2O3: Effect of Substrate and Time on Sorption Complexes journal December 1998
23 Na and 133 Cs NMR study of cation adsorption on mineral surfaces: Local environments, dynamics, and effects of mixed cations journal December 1997
Revisiting the free energy profile for the nucleophilic attack of hydroxide on formamide in aqueous solution journal April 2006
Get charged up: Nonlinear optical voltammetry for quantifying the thermodynamics and electrostatics of metal cations at aqueous/oxide interfaces journal October 2010
Prediction of the speciation of alkaline earths adsorbed on mineral surfaces in salt solutions journal May 2006
Absolute acidity of clay edge sites from ab-initio simulations journal October 2012
Understanding surface acidity of gibbsite with first principles molecular dynamics simulations journal November 2013
Surface complexation of heavy metal cations on clay edges: insights from first principles molecular dynamics simulation of Ni(II) journal April 2017
Temperature effects on alkaline earth metal ions adsorption on gibbsite: Approaches from macroscopic sorption experiments and molecular dynamics simulations journal June 2013
Calorimetric study of alkali and alkaline-earth cation adsorption and exchange at the quartz-solution interface journal October 2017
Interaction of NaOH solutions with silica surfaces journal April 2018
Bimodal or Trimodal? The Influence of Starting pH on Site Identity and Distribution at the Low Salt Aqueous/Silica Interface journal July 2015
How Ion Condensation Occurs at a Charged Surface: A Molecular Dynamics Investigation of the Stern Layer for Water–Silica Interfaces journal January 2016
p K a at Quartz/Electrolyte Interfaces journal August 2016
pH-Dependent Inversion of Hofmeister Trends in the Water Structure of the Electrical Double Layer journal June 2017
Free-Energy Landscape of the Dissolution of Gibbsite at High pH journal March 2018
Effect of Ions on H-Bond Structure and Dynamics at the Quartz(101)–Water Interface journal October 2016
The Silica–Water Interface: How the Silanols Determine the Surface Acidity and Modulate the Water Properties journal February 2012
The Solvation Structure of Na + and K + in Liquid Water Determined from High Level ab Initio Molecular Dynamics Simulations journal March 2012
The Adsorption of Gases on Plane Surfaces of Glass, mica and Platinum. journal September 1918
Ion Solvation Thermodynamics from Simulation with a Polarizable Force Field journal December 2003
Counterion Effect on Interfacial Water at Charged Interfaces and Its Relevance to the Hofmeister Series journal April 2014
Unique Lead Adsorption Behavior of Activated Hydroxyl Group in Two-Dimensional Titanium Carbide journal March 2014
Elucidating the Bimodal Acid−Base Behavior of the Water−Silica Interface from First Principles journal December 2009
Dissociative Water Potential for Molecular Dynamics Simulations journal August 2007
Intrinsic Acidity of Surface Sites in Calcium Silicate Hydrates and Its Implication to Their Electrokinetic Properties journal May 2014
Computational Molecular Simulation of the Oxidative Adsorption of Ferrous Iron at the Hematite (001)–Water Interface journal April 2015
Ion-specific adsorption and electroosmosis in charged amorphous porous silica journal January 2015
Redox potentials and pKa for benzoquinone from density functional theory based molecular dynamics journal October 2009
A reactive molecular dynamics simulation of the silica-water interface journal May 2010
Predicting the acidity constant of a goethite hydroxyl group from first principles journal March 2012
Lead and selenite adsorption at water–goethite interfaces from first principles journal August 2017
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Generalized Gradient Approximation Made Simple journal October 1996
In Situ X-ray Absorption Study of Surface Complexes: Selenium Oxyanions on agr-FeOOH journal November 1987
First Solvation Shell of the Cu(II) Aqua Ion: Evidence for Fivefold Coordination journal February 2001
Cadmium(II) Complexes Adsorbed on Clay Edge Surfaces: Insight From First Principles Molecular Dynamics Simulation journal August 2016
The Effect of Substrate Type and 2,2′-Bipyridine on the Sorption of Copper(II) on Silica and Alumina journal January 1996
Competitive Adsorption of Heavy Metals by Soils journal July 1986
XAFS study of Cu model compounds and Cu 2+ sorption products on amorphous SiO 2 , γ-Al 2 O 3 , and anatase journal January 2000

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