Molecular origins of the zeta potential

Predota, Milan; Machesky, Michael L.; Wesolowski, David J.

doi:10.1021/acs.langmuir.6b02493

Title: Molecular origins of the zeta potential

Journal Article · Mon Sep 19 00:00:00 EDT 2016 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.6b02493· OSTI ID:1333097

Predota, Milan ^[1]; Machesky, Michael L. ^[2]; Wesolowski, David J. ^[3]

Univ. of South Bohemia, Ceske Budejovice (Czech Republic)
Univ. of Illinois, Champaign, IL (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The zeta potential (ZP) is an oft-reported measure of the macroscopic charge state of solid surfaces and colloidal particles in contact with solvents. However, the origin of this readily measurable parameter has remained divorced from the molecular-level processes governing the underlying electrokinetic phenomena, which limits its usefulness. Here, we connect the macroscopic measure to the microscopic realm through nonequilibrium molecular dynamics simulations of electroosmotic flow between parallel slabs of the hydroxylated (110) rutile (TiO₂) surface. These simulations provided streaming mobilities, which were converted to ZP via the commonly used Helmholtz-Smoluchowski equation. A range of rutile surface charge densities (0.1 to –0.4 C/m²), corresponding to pH values between about 2.8 and 9.4, in RbCl, NaCl, and SrCl₂ aqueous solutions, were modeled and compared to experimental ZPs for TiO₂ particle suspensions. Simulated ZPs qualitatively agree with experiment and show that “anomalous” ZP values and inequalities between the point of zero charge derived from electrokinetic versus pH titration measurements both arise from differing co- and counterion sorption affinities. We show that at the molecular level the ZP arises from the delicate interplay of spatially varying dynamics, structure, and electrostatics in a narrow interfacial region within about 15 Å of the surface, even in dilute salt solutions. This contrasts fundamentally with continuum descriptions of such interfaces, which predict the ZP response region to be inversely related to ionic strength. In reality the properties of this interfacial region are dominated by relatively immobile and structured water. Furthermore, viscosity values are substantially greater than in the bulk, and electrostatic potential profiles are oscillatory in nature.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1333097

Journal Information:: Langmuir, Vol. 32, Issue 40; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 76 works

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References (57)

Measurement and Interpretation of Electrokinetic Phenomena (IUPAC Technical Report) Delgado, A. V.; González-Caballero, F.; Hunter, R. J. Pure and Applied Chemistry, Vol. 77, Issue 10 https://doi.org/10.1351/pac200577101753	journal	January 2005
Electrokinetic Particle Transport in Micro-/Nanofluidics: Direct Numerical Simulation Analysis Qian, Shizhi; Ai, Ye https://doi.org/10.1201/b12128	reference-book	January 2012
Applications of the Zeta Potential Hunter, Robert J. Zeta Potential in Colloid Science https://doi.org/10.1016/B978-0-12-361961-7.50010-9	book	January 1981
Size-Dependent Reactivity of Diamond Nanoparticles Williams, Oliver A.; Hees, Jakob; Dieker, Christel ACS Nano, Vol. 4, Issue 8 https://doi.org/10.1021/nn100748k	journal	July 2010
Stability and Aggregation of Metal Oxide Nanoparticles in Natural Aqueous Matrices Keller, Arturo A.; Wang, Hongtao; Zhou, Dongxu Environmental Science & Technology, Vol. 44, Issue 6 https://doi.org/10.1021/es902987d	journal	March 2010
Aggregation and Stability of Reduced Graphene Oxide: Complex Roles of Divalent Cations, pH, and Natural Organic Matter Chowdhury, Indranil; Mansukhani, Nikhita D.; Guiney, Linda M. Environmental Science & Technology, Vol. 49, Issue 18 https://doi.org/10.1021/acs.est.5b01866	journal	July 2015
Gold Nanoparticles Capped with Polyethyleneimine for Enhanced siRNA Delivery Song, Wen-Jing; Du, Jin-Zhi; Sun, Tian-Meng Small, Vol. 6, Issue 2 https://doi.org/10.1002/smll.200901513	journal	January 2010
Citric Acid Adsorption on TiO ₂ Nanoparticles in Aqueous Suspensions at Acidic and Circumneutral pH: Surface Coverage, Surface Speciation, and Its Impact on Nanoparticle−Nanoparticle Interactions Mudunkotuwa, Imali A.; Grassian, Vicki H. Journal of the American Chemical Society, Vol. 132, Issue 42 https://doi.org/10.1021/ja106091q	journal	October 2010
Removal and Utilization of Capping Agents in Nanocatalysis Niu, Zhiqiang; Li, Yadong Chemistry of Materials, Vol. 26, Issue 1 https://doi.org/10.1021/cm4022479	journal	September 2013
The surface charge of suspended particles in estuarine and coastal waters Hunter, K. A.; Liss, P. S. Nature, Vol. 282, Issue 5741 https://doi.org/10.1038/282823a0	journal	December 1979
Time Evolution of the Nanoparticle Protein Corona Casals, Eudald; Pfaller, Tobias; Duschl, Albert ACS Nano, Vol. 4, Issue 7 https://doi.org/10.1021/nn901372t	journal	June 2010
Re-examining the Size/Charge Paradigm: Differing in Vivo Characteristics of Size- and Charge-Matched Mesoporous Silica Nanoparticles Townson, Jason L.; Lin, Yu-Shen; Agola, Jacob O. Journal of the American Chemical Society, Vol. 135, Issue 43 https://doi.org/10.1021/ja4082414	journal	October 2013
The relationship between pH and zeta potential of ∼ 30 nm metal oxide nanoparticle suspensions relevant to in vitro toxicological evaluations Berg, J. Michael; Romoser, Amelia; Banerjee, Nivedita Nanotoxicology, Vol. 3, Issue 4 https://doi.org/10.3109/17435390903276941	journal	November 2009
Characterization of size, surface charge, and agglomeration state of nanoparticle dispersions for toxicological studies Jiang, Jingkun; Oberdörster, Günter; Biswas, Pratim Journal of Nanoparticle Research, Vol. 11, Issue 1 https://doi.org/10.1007/s11051-008-9446-4	journal	June 2008
Surface Charge-Dependent Toxicity of Silver Nanoparticles El Badawy, Amro M.; Silva, Rendahandi G.; Morris, Brian Environmental Science & Technology, Vol. 45, Issue 1 https://doi.org/10.1021/es1034188	journal	January 2011
Impact of Silica Nanoparticle Design on Cellular Toxicity and Hemolytic Activity Yu, Tian; Malugin, Alexander; Ghandehari, Hamidreza ACS Nano, Vol. 5, Issue 7 https://doi.org/10.1021/nn2013904	journal	June 2011
High Temperature Microelectrophoresis Studies of the Rutile/Aqueous Solution Interface Fedkin, Mark V.; Zhou, Xiangyang Y.; Kubicki, James D. Langmuir, Vol. 19, Issue 9 https://doi.org/10.1021/la0268653	journal	April 2003
Characterization and Surface-Reactivity of Nanocrystalline Anatase in Aqueous Solutions Ridley, Moira K.; Hackley, Vincent A.; Machesky, Michael L. Langmuir, Vol. 22, Issue 26 https://doi.org/10.1021/la061774h	journal	December 2006
Ion Adsorption into the Hydrothermal Regime: Experimental and Modeling Approaches Machesky, M. L.; Wesolowski, D. J.; Palmer, D. A. Interface Science and Technology https://doi.org/10.1016/S1573-4285(06)80056-6	book	January 2006
Surface charges and electrokinetic charges: Distinctions and juxtapositionings Lyklema, Johannes Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 376, Issue 1-3 https://doi.org/10.1016/j.colsurfa.2010.09.021	journal	February 2011
Electrokinetics: The Properties of the Stagnant Layer Unraveled Lyklema, J.; Rovillard, S.; De Coninck, J. Langmuir, Vol. 14, Issue 20 https://doi.org/10.1021/la980399t	journal	September 1998
Molecular interpretation of electrokinetic potentials Lyklema, Johannes Current Opinion in Colloid & Interface Science, Vol. 15, Issue 3 https://doi.org/10.1016/j.cocis.2010.01.001	journal	June 2010
Electro-osmosis in a nanometer-scale channel studied by atomistic simulation Freund, Jonathan B. The Journal of Chemical Physics, Vol. 116, Issue 5 https://doi.org/10.1063/1.1431543	journal	February 2002
Interfacial Water at Hydrophobic and Hydrophilic Surfaces: Slip, Viscosity, and Diffusion Sendner, Christian; Horinek, Dominik; Bocquet, Lyderic Langmuir, Vol. 25, Issue 18 https://doi.org/10.1021/la901314b	journal	September 2009
Molecular dynamics simulation of electroosmotic flow in rough nanochannels Zhang, Chengbin; Lu, Pengfei; Chen, Yongping International Communications in Heat and Mass Transfer, Vol. 59 https://doi.org/10.1016/j.icheatmasstransfer.2014.10.024	journal	December 2014
Physical origins of apparently enhanced viscosity of interfacial fluids in electrokinetic transport Wu, Peng; Qiao, Rui Physics of Fluids, Vol. 23, Issue 7 https://doi.org/10.1063/1.3614534	journal	July 2011
Estimation of zeta potentials of titania nanoparticles by molecular simulation English, Niall J.; Long, William F. Physica A: Statistical Mechanics and its Applications, Vol. 388, Issue 19 https://doi.org/10.1016/j.physa.2009.06.026	journal	October 2009
Ion-Specific Anomalous Electrokinetic Effects in Hydrophobic Nanochannels Huang, David M.; Cottin-Bizonne, Cécile; Ybert, Christophe Physical Review Letters, Vol. 98, Issue 17 https://doi.org/10.1103/PhysRevLett.98.177801	journal	April 2007
Recent advances in the modelling and simulation of electrokinetic effects: bridging the gap between atomistic and macroscopic descriptions Pagonabarraga, I.; Rotenberg, B.; Frenkel, D. Physical Chemistry Chemical Physics, Vol. 12, Issue 33 https://doi.org/10.1039/c004012f	journal	January 2010
Electrokinetics: insights from simulation on the microscopic scale Rotenberg, Benjamin; Pagonabarraga, Ignacio Molecular Physics, Vol. 111, Issue 7 https://doi.org/10.1080/00268976.2013.791731	journal	April 2013
Electric Double Layer at the Rutile (110) Surface. 1. Structure of Surfaces and Interfacial Water from Molecular Dynamics by Use of ab Initio Potentials Předota, M.; Bandura, A. V.; Cummings, P. T. The Journal of Physical Chemistry B, Vol. 108, Issue 32 https://doi.org/10.1021/jp037197c	journal	August 2004
Electric Double Layer at the Rutile (110) Surface. 2. Adsorption of Ions from Molecular Dynamics and X-ray Experiments Předota, M.; Zhang, Z.; Fenter, P. The Journal of Physical Chemistry B, Vol. 108, Issue 32 https://doi.org/10.1021/jp037199x	journal	August 2004
Electric Double Layer at the Rutile (110) Surface. 3. Inhomogeneous Viscosity and Diffusivity Measurement by Computer Simulations Předota, M.; Cummings, P. T.; Wesolowski, D. J. The Journal of Physical Chemistry C, Vol. 111, Issue 7 https://doi.org/10.1021/jp065165u	journal	January 2007
Determination of the distance-dependent viscosity of mixtures in parallel slabs using non-equilibrium molecular dynamics Pařez, Stanislav; Předota, Milan Physical Chemistry Chemical Physics, Vol. 14, Issue 10 https://doi.org/10.1039/c2cp22136e	journal	January 2012
Dynamics and Structure of Hydration Water on Rutile and Cassiterite Nanopowders Studied by Quasielastic Neutron Scattering and Molecular Dynamics Simulations Mamontov, E.; Vlcek, L.; Wesolowski, D. J. The Journal of Physical Chemistry C, Vol. 111, Issue 11 https://doi.org/10.1021/jp067242r	journal	February 2007
Dynamics of Hydration Water on Rutile Studied by Backscattering Neutron Spectroscopy and Molecular Dynamics Simulation Mamontov, E.; Wesolowski, D. J.; Vlcek, L. The Journal of Physical Chemistry C, Vol. 112, Issue 32 https://doi.org/10.1021/jp711965x	journal	July 2008
Comment on Parts 1 and 2 of the Series “Electric Double Layer at the Rutile (110) Surface” Předota, M.; Vlček, L. The Journal of Physical Chemistry B, Vol. 111, Issue 5 https://doi.org/10.1021/jp068250a	journal	February 2007
Electric Double Layer at the Rutile (110) Surface. 4. Effect of Temperature and pH on the Adsorption and Dynamics of Ions Předota, M.; Machesky, M. L.; Wesolowski, D. J. The Journal of Physical Chemistry C, Vol. 117, Issue 44 https://doi.org/10.1021/jp407124p	journal	October 2013
The missing term in effective pair potentials Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P. The Journal of Physical Chemistry, Vol. 91, Issue 24 https://doi.org/10.1021/j100308a038	journal	November 1987
Ion Adsorption at the Rutile−Water Interface: Linking Molecular and Macroscopic Properties Zhang, Z.; Fenter, P.; Cheng, L. Langmuir, Vol. 20, Issue 12 https://doi.org/10.1021/la0353834	journal	June 2004
Constrained Surface Complexation Modeling: Rutile in RbCl, NaCl, and NaCF ₃ SO ₃ Media to 250 °C Machesky, Michael L.; Předota, Milan; Ridley, Moira K. The Journal of Physical Chemistry C, Vol. 119, Issue 27 https://doi.org/10.1021/acs.jpcc.5b02841	journal	June 2015
Ion-specific adsorption and electroosmosis in charged amorphous porous silica Hartkamp, Remco; Siboulet, Bertrand; Dufrêche, Jean-François Physical Chemistry Chemical Physics, Vol. 17, Issue 38 https://doi.org/10.1039/C5CP03818A	journal	January 2015
How Electrostatics Influences Hydrodynamic Boundary Conditions: Poiseuille and Electro-osmostic Flows in Clay Nanopores. Boţan, A.; Marry, V.; Rotenberg, B. The Journal of Physical Chemistry C, Vol. 117, Issue 2 https://doi.org/10.1021/jp3092336	journal	January 2013
The electrophoretic mobility of an uncharged particle O’Brien, Richard W.; Beattie, James K.; Djerdjev, Alex M. Journal of Colloid and Interface Science, Vol. 420 https://doi.org/10.1016/j.jcis.2013.10.047	journal	April 2014
Aqueous Electrolytes near Hydrophobic Surfaces: Dynamic Effects of Ion Specificity and Hydrodynamic Slip Huang, David M.; Cottin-Bizonne, Cécile; Ybert, Christophe Langmuir, Vol. 24, Issue 4 https://doi.org/10.1021/la7021787	journal	December 2007
High-ionic-strength electroosmotic flows in uncharged hydrophobic nanochannels Kim, Daejoong; Darve, Eric Journal of Colloid and Interface Science, Vol. 330, Issue 1 https://doi.org/10.1016/j.jcis.2008.10.029	journal	February 2009
Hierarchical Multiscale Simulation of Electrokinetic Transport in Silica Nanochannels at the Point of Zero Charge Joseph, Sony; Aluru, N. R. Langmuir, Vol. 22, Issue 21 https://doi.org/10.1021/la0610147	journal	October 2006
Electrokinetics at High Ionic Strength and Hypothesis of the Double Layer with Zero Surface Charge Dukhin, A.; Dukhin, S.; Goetz, P. Langmuir, Vol. 21, Issue 22 https://doi.org/10.1021/la050480d	journal	July 2005
Application of Extended DLVO Theory Yotsumoto, Hiroki; Yoon, Roe-Hoan Journal of Colloid and Interface Science, Vol. 157, Issue 2 https://doi.org/10.1006/jcis.1993.1205	journal	May 1993
Surface Protonation at the Rutile (110) Interface: Explicit Incorporation of Solvation Structure within the Refined MUSIC Model Framework Machesky, Michael L.; Předota, Milan; Wesolowski, David J. Langmuir, Vol. 24, Issue 21 https://doi.org/10.1021/la801356m	journal	November 2008
Electroacoustics for Concentrated Dispersions Dukhin, A. S.; Ohshima, H.; Shilov, V. N. Langmuir, Vol. 15, Issue 10 https://doi.org/10.1021/la9813836	journal	May 1999
The influence of pH and NaCl on the zeta potential and rheology of anatase dispersions Gustafsson, Jan; Mikkola, Pasi; Jokinen, Mika Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 175, Issue 3 https://doi.org/10.1016/S0927-7757(00)00634-8	journal	December 2000
Electroacoustic study of titania at high concentrations of 1-2, 2-1 and 2-2 electrolytes Kosmulski, Marek; Prochniak, Piotr; Rosenholm, Jarl B. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 345, Issue 1-3 https://doi.org/10.1016/j.colsurfa.2009.04.041	journal	August 2009
On Points of Zero Charge Sposito, Garrison Environmental Science & Technology, Vol. 32, Issue 19 https://doi.org/10.1021/es9802347	journal	October 1998
Hydrolysis versus Ion Correlation Models in Electrokinetic Charge Inversion: Establishing Application Ranges Jiménez, María L.; Delgado, Ángel V.; Lyklema, Johannes Langmuir, Vol. 28, Issue 17 https://doi.org/10.1021/la3010773	journal	April 2012
Molecular Dynamics of Ionic Transport and Electrokinetic Effects in Realistic Silica Channels Lorenz, Christian D.; Crozier, Paul S.; Anderson, Joshua A. The Journal of Physical Chemistry C, Vol. 112, Issue 27 https://doi.org/10.1021/jp711510k	journal	June 2008
Dielectric Properties of Water at Rutile and Graphite Surfaces: Effect of Molecular Structure Parez, Stanislav; Předota, Milan; Machesky, Michael The Journal of Physical Chemistry C, Vol. 118, Issue 9 https://doi.org/10.1021/jp4128012	journal	February 2014

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