Interfacial Reactivity and Speciation Emerging from Na-Montmorillonite Interactions with Water and Formic Acid at 200 °C: Insights from Reactive Molecular Dynamics Simulations, Infrared Spectroscopy, and X-ray Scattering Measurements

Muraleedharan, Murali Gopal; Asgar, Hassnain; Hahn, Seung Ho; Dasgupta, Nabankur; Gadikota, Greeshma; van Duin, Adri C. T.

doi:10.1021/acsearthspacechem.0c00286

Interfacial Reactivity and Speciation Emerging from Na-Montmorillonite Interactions with Water and Formic Acid at 200 °C: Insights from Reactive Molecular Dynamics Simulations, Infrared Spectroscopy, and X-ray Scattering Measurements

Journal Article · Fri Apr 23 00:00:00 EDT 2021 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.0c00286· OSTI ID:1866124

^[1]; ^[2]; ^[3]; ^[3]; Gadikota, Greeshma ^[2]; ^[3]

Pennsylvania State Univ., State College, PA (United States); University of Utah
Cornell Univ., Ithaca, NY (United States)
Pennsylvania State Univ., State College, PA (United States)

Reactive organic fluid - mineral interactions at elevated temperatures contribute to the evolution of planetary matter. One of the less studied but important transformations in this regard involves the reactions of formic acid with naturally occurring clays such as sodium montmorillonite. To advance a mechanistic understanding of these interactions, we use ReaxFF reactive molecular dynamics simulations in conjunction with infrared (IR) spectroscopy and X-ray scattering experiments to investigate the speciation behavior of water-formic acid mixtures on sodium montmorillonite interfaces at 473 K and 1 atm. Using a newly developed reactive forcefield, we show that the experimental IR spectra of unreacted and reacted mixture can be accurately reproduced by ReaxFF/MD. We further benchmark the simulation predictions of sodium carbonate and bicarbonate formation in the clay interlayers using Small and Wide-Angle X-ray Scattering measurements. Subsequently, leveraging the benchmarked forcefield, we interrogate the pathway of speciation reactions with emphasis on carbonate, formate, and hydroxide groups elucidating the energetics, transition states, intermediates, and preferred products. Further, we also delineate the differences in reactivities and catalytic effects of clay edges, facets, and interlayers owing to their local chemical environments, which have far reaching consequences in their speciation behavior. The experimental and simulation approaches described in this study and the transferable forcefields can be applied translationally to advance the science of clay-fluid interactions for several applications including subsurface fluid storage and recovery and clay-pollutant dynamics.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Utah, Salt Lake City, UT (United States); Energy Frontier Research Centers (EFRC) (United States). Multi-Scale Fluid−Solid Interactions in Architected and Natural Materials (MUSE)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0019285

OSTI ID:: 1866124

Alternate ID(s):: OSTI ID: 1853017

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 5 Vol. 5; ISSN 2472-3452

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (66)

FTIR spectra of hydroxyls and dehydroxylation kinetics mechanism in montmorillonite Malhotra, V. M.; Ogloza, A. A. Physics and Chemistry of Minerals, Vol. 16, Issue 4 https://doi.org/10.1007/BF00199560	journal	February 1989
Colloidal magnesium aluminum hydroxide and heterocoagulation with a clay mineral. I. Properties of colloidal magnesium aluminum hydroxide Lagaly, G.; Mecking, O.; Penner, D. Colloid & Polymer Science, Vol. 279, Issue 11 https://doi.org/10.1007/s003960100525	journal	November 2001
Fenton-like processes and adsorption using iron oxide-pillared clay with magnetic properties for organic compound mitigation Tireli, Aline Auxiliadora; Guimarães, Iara do Rosário; Terra, Júlio César de Souza Environmental Science and Pollution Research, Vol. 22, Issue 2 https://doi.org/10.1007/s11356-014-2973-x	journal	May 2014
Ultra-Small-Angle X-ray Scattering Instrument at the Advanced Photon Source: History, Recent Development, and Current Status Ilavsky, J.; Zhang, F.; Allen, A. J. Metallurgical and Materials Transactions A, Vol. 44, Issue 1 https://doi.org/10.1007/s11661-012-1431-y	journal	October 2012
Montmorillonite and serpentine in Orgueil meteorite Bass, Manuel N. Geochimica et Cosmochimica Acta, Vol. 35, Issue 2 https://doi.org/10.1016/0016-7037(71)90053-6	journal	February 1971
Thermodynamics of interlayer adsorption of water in clays. I.—Sodium vermiculite van Olphen, H. Journal of Colloid Science, Vol. 20, Issue 8 https://doi.org/10.1016/0095-8522(65)90055-3	journal	October 1965
The far infrared absorption spectrum and the assignment of the lattice modes of sodium formate Maas, J. P. M. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 33, Issue 8 https://doi.org/10.1016/0584-8539(77)80114-1	journal	January 1977
Carbon dioxide reaction processes in a model brine aquifer at 200 °C and 200 bars: implications for geologic sequestration of carbon Kaszuba, John P.; Janecky, David R.; Snow, Marjorie G. Applied Geochemistry, Vol. 18, Issue 7 https://doi.org/10.1016/S0883-2927(02)00239-1	journal	July 2003
Understanding the chemistry of cation leaching in illite/water interfacial system using reactive molecular dynamics simulations and hydrothermal experiments Muraleedharan, Murali Gopal; Herz-Thyhsen, Ryan; Dewey, Janet C. Acta Materialia, Vol. 186 https://doi.org/10.1016/j.actamat.2019.12.059	journal	March 2020
Reactions between organic acids and montmorillonite clay under Earth-forming conditions Montgomery, W.; Tuff, J.; Kohn, S. C. Chemical Geology, Vol. 283, Issue 3-4 https://doi.org/10.1016/j.chemgeo.2010.12.023	journal	April 2011
Coupled dissolution and precipitation at mineral–fluid interfaces Ruiz-Agudo, E.; Putnis, C. V.; Putnis, A. Chemical Geology, Vol. 383 https://doi.org/10.1016/j.chemgeo.2014.06.007	journal	September 2014
Reactive molecular dynamics simulation of the mechanical behavior of sodium aluminosilicate geopolymer and calcium silicate hydrate composites Sadat, Mohammad Rafat; Muralidharan, Krishna; Zhang, Lianyang Computational Materials Science, Vol. 150 https://doi.org/10.1016/j.commatsci.2018.04.041	journal	July 2018
ReaxFF molecular dynamics simulations on the structure and dynamics of electrolyte water systems at ambient temperature Dasgupta, Nabankur; Kyung Shin, Yun; Fedkin, Mark V. Computational Materials Science, Vol. 172 https://doi.org/10.1016/j.commatsci.2019.109349	journal	February 2020
Towards understanding the microstructural and structural changes in natural hierarchical materials for energy recovery: In-operando multi-scale X-ray scattering characterization of Na- and Ca-montmorillonite on heating to 1150 °C Gadikota, Greeshma; Zhang, Fan; Allen, Andrew J. Fuel, Vol. 196 https://doi.org/10.1016/j.fuel.2017.01.092	journal	May 2017
Atomic-scale structures of interfaces between phyllosilicate edges and water Liu, Xiandong; Lu, Xiancai; Meijer, Evert Jan Geochimica et Cosmochimica Acta, Vol. 81 https://doi.org/10.1016/j.gca.2011.12.009	journal	March 2012
Illite dissolution kinetics from 100 to 280 °C and pH 3 to 9 Smith, Megan M.; Dai, Zurong; Carroll, Susan A. Geochimica et Cosmochimica Acta, Vol. 209 https://doi.org/10.1016/j.gca.2017.04.005	journal	July 2017
Extraction of vanadium from black shale using pressure acid leaching Li, Minting; Wei, Chang; Fan, Gang Hydrometallurgy, Vol. 98, Issue 3-4 https://doi.org/10.1016/j.hydromet.2009.05.005	journal	September 2009
Interaction of carbon dioxide with Na-exchanged montmorillonite at pressures to 640bars: Implications for CO2 sequestration Giesting, Paul; Guggenheim, Stephen; Koster van Groos, August F. International Journal of Greenhouse Gas Control, Vol. 8 https://doi.org/10.1016/j.ijggc.2012.01.011	journal	May 2012
Carbonate formation in Wyoming montmorillonite under high pressure carbon dioxide Hur, Tae-Bong; Baltrus, John P.; Howard, Bret H. International Journal of Greenhouse Gas Control, Vol. 13 https://doi.org/10.1016/j.ijggc.2012.12.001	journal	March 2013
Capture and sequestration of CO2 in the interlayer space of hydrated calcium Montmorillonite clay under various geological burial depth Yang, W.; Zaoui, A. Physica A: Statistical Mechanics and its Applications, Vol. 449 https://doi.org/10.1016/j.physa.2015.12.032	journal	May 2016
The effect of high pressure on the structure and stability of sodium formate: Probed by in situ synchrotron X-ray diffraction technique Kang, Lei; Li, Shourui; Wang, Bo Solid State Communications, Vol. 289 https://doi.org/10.1016/j.ssc.2018.12.009	journal	February 2019
Elucidating Thermally Induced Structural and Chemical Transformations in Kaolinite Using Reactive Molecular Dynamics Simulations and X-ray Scattering Measurements Muraleedharan, Murali Gopal; Asgar, Hassnain; Mohammed, Sohaib Chemistry of Materials, Vol. 32, Issue 2 https://doi.org/10.1021/acs.chemmater.9b03929	journal	November 2019
Dissolution of Minerals and Precipitation of an Aluminosilicate Phase during Experimentally Simulated Hydraulic Fracturing of a Mudstone and a Tight Sandstone in the Powder River Basin, WY Herz-Thyhsen, Ryan J.; Kaszuba, John P.; Dewey, Janet C. Energy & Fuels, Vol. 33, Issue 5 https://doi.org/10.1021/acs.energyfuels.8b04443	journal	April 2019
Evaluating Water Reactivity at Silica Surfaces Using Reactive Potentials Mahadevan, Thiruvilla S.; Du, Jincheng The Journal of Physical Chemistry C, Vol. 122, Issue 18 https://doi.org/10.1021/acs.jpcc.7b12653	journal	April 2018
Development of a ReaxFF Reactive Force Field for NaSiO x /Water Systems and Its Application to Sodium and Proton Self-Diffusion Hahn, Seung Ho; Rimsza, Jessica; Criscenti, Louise The Journal of Physical Chemistry C, Vol. 122, Issue 34 https://doi.org/10.1021/acs.jpcc.8b05852	journal	July 2018
Surface Reactivity and Leaching of a Sodium Silicate Glass under an Aqueous Environment: A ReaxFF Molecular Dynamics Study Hahn, Seung Ho; van Duin, Adri C. T. The Journal of Physical Chemistry C, Vol. 123, Issue 25 https://doi.org/10.1021/acs.jpcc.9b02940	journal	May 2019
Interactions of Oxytetracycline with a Smectite Clay: A Spectroscopic Study with Molecular Simulations Aristilde, Ludmilla; Marichal, Claire; Miéhé-Brendlé, Jocelyne Environmental Science & Technology, Vol. 44, Issue 20 https://doi.org/10.1021/es102136y	journal	October 2010
Electronegativity-equalization method for the calculation of atomic charges in molecules Mortier, Wilfried J.; Ghosh, Swapan K.; Shankar, S. Journal of the American Chemical Society, Vol. 108, Issue 15 https://doi.org/10.1021/ja00275a013	journal	July 1986
Dynamics of Confined Reactive Water in Smectite Clay–Zeolite Composites Pitman, Michael C.; van Duin, Adri C. T. Journal of the American Chemical Society, Vol. 134, Issue 6 https://doi.org/10.1021/ja208894m	journal	February 2012
Intensities of the Vibrational Spectra of Siliceous Zeolites by Molecular Dynamics Calculations. I. Infrared Spectra Bornhauser, P.; Bougeard, D. The Journal of Physical Chemistry B, Vol. 105, Issue 1 https://doi.org/10.1021/jp0014925	journal	January 2001
ReaxFF: A Reactive Force Field for Hydrocarbons van Duin, Adri C. T.; Dasgupta, Siddharth; Lorant, Francois The Journal of Physical Chemistry A, Vol. 105, Issue 41 https://doi.org/10.1021/jp004368u	journal	October 2001
Large-Scale Molecular Dynamics Study of Montmorillonite Clay: Emergence of Undulatory Fluctuations and Determination of Material Properties Suter, James L.; Coveney, Peter V.; Greenwell, H. Chris The Journal of Physical Chemistry C, Vol. 111, Issue 23 https://doi.org/10.1021/jp070294b	journal	June 2007
An ab Initio and Classical Molecular Dynamics Investigation of the Structural and Vibrational Properties of Talc and Pyrophyllite Larentzos, James P.; Greathouse, Jeffery A.; Cygan, Randall T. The Journal of Physical Chemistry C, Vol. 111, Issue 34 https://doi.org/10.1021/jp072959f	journal	August 2007
Molecular Dynamics Simulation of Thermomechanical Properties of Montmorillonite Crystal. 1. Isolated Clay Nanoplate Mazo, Mikhail A.; Manevitch, Leonid I.; Gusarova, Elena B. The Journal of Physical Chemistry B, Vol. 112, Issue 10 https://doi.org/10.1021/jp076022q	journal	March 2008
Carbon Dioxide in Montmorillonite Clay Hydrates: Thermodynamics, Structure, and Transport from Molecular Simulation Botan, Alexandru; Rotenberg, Benjamin; Marry, Virginie The Journal of Physical Chemistry C, Vol. 114, Issue 35 https://doi.org/10.1021/jp1043305	journal	August 2010
Hydration Properties and Interlayer Organization of Water and Ions in Synthetic Na-Smectite with Tetrahedral Layer Charge. Part 2. Toward a Precise Coupling between Molecular Simulations and Diffraction Data Ferrage, Eric; Sakharov, Boris A.; Michot, Laurent J. The Journal of Physical Chemistry C, Vol. 115, Issue 5 https://doi.org/10.1021/jp105128r	journal	December 2010
Formate Ion: Structure and Spectroscopic Properties Moreno, M. A.; Gálvez, O.; Maté, B. The Journal of Physical Chemistry A, Vol. 115, Issue 1 https://doi.org/10.1021/jp108326x	journal	January 2011
Density Functional Theory Study of Pyrophyllite and M-Montmorillonites (M = Li, Na, K, Mg, and Ca): Role of Dispersion Interactions Voora, Vamsee K.; Al-Saidi, W. A.; Jordan, Kenneth D. The Journal of Physical Chemistry A, Vol. 115, Issue 34 https://doi.org/10.1021/jp201277f	journal	September 2011
ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation Chenoweth, Kimberly; van Duin, Adri C. T.; Goddard, William A. The Journal of Physical Chemistry A, Vol. 112, Issue 5 https://doi.org/10.1021/jp709896w	journal	February 2008
An investigation of water uptake on clays minerals using ATR-FTIR spectroscopy coupled with quartz crystal microbalance measurements Schuttlefield, Jennifer D.; Cox, David; Grassian, Vicki H. Journal of Geophysical Research, Vol. 112, Issue D21 https://doi.org/10.1029/2007JD008973	journal	January 2007
Intergrown mica and montmorillonite in the Allende carbonaceous chondrite Tomeoka, Kazushige; Buseck, Peter R. Nature, Vol. 299, Issue 5881 https://doi.org/10.1038/299326a0	journal	September 1982
The ReaxFF reactive force-field: development, applications and future directions Senftle, Thomas P.; Hong, Sungwook; Islam, Md Mahbubul npj Computational Materials, Vol. 2, Issue 1 https://doi.org/10.1038/npjcompumats.2015.11	journal	March 2016
Molecular simulation of swelling and interlayer structure for organoclay in supercritical CO ₂ Yu, Yanruo; Yang, Xiaoning Phys. Chem. Chem. Phys., Vol. 13, Issue 1 https://doi.org/10.1039/C0CP00505C	journal	January 2011
Organic compounds in carbonaceous meteorites Sephton, Mark A. Natural Product Reports, Vol. 19, Issue 3 https://doi.org/10.1039/b103775g	journal	March 2002
Polarized Infrared Spectrum of Sodium Nitrite Newman, Roger The Journal of Chemical Physics, Vol. 20, Issue 3 https://doi.org/10.1063/1.1700439	journal	March 1952
Tailless X‐Ray Single‐Crystal Reflection Curves Obtained by Multiple Reflection Bonse, U.; Hart, M. Applied Physics Letters, Vol. 7, Issue 9 https://doi.org/10.1063/1.1754396	journal	November 1965
A reactive molecular dynamics simulation of the silica-water interface Fogarty, Joseph C.; Aktulga, Hasan Metin; Grama, Ananth Y. The Journal of Chemical Physics, Vol. 132, Issue 17 https://doi.org/10.1063/1.3407433	journal	May 2010
The hydrophilic-to-hydrophobic transition in glassy silica is driven by the atomic topology of its surface Yu, Yingtian; Krishnan, N. M. Anoop; Smedskjaer, Morten M. The Journal of Chemical Physics, Vol. 148, Issue 7 https://doi.org/10.1063/1.5010934	journal	February 2018
ReaxFF molecular dynamics simulations of electrolyte–water systems at supercritical temperature Dasgupta, Nabankur; Shin, Yun Kyung; Fedkin, Mark V. The Journal of Chemical Physics, Vol. 152, Issue 20 https://doi.org/10.1063/5.0006676	journal	May 2020
The Effects of Isotopic Dilution on the Infrared Spectrum of Solid Sodium Formate Spinner, E.; Rowe, Je Australian Journal of Chemistry, Vol. 32, Issue 3 https://doi.org/10.1071/CH9790481	journal	January 1979
Atomic-scale modelling of elastic and failure properties of clays Hantal, György; Brochard, Laurent; Laubie, Hadrien Molecular Physics, Vol. 112, Issue 9-10 https://doi.org/10.1080/00268976.2014.897393	journal	February 2014
The State of NaOH in NaOH/Poly(Sodium Acrylate) Composite Jin, Fu-Qiang; Yang, Ru; Zhang, Jian-Chun Journal of Dispersion Science and Technology, Vol. 30, Issue 8 https://doi.org/10.1080/01932690802701614	journal	August 2009
Thermal Transport in Disordered Materials DeAngelis, Freddy; Muraleedharan, Murali Gopal; Moon, Jaeyun Nanoscale and Microscale Thermophysical Engineering, Vol. 23, Issue 2 https://doi.org/10.1080/15567265.2018.1519004	journal	November 2018
Thermal conductivity calculation of nano-suspensions using Green–Kubo relations with reduced artificial correlations Muraleedharan, Murali Gopal; Sundaram, Dilip Srinivas; Henry, Asegun Journal of Physics: Condensed Matter, Vol. 29, Issue 15 https://doi.org/10.1088/1361-648X/aa5f08	journal	March 2017
Silver behenate and silver stearate powders for calibration of SAS instruments Nyam-Osor, M.; Soloviov, D. V.; Kovalev, Yu S. Journal of Physics: Conference Series, Vol. 351 https://doi.org/10.1088/1742-6596/351/1/012024	journal	March 2012
Computer Simulation of Liquids Allen, Michael P.; Tildesley, Dominic J. https://doi.org/10.1093/oso/9780198803195.001.0001	book	June 2017
Irena : tool suite for modeling and analysis of small-angle scattering Ilavsky, Jan; Jemian, Peter R. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889809002222	journal	February 2009
Nika : software for two-dimensional data reduction Ilavsky, Jan Journal of Applied Crystallography, Vol. 45, Issue 2 https://doi.org/10.1107/S0021889812004037	journal	March 2012
THE INFLUENCE OF IRON AND ALUMINIUM HYDROXIDES ON THE SWELLING OF Na-MONTMORILLONITE AND THE PERMEABILITY OF A Na-SOIL El Rayah, H. M. E.; Rowell, D. L. Journal of Soil Science, Vol. 24, Issue 1 https://doi.org/10.1111/j.1365-2389.1973.tb00749.x	journal	March 1973
Why Mineral Interfaces Matter Putnis, A. Science, Vol. 343, Issue 6178 https://doi.org/10.1126/science.1250884	journal	March 2014
Organic Molecules in the Interstellar Medium, Comets, and Meteorites: A Voyage from Dark Clouds to the Early Earth Ehrenfreund, Pascale; Charnley, Steven B. Annual Review of Astronomy and Astrophysics, Vol. 38, Issue 1 https://doi.org/10.1146/annurev.astro.38.1.427	journal	September 2000
Formation, Compositions, and Properties of Hydroxy-Al- and Hydroxy-Mg-Montmorillonite Brindley, G. W. Clays and Clay Minerals, Vol. 28, Issue 6 https://doi.org/10.1346/CCMN.1980.0280605	journal	January 1980
Ab initio determination of edge surface structures for dioctahedral 2:1 phyllosilicates: implications for acid-base for reactivity Bickmore, Barry R.; Rosso, Kevin M.; Nagy, Kathryn L. Clays and Clay Minerals, Vol. 51, Issue 4 https://doi.org/10.1346/CCMN.2003.0510401	journal	August 2003
Quantitative Analysis of Sodium Carbonate and Sodium Bicarbonate in Solid Mixtures Using Fourier Transform Infrared Spectroscopy (FT-IR) Joshi, Shailesh; Kalyanasundaram, Sivasubramanian; Balasubramanian, Venkatraman Applied Spectroscopy, Vol. 67, Issue 8 https://doi.org/10.1366/12-06915	journal	August 2013
Fast parallel algorithms for short-range molecular dynamics Plimpton, S. https://doi.org/10.2172/10176421	report	May 1993
Basic Research Needs Workshop on Synthesis Science for Energy Relevant Technology De Yoreo, Jim; Mandrus, David; Soderholm, Lynda https://doi.org/10.2172/1616513	report	May 2016

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