Materials Chemistry Geochemistry

James Kirkpatrick

Professor

226A CEM

517-353-1132

Primary Research Area

Material (Ma)

Other Area(s) of Interest

Geochemistry (G)

Research

Research in the Kirkpatrick laboratory focuses on understanding the structure, dynamics and energetics of materials of importance in geochemistry and in materials applications. Current efforts are on H2O, CO2, CH4, and a range of cations in 2-D nano-confinement and in meso-scale pores with applications to fluids in soils and other near-surface geochemical environments, and to geological C-sequestration and enhanced oil and gas production. Our research approach involves the combined application of experimental solid-state NMR, other spectroscopic methods, and X-ray diffraction with computational molecular modeling. The NMR studies include MAS experiments using newly developed in situ high pressure and temperature techniques.  The computational modeling uses principally molecular dynamics (MD) approaches, including recently developed grand canonical MD methods (GCMD).

Recent results show, for instance, that CO2 and CH4 are readily incorporated into the ~0.4 to 1 nm interlayer galleries of smectite clays (Figure 1). The results provide a structural and energetic basis for understanding fluid transport in shales and other rocks in C-sequestration and petroleum reservoirs.

 

Figure 1. GCMD simulation showing water molecules surrounding Ca2+ ions (green) with clusters of CO2 molecules between the hydrated cations. NMR and GCMD results show that the CO2 molecules undergo rapid librational motion around the axis perpendicular to their O-C-O axis.
Figure 1. GCMD simulation showing water molecules surrounding Ca2+ ions (green) with clusters of CO2 molecules between the hydrated cations. NMR and GCMD results show that the CO2 molecules undergo rapid librational motion around the axis perpendicular to their O-C-O axis.

NMR of nano-confined cations show complex dynamical behavior including exchange among sites with different hydration states (Figure 2) that depend on the cation, the thermodynamic activity of water, and temperature.

Figure 1. GCMD simulation showing water molecules surrounding Ca2+ ions (green) with clusters of CO2 molecules between the hydrated cations. NMR and GCMD results show that the CO2 molecules undergo rapid librational motion around the axis perpendicular to their O-C-O axis.
Figure 2. Variable temperature 23Na MAS NMR spectra of a Na-smectite clay showing the presence of three hydrated Na-environments that undergo dynamical averaging near room temperature and two non-hydrated Na-sites that do not participate in this averaging.

 

Computational MD modeling and NMR spectroscopy also show that the molecular scale aggregation of natural organic matter (NOM) on the surfaces of clay minerals is driven by a combination of cation bridging and hydrophobic interactions, depending on the pH and cation in solution (Figure 3). He ion microscopy shows the presence of these clusters (Figure 4).

 

Figure 3. Snapshot from an MD simulation showing aggregation of 16 NOM molecules in a Ca-dominated solution and the attachment of the molecular cluster to the surface of a clay particle.
Figure 3. Snapshot from an MD simulation showing aggregation of 16 NOM molecules in a Ca-dominated solution and the attachment of the molecular cluster to the surface of a clay particle.

 

Figure 4. He ion micrograph showing chains of aggregated NOM molecules.
Figure 4. He ion micrograph showing chains of aggregated NOM molecules.

 

Selected Publications

Krishnan, M., Saharay, M., and Kirkpatrick, R.J., 2013, Structure and dynamics of nano-confined CO2 and poly(ethylene glycol) in montmorillonite composites, J. Phys. Chem. C., 117, 20592 – 20609.

Saharay, M., and Kirkpatrick, R. J., 2014, Onset of orientational order in amorphous calcium carbonate (ACC) upon dehydration, Chem. Phys. Letters, 591, 287-291.

Bowers, G.M., Singer, J.W., Bish, D.L., and Kirkpatrick, R.J., 2014, Structural and dynamical relationships of Ca2+ and H2O in smectite/2H2O systems, American Mineralogist, 99, 318-331.

Bowers, G.M., Hoyt, D.W., Burton, S.D., Ferguson, B.O., Varga, T., and Kirkpatrick, R.J., 2014, In situ 13C and 23Na MAS NMR investigation of supercritical CO2 incorporation in smectite-natural organic matter composites, J. Phys. Chem. C, 118, 3564-3573.

Saharay, M., and Kirkpatrick, R. J., 2014, Ab initio and metadynamics studies on the role of essentialfunctional groups in biomineralization of calcium carbonate and environmental situations, Phys. Chem. Chem. Phys., 16, 26843-26854.

Kirkpatrick, R.J. Kalinichev, A.G., Bowers, G. M., Yazaydin, A.O., Krishnan, M., Saharay M., and Morrow, C.P., 2015, NMR and computational molecular modeling studies of mineral surfaces and interlayer galleries, American Mineralogist, 100, 1341-1354, Invited, American Mineralogist Centennial Article.

Greathouse, J.A., Hart, D.B., Bowers, G.M., Kirkpatrick, R.J., and Cygan, R.T., 2015, Molecular simulation of structure and diffusion at smectite-water interfaces: using expanded clay interlayers as model nanopores,  J. Phys. Chem. C, 119, 17126-17136.

Bowers, G.M., Argersinger, H.E., Reddy, U. V., Johnson, T.A, Arey, B., Bowden, M., and Kirkpatrick, R.J., 2015, Integrated molecular and microscopic scale insight into morphology and ion dynamics in Ca2+-mediated natural organic matter floccs, J. Phys. Chem. C, 119, 17773-17783.

Yazaydin, A.O., Bowers, G.M., and Kirkpatrick, R.J., 2015, Molecular dynamics modeling of carbon dioxide, water and natural organic matter in Na-hectorite, Physical Chemistry Chemical Physics, 17, 23356-23367.

Sena, M.M., Morrow, C.P., Kirkpatrick, R.J., and Krishnan M., 2015, Structure, energetics, and dynamics of supercritical carbon dioxide at smectite mineral-water interfaces: molecular dynamics and adaptive biasing force investigation of CO2/H2O mixtures nanoconfined in Na-montmorillonite, Chemistry of Materials, 27, 6946-6959.

Loganathan, N., Yazaydin, A.O., Bowers, G.M., Kalinichev, A.G., and Kirkpatrick, R. J., 2016, Structure, energetics, and dynamics of Cs+ and H2O in hectorite: molecular dynamics simulations with an unconstrained substrate surface, J. Phys. Chem., C, 10290-10310.

Reddy, U.V., Bowers, G.M., Loganathan, N., Bowden, M., Yazaydin, A.O., and Kirkpatrick, R.J., 2016, Water structure and dynamics in smectites: X-ray diffraction and 2H NMR spectroscopy of Mg-, Ca-, Sr-, Na-, K-, Cs-, and Pb-hectorite, J. Phys. Chem. C, 120, 8863-8876.

Loganathan, N., Yazaydin, A.O., Bowers, G.M., Kalinichev, A.G., and Kirkpatrick, R. J., 2016, Cation and water structure, dynamics and energetics in smectite clays: a molecular dynamics study of Cahectorite, J. Phys. Chem. C, 120, 12429-12439.

Bowers, G.M., Schaef, H.T., Loring J.S., Hoyt, D.W., Burton, S.D., Walter E.D., and Kirkpatrick, R.J., 2017, Role of cations in CO2 adsorption, dynamics, and hydration in smectite clays under in situ supercritical CO2 conditions, J. Phys. Chem. C, 121, 577-592.    

Schaef, H.T., Loganathan, N., Bowers, G.M., Kirkpatrick, R.J., Yazaydin, A.O., Burton, S.D., Hoyt, D.W., Ilton, E.S., Thanthiriwatte, K.S., Dixon, D.A., McGrail, B.P., Rosso, and Loring, J.S., 2017, Tipping point for expansion of layered aluminosilicates in weakly polar solvents: supercritical CO2, ACS Applied Materials and Interfaces, 9, 36783-36791.

Saharay, M., and Kirkpatrick, R.J., 2017, Water dynamics in hydrated amorphous materials: a molecular dynamics study of the effects of dehydration in amorphous calcium carbonate, Phys. Chem. Chem Phys., 19, 29594-29600.

Loganathan, N., Bowers, G.M., Yazaydin, A.O., Schaef, H.T., Loring, J.S., Kalinichev, A.G., and Kirkpatrick, R.J. 2018, Clay swelling in dry supercritical carbon dioxide: effects of interlayer cations on the structure, dynamics and energetics of CO2 intercalation probed by XRD, NMR, and GCMD simulations, J. Phys. Chem. C, 122, 4391-4402.

CV

A.B., 1968, Cornell University

Ph.D., 1972, Univ. of Illinois at Urbana-Champaign

Senior Research Geologist, 1972-1973

Exxon Production Research

Post-doctoral Fellow in Geophysics, 1973-1975, Harvard University

Assistant Research Geologist, 1976-1978

Scripps Institution of Oceanography

Assistant, Associate and Full Professor, 1978-2007

Department Head (Geology), 1988-1997

R. E. Grim Professor, 2005-2007,

Executive Associate dean, 1997-2007

University of Illinois at Urbana-Champaign

Dean, College of Natural Science 2007-2017, Michigan State University

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Awards/Honors

2018 MSU Foundation Professor Michigan State University
2015 Marilyn and Sturges W. Bailey Distinguished Member Clay Minerals Society
2005 R. E. Grim Professor University of Illinois (Department of Geology)
2004 Dana Medal Mineralogical Society of America
2000 Brunauer Award American Ceramic Society
1996 Donnay Lecturer Carnegie Institution of Washington
1985 Overseas Fellow Churchill College
Fellow Geological Society of America
Fellow Mineralogical Society of America
Who's Who in America
Fellow American Association for the Advancement of Science
American Men and Women of Science
Fellow American Ceramic Society