Materials Chemistry Geochemistry
Primary Research Area
Other Area(s) of Interest
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.
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.
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).
Bowers, G.M., Loring, J.S., Schaef, H.T., Walter E.D., Burton S.D., Hoyt, D.W., Cunniff, S.S., Loganathan N., and Kirkpatrick, R.J., 2018, Interaction of hydrocarbons with clays at reservoir conditions: in situ IR and NMR spectroscopy and X-ray diffraction for expandable clays with variably wet supercritical methane, ACS Earth and Space Chemistry, 2, 640-652.
Nanda, R., Reddy, U.V., Bowers, G.M., Bowden, M., and Kirkpatrick, R.J., 2018, The structural and dynamical role of water in natural organic matter: a 2H NMR study, Organic Geochemistry, 123, 90-102.
Loganathan, N., Yazaydin, A.O., Bowers, G.M., Kalinichev, A.G., and Kirkpatrick, R.J., 2018, Competitive adsorption of H2O and CO2 in 2-dimensional nanoconfinement: GCMD simulations of Cs- and Ca-hectorite, J. Phys. Chem C, 122, 23460-23469.
Loganathan, N., Yazaydin, A.O., Bowers, G.M., and Kirkpatrick, R.J., 2019, Tuning the hydrophobicity of layer-structure silicates to promote adsorption of non-aqueous fluids: effects of F- for OH- substitution on CO2 partitioning into smectite interlayers, J. Phys. Chem. C., 123, 4848-4855.
Bowers, G.M., Schaef, H.T., Miller, Q.R.S., Loring, J.S., Walter, E.D., Burton, S.D., Hoyt, D.W., McGrail, B.P., and Kirkpatrick, R.J., 2019, 13C NMR spectroscopy of methane and carbon dioxide in a natural shale, ACS Earth and Space Chemistry, 3, 324-328.
Loganathan, N., Bowers, G.M., Ngouana, W.B.F., Kalinichev, A.G., Kirkpatrick, R.J., and Yazaydin, A.O., 2019, Understanding methane/carbon dioxide partitioning in clay nano- and meso-pores with constant reservoir composition molecular dynamics modeling, Phys. Chem. Chem. Phys., 21, 6917-6924.
Nanda, R., Bowers, G.M., Burton, S., Loganathan, N., and Kirkpatrick, R.J., 2019, Structure and dynamics in smectite interlayers: 23Na NMR spectroscopy and computational molecular modeling of Na hectorite, RSC Advances, 9, 12755-12765.
Bowers, G.M., Schaef, H.T., Cunniff, S.S., Loring, J.S., Walter, E.D., Burton, S.D., Larsen IV, R.K., Miller, Q.R.S., Ilton, E.S., and Kirkpatrick, R.J., 2019, Chemical trapping of CO2 by clay minerals at reservoir conditions: two mechanisms observed by insitu high pressure and temperature experimental studies, ACS Earth and Space Chemistry, 3, 1034-1046.
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
|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|