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David Grills

David Grills


Chemistry Division
Building 555
Brookhaven National Laboratory
P.O. Box 5000
Upton, NY 11973-5000

Phone: (631) 344-4332
FAX:    (631) 344-5815

Artificial Photosynthesis
Electron- and Photo-Induced Processes for Molecular Energy Conversion

Research Interests

Fundamental radiation chemistry of organic liquids, including the development of new radical scavengers. Photochemistry and radiation chemistry of transition metal complexes and other systems in conventional solvents, supercritical fluids, and ionic liquids, to gain a fundamental understanding of processes in solar fuels production and catalysis, e.g., CO2 reduction, H2 production, and small molecule activation. Development of advanced, nanosecond time-resolved infrared (TRIR) detection methods for pulse radiolysis and laser flash photolysis, and their use in mechanistic investigations of catalytic and other processes. Transient spectroscopic techniques (UV-visible and time-resolved infrared (TRIR)) on fast and ultrafast timescales.


Ph.D., Inorganic Photochemistry - University of Nottingham, Nottingham, UK, 1999.
B.Sc., Chemistry - University of Nottingham, Nottingham, UK, 1995.

Professional Employment

Chemist, Brookhaven National Laboratory, 2012-present
Associate Chemist, Brookhaven National Laboratory, 2008-2012
Assistant Chemist, Brookhaven National Laboratory, 2006-2008
Postdoctoral Research Associate, Brookhaven National Laboratory, 2003-2006
Postdoctoral Research Associate, University of Nottingham/Rutherford Appleton Laboratory, UK, 1999-2003


F. S. Kipping Scholarship, University of Nottingham
Zeneca Award, University of Nottingham
University Exhibition/Boots Drummond Memorial Prizes, University of Nottingham

Selected Professional Activities

Member of the editorial/review board of the Journal of Saudi Chemical Society (since Dec. 2016).

Co-organizer of a 244th ACS National Meeting Symposium: "Green Chemistry for Energy and Fuels", Division of Energy and Fuels, Philadelphia, PA, August 19-23rd, 2012.

Panel member at the NSF Workshop "Reversing Global Warming: Chemical Recycling and Utilization of CO2", University of Southern California, Los Angeles, CA, July 9-10th, 2008

Representative Publications

  1. “Turning on the Protonation-First Pathway for Electrocatalytic CO2 Reduction by Manganese Bipyridyl Tricarbonyl Complexes” Ngo, K. T.; McKinnon, M.; Mahanti, B.; Narayan, R.; Grills, D. C.; Ertem, M. Z.; Rochford, J. J. Am. Chem. Soc., under revision.
  2. “Experimental Insight into the Thermodynamics of the Dissolution of Electrolytes in Room-Temperature Ionic Liquids: From the Mass Action Law to the Absolute Standard Chemical Potential of a Proton” Matsubara, Y.; Grills, D. C.; Koide, Y. ACS Omega 2016, 1, 1393-1411.
  3. “Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects” Hack, J.; Grills, D. C.; Miller, J. R.; Mani, T. J. Phys. Chem. B 2016 , 120, 1149-1157.
  4. “Electrocatalytic Reduction of Carbon Dioxide with a Well-Defined PN3-Ru Pincer Complex” Min, S.; Rasul, S.; Li, H.; Grills, D. C.; Takanabe, K.; Li, L.-J.; Huang, K.-W. ChemPlusChem 2016, 81, 166-171.
  5. “Thermodynamic Aspects of Electrocatalytic CO2 Reduction in Acetonitrile and with an Ionic Liquid as Solvent or Electrolyte” Matsubara, Y.; Grills, D. C.; Kuwahara, Y. ACS Catal. 2015, 5, 6440-6452.
  6. “Electron Localization of Anions Probed by Nitrile Vibrations” Mani, T.; Grills, D. C.; Newton, M. D.; Miller, J. R. J. Am. Chem. Soc. 2015, 137, 10979-10991.
  7. “Development of Nanosecond Time-Resolved Infrared Detection at the LEAF Pulse Radiolysis Facility” Grills, D. C.; Farrington, J. A.; Layne, B. H.; Preses, J. M.; Bernstein, H. J.; Wishart, J. F. Rev. Sci. Instrum. 2015, 86, 044102.
  8. “Vibrational Stark Effects to Identify Ion Pairing and Determine Reduction Potentials in Electrolyte-Free Environments” Mani, T.; Grills, D. C.; Miller, J. R. J. Am. Chem. Soc. 2015, 137, 1136-1140.
  9. “Mechanism of the Formation of a Mn-Based CO2 Reduction Catalyst Revealed by Pulse Radiolysis with Time-Resolved Infrared Detection” Grills, D. C.; Farrington, J. A.; Layne, B. H.; Lymar, S. V.; Mello, B. A.; Preses, J. M.; Wishart, J. F. J. Am. Chem. Soc. 2014 , 136, 5563-5566.
  10. “Electrocatalytic CO2 Reduction with a Homogeneous Catalyst in Ionic Liquid: High Catalytic Activity at Low Overpotential” Grills, D. C.; Matsubara, Y.; Kuwahara, Y.; Golisz, S. R.; Kurtz, D. A.; Mello, B. A. J. Phys. Chem. Lett. 2014, 5, 2033-2038 (ACS Editors’ Choice Article).
  11. “Kinetic and Mechanistic Studies of Carbon-to-Metal Hydrogen Atom Transfer Involving Os-Centered Radicals: Evidence for Tunneling” Lewandowska-Andralojc, A.; Grills, D. C.; Zhang, J.; Bullock, R. M.; Miyazawa, A.; Kawanishi, Y.; Fujita, E. J. Am. Chem. Soc. 2014, 136, 3572-3578.
  12. “The Reaction of Cobaloximes with Hydrogen: Products and Thermodynamics” Estes, D. P; Grills, D. C.; Norton, J. R. J. Am. Chem. Soc. 2014, 136, 17362-17365.
  13. “Reactivity of a fac-ReCl(α-diimine)(CO)3 Complex with an NAD+ Model Ligand Toward CO2 Reduction” Matsubara, Y.; Hightower, S. E.; Chen, J.; Grills, D. C.; Polyansky, D. E.; Muckerman, J. T.; Tanaka, K.; Fujita, E. Chem. Commun. 2014, 50, 728-730.
  14. “Radiation Stability of Cations in Ionic Liquids. 5. Task-Specific Ionic Liquids Consisting of Biocompatible Cations and the Puzzle of Radiation Hypersensitivity” Shkrob, I. A.; Marin, T. W.; Wishart, J. F.; Grills, D. C. J. Phys. Chem. B 2014, 118, 10477-10492.
  15. “Giant Infrared Absorption Bands of Electrons and Holes in Conjugated Molecules” Zamadar, M.; Asaoka, S.; Grills, D. C.; Miller, J. R. Nature Commun. 2013, 4:2818.
  16. “Photocatalytic Reduction of CO2 under Supercritical CO2 Conditions: Effect of Pressure, Temperature, and Solvent on Catalytic Efficiency” Kawanami, H.; Grills, D. C.; Ishizaka, T.; Chatterjee, M.; Suzuki, A. J. CO2 Util. 2013, 3-4, 93-97.
  17. “Kinetics and Thermodynamics of Small Molecule Binding to Pincer-PCP Rhodium(I) Complexes” Doherty, M. D.; Grills, D. C.; Huang, K.-W.; Muckerman, J. T.; Polyansky, D. E.; van Eldik, R.; Fujita, E. Inorg. Chem. 2013, 52, 4160-4172.
  18. “Investigation of Monomeric Versus Dimeric fac-Rhenium(I) Tricarbonyl Systems Containing the Noninnocent 8-Oxyquinolate Ligand” Zhao, H. C.; Mello, B.; Fu, B.-L.; Chowdury, H.; Szalda, D. J.; Tsai, M.-K.; Grills, D. C.; Rochford, J. Organometallics 2013, 32, 1832-1841.
  19. “Isolation and X-Ray Structures of Four Rh(PCP) Complexes Including a Rh(I) Dioxygen Complex with a Short O-O Bond” Hayashi, Y.; Szalda, D. J.; Grills, D. C.; Hanson, J.; Huang, K.-W.; Muckerman, J. T.; Fujita, E. Polyhedron 2013, 58, 106-114.
  20. “Application of External-Cavity Quantum Cascade Infrared Lasers to Nanosecond Time-Resolved Infrared Spectroscopy of Condensed-Phase Samples Following Pulse Radiolysis” Grills, D. C.; Cook, A. R.; Fujita, E.; George, M. W.; Preses, J. M.; Wishart, J. F. Appl. Spectrosc. 2010, 64, 563-570 (Cover Article).
  21. “New Directions for the Photocatalytic Reduction of CO2: Supramolecular, scCO2 or Biphasic Ionic Liquid-scCO2 Systems” Grills, D. C.; Fujita, E. J. Phys. Chem. Lett. 2010, 1, 2709-2718.
  22. “Toward More Efficient Photochemical CO2 Reduction: Use of scCO2 or Photogenerated Hydrides” Doherty, M. D.; Grills, D. C.; Muckerman, J. T.; Polyansky, D. E.; Fujita, E. Coord. Chem. Rev. 2010, 254, 2472-2482.
  23. “Synthesis of Fluorinated ReCl(4,4′-R2-2,2′-bipyridine)(CO)3 Complexes and Their Photophysical Characterization in CH3CN and Supercritical CO2” Doherty, M. D.; Grills, D. C.; Fujita, E. Inorg. Chem. 2009, 48, 1796-1798.
  24. “Selective Decarbonylation by a Pincer PCP-Rhodium(I) Complex” Huang, K.-W.; Grills, D. C.; Han, J. H.; Szalda, D. J.; Fujita, E. Inorg. Chim. Acta 2008, 361, 3327-3331.
  25. “Metal-Dependent Reactivity Differences for Transients Formed by Flash Photolysis of (PNP)M(CO), M = Co and Rh” Rimmer, R. D.; Grills, D. C.; Fan, H.; Ford, P. C.; Caulton, K. G. J. Am. Chem. Soc. 2007, 129, 15430-15431.
  26. “Direct Measurements of Rate Constants and Activation Volumes for the Binding of H2, D2, N2, C2H4, and CH3CN to W(CO)3(PCy3)2: Theoretical and Experimental Studies with Time-Resolved Step-Scan FTIR and UV-Vis Spectroscopy” Grills, D. C.; van Eldik, R.; Muckerman, J. T.; Fujita, E. J. Am. Chem. Soc. 2006, 128, 15728-15741.
  27. “Kinetic Studies of the Photoinduced Formation of Transition Metal-Dinitrogen Complexes Using Time-Resolved Infrared and UV-Vis Spectroscopy” Grills, D. C.; Huang, K.-W.; Muckerman, J. T.; Fujita, E. Coord. Chem. Rev. 2006, 250, 1681-1695.
  28. “Carbon-to-Metal Hydrogen Atom Transfer: Direct Observation Using Time-Resolved Infrared Spectroscopy” Zhang, J.; Grills, D. C.; Huang, K.-W.; Fujita, E.; Bullock, R. M. J. Am. Chem. Soc. 2005, 127, 15684-15685.