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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

Participant at the Department of Energy Basic Research Needs for Future Nuclear Energy Workshop, Rockville, MD, August 9th-11th, 2017.

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 in Energy and Fuels”, Division of Energy and Fuels, Philadelphia, PA, August 19th-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 9th-10th, 2008.

Representative Publications

  1. “Investigation of Excited State, Reductive Quenching, and Intramolecular Electron Transfer of Ru(II)-Re(I) Supramolecular Photocatalysts for CO2 Reduction Using Time-Resolved IR Measurements” Koike, K.; Grills, D. C.; Tamaki, Y.; Fujita, E.; Ishitani, O. Chem. Sci., submitted.
  2. “Application of Pulse Radiolysis to Mechanistic Investigations of Catalysis Relevant to Artificial Photosynthesis” Grills, D. C.; Polyansky, D. E.; Fujita, E. ChemSusChem, submitted.
  3. “Probing Intermolecular Electron Delocalization in Dimer Radical Anions by Vibrational Spectroscopy” Mani, T.; Grills, D. C. J. Phys. Chem. B 2017, 121, 7327-7335. DOI: 10.1021/acs.jpcb.5b11893
  4. “Turning on the Protonation-First Pathway for Electrocatalytic CO2 Reduction by Manganese Bipyridyl Tricarbonyl Complexes” Ngo, K. T.; McKinnon, M.; Mahanti, B.; Narayanan, R.; Grills, D. C.; Ertem, M. Z.; Rochford, J. J. Am. Chem. Soc. 2017, 139, 2604-2618. DOI: 10.1021/jacs.6b08776
  5. “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. DOI: 10.1021/acsomega.6b00129
  6. “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. DOI: 10.1021/acs.jpcb.5b11893
  7. “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. DOI: 10.1002/cplu.201500474
  8. “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. DOI: 10.1021/acscatal.5b00656
  9. “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. DOI: 10.1021/jacs.5b04648
  10. “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. DOI: 10.1063/1.4918728
  11. “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. DOI: 10.1021/ja512302c
  12. “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. DOI: 10.1021/ja501051s
  13. “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). DOI: 10.1021/jz500759x
  14. “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. DOI: 10.1021/ja4123076
  15. “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. DOI: 10.1021/ja508200g
  16. “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. DOI: 10.1039/C3CC47699E
  17. “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. DOI: 10.1021/jp5049716
  18. “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. DOI: 10.1038/ncomms3818
  19. “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. DOI: 10.1016/j.jcou.2013.07.008
  20. “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. DOI: 10.1021/ic300672g
  21. “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. DOI: 10.1021/om301250v
  22. “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. DOI: 10.1016/j.poly.2012.10.006
  23. “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). URL:
  24. “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. DOI: 10.1021/jz1010237
  25. “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. DOI: 10.1016/j.ccr.2009.12.013
  26. “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. DOI: 10.1021/ic8019556
  27. “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. DOI: 10.1016/j.ica.2008.01.045
  28. “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. DOI: 10.1021/ja076357l
  29. “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. DOI: 10.1021/ja064627e
  30. “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. DOI: 10.1016/j.ccr.2006.01.002
  31. “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. DOI: 10.1021/ja0555724