David Grills

Brookhaven National Laboratory

Chemistry Division
Bldg. 555
P.O. Box 5000
Upton, NY 11973-5000

(631) 344-4332
dcgrills@bnl.gov

Research | Education | Appointments | Publications | Awards

Research Activities

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.

Education

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

Professional Appointments

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

Selected Professional Activities

Participant at the Department of Energy Basic Research Needs for Future Nuclear Energy Workshop, Rockville, MD, August 9^th-11^th, 2017.
Member of the editorial/review board of the Journal of Saudi Chemical Society (since Dec. 2016).
Co-organizer of a 244^th ACS National Meeting Symposium: “Green Chemistry in Energy and Fuels”, Division of Energy and Fuels, Philadelphia, PA, August 19^th-23^rd, 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^th-10^th, 2008.

Selected Publications

• Koike K, Grills DC, Tamaki Y, Fujita E, Okubo K, Yamazaki Y, Saigo M, Mukuta T, Onda K, Ishitani O (2018) Investigation of excited state, reductive quenching, and intramolecular electron transfer of Ru(ii)–Re(i) supramolecular photocatalysts for CO2reduction using time-resolved IR measurements. Chemical Science 9:2961–2974. doi: 10.1039/c7sc05338j
• Grills DC, Polyansky DE, Fujita E (2017) Application of Pulse Radiolysis to Mechanistic Investigations of Catalysis Relevant to Artificial Photosynthesis. ChemSusChem 10:4359–4373. doi: 10.1002/cssc.201701559
• Hack J, Grills DC, Miller JR, Mani T (2016) Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects. The Journal of Physical Chemistry B 120:1149–1157. doi: 10.1021/acs.jpcb.5b11893
• Ngo KT, McKinnon M, Mahanti B, Narayanan R, Grills DC, Ertem MZ, Rochford J (2017) Turning on the Protonation-First Pathway for Electrocatalytic CO2 Reduction by Manganese Bipyridyl Tricarbonyl Complexes. Journal of the American Chemical Society 139:2604–2618. doi: 10.1021/jacs.6b08776
• Matsubara Y, Grills DC, Koide Y (2016) 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. ACS Omega 1:1393–1411. doi: 10.1021/acsomega.6b00129
• Hack J, Grills DC, Miller JR, Mani T (2016) Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects. The Journal of Physical Chemistry B 120:1149–1157. doi: 10.1021/acs.jpcb.5b11893
• Min S, Rasul S, Li H, Grills DC, Takanabe K, Li L-J, Huang K-W (2015) Electrocatalytic Reduction of Carbon Dioxide with a Well-Defined PN3−Ru Pincer Complex. ChemPlusChem 81:166–171. doi: 10.1002/cplu.201500474
• Matsubara Y, Grills DC, Kuwahara Y (2015) Thermodynamic Aspects of Electrocatalytic CO2Reduction in Acetonitrile and with an Ionic Liquid as Solvent or Electrolyte. ACS Catalysis 5:6440–6452. doi: 10.1021/acscatal.5b00656
• Mani T, Grills DC, Newton MD, Miller JR (2015) Electron Localization of Anions Probed by Nitrile Vibrations. Journal of the American Chemical Society 137:10979–10991. doi: 10.1021/jacs.5b04648
• Grills DC, Farrington JA, Layne BH, Preses JM, Bernstein HJ, Wishart JF (2015) Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility. Review of Scientific Instruments 86:044102. doi: 10.1063/1.4918728
• Mani T, Grills DC, Miller JR (2015) Vibrational Stark Effects To Identify Ion Pairing and Determine Reduction Potentials in Electrolyte-Free Environments. Journal of the American Chemical Society 137:1136–1140. doi: 10.1021/ja512302c
• Grills DC, Farrington JA, Layne BH, Lymar SV, Mello BA, Preses JM, Wishart JF (2014) Mechanism of the Formation of a Mn-Based CO2 Reduction Catalyst Revealed by Pulse Radiolysis with Time-Resolved Infrared Detection. Journal of the American Chemical Society 136:5563–5566. doi: 10.1021/ja501051s
• Grills DC, Matsubara Y, Kuwahara Y, Golisz SR, Kurtz DA, Mello BA (2014) Electrocatalytic CO2Reduction with a Homogeneous Catalyst in Ionic Liquid: High Catalytic Activity at Low Overpotential. The Journal of Physical Chemistry Letters 5:2033–2038. doi: 10.1021/jz500759x
• Lewandowska-Andralojc A, Grills DC, Zhang J, Bullock RM, Miyazawa A, Kawanishi Y, Fujita E (2014) Kinetic and Mechanistic Studies of Carbon-to-Metal Hydrogen Atom Transfer Involving Os-Centered Radicals: Evidence for Tunneling. Journal of the American Chemical Society 136:3572–3578. doi: 10.1021/ja4123076
• Estes DP, Grills DC, Norton JR (2014) The Reaction of Cobaloximes with Hydrogen: Products and Thermodynamics. Journal of the American Chemical Society 136:17362–17365. doi: 10.1021/ja508200g
• Matsubara Y, Hightower SE, Chen J, Grills DC, Polyansky DE, Muckerman JT, Tanaka K, Fujita E (2014) Reactivity of a fac-ReCl(α-diimine)(CO)3complex with an NAD+model ligand toward CO2reduction. Chem Commun 50:728–730. doi: 10.1039/c3cc47699e
• Shkrob IA, Marin TW, Wishart JF, Grills DC (2014) Radiation Stability of Cations in Ionic Liquids. 5. Task-Specific Ionic Liquids Consisting of Biocompatible Cations and the Puzzle of Radiation Hypersensitivity. The Journal of Physical Chemistry B 118:10477–10492. doi: 10.1021/jp5049716
• Zamadar M, Asaoka S, Grills DC, Miller JR (2013) Giant infrared absorption bands of electrons and holes in conjugated molecules. Nature Communications. doi: 10.1038/ncomms3818
• Kawanami H, Grills DC, Ishizaka T, Chatterjee M, Suzuki A (2013) Photocatalytic reduction of CO2 under supercritical CO2 conditions: Effect of pressure, temperature, and solvent on catalytic efficiency. Journal of CO2 Utilization 3-4:93–97. doi: 10.1016/j.jcou.2013.07.008
• Doherty MD, Grills DC, Huang K-W, Muckerman JT, Polyansky DE, van Eldik R, Fujita E (2013) Kinetics and Thermodynamics of Small Molecule Binding to Pincer-PCP Rhodium(I) Complexes. Inorganic Chemistry 52:4160–4172. doi: 10.1021/ic300672g
• Zhao HC, Mello B, Fu B-L, Chowdhury H, Szalda DJ, Tsai M-K, Grills DC, Rochford J (2013) Investigation of Monomeric versus Dimericfac-Rhenium(I) Tricarbonyl Systems Containing the Noninnocent 8-Oxyquinolate Ligand. Organometallics 32:1832–1841. doi: 10.1021/om301250v
• Hayashi Y, Szalda DJ, Grills DC, Hanson JC, Huang K-W, Muckerman JT, Fujita E (2013) Isolation and X-ray structures of four Rh(PCP) complexes including a Rh(I) dioxygen complex with a short O–O bond. Polyhedron 58:106–114. doi: 10.1016/j.poly.2012.10.006
• Grills DC, Cook AR, Fujita E, George MW, Preses JM, Wishart JF (2010) Application of External-Cavity Quantum Cascade Infrared Lasers to Nanosecond Time-Resolved Infrared Spectroscopy of Condensed-Phase Samples following Pulse Radiolysis. Applied Spectroscopy 64:563–570. doi: 10.1366/000370210791414344
• Grills DC, Fujita E (2010) New Directions for the Photocatalytic Reduction of CO2: Supramolecular, scCO2or Biphasic Ionic Liquid−scCO2Systems. The Journal of Physical Chemistry Letters 1:2709–2718. doi: 10.1021/jz1010237
• Doherty MD, Grills DC, Muckerman JT, Polyansky DE, Fujita E (2010) Toward more efficient photochemical CO2 reduction: Use of scCO2 or photogenerated hydrides. Coordination Chemistry Reviews 254:2472–2482. doi: 10.1016/j.ccr.2009.12.013
• Doherty MD, Grills DC, Fujita E (2009) Synthesis of Fluorinated ReCl(4,4′-R2-2,2′-bipyridine)(CO)3Complexes and Their Photophysical Characterization in CH3CN and Supercritical CO2. Inorganic Chemistry 48:1796–1798. doi: 10.1021/ic8019556
• Huang K-W, Grills DC, Han JH, Szalda DJ, Fujita E (2008) Selective decarbonylation by a pincer PCP-rhodium(I) complex. Inorganica Chimica Acta 361:3327–3331. doi: 10.1016/j.ica.2008.01.045
• Rimmer RD, Grills DC, Fan H, Ford PC, Caulton KG (2007) Metal-Dependent Reactivity Differences for Transients Formed By Flash Photolysis of (PNP)M(CO), M = Co and Rh. Journal of the American Chemical Society 129:15430–15431. doi: 10.1021/ja076357l
• Grills DC, van Eldik R, Muckerman JT, Fujita E (2006) 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. Journal of the American Chemical Society 128:15728–15741. doi: 10.1021/ja064627e
• Grills DC, Huang K-W, Muckerman JT, Fujita E (2006) Kinetic studies of the photoinduced formation of transition metal–dinitrogen complexes using time-resolved infrared and UV–vis spectroscopy. Coordination Chemistry Reviews 250:1681–1695. doi: 10.1016/j.ccr.2006.01.002
• Zhang J, Grills DC, Huang K-W, Fujita E, Bullock RM (2005) Carbon-to-Metal Hydrogen Atom Transfer:  Direct Observation Using Time-Resolved Infrared Spectroscopy. Journal of the American Chemical Society 127:15684–15685. doi: 10.1021/ja0555724

Awards & Recognition

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