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Staff information


Dan DuBois

Catalysis Science
Laboratory Fellow


Dr. DuBois is currently a Senior Scientist at Pacific Northwest National Laboratory. He joined PNNL in January 2006. From 1981-2005 Dr. DuBois was a Principal Scientist at the National Renewable Energy Laboratory and manager of the Synthesis and Catalysis team at NREL from 1985 to 2005. His research interests include studies of fuel production and fuel utilization reactions using molecular catalysts, synthetic organometallic and inorganic chemistry, and thermodynamic studies relevant to catalysis. New classes of molecular catalysts have been developed for CO2 reduction, electrochemical CO2 pumping, and for hydrogen oxidation and production. Methods for determining the thermodynamic properties of transition-metal hydride complexes are being developed to support a better understanding of the energetics of catalytic intermediates. Current research is also focusing on the role of proton relays in molecular electrocatalytic processes involving multiple proton and electron transfer reactions.

Research Interests

  • Molecular electrocatalysis
  • Thermodynamics of transition metal hydrides
  • CO2 reduction catalysts
  • Hydrogen production and oxidation catalysts

Education and Credentials

  • Ph.D. in chemistry from Ohio State University
  • B.A. in chemistry from Indiana Central University.

PNNL Publications


  • DuBois DL. 2014. "Development of Molecular Electrocatalysts for Energy Storage." Inorganic Chemistry 53(8):3935-3960.  doi:10.1021/ic4026969
  • Chen S, MH Ho, RM Bullock, DL DuBois, M Dupuis, RJ Rousseau, and S Raugei. 2014. "Computing Free Energy Landscapes: Application to Ni-based Electrocatalysts with Pendant Amines for H2 Production and Oxidation." ACS Catalysis 4(1):229-242.  doi:10.1021/cs401104w
  • Liu TL, X Wang, C Hoffmann, DL DuBois, and RM Bullock. 2014. "Heterolytic Cleavage of Hydrogen by an Iron Hydrogenase Model: An Fe-H - - - H-N Dihydorgen Bond Characterized by Neutron Diffraction." Angewandte Chemie International Edition 53(21):5300-5304.  doi:10.1002/anie.201402090


  • Appel AM, JE Bercaw, AB Bocarsly, H Dobbek, DL DuBois, M Dupuis, JG Ferry, E Fujita, R Hille, P Kenis, CA Kerfeld, RH Morris, CHF Peden, A Portis, S Ragsdale, TB Rauchfuss, J Reek, LC Seefeldt, RK Thauer, and GL Waldrop. 2013. "Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2." Chemical Reviews 113(8):6621-6658.  doi:10.1021/cr300463y
  • Franz JA, MJ O'Hagan, MH Ho, TL Liu, ML Helm, S Lense, DL DuBois, WJ Shaw, AM Appel, S Raugei, and RM Bullock. 2013. "Conformational Dynamics and Proton Relay Positioning in Nickel Catalysts for Hydrogen Production and Oxidation." Organometallics 32(23):7034-7042.  doi:10.1021/om400695w
  • Hulley EB, KD Welch, AM Appel, DL DuBois, and RM Bullock. 2013. "Rapid, Reversible Heterolytic Cleavage of Bound H2." Journal of the American Chemical Society 135(32):11736-11739.  doi:10.1021/ja405755j
  • Liu TL, DL DuBois, and RM Bullock. 2013. "An iron complex with pendant amines as a molecular electrocatalyst for oxidation of hydrogen." Nature Chemistry 5(3):228-233.  doi:10.1038/NCHEM.1571
  • Shaw WJ, ML Helm, and DL DuBois. 2013. "A Modular, Energy-Based Approach to the Development of Nickel Containing Molecular Electrocatalysts for Hydrogen Production and Oxidation." Biochimica et Biophysica Acta--Bioenergetics 1827(8-9):1123-1139.  doi:10.1016/j.bbabio.2013.01.003
  • Wiedner ES, AM Appel, DL DuBois, and RM Bullock. 2013. "Thermochemical and Mechanistic Studies of Electrocatalytic Hydrogen Production by Cobalt Complexes Containing Pendant Amines." Inorganic Chemistry 52(24):14391-14403.  doi:10.1021/ic4025475
  • Wiedner ES, JA Roberts, WG Dougherty, WS Kassel, DL DuBois, and RM Bullock. 2013. "Synthesis and Electrochemical Studies of Cobalt(III) Monohydride Complexes Containing Pendant Amines." Inorganic Chemistry 52(17):9975-9988.  doi:10.1021/ic401232g
  • Wiese S, UJ Kilgore, MH Ho, S Raugei, DL DuBois, RM Bullock, and ML Helm. 2013. "Hydrogen Production using Nickel Electrocatalysts with Pendant Amines: Ligand Effects on Rates and Overpotentials." ACS Catalysis 3(11):2527-2535.  doi:10.1021/cs400638f
  • Yang JY, SE Smith, TL Liu, WG Dougherty, WA Hoffert, WS Kassel, M Rakowski DuBois, DL DuBois, and RM Bullock. 2013. "Two Pathways for Electrocatalytic Oxidation of Hydrogen by a Nickel Bis(diphosphine) Complex with Pendant Amines in the Second Coordination Sphere." Journal of the American Chemical Society 135(26):9700-9712.  doi:10.1021/ja400705a


  • Jain A, ML Helm, JC Linehan, DL DuBois, and WJ Shaw. 2012. "Biologically Inspired Phosphino Platinum Complexes." Inorganic Chemistry Communications 22:65-67.  doi:10.1016/j.inoche.2012.04.039
  • Liu TL, S Chen, MJ O'Hagan, M Rakowski DuBois, RM Bullock, and DL DuBois. 2012. "Synthesis, Characterization and Reactivity of Fe Complexes Containing Cyclic Diazadiphosphine Ligands: The Role of the Pendant Base in Heterolytic Cleavage of H2 ." Journal of the American Chemical Society 134(14):6257-6272.  doi:10.1021/ja211193j
  • O'Hagan MJ, MH Ho, JY Yang, AM Appel, M Rakowski DuBois, S Raugei, WJ Shaw, DL DuBois, and RM Bullock. 2012. "Proton Delivery and Removal in [Ni(PR2NR'2)2]2+ Hydrogen Production and Oxidation Catalysts." Journal of the American Chemical Society 134(47):19409-19424.  doi:10.1021/ja307413x
  • Raugei S, S Chen, MH Ho, B Ginovska-Pangovska, RJ Rousseau, M Dupuis, DL DuBois, and RM Bullock. 2012. "The Role of Pendant Amines in the Breaking and Forming of Molecular Hydrogen Catalyzed by Nickel Complexes." Chemistry - A European Journal 18(21):6493-6506.  doi:10.1002/chem.201103346
  • Seu C, AM Appel, MD Doud, DL DuBois, and C Kubiak. 2012. "Formate oxidation via ß-deprotonation in [Ni(PR2NR'2)2(CH3CN)]2+ complexes." Energy & Environmental Science 5(4):6480-6490.  doi:10.1039/c2ee03341k
  • Smith SE, JY Yang, DL DuBois, and M Bullock. 2012. "Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic." Angewandte Chemie International Edition 51(13):3152-3155.  doi:10.1002/anie.201108461
  • Waggoner NW, LS Spreer, BJ Boro, DL DuBois, and ML Helm. 2012. "Group 10 complexes containing phosphinomethylamine ligands: Synthesis, structural analysis and electrochemical studies." Inorganica Chimica Acta 380:14-21.  doi:10.1016/j.ica.2011.07.001
  • Weiss CJ, AN Groves, MT Mock, WG Dougherty, WS Kassel, ML Helm, DL DuBois, and RM Bullock. 2012. "Synthesis and reactivity of molybdenum and tungsten bis(dinitrogen) complexes supported by diphosphine chelates containing pendant amines." Dalton Transactions 41(15):4517-4529.  doi:10.1039/C2DT12224C
  • Wiedner ES, JY Yang, S Chen, S Raugei, WG Dougherty, WS Kassel, ML Helm, RM Bullock, M Rakowski DuBois, and DL DuBois. 2012. "Stabilization of Nickel Complexes with Ni0···H-N Bonding Interactions Using Sterically Demanding Cyclic Diphosphine Ligands." Organometallics 31(1):144-156.  doi:10.1021/om200709z
  • Wiese S, UJ Kilgore, DL DuBois, and RM Bullock. 2012. "[Ni(PMe2NPh2)2](BF4)2 as an Electrocatalyst for H2 Production." ACS Catalysis 2(5):720-727.  doi:10.1021/cs300019h


  • DuBois DL, and RM Bullock. 2011. "Molecular Electrocatalysts for the Oxidation of Hydrogen and the Production of Hydrogen - The Role of Pendant Amines as Proton Relays." European Journal of Inorganic Chemistry 2011(7):1017-1027.  doi:10.1002/ejic.201001081
  • Jain A, S Lense, JC Linehan, S Raugei, HM Cho, DL DuBois, and WJ Shaw. 2011. "Incorporating Peptides in the Outer Coordination Sphere of Bio-inspired Electrocatalysts for Hydrogen Production ." Inorganic Chemistry 50(9):4073-4085.  doi:10.1021/ic1025872
  • Appel AM, DH Pool, MJ O'Hagan, WJ Shaw, JY Yang, M Rakowski DuBois, DL DuBois, and RM Bullock. 2011. "[Ni(PPh2NBn2)2(CH3CN)]2+ as an Electrocatalyst for H2 Production: Dependence on Acid Strength and Isomer Distribution." ACS Catalysis 1(7):777-785.  doi:10.1021/cs2000939
  • Campbell CT, AK Datye, GA Henkelman, RF Lobo, WF Schneider, LD Spicer, WT Tysoe, JM Vohs, DR Baer, DW Hoyt, S Thevuthasan, KT Mueller, CM Wang, NM Washton, I Lyubinetsky, RG Teller, A Andersen, N Govind, K Kowalski, BC Kabius, H Wang, AA Campbell, WA Shelton, EJ Bylaska, CHF Peden, Y Wang, DL King, MA Henderson, RJ Rousseau, J Szanyi, Z Dohnalek, D Mei, BC Garrett, D Ray, JH Futrell, J Laskin, DL DuBois, LR Kuprat, and C Plata. 2011. EMSL and Institute for Integrated Catalysis (IIC) Catalysis WorkshopPNNL-20426, Pacific Northwest National Laboratory, Richland, WA. 
  • Chen S, RJ Rousseau, S Raugei, M Dupuis, DL DuBois, and RM Bullock. 2011. "Comprehensive Thermodynamics of Nickel Hydride Bis(Diphosphine) Complexes: A Predictive Model through Computations." Organometallics 30(22):6108-6118.  doi:10.1021/om200645x
  • Dupuis M, S Chen, S Raugei, DL DuBois, and RM Bullock. 2011. "Comment on 'New Insights in the Electrocatalytic Proton Reduction and Hydrogen Oxidation by Bioinspired Catalysts: A DFT Investigation'." Journal of Physical Chemistry A 115(18):4861-4865.  doi:10.1021/jp111479z
  • Galan BR, J Schoffel, JC Linehan, C Seu, AM Appel, JA Roberts, ML Helm, UJ Kilgore, JY Yang, DL DuBois, and C Kubiak. 2011. "Electrocatalytic Oxidation of Formate by [Ni(PR2NR`2)2(CH3CN)]2+ Complexes." Journal of the American Chemical Society 113(35):12767-12779.  doi:10.1021/ja204489e
  • Helm ML, MP Stewart, II, RM Bullock, M Rakowski DuBois, and DL DuBois. 2011. "A Synthetic Nickel Electrocatalyst With a Turnover Frequency Above 100,000 s-1 for H2 Production." Science 333(6044):863-866.  doi:10.1126/science.1205864
  • Kilgore UJ, JA Roberts, DH Pool, AM Appel, MP Stewart, II, M Rakowski DuBois, WG Dougherty, WS Kassel, RM Bullock, and DL DuBois. 2011. "[Ni(PPh2NC6H4X2)2]2+ Complexes as Electrocatalysts for H2 Production: Effect of Substituents, Acids, and Water on Catalytic Rates." Journal of the American Chemical Society 133(15):5861-5872.  doi:10.1021/ja109755f
  • Kilgore UJ, MP Stewart, II, ML Helm, WG Dougherty, WS Kassel, M Rakowski DuBois, DL DuBois, and RM Bullock. 2011. "Studies of a Series of [Ni(PR2NPh2)2(CH3CN)]2+ Complexes as Electrocatalysts for H2 Production: Substituent Variation at the Phosphorus Atom of the P2N2 Ligand." Inorganic Chemistry 50(21):10908-10918. 
  • Mock MT, RG Potter, MJ O'Hagan, DM Camaioni, WG Dougherty, WS Kassel, and DL DuBois. 2011. "Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds ." Inorganic Chemistry 50(23):11914-11928.  doi:10.1021/ic200857x
  • Mock MT, S Chen, RJ Rousseau, MJ O'Hagan, WG Dougherty, WS Kassel, DL DuBois, and RM Bullock. 2011. "A Rare Terminal Dinitrogen Complex of Chromium." Chemical Communications 47(44):12212-12214.  doi:10.1039/C1CC15430C
  • O'Hagan MJ, WJ Shaw, S Raugei, S Chen, JY Yang, UJ Kilgore, DL DuBois, and RM Bullock. 2011. "Moving Protons with Pendant Amines: Proton Mobility in a Nickel Catalyst for Oxidation of Hydrogen." Journal of the American Chemical Society 133(36):14301-14312.  doi:10.1021/ja201838x
  • Roberts JA, DL DuBois, and RM Bullock. 2011. "Experimental and Digital Modeling Studies of the Electrochemical Oxidation of the Metal Anion [CpW(CO)2(IMes)]- and the 17-Electron Metal Radical CpW(CO)2(IMes)·. Kinetics and Thermodynamics of Capture and Release of MeCN by a Metal Radical and a Metal Cation." Organometallics 30(17):4555-4563.  doi:10.1021/om2002816
  • Roberts JA, AM Appel, DL DuBois, and RM Bullock. 2011. "Comprehensive Thermochemistry of W-H Bonding in the Metal Hydrides CpW(CO)2(IMes)H, [CpW(CO)2(IMes)H]·+, and [CpW(CO)2(IMes)(H)2]+. Influence of an N-Heterocyclic Carbene Ligand on Metal Hydride Bond Energies." Journal of the American Chemical Society 133(37):14604-14613.  doi:10.1021/ja202830w
  • Roberts JA, JA Franz, EF van der Eide, ED Walter, JL Petersen, DL DuBois, and RM Bullock. 2011. "Comproportionation of Cationic and Anionic Tungsten Complexes Having an N-Heterocyclic Carbene Ligand to Give the Isolable 17-Electron Tungsten Radical, CpW(CO)2(IMes)· ." Journal of the American Chemical Society 133(37):14593-14603.  doi:10.1021/ja202754e
  • Small YA, DL DuBois, E Fujita, and JT Muckerman. 2011. "Proton management as a design principle for hydrogenase-inspired catalysts." Energy & Environmental Science 4(11):3008-3020.  doi:10.1039/C1EE01170G
  • Yang JY, RM Bullock, M Rakowski DuBois, and DL DuBois. 2011. "Fast and efficient molecular electrocatalysts for H2 production: Using hydrogenase enzymes as guides." MRS Bulletin 36(1):39-47.  doi:10.1557/mrs.2010.8


  • DuBois DL, and M Rakowski DuBois. 2010. "Nickel Complexes of Bis(Diethylphosphinomethyl) Methylamine." Chapter 7 in Inorganic Syntheses, vol. 35, ed. TB Rauchfuss, pp. 132-137.  John Wiley & Sons, Inc., Hoboken, NJ. 
  • Rakowski DuBois M, and DL DuBois. 2010. "A Modular Approach to the Development of Molecular Electrocatalysts for H2 Oxidation and Production Based on Inexpensive Metals." Chapter 7 in Catalysis without Precious Metals , ed. RM Bullock, pp. 165-180.  John Wiley & Sons, Inc., Hoboken, NJ. 
  • Welch KD, WG Dougherty, WS Kassel, DL DuBois, and RM Bullock. 2010. "Synthesis, Structures, and Reactions of Manganese Complexes Containing Diphosphine Ligands With Pendant Amines." Organometallics 29(20):4532-4540.  doi:10.1021/om100668e
  • Wiedner ES, JY Yang, WG Dougherty, WS Kassel, RM Bullock, M Rakowski DuBois, and DL DuBois. 2010. "Comparison of Cobalt and Nickel Complexes with Sterically Demanding Cyclic Diphosphine Ligands: Electrocatalytic H2 Production by [Co(PtBu2NPh2)(CH3CN)3](BF4)2." Organometallics 29(21):5390-5401.  doi:10.1021/om100395r
  • Wilson AD, AJ Miller, DL DuBois, JA Labinger, and JE Bercaw. 2010. "Thermodynamic Studies of [H2Rh(diphosphine)2]+ and [HRh(diphosphine)2(CH3CN)]2+ Complexes in Acetonitrile." Inorganic Chemistry 49(8):3918-3926. 
  • Yang JY, RM Bullock, WG Dougherty, WS Kassel, B Twamley, DL DuBois, and M Rakowski DuBois. 2010. "Reduction of Oxygen Catalyzed by Nickel Diphosphine Complexes with Positioned Pendant Amines." Dalton Transactions 39(12):3001-3010. 
  • Yang JY, S Chen, WG Dougherty, WS Kassel, RM Bullock, DL DuBois, S Raugei, RJ Rousseau, M Dupuis, and M Rakowski DuBois. 2010. "Hydrogen Oxidation Catalysis by a Nickel Diphosphine Complex with Pendant tert-Butyl Amines." Chemical Communications 46:8618-8620.  doi:10.1039/C0CC03246H


  • Appel AM, SJ Lee, JA Franz, DL DuBois, and M Rakowski DuBois. 2009. "Free Energy Landscapes for S-H Bonds in (Cp2Mo2S4)-Mo-star Complexes." Journal of the American Chemical Society 131(14):5224-5232.  doi:10.1021/ja8093179
  • Appel AM, SJ Lee, JA Franz, DL DuBois, M Rakowski DuBois, and B Twamley. 2009. "Determination of S-H Bond Strengths in Dimolybdenum Tetrasulfide Complexes." Organometallics 28(3):749-754. 
  • Mock MT, RG Potter, DM Camaioni, J Li, WG Dougherty, WS Kassel, B Twamley, and DL DuBois. 2009. "Thermodynamic Studies and Hydride Transfer Reactions from a Rhodium Complex to BX3 Compounds ." Journal of the American Chemical Society 131(40):14454-14465. 
  • Pool DH, and DL DuBois. 2009. "[Ni(PPh2NAr2)2(NCMe)][BF4]2 as an electrocatalyst for H2 production: PPh2NAr2 = 1,5-(di(4-(thiophene-3-yl)phenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane)." Journal of Organometallic Chemistry 694(17):2858-2865. 
  • Rakowski DuBois M, and DL DuBois. 2009. "Development of Molecular Electrocatalysts for CO2 Reduction and H2 Production/Oxidation." Accounts of Chemical Research 42(12):1974-1982. 
  • Rakowski DuBois M, and DL DuBois. 2009. "The roles of the first and second coordination spheres in the design of molecular catalysts for H2 production and oxidation." Chemical Society Reviews 38(1):62-72.  doi:10.1039/b801197b
  • Yang JY, RM Bullock, WJ Shaw, B Twamley, K Fraze, M Rakowski DuBois, and DL DuBois. 2009. "Mechanistic Insights into Catalytic H2 Oxidation by Ni Complexes Containing a Diphosphine Ligand with a Positioned Amine Base." Journal of the American Chemical Society 131(16):5935-5945. 


  • Appel AM, SJ Lee, JA Franz, DL DuBois, M Rakowski DuBois, JC Birnbaum, and B Twamley. 2008. "Formation and Reactivity of a Persistent Radical in a Dinuclear Molybdenum Complex." Journal of the American Chemical Society 130(28):8940-8951.  doi:10.1021/ja078115r
  • Jacobsen GM, JY Yang, B Twamley, A Wilson, RM Bullock, M Rakowski DuBois, and DL DuBois. 2008. "Hydrogen Production Using Cobalt-Based Molecular Catalysts Containing a Proton Relay in the Second Coordination Sphere." Energy & Environmental Science 1(1):167-174.  doi:10.1039/b805309j
  • Liu J, GH Cao, Z Yang, D Wang, DL DuBois, XD Zhou, GL Graff, LR Pederson, and J Zhang. 2008. "Oriented Nanostructures for Energy Conversion and Storage." ChemSusChem 1(8-9):676-697. 
  • Nimlos M, CH Chang, CJ Curtis, A Miedaner, HM Pilath, and DL DuBois. 2008. "Calculated Hydride Donor Abilities of Five-Coordinate Transition Metal Hydrides [HM(diphosphine)2]+ (M = Ni, Pd, Pt) as a Function of the Bite Angle and Twist Angle of Diphosphine Ligands." Organometallics 27(12):2715-2722. 
  • Nimlos MR, CH Chang, CJ Curtis, A Miedaner, HM Pilath, and DL DuBois. 2008. "Calculated Hydride Donor Abilities of Five-Coordinate Transition Metal Hydrides [HM(diphosphine)2] (+) (M = Ni, Pd, Pt) as a Function of the Bite Angle and Twist Angle of Diphosphine Ligands." Organometallics 27(12):2715-2722.  doi:10.1021/om701218x
  • Rakowski DuBois M, and DL DuBois. 2008. "The Role of Pendant Bases in Molecular Catalysts for H-2 Oxidation and Production." Comptes Rendus de L'Academie des Sciences. Serie IIc. Chimie 11(8):805-817.  doi:10.1016/j.crci.2008.01.019
  • Wilson A, K Fraze, B Twamley, SM Miller, DL DuBois, and M Rakowski DuBois. 2008. "The role of the second coordination sphere of [Ni(PCy2NBz2)2](BF4)2 in reversible carbon monoxide binding." Journal of the American Chemical Society 130(3):1061-1068.  doi:10.1021/ja077328d


  • Fraze K, A Wilson, AM Appel, M Rakowski DuBois, and DL DuBois. 2007. "Thermodynamic Properties of the Ni-H Bond in Complexes of the Type [HNi(P2RN2R')2](BF4) and Evaluation of Factors that Control Catalytic Activity for Hydrogen Oxidation/Production." Organometallics 26(16):3918-3924.  doi:10.1021/om070143v
  • Jacobsen GM, RK Shoemaker, M Rakowski DuBois, and DL DuBois. 2007. "Syntheses and Reactions of Iron(II) Complexes Containing Diphosphine Ligands with Pendant Nitrogen Bases." Organometallics 26(20):4964-4971.  doi:10.1021/om700510b
  • Jacobsen GM, RK Shoemaker, MJ McNevin, M Rakowski DuBois, and DL DuBois. 2007. "Syntheses and Structural Characterizations of Iron(II) Complexes Containing Cyclic Diphosphine Ligands with Positioned Pendant Nitrogen Bases." Organometallics 26(20):5003-5009.  doi:10.1021/om700601h
  • Redin K, A Wilson, R Newell, MR DuBois, and DL DuBois. 2007. "Studies of Structural Effects on the Half-wave Potentials of Mononuclear and Dinuclear Nickel(II) Diphosphine/Dithiolate Complexes." Inorganic Chemistry 46(4):1268-1276.  doi:10.1021/ic061740x
  • Wilson A, RK Shoemaker, A Miedaner, JT Muckerman, DL DuBois, and MR DuBois. 2007. "Nature of Hydrogen Interactions with Ni(II) Complexes Containing Cyclic Phosphine Ligands with Pendant Nitrogen Bases ." Proceedings of the National Academy of Sciences of the United States of America 104(17):6951-6956.  doi:10.1073/pnas.0608928104


  • DuBois DL, DM Blake, A Miedaner, CJ Curtis, MR DuBois, JA Franz, and JC Linehan. 2006. "Hydride Transfer from Rhodium Complexes to Triethylborane." Organometallics 25(18):4414-4419.  doi:10.1021/om060584z

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