A growing awareness of issues related to anthropogenic climate change and an increase in global energy demand have made the search for viable carbon-neutral sources of renewable energy one of the most important challenges in science today1. The chemical community is therefore seeking efficient and inexpensive catalysts that can produce large quantities of hydrogen gas from water1,2,3,4,5,6,7. Here we identify a molybdenum-oxo complex that can catalytically generate gaseous hydrogen either from water at neutral pH or from sea water. This work shows that high-valency metal-oxo species can be used to create reduction catalysts that are robust and functional in water, a concept that has broad implications for the design of ‘green’ and sustainable chemistry cycles.
Your institute does not have access to this article
Open Access articles citing this article.
Scientific Reports Open Access 28 February 2020
Subscribe to Journal
Get full journal access for 1 year
only $3.90 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
Lewis, N. S. & Nocera, D. G. Powering the planet: chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 103, 15729–15735 (2006)
Turner, J. A. Sustainable hydrogen production. Science 305, 972–974 (2004)
Du, P., Knowles, K. & Eisenberg, R. A homogeneous system for the photogeneration of hydrogen from water based on a platinum(II) terpyridyl acetylide chromophore and a molecular cobalt catalyst. J. Am. Chem. Soc. 130, 12576–12577 (2008)
Fihri, A. et al. Cobaloxime-based photocatalytic devices for hydrogen production. Angew. Chem. Int. Edn Engl. 47, 564–567 (2008)
Esswein, A. J. & Nocera, D. G. Hydrogen production by molecular photocatalysis. Chem. Rev. 107, 4022–4047 (2007)
Tard, C. et al. Synthesis of the H-cluster framework of iron-only hydrogenase. Nature 433, 610–613 (2005)
Sun, L., Åkermark, B. & Ott, S. Iron hydrogenase active site mimics in supramolecular systems aiming for light-driven hydrogen production. Coord. Chem. Rev. 249, 1653–1663 (2005)
Frey, M. Hydrogen-activating enzymes. ChemBioChem 3, 153–160 (2002)
Armstrong, F. A. Hydrogenases: active site puzzles and progress. Curr. Opin. Chem. Biol. 8, 133–140 (2004)
Evans, D. J. & Pickett, C. J. Chemistry and the hydrogenases. Chem. Soc. Rev. 32, 268–275 (2003)
Darensbourg, M. Y., Lyon, E. J., Zhao, X. & Georgakaki, I. P. The organometallic active site of [Fe]hydrogenase: models and entatic states. Proc. Natl Acad. Sci. USA 100, 3683–3688 (2003)
Gloaguen, F. & Rauchfuss, T. B. Small molecule mimics of hydrogenases: hydrides and redox. Chem. Soc. Rev. 38, 100–108 (2009)
Felton, G. A. N. et al. Hydrogen generation from weak acids: electrochemical and computational studies of a diiron hydrogenase mimic. J. Am. Chem. Soc. 129, 12521–12530 (2007)
Baffert, C., Artero, V. & Fontecave, M. Cobaloximes as functional models for hydrogenases. 2. Proton electroreduction catalyzed by difluoroborylbis(dimethylglyoximato)cobalt(II) complexes in organic media. Inorg. Chem. 46, 1817–1824 (2007)
Hu, X., Brunschwig, B. S. & Peters, J. C. Electrocatalytic hydrogen evolution at low overpotentials by cobalt macrocyclic glyoxime and tetraimine complexes. J. Am. Chem. Soc. 129, 8988–8998 (2007)
Wilson, A. D. et al. Hydrogen oxidation and production using nickel-based molecular catalysts with positioned proton relays. J. Am. Chem. Soc. 128, 358–366 (2006)
Appel, A. M., DuBois, D. L. & DuBois, M. R. Molybdenum-sulfur dimers as electrocatalysts for the production of hydrogen at low overpotentials. J. Am. Chem. Soc. 127, 12717–12726 (2005)
Goldsmith, J. I., Hudson, W. R., Lowry, M. S., Anderson, T. H. & Bernhard, S. Discovery and high-throughput screening of heteroleptic iridium complexes for photoinduced hydrogen production. J. Am. Chem. Soc. 127, 7502–7510 (2005)
Klein Gebbink, R. J. M., Jonas, R. T., Goldsmith, C. R. & Stack, T. D. P. A periodic walk: a series of first-row transition metal complexes with the pentadentate ligand PY5. Inorg. Chem. 41, 4633–4641 (2002)
Jaksic, M. M. & Csonka, I. M. Acceleration of sodium amalgam decomposition by depolarization with molybdenum graphite in the mercury cell process. Electrochem. Technol. 4, 49–56 (1966)
Collin, J. P., Jouaiti, A. & Sauvage, J. P. Electrocatalytic properties of Ni(cyclam)2+ and Ni2(biscyclam)4+ with respect to carbon dioxide and water reduction. Inorg. Chem. 27, 1986–1990 (1988)
Bernhardt, P. V. & Jones, L. A. Electrochemistry of macrocyclic cobalt(III/II) hexaamines: electrocatalytic hydrogen evolution in aqueous solution. Inorg. Chem. 38, 5086–5090 (1999)
Armstrong, F. A. et al. Dynamic electrochemical investigations of hydrogen oxidation and production by enzymes and implications for future technology. Chem. Soc. Rev. 38, 36–51 (2009)
Hinnemann, B. et al. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J. Am. Chem. Soc. 127, 5308–5309 (2005)
Jaramillo, T. F. et al. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317, 100–102 (2007)
Dance, I. The hydrogen chemistry of the FeMo-co active site of nitrogenase. J. Am. Chem. Soc. 127, 10925–10942 (2005)
Yoon, M. & Tyler, D. R. Activation of water by permethyltungstenocene; evidence for the oxidative addition of water. Chem. Commun. 639 (1997)
Blum, O. & Milstein, D. Oxidative addition of water and aliphatic alcohols by IrCl(trialkylphosphine)3 . J. Am. Chem. Soc. 124, 11456–11467 (2002)
Ozerov, O. V. Oxidative addition of water to transition metal complexes. Chem. Soc. Rev. 38, 83–88 (2009)
Kohl, S. W. et al. Consecutive thermal H2 and light-induced O2 evolution from water promoted by a metal complex. Science 324, 74–77 (2009)
We acknowledge the NSF (grant number CHE-0617063) for research funding in the initial stages of this project. For the later stages, we acknowledge the Helios Solar Energy Research Center, which is supported by the Office of Science, Office of Basic Energy Sciences of the US Department of Energy under contract number DE-AC02-05CH11231. C.J.C. is an Investigator with the Howard Hughes Medical Institute. We thank Tyco Electronics for the partial support of H.I.K. We also thank M. Majda for discussions, D. M. Jenkins and P. Dechambenoit for experimental assistance, A. T. Iavarone for obtaining the mass spectra, and J. D. Breen for fabrication of the electrochemical cells.
The authors declare no competing financial interests.
X-ray coordinates from the crystal structure determinations have been deposited with the Cambridge Crystallographic Data Centre with reference codes 720362 (compound 1), 720363 (compound 2), 753993 (compound 5), 753992 (compound 6) and 720364 (compound 7).
About this article
Cite this article
Karunadasa, H., Chang, C. & Long, J. A molecular molybdenum-oxo catalyst for generating hydrogen from water. Nature 464, 1329–1333 (2010). https://doi.org/10.1038/nature08969
Mo3+ hydride as the common origin of H2 evolution and selective NADH regeneration in molybdenum sulfide electrocatalysts
Nature Catalysis (2022)
Difunctional hierarchical CoxP QDs-MoS2@Ni3S2/NF nanostructure as advanced electrocatalyst for water electrolysis
Journal of Materials Science: Materials in Electronics (2021)
Polyoxometalate based hybrid compound as a pre-catalyst for electrocatalytic water reduction at neutral pH
Journal of Chemical Sciences (2021)
Scientific Reports (2020)