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A molecular molybdenum-oxo catalyst for generating hydrogen from water

Abstract

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.

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Figure 1: Reaction of [(PY5Me2)Mo(CF3SO3)]1+ with water to form [(PY5Me2)MoO]2+ and release H2.
Figure 2: Cyclic voltammograms of compounds 2 and 7.
Figure 3: Electrochemical data for a 7.7 µM solution of [(PY5Me2)MoO](PF6)2 (7) in a 0.6 M phosphate buffer at pH 7.
Figure 4: Extended electrolysis.
Figure 5: Speculative electrocatalytic cycle for the reduction of water to release hydrogen and hydroxide anions.

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Acknowledgements

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.

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Authors

Contributions

H.I.K., C.J.C. and J.R.L. planned the research, and H.I.K. performed the experiments. H.I.K., C.J.C. and J.R.L. prepared the manuscript.

Corresponding authors

Correspondence to Christopher J. Chang or Jeffrey R. Long.

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The authors declare no competing financial interests.

Additional information

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).

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This file contains Supplementary Methods, a Supplementary Discussion, Supplementary Tables S1-S2, Supplementary Figures S1-S9 with legends and References. (PDF 742 kb)

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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

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