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Molecular engineering of a cobalt-based electrocatalytic nanomaterial for H2 evolution under fully aqueous conditions

Abstract

The viability of a hydrogen economy depends on the design of efficient catalytic systems based on earth-abundant elements. Innovative breakthroughs for hydrogen evolution based on molecular tetraimine cobalt compounds have appeared in the past decade. Here we show that such a diimine–dioxime cobalt catalyst can be grafted to the surface of a carbon nanotube electrode. The resulting electrocatalytic cathode material mediates H2 generation (55,000 turnovers in seven hours) from fully aqueous solutions at low-to-medium overpotentials. This material is remarkably stable, which allows extensive cycling with preservation of the grafted molecular complex, as shown by electrochemical studies, X-ray photoelectron spectroscopy and scanning electron microscopy. This clearly indicates that grafting provides an increased stability to these cobalt catalysts, and suggests the possible application of these materials in the development of technological devices.

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Figure 1: Synthetic methodology for the preparation of the CNT/Co material.
Figure 2: Electrochemical characterization.
Figure 3: XPS analysis.
Figure 4: Electrocatalytic hydrogen evolution.

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Acknowledgements

This work was supported by the French National Research Agency (ANR) through Grant 07-BLAN-0298-01, Labex program (ARCANE, 11-LABX-003) and Carnot funding (Institut Leti). The authors thank the New Technologies for Energy Program of CEA (project pH2oton) and P. Jegou for XPS measurements.

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Authors

Contributions

V.A., B.J., S.P. and M.F. designed the research, E.S.A., P-A.J., P.D.T., A.L., M.C-K., M.M. and V.A. performed the research, J.P. performed the X-ray crystallographic studies and V.A. and E.S.A. co-wrote the paper.

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Correspondence to Vincent Artero.

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Patent applications (EP-08 290 988.8 and E.N.10 53019) have been filed for the preparation of azide-appended diimine–dioxime complexes such as 2 and their grafting onto electrode materials.

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Crystallographic data for compound 2. (CIF 19 kb)

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Andreiadis, E., Jacques, PA., Tran, P. et al. Molecular engineering of a cobalt-based electrocatalytic nanomaterial for H2 evolution under fully aqueous conditions. Nature Chem 5, 48–53 (2013). https://doi.org/10.1038/nchem.1481

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