We would like to thank Dr. Daniel DuBois for useful discussions. This work was funded by the Office of Science Early Career Research Program through the US DOE, BES (A.D., W.J.S.), and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US DOE, BES (J.A.S.R.). Part of the research was conducted at the W.R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by US DOE’s Office of Biological and Environmental Research program located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the US DOE. We thank Dr. Charles Weiss and Dr. Jonathan Darmon for the preparation of the table-of-contents graphic.
Arginine-Containing Ligands Enhance H2 Oxidation Catalyst Performance†
Article first published online: 12 MAY 2014
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Volume 126, Issue 25, pages 6605–6609, June 16, 2014
How to Cite
Dutta, A., Roberts, J. A. S. and Shaw, W. J. (2014), Arginine-Containing Ligands Enhance H2 Oxidation Catalyst Performance. Angew. Chem., 126: 6605–6609. doi: 10.1002/ange.201402304
- Issue published online: 11 JUN 2014
- Article first published online: 12 MAY 2014
- Manuscript Received: 11 FEB 2014
- US DOE, BES
- Bioinspirierte Katalysatoren;
- Homogene Elektrokatalyse;
Hydrogenase enzymes use Ni and Fe to oxidize H2 at high turnover frequencies (TOF) (up to 10 000 s−1) and low overpotentials (<100 mV). In comparison, the fastest reported synthetic electrocatalyst, [NiII(PCy2NtBu2)2]2+, oxidizes H2 at 60 s−1 in MeCN under 1 atm H2 with an unoptimized overpotential of ca. 500 mV using triethylamine as a base.1 Here we show that a structured outer coordination sphere in a Ni electrocatalyst enhances H2 oxidation activity: [NiII(PCy2NArg2)2]8+ (Arg=arginine) has a TOF of 210 s−1 in water with high energy efficiency (180 mV overpotential) under 1 atm H2, and 144 000 s−1 (460 mV overpotential) under 133 atm H2. The complex is active from pH 0–14 and is faster at low pH, the most relevant condition for fuel cells. The arginine substituents increase TOF and may engage in an intramolecular guanidinium interaction that assists in H2 activation, while the COOH groups facilitate rapid proton movement. These results emphasize the critical role of features beyond the active site in achieving fast, efficient catalysis.