Characterization of paramagnetic states in an organometallic nickel hydrogen evolution electrocatalyst

Sagnik Chakrabarti, Soumalya Sinha, Giang N. Tran, Hanah Na and Liviu M. Mirica ()
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Sagnik Chakrabarti: University of Illinois at Urbana-Champaign
Soumalya Sinha: University of Illinois at Urbana-Champaign
Giang N. Tran: University of Illinois at Urbana-Champaign
Hanah Na: University of Illinois at Urbana-Champaign
Liviu M. Mirica: University of Illinois at Urbana-Champaign

Nature Communications, 2023, vol. 14, issue 1, 1-11

Abstract: Abstract Significant progress has been made in the bioinorganic modeling of the paramagnetic states believed to be involved in the hydrogen redox chemistry catalyzed by [NiFe] hydrogenase. However, the characterization and isolation of intermediates involved in mononuclear Ni electrocatalysts which are reported to operate through a NiI/III cycle have largely remained elusive. Herein, we report a NiII complex (NCHS2)Ni(OTf)2, where NCHS2 is 3,7-dithia-1(2,6)-pyridina-5(1,3)-benzenacyclooctaphane, that is an efficient electrocatalyst for the hydrogen evolution reaction (HER) with turnover frequencies of ~3,000 s−1 and a overpotential of 670 mV in the presence of trifluoroacetic acid. This electrocatalyst follows a hitherto unobserved HER mechanism involving C-H activation, which manifests as an inverse kinetic isotope effect for the overall hydrogen evolution reaction, and NiI/NiIII intermediates, which have been characterized by EPR spectroscopy. We further validate the possibility of the involvement of NiIII intermediates by the independent synthesis and characterization of organometallic NiIII complexes.

Date: 2023
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DOI: 10.1038/s41467-023-36609-7

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