Characterization of paramagnetic states in an organometallic nickel hydrogen evolution electrocatalyst

Chakrabarti, Sagnik; Sinha, Soumalya; Tran, Giang N.; Na, Hanah; Mirica, Liviu M.

doi:10.1038/s41467-023-36609-7

Title: Characterization of paramagnetic states in an organometallic nickel hydrogen evolution electrocatalyst

Journal Article · 16 February 2023 · Nature Communications

DOI: https://doi.org/10.1038/s41467-023-36609-7 · OSTI ID:1957666

Chakrabarti, Sagnik; Sinha, Soumalya; Tran, Giang N.;

;

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 Ni ^I/III cycle have largely remained elusive. Herein, we report a Ni ^II 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 Ni ^I /Ni ^III intermediates, which have been characterized by EPR spectroscopy. We further validate the possibility of the involvement of Ni ^III intermediates by the independent synthesis and characterization of organometallic Ni ^III complexes.

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Research Organization:: Washington Univ., St. Louis, MO (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0006862

OSTI ID:: 1957666

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 14; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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