TY - JOUR
T1 - Characterization of paramagnetic states in an organometallic nickel hydrogen evolution electrocatalyst
AU - Chakrabarti, Sagnik
AU - Sinha, Soumalya
AU - Tran, Giang N.
AU - Na, Hanah
AU - Mirica, Liviu M.
N1 - Publisher Copyright:
© 2023, The Author(s).
PY - 2023/12
Y1 - 2023/12
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85148357676&partnerID=8YFLogxK
U2 - 10.1038/s41467-023-36609-7
DO - 10.1038/s41467-023-36609-7
M3 - Article
C2 - 36807358
AN - SCOPUS:85148357676
SN - 2041-1723
VL - 14
JO - Nature communications
JF - Nature communications
IS - 1
M1 - 905
ER -