Authors
Sachin Kumar, Martina Marsotto, Anubhi Rawat, Irena Saltsman, Natalia Fridman, Gabriele Magna, Manuela Stefanelli, Atif Mahammed, Roberto Paolesse, Zeev Gross
Published in
Inorganic chemistry. Volume 65. Issue 35. Pages 20567-20573. Sep 07, 2026.
Abstract
The development of efficient, earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) is central to advancing sustainable hydrogen production. Here, we report a systematic investigation of three cobalt corroles featuring progressively stronger electron-donating meso-positions and β-pyrrole substituents. The highly electron-rich β-octaalkyl-substituted cobalt corrole was synthesized and fully characterized by single-crystal X-ray diffraction, NMR, UV-vis spectroscopy, and high-resolution mass spectrometry. Electrochemical studies reveal a monotonic shift of the Co-centered redox couples to more negative potentials with increasing electron donation by the macrocycle. The difference between the redox and catalytic onset potentials was determined to be largest for the most electron-rich corrole when examined under homogeneous conditions using acetic acid as the proton source. HER catalysis by this complex was also most efficient, proceeding with a turnover frequency of up to 5105 s-1. All three complexes were successfully immobilized onto high-surface-area carbon (BP2000) and used for catalyzing HER in acidic aqueous media. Under these heterogeneous conditions, the catalysts with 2,6-dimethoxyphenyl substituents on the meso-positions perform best, with a low overpotential of 0.2 V. These findings demonstrate that proper tuning of the electron-donating capability of the cobalt-chelating corroles can be used for enhancing HER catalytic efficacy.
PMID:
42704180
Bibliographic data and abstract were imported from PubMed on 07 Sep 2026.
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