Facile electrocatalytic proton reduction by a [Fe–Fe]-hydrogenase bio-inspired synthetic model bearing a terminal CN— ligand

Nayek, Abhijit; Dey, Subal; Patra, Suman; Rana, Atanu; Serrano, Pauline N.; George, Simon J.; Cramer, Stephen P.; Ghosh Dey, Somdatta; Dey, Abhishek

doi:10.1039/d3sc05397k

Title: Facile electrocatalytic proton reduction by a [Fe–Fe]-hydrogenase bio-inspired synthetic model bearing a terminal CN^— ligand

Journal Article · 01 January 2024 · Chemical Science

DOI: https://doi.org/10.1039/d3sc05397k · OSTI ID:2337820

^[1];

^[1]; Patra, Suman ^[1]; Rana, Atanu ^[1]; Serrano, Pauline N. ^[2];

^[3]; Cramer, Stephen P. ^[4]; Ghosh Dey, Somdatta ^[1]; Dey, Abhishek ^[1]

Indian Association for the Cultivation of Science (IACS), Kolkata (India)
Univ. of California, Davis, CA (United States)
Univ. of California, Davis, CA (United States); SETI Institute, Mountain View, CA (United States)
Univ. of California, Davis, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SETI Institute, Mountain View, CA (United States)

An azadithiolate bridged CN^— bound pentacarbonyl bis-iron complex, mimicking the active site of [Fe–Fe] H₂ase is synthesized. The geometric and electronic structure of this complex is elucidated using a combination of EXAFS analysis, infrared and Mössbauer spectroscopy and DFT calculations. The electrochemical investigations show that complex 1 effectively reduces H⁺ to H₂ between pH 0–3 at diffusion-controlled rates (10¹¹ M^—1 s^—1) i.e. 10⁸ s^—1 at pH 3 with an overpotential of 140 mV. Electrochemical analysis and DFT calculations suggests that a CN— ligand increases the pK_a of the cluster enabling hydrogen production from its Fe(I)–Fe(0) state at pHs much higher and overpotential much lower than its precursor bis-iron hexacarbonyl model which is active in its Fe(0)–Fe(0) state. The formation of a terminal Fe–H species, evidenced by spectroelectrochemistry in organic solvent, via a rate determining proton coupled electron transfer step and protonation of the adjacent azadithiolate, lowers the kinetic barrier leading to diffusion controlled rates of H₂ evolution. The stereo-electronic factors enhance its catalytic rate by 3 order of magnitude relative to a bis-iron hexacarbonyl precursor at the same pH and potential.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2337820

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 6 Vol. 15; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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