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Updated: Mar 28, 2026

Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production
Published on: December 6, 2021
Highly functionalizable penta-coordinate iron hydrogen production catalysts with low overpotentials
Shawn C Eady1, Tanya Breault2, Levi Thompson2
1Department of Chemistry, University of Michigan, 930 North University Ave, Ann Arbor, Michigan 48109-1055, USA. lehnertn@umich.edu.
New iron carbonyl complexes featuring the Fe(PNP) motif catalyze dihydrogen production electrocatalysis. Activity correlates with ligand substituents, with electron-withdrawing groups and aliphatic linkers enhancing performance.
Area of Science:
- Inorganic Chemistry
- Electrochemistry
- Catalysis
Background:
- Penta-coordinate iron carbonyl complexes with the Fe(PNP) motif offer tunable ligand spheres.
- Developing efficient electrocatalysts for dihydrogen production is crucial for sustainable energy technologies.
Purpose of the Study:
- To synthesize and characterize novel Fe(PNP) complexes for electrocatalytic dihydrogen production.
- To investigate the structure-activity relationships governing the catalytic performance.
Main Methods:
- Synthesis and characterization of penta-coordinate iron carbonyl complexes.
- Electrocatalytic evaluation for dihydrogen production under acidic conditions.
- Spectroscopic and structural analyses to elucidate reaction mechanisms.
Main Results:
- The synthesized [Fe(S2C6H4)(PNP)(CO)] complexes exhibit efficient dihydrogen production electrocatalysis.
- Overpotentials ranged from 0.09-0.21 V vs. Pt, with a maximum turnover frequency (TOF) of 3.51 s(-1) at 0.15 V.
- Catalyst activity is enhanced by electron-withdrawing PNP substituents and aliphatic linkers.
Conclusions:
- Fe(PNP) complexes are promising electrocatalysts for dihydrogen production.
- Ligand design significantly impacts catalytic activity and stability.
- An EC-type mechanism involving Fe(II) reduction and an Fe(III) hydride intermediate is proposed.
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