The ferrocene effect: enhanced electrocatalytic hydrogen production using meso-tetraferrocenyl porphyrin palladium(II) and copper(II) complexes

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 44; no. 33; pp. 14646 - 14655
• Main Authors: Sirbu, D, Turta, C, Gibson, E A, Benniston, A C
• Format: Journal Article
• Language: English
• Published: England 01.01.2015
• Subjects: Catalysis; Catalysts; Electrodes; Ferrocenes; Gas analysis; Hydrogen production; Mathematical analysis; Porphyrins
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c5dt02191j

Copper(ii) and palladium(ii) meso-tetraferrocenylporphyrins ( and ) were employed as catalysts for electrochemical proton reduction in DMF using trifluoroacetic acid (TFA) or triethylamine hydrochloride (TEAHCl) as acids. Gas analysis under electrocatalytic conditions at a glassy carbon working electrode confirmed the product as H2. showed catalytic behavior for both TFA and TEAHCl, whereas only TFA worked for . The performance of the two compounds for electrocatalytic hydrogen generation was compared to the analogous copper(ii) and palladium(ii) meso-tetraphenylporphyrins ( and ) under identical conditions. The presence of the ferrocence groups on the porphyrin favourably shift the overpotential to a less negative value by around 200 mV and increases the catalytic rate of hydrogen production in DMF/TFA by an order of magnitude to 6 × 10(3) s(-1). Moreover, while is fully inactive in a DMF/TEAHCl mixture, the ferrocene subunits activate the catalyst. Spectroelectrochemistry experiments and DFT calculations were consistent with a catalytic process proceeding via the phlorin anion.