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

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

Dalton transactions (Cambridge, England : 2003) (2015-07-28)
D Sirbu, C Turta, E A Gibson, A C Benniston
RESUMO

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.

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Sigma-Aldrich
Rhodium, powder, 99.95% trace metals basis
Sigma-Aldrich
trans-2-[3-(4-tert-Butylphenyl)-2-methyl-2-propenylidene]malononitrile, ≥98%
Rhodium, foil, not light tested, 25x25mm, thickness 0.00025mm, permanent polyester support, 99.9%
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Rhodium, microfoil, disks, 10mm, thinness 0.1μm, specific density 124μg/cm2, permanent mylar 3.5μm support, 99.9%
Rhodium, foil, not light tested, 50x50mm, thickness 0.006mm, as rolled, 99.9%
Rhodium, foil, 12mm disks, thickness 0.5mm, as rolled, 99.9%
Rhodium, foil, not light tested, 25x25mm, thickness 0.012mm, as rolled, 99.9%
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Rhodium, microfoil, disks, 25mm, thinness 0.25μm, specific density 310μg/cm2, permanent mylar 3.5μm support, 99.99%
Rhodium, microfoil, disks, 10mm, thinness 0.25μm, specific density 310μg/cm2, permanent mylar 3.5μm support, 99.99%
Rhodium, foil, light tested, 25x25mm, thickness 0.05mm, as rolled, 99.9%
Rhodium, foil, 25x25mm, thickness 0.15mm, as rolled, 99.9%
Rhodium, microfoil, disks, 10mm, thinness 0.50μm, specific density 620μg/cm2, permanent mylar 3.5μm support, 99.99%
Rhodium, foil, light tested, 25x25mm, thickness 0.05mm, as rolled, x-ray quality, 99.9%
Rhodium, foil, light tested, 15x15mm, thickness 0.05mm, as rolled, 99.9%
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Rhodium, wire reel, 0.05m, diameter 0.25mm, hard, 99.9%
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Rhodium, foil, not light tested, 25x25mm, thickness 0.001mm, permanent polyester support, 99.85%
Rhodium, foil, not light tested, 50x50mm, thickness 0.00075mm, permanent polyester support, 99.85%
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Rhodium, wire reel, 0.05m, diameter 0.5mm, as drawn, 99.9%
Rhodium, foil, not light tested, 50x50mm, thickness 0.001mm, permanent polyester support, 99.85%
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