Details

Autor(en) / Beteiligte

• Zhang, Daoyang
• Crawley, Matthew R
• Fang, Ming
• Kyle, Lea J
• Cook, Timothy R

Titel

The rigidity of self-assembled cofacial porphyrins influences selectivity and kinetics of oxygen reduction electrocatalysis

Ist Teil von

• Dalton transactions : an international journal of inorganic chemistry, 2022-12, Vol.51 (48), p.18373-18377

Ort / Verlag

England: Royal Society of Chemistry

Erscheinungsjahr

2022

Quelle

MEDLINE

Beschreibungen/Notizen

• We report the electrocatalytic Oxygen Reduction Reaction on a rigid Co( ii ) porphyrin prism scaffold bridged by Ag( i ) ions. The reactivity of this scaffold differs significantly from previous prism catalysts in that its selectivity is similar to that of monomer (∼35% H 2 O) yet it displays sluggish kinetics, with an order of magnitude lower k s of ∼0.5 M −1 s −1 . The deleterious cofacial effect is not simply due to metal-metal separation, which is similar to our most selective prism catalysts. Instead we conclude the structural rigidity is responsible for these differences. Cofacial porphyrin prisms are electrocatalysts for the Oxygen Reduction Reaction. When they are structurally rigidified at their metal nodes, their selectivity changes significantly from >95% to 35% despite similar metal-metal separations.