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The rigidity of self-assembled cofacial porphyrins influences selectivity and kinetics of oxygen reduction electrocatalysis
Dalton Transactions ( IF 3.5 ) Pub Date : 2022-11-15 , DOI: 10.1039/d2dt02724k Daoyang Zhang 1 , Matthew R Crawley 1 , Ming Fang 1 , Lea J Kyle 1 , Timothy R Cook 1
Dalton Transactions ( IF 3.5 ) Pub Date : 2022-11-15 , DOI: 10.1039/d2dt02724k Daoyang Zhang 1 , Matthew R Crawley 1 , Ming Fang 1 , Lea J Kyle 1 , Timothy R Cook 1
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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% H2O) yet it displays sluggish kinetics, with an order of magnitude lower ks 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.
中文翻译：
自组装共面卟啉的刚性影响氧还原电催化的选择性和动力学
我们报告了由 Ag( I ) 离子桥接的刚性 Co( II ) 卟啉棱柱支架上的电催化氧还原反应。该支架的反应性与之前的棱柱催化剂显着不同，因为它的选择性与单体（~35% H 2 O）的选择性相似，但它表现出缓慢的动力学，k s低一个数量级，为~0.5 M -1 s -1。有害的共面效应不仅仅是由于金属-金属分离，这类似于我们最具选择性的棱柱催化剂。相反，我们得出结论，结构刚性是造成这些差异的原因。
更新日期：2022-11-15
中文翻译：
自组装共面卟啉的刚性影响氧还原电催化的选择性和动力学
我们报告了由 Ag( I ) 离子桥接的刚性 Co( II ) 卟啉棱柱支架上的电催化氧还原反应。该支架的反应性与之前的棱柱催化剂显着不同，因为它的选择性与单体（~35% H 2 O）的选择性相似，但它表现出缓慢的动力学，k s低一个数量级，为~0.5 M -1 s -1。有害的共面效应不仅仅是由于金属-金属分离，这类似于我们最具选择性的棱柱催化剂。相反，我们得出结论，结构刚性是造成这些差异的原因。
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