The rigidity of self-assembled cofacial porphyrins influences selectivity and kinetics of oxygen reduction electrocatalysis
The rigidity of self-assembled cofacial porphyrins influences selectivity and kinetics of oxygen reduction electrocatalysis
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自组装面卟啉的刚性影响氧还原电催化的选择性和动力学
DOI：
10.1039/d2dt02724k
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发表时间：
2022
影响因子：
4
通讯作者：
Cook, Timothy R.
中科院分区：
文献类型：
--
作者：
Zhang, Daoyang;Crawley, Matthew R.;Fang, Ming;Kyle, Lea J.;Cook, Timothy R.
本文报道了在Ag(I)离子桥接的刚性Co（II）卟啉棱镜支架上的电催化氧还原反应。该支架的反应活性与以前的棱镜催化剂有很大不同，因为它的选择性与单体（~ 35% H2O）相似，但它表现出缓慢的动力学，ks低了一个数量级，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，这与我们最具选择性的棱镜催化剂相似。相反，我们得出结论，结构刚度是造成这些差异的原因。
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.