Supramolecular Modulation of Molecular Conformation of Metal Porphyrins toward Remarkably Enhanced Multipurpose Electrocatalysis and Ultrahigh-Performance Zinc–Air Batteries,Advanced Energy Materials

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Supramolecular Modulation of Molecular Conformation of Metal Porphyrins toward Remarkably Enhanced Multipurpose Electrocatalysis and Ultrahigh-Performance Zinc–Air Batteries
Advanced Energy Materials ( IF 24.4 ) Pub Date : 2021-10-13 , DOI: 10.1002/aenm.202102062
Kai Cui _{1,

2} , Qingtao Wang ₂ , Zenan Bian ₃ , Gongming Wang ₃ , Yuxi Xu ₁

Affiliation

Modulating the intrinsic catalytic activity of molecular catalysts to improve electrocatalytic performance is significant but challenging. Herein, a simple yet effective strategy to induce molecular flattening of Co (III) meso-tetra (N-methyl-4-pyridyl) porphyrine (Co-TMPyP) by supramolecular assembly with chemically converted graphene (CCG) via synergistic electrostatic and π–π interactions is reported. This unique variation in molecular conformation leads to a shortened CoN coordination bond and enhanced electron transfer from the porphyrin macrocycle to the metal ion, thereby optimizing the electronic structure of the catalytic active center in Co-TMPyP molecule. Thus, the flattened Co-TMPyP on CCG (Co-TMPyP/CCG) demonstrates remarkable electrocatalytic performance for the oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), and oxygen evolution reaction (OER) simultaneously as a tri-functional molecular catalyst for the first time with a high half-wave potential of 0.824 V for ORR and a low overpotential for HER (320 mV) and OER (379 mV) at 10 mA cm^–2, respectively, not only much better than the pristine Co-TMPyP but also among the best results of molecular catalysts in each aspect of ORR, OER, and HER achieved thus far. As a practical demonstration, the Co-TMPyP/CCG catalyst is used to assemble a rechargeable Zn–air battery, which shows the highest specific capacity (793 mAh g^–1) and power density (225.4 mW cm^–2) among all molecular catalyst-based Zn–air batteries ever reported.

中文翻译：

金属卟啉分子构象的超分子调控显着增强多用途电催化和超高性能锌-空气电池

调节分子催化剂的内在催化活性以提高电催化性能是重要但具有挑战性的。在本文中，一个简单而有效的策略，以诱导的Co（III）的分子平坦内消旋-四（Ñ甲基-4-吡啶基）卟啉（联合TMPyP）由超分子组装体通过协同静电和化学转化的石墨烯（CCG）π- π 相互作用被报告。这种分子构象的独特变化导致 Co 缩短N 配位键并增强了从卟啉大环到金属离子的电子转移，从而优化了 Co-TMPyP 分子中催化活性中心的电子结构。因此，CCG上的扁平Co-TMPyP（Co-TMPyP/CCG）作为三功能分子同时表现出对氧还原反应（ORR）、析氢反应（HER）和析氧反应（OER）的显着电催化性能。催化剂首次具有 0.824 V 的高半波电位 ORR 和低过电位 HER (320 mV) 和 OER (379 mV) 在 10 mA cm ^–2分别比原始的 Co-TMPyP 好得多，而且在 ORR、OER 和 HER 的各个方面都是迄今为止分子催化剂的最佳结果。作为实际演示，Co-TMPyP/CCG 催化剂用于组装可充电锌空气电池，在所有分子催化剂中表现出最高的比容量（793 mAh g ^–1）和功率密度（225.4 mW cm ^–2）基于锌空气电池的报道。

更新日期：2021-12-09

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