@article{Sun2025, 
author = {Yinggang Sun and Peng Sun and Jigang Wang and Yanqiong Zhuang and Likai Wang and Ang Li and Zhongfang Li},
title = {Facile method to synthesize conjugated poly(1,4-phenyldiimine) porphyrin cobalt with “electron pump” for enhancing bifunctional catalytic oxygen reaction performance},
year = {2025},
journal = {Nano Research},
volume = {18},
number = {12},
pages = {94907789},
keywords = {novel synthesis method, fully conjugated covalent organic frameworks, electron pump, catalytic oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) performance, methylene alcohol terminated poly(1,4-phenyldiimine) porphyrin cobalt (M-PImPorCo)/three-dimensional graphene (3D-G)},
url = {https://www.sciopen.com/article/10.26599/NR.2025.94907789},
doi = {10.26599/NR.2025.94907789},
abstract = {To solve the slow dynamics of catalytic oxygen reaction energy devices, a facile method was developed for the synthesis of methylene alcohol terminated poly(1,4-phenyldiimine) porphyrin cobalt (M-PImPorCo), which was synthesized by RuCl3 catalyzed redox reaction of meso-5,10,15,20-tetra(4-nitrophenyl) porphyrin cobalt (TNO2PorCo) and 1,4-phenyldimethanol. M-PImPorCo is a fully conjugated covalent organic framework (COF) with high thermal and chemical stability. COFs with different edge groups were synthesized to compare the effect of different groups (–CH2–OH and –NO2) on catalytic bifunctional oxygen reaction activity. C=N as nitrogen-rich environment of M-PImPorCo leads to the protonation process of oxygen catalysis and reduces the energy barrier of adsorption in the oxygen intermediate. C=N and –CH2–OH form an “electron pump” structure to deliver electrons to the Co–N4 site in M-PImPorCo, and the π–π interaction between M-PImPorCo and three-dimensional graphene (3D-G) can further enrich the electron cloud density of Co–N4 sites. M-PImPorCo/3D-G has remarkable oxygen catalytic performance, with a half-wave potential (E1/2) of 0.91 V vs. reversible hydrogen electrode (RHE). M-PImPorCo/3D-G has low potential (Ej=10 is 1.49 V vs. RHE) at a current density of 10 mA·cm−2. It exhibits a good bifunctional catalytic performance (potential difference (ΔE) = 0.58 V). The smaller charge–discharge band gap of zinc-air batteries (ZABs) and flexible ZABs (F-ZABs) equipped with M-PImPorCo/3D-G suggests the potential for catalytic oxygen reaction bifunctional applications. This work provides a new idea for the synthesis of Schiff-base porphyrin-based COF catalyst and its potential application to oxygen reaction catalytic energy storage devices.}
}