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Regulating Electrocatalytic Oxygen Reduction Activity of a Metal Coordination Polymer via d–π Conjugation
Author(s) -
Ni Youxuan,
Lin Liu,
Shang Yuxin,
Luo Lin,
Wang Liubin,
Lu Yong,
Li Yixin,
Yan Zhenhua,
Zhang Kai,
Cheng Fangyi,
Chen Jun
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202104494
Subject(s) - electrocatalyst , rational design , catalysis , transition metal , oxygen reduction , chemistry , combinatorial chemistry , metal , oxygen , polymer , materials science , nanotechnology , electrochemistry , electrode , organic chemistry
Non‐noble transition metal complexes have attracted growing interest as efficient electrocatalysts for oxygen reduction reaction (ORR) while their activities still lack rational and effective regulation. Herein, we propose a d–π conjugation strategy for rough and fine tuning of ORR activity of TM‐BTA (TM=Mn/Fe/Co/Ni/Cu, BTA=1,2,4,5‐benzenetetramine) coordination polymers. By first‐principle calculations, we elucidate that the strong d–π conjugation elevates the d xz /d yz orbitals of TM centers to enhance intermediate adsorption and strengthens the electronic modulation effect from substitute groups on ligands. Based on this strategy, Co‐TABQ (tetramino benzoquinone) is found to approach the top of ORR activity volcano. The synthesized Co‐TABQ with atomically distributed Co on carbon nanotubes exhibits a half‐wave potential of 0.85 V and a specific current of 127 mA mg metal −1 at 0.8 V, outperforming the benchmark Pt/C. The high activity, low peroxide yield, and considerable durability of Co‐BTA and Co‐TABQ promise their application in oxygen electrocatalysis. This study provides mechanistic insight into the rational design of transition metal complex catalysts.