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Tailoring Electronic Structure and Size of Ultrastable Metalated Metal–Organic Frameworks with Enhanced Electroconductivity for High‐Performance Supercapacitors
Author(s) -
Xia Zhengqiang,
Jia Xu,
Ge Xi,
Ren Chongting,
Yang Qi,
Hu Jun,
Chen Zhong,
Han Jing,
Xie Gang,
Chen Sanping,
Gao Shengli
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.202100123
Subject(s) - supercapacitor , delocalized electron , materials science , electrolyte , metal organic framework , ligand (biochemistry) , conductivity , capacitance , chemical engineering , metal , electrode , nanoscopic scale , doping , nanotechnology , optoelectronics , chemistry , organic chemistry , metallurgy , biochemistry , receptor , adsorption , engineering
Abstract Utilization of metal–organic frameworks (MOFs) as electrodes for energy storage/conversion is challenging because of the low chemical stability and poor electrical conductivity of MOFs in electrolytes. A nanoscale MOF, Co 0.24 Ni 0.76 ‐bpa‐200 , possessing ultrahigh stability with uncommon semiconductor behavior ( σ =4.2×10 −3 S m −1 ) was fabricated. The MOF comprises a robust hydrophobic paddlewheel and an optimized Co/Ni ratio, with consequent control over MOF size and the degree of conjugation of the coligand. A DFT study revealed that appropriate Ni 2+ doping reduces the activation energy of the system, thus providing a higher carrier concentration, and the strongly delocalized N‐donor ligand notably increases the metal–ligand orbital overlap to achieve efficient charge migration, leading to continuous through‐bond (‐CoNi‐N‐CoNi‐) ∞ conduction paths. These structural features endow the MOF with a good cycling stability of 86.5 % (10 000 cycles) and a high specific capacitance of 1927.14 F g −1 among pristine MOF‐based electrodes.