材料科学
分子内力
共价键
电化学
密度泛函理论
合理设计
氢键
催化作用
纳米技术
氧气
化学工程
电子结构
化学物理
氢
析氧
工作(物理)
活动站点
氧还原
组合化学
氧化还原
可持续能源
电催化剂
光化学
吸附
作者
Zhongping Li,Xinjiang Wang,Songlin Zhao,Changqing Li,Won‐Yeong Kim,Yucheng Jin,Feng Tang,Jong‐Pil Jeon,Siliu Lyu,Sang‐Young Lee,Jong‐Beom Baek
标识
DOI:10.1002/adfm.202520634
摘要
Abstract Accurately identifying and enhancing catalytic activity in metal‐free, carbon‐based electrocatalysts remains a fundamental challenge, largely due to the difficulty of concurrently optimizing hydrophilicity and oxygen affinity at active sites. Herein, a hydrogen‐bonding‐driven strategy is presented to boost oxygen reduction reaction (ORR) performance in covalent organic frameworks (COFs). By integrating hydrazone linkages with alkoxy‐functionalized pore walls, a hydrophilic skeleton capable of forming tunable intramolecular hydrogen‐bonding networks is constructed. These interactions induce asymmetric electron distributions that enhance the simultaneous adsorption of water and oxygen molecules. Consequently, the hydrazone‐linked COFs exhibit a half‐wave potential of 0.78 V, outperforming all previously reported metal‐free COF‐based electrocatalysts. Density functional theory (DFT) calculations reveal that the improved activity originates from favorable * OOH and * OH adsorption energies at hydrogen‐bonding centers, along with stabilized O 2 /H 2 O binding. This synergistic modulation of the local microenvironment—through hydrogen bonding and electronic structure engineering—affords enhanced activity, selectivity, and long‐term durability. This work offers a rational design paradigm for advancing metal‐free COF electrocatalysts toward sustainable energy conversion.
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