Periodically Interrupting Bonding Behavior to Reformat Delocalized Electronic States of Graphdiyne for Improved Electrocatalytic Hydrogen Evolution

作者：Kaikai Ma, Jing Wu, Xin Wang, Yu Sun, Zhaozhao Xiong, Fulong Dai, Haokun Bai, Yong Xie, Zhuo Kang, Yue Zhang · 发表于：Angewandte Chemie International Edition · 年份：2022 · DOI：10.1002/anie.202211094 · 被引用次数：48 · 研究领域：Electrocatalysts for Energy Conversion、Advanced battery technologies research、Molecular Junctions and Nanostructures

Abstract π electron configuration plays a pivotal role in metal‐free carbon catalysts, and its delocalization degree overwhelmingly dominates catalytic activity. However, precise and targeted regulation of inherent π electrons still remain challenging. Here, one chemical‐bond‐targeted physical clipping strategy is proposed and effectively adopted in the cutting‐edge carbon material system of graphdiyne (GDY) as a concept‐of‐proof. The delocalized electrons are expected to be periodically reformatted for substantially enhancing π electron delocalization. Via theoretical screening and well‐designed experiments, periodical interruption of Csp−Csp 2 bonds in GDY can render sp−C sites with decent activity, ultimately yielding top‐ranking electrocatalytic performance without intentionally introducing external decoration. The as‐proposed concept endows a universal prescription to push the limit of delocalization degree, thus shedding novel light on the rational design of decent metal‐free catalysts.