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

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.