Graphdiyne-based metal-free catalysts demonstrate outstanding performances in electrocatalysis. In order to accurately understand the activity origin of metal-free electrocatalytic hydrogen production at the atomic level, we have successfully designed and prepared a new metal-free catalyst of 1,2,4-triamino-graphdiyne (TAGDY). Structural characterizations showed that TAGDY has unique nanostructure, which guarantees the fast proton-electron transfer during the catalytic process. Experimental studies revealed that TAGDY possesses excellent electrocatalytic activities and long-term durability towards hydrogen evolution in acidic conditions, better than the most reported metal-free electrocatalysts. Density functional theory calculations and Born-Oppenheimer molecular dynamics simulations revealed that the interaction of (H⁺+e⁻) pair with alkyne bond induces the transition between CC and CC in TAGDY, which effectively enhanced the catalytic activities of initial inert carbon sites. Combination of theory and experiment as well as the structural characterization, a new level of knowledge for the activity origin and catalytic mechanism of graphdiyne-based metal-free electrocatalysts are presented.

石墨二炔基无金属催化剂在电催化方面表现出出色的性能。为了准确地了解在原子水平上无金属的电催化制氢的活性来源，我们成功设计并制备了一种新型的1,2,4-三氨基-石墨二炔（TAGDY）的无金属催化剂。结构表征表明，TAGDY具有独特的纳米结构，可确保催化过程中快速的质子电子转移。实验研究表明，TAGDY具有优异的电催化活性和在酸性条件下对氢析出的长期耐久性，优于大多数报道的不含金属的电催化剂。密度泛函理论计算和Born-Oppenheimer分子动力学模拟显示（H ⁺+ E ^- ）一对与炔键诱导之间的过渡Ç Ç和Ç Ç在TAGDY，从而有效地增强了初始惰性碳位点的催化活性。结合理论和实验以及结构表征，对石墨二炔基无金属电催化剂的活性来源和催化机理有了新的认识。