Efficient Hydrogen Evolution on Nanoscale Graphdiyne

Abstract Self‐active metal‐free graphdiyne (GDY) is used, which has a precise chemical structure, as a model carbon‐based metal‐free electrocatalyst to assess its activity in the hydrogen evolution reaction (HER) and to understand the origin of electrocatalytic performance at the atomic level. The studies reveal that the unusual electrocatalytic properties of GDY originate from its unique nanostructure, which can simultaneously provide highly active sites for hydrogen adsorption and facilitate the electron‐transfer process for proton reduction. Accordingly, GDY can act as a metal‐free efficient HER electrocatalyst with Pt‐like HER activity, but with long‐term durability superior to that of Pt/C under the wide pH range (from acidic to basic). To the best of knowledge, such HER performance is better than that of other reported metal‐free electrocatalysts and most transition‐metal electrocatalysts—even Pt‐based ones.