Three‐Dimensional Graphene Networks with Abundant Sharp Edge Sites for Efficient Electrocatalytic Hydrogen Evolution

To achieve sustainable production of hydrogen (H2) through water splitting, establishing efficient and earth‐abundant electrocatalysts is of great necessity. Morphology engineering of graphene is now shown to modulate the electronic structure of carbon skeleton and in turn endow it with excellent ability of proton reduction. Three‐dimensional (3D) graphene networks with a high density of sharp edge sites are synthesized. Electrocatalytic measurements indicate that the obtained 3D graphene networks can electrocatalyze H2 evolution with an extremely low onset potential of about 18 mV in 0.5 m H2SO4 solution, together with good stability. A combination of control experiments and density functional theory (DFT) investigations indicates that the exceptional H2 evolution performance is attributed to the abundant sharp edge sites of the advanced frameworks, which are responsible for promoting the adsorption and reduction of protons. Sharp catalysis: 3D graphene networks with abundant sharp edge sites are fabricated by a simple one‐step chemical vapor deposition strategy. The networks exhibit superior electrocatalytic performance in the hydrogen evolution reaction over metal‐hybrid or heteroatom‐doped carbon materials. Experiments and theoretical investigations reveal that the performance originates from abundant exposed pristine graphene edges.