The interplay between chemical dopants and topological defects plays a crucial role in electrocatalysis of doped graphene. By systematically tuning the curvatures, thereby the density of topological defects, of 3D nanoporous graphene, the intrinsic correlation of topological defects with chemical doping contents and dopant configurations is revealed, shining lights into the structural and chemical origins of HER activities of graphene.

Three-dimensional bicontinuous open (3DBO) nanoporosity has been recognized as an important nanoarchitecture for catalysis, sensing, and energy storage. Dealloying, i.e., selectively removing a component from an alloy, is an efficient way to fabricate nanoporous materials. However, current electrochemical and liquid-metal dealloying methods can only be applied to a limited number of alloys and usually require an etching process with chemical waste. Here, we report a green and universal approach, vapor-phase dealloying, to fabricate nanoporous materials by utilizing the vapor pressure difference between constituent elements in an alloy to selectively remove a component with a high partial vapor pressure for 3DBO nanoporosity. We demonstrate that extensive elements, regardless of chemical activity, can be fabricated as nanoporous materials with tunable pore sizes. Importantly, the evaporated components can be fully recovered. This environmentally friendly dealloying method paves a way to fabricate 3DBO nanoporous materials for a wide range of structural and functional applications.

The development of noble-metal-free hydrogen evolution reaction (HER) materials for electrochemical water splitting is the key to achieving low-cost and efficient electrocatalysis that drives electrochemical hydrogen evolution. However, the electrocatalytic activities of most non-noble metals decrease in acidic electrolytes. Here, we have fabricated non-noble-metal electrodes using a bicontinuous and open porous NiMo alloy covered by nitrogen-doped (N-doped) graphene with nanometersized holes. This noble-metal-free HER catalyst exhibits performance almost identical with that of a Pt/C electrode, while its original catalytic activity is preserved even in acidic electrolytes. Density functional theory calculations indicate that the interfacial fringes between the nanoholes and NiMo surface induce charge transfer and promote hydrogen adsorption and desorption. The nanometer-sized holes simultaneously provide minimal surface area for chemical reactions, while delaying NiMo dissolution in excessive amounts of acidic electrolyte. Our method for the fabrication of the NiMo alloy provides a route to a promising class of electrochemical hydrogen-producing electrodes.