Vertical Conductive Metal–Organic Framework Single‐Crystalline Nanowire Arrays for Efficient Electrocatalytic Hydrogen Evolution

Abstract The construction of crystalline metal–organic frameworks with regular architectures supportive of enhanced mass transport and bubble diffusion is imperative for electrocatalytic applications; however, this poses a formidable challenge. Here, a method is presented that confines the growth of nano‐architectures to the liquid‐liquid interface. Using this method, vertically oriented single crystalline nanowire arrays of an Ag‐benzenehexathiol (BHT) conductive metal‐organic framework (MOF) are fabricated via an “in‐plane self‐limiting and out‐of‐plane epitaxial growth” mechanism. This material has excellent electrocatalytic features, including highly exposed active sites, intrinsically high electrical conductivity, and superhydrophilic and superaerophobic properties. Leveraging these advantages, the carefully designed material demonstrates superior electrocatalytic hydrogen evolution activity, resulting in a low Tafel slope of 66 mV dec −1 and a low overpotential of 275 mV at a high current density of 1 A cm −2 . Finite element analysis (FEA) and in situ microscopic verification indicates that the nanowire array structure significantly enhances the electrolyte transport kinetics and promotes the rapid release of gas bubbles. The findings highlight the potential of using MOF‐based ordered nanoarray structures for advanced electrocatalytic applications.