pH-Controlled Dealloying Route to Hierarchical Bulk Nanoporous Zn Derived from Metastable Alloy for Hydrogen Generation by Hydrolysis of Zn in Neutral Water

Abstract

Dealloyed nanoporous metals made of very-reactive elements have rarely been reported. Instead, reactive materials are used as sacrificial components in dealloying. The high chemical reactivity of nonprecious nanostructured metals makes them suitable for a broad range of applications such as splitting water into H₂ gas and metal hydroxide. On the other hand, the same high chemical reactivity hinders the synthesis of nanostructured metals. Here we use a pH-controlled dealloying strategy to fabricate bulk nanoporous Zn with bulk dimensions in the centimeter range via the selective removal of Al from metastable face-centered cubic bulk Zn₂₀Al₈₀ at. % parent alloys. The corresponding bulk nanoporous Zn exhibits a hierarchical ligament/pore architecture characterized by primary ligaments and pores with an average feature size in the submicrometer range. These primary structures are made of ultrafine secondary ligaments and pores with a characteristic feature size in the range of 10–20 nm. Our bulk nanoporous Zn can split water into H₂ and Zn­(OH)₂ at ambient temperature and pressure and continuously produce H₂ at a constant rate of 0.08 mL/min per gram of Zn over 8 h. We anticipate that in this hierarchical bulk architecture, the macropores facilitate the flow of water in the bulk of the material, while the mesopores and ultrafine ligaments provide a high surface area for the reaction of water with Zn. The bulk nanoporous Zn/water system can be used for on-board or on-demand H₂ applications, during which H₂ is produced when needed, without prior storage of this gas compressed in cylinders as it is currently the case