A successful working model for nanoporosity evolution during dealloying was introduced 15 years ago. Since that time, the field has rapidly expanded, with research groups from across the world studying dealloying and dealloyed materials. Dealloying has grown into a rich field, with some groups focusing on fundamentals and mechanisms of dealloying, other groups creating new porous metals and alloys, and even more groups studying their properties. Dealloying was originally considered only in the context of corrosion, but now it is considered a facile self-organization technique to fabricate high-surface-area, bicontinuous nanoporous materials. Owing to their high interfacial area and the versatility of metallic materials, nanoporous metals have found application in catalysis, sensing, actuation, electrolytic and ultracapacitor materials, high-temperature templates/scaffolds, battery anodes, and radiation damage–tolerant materials. In this review, we discuss the fundamental materials principles underlying the formation of dealloyed materials and then look at two major applications: catalysis and nanomechanics.

Liquid metal dealloying has emerged as a novel technique to produce topologically complex nanoporous and nanocomposite structures with ultra-high interfacial area and other unique properties relevant for diverse material applications. This process is empirically known to require the selective dissolution of one element of a multicomponent solid alloy into a liquid metal to obtain desirable structures. However, how structures form is not known. Here we demonstrate, using mesoscale phase-field modelling and experiments, that nano/microstructural pattern formation during dealloying results from the interplay of (i) interfacial spinodal decomposition, forming compositional domain structures enriched in the immiscible element, and (ii) diffusion-coupled growth of the enriched solid phase and the liquid phase into the alloy. We highlight how those two basic mechanisms interact to yield a rich variety of topologically disconnected and connected structures. Moreover, we deduce scaling laws governing microstructural length scales and dealloying kinetics.

The synthesis of alloys with long-range atomic-scale ordering (ordered intermetallics) is an emerging field of nanochemistry. Ordered intermetallic nanoparticles are useful for a wide variety of applications such as catalysis, superconductors, and magnetic devices. However, the preparation of nanostructured ordered intermetallics is challenging in comparison to disordered alloys, hindering progress in material development. Herein, we report a process for converting colloidally synthesized ordered intermetallic PdBi2 to ordered intermetallic Pd3Bi nanoparticles under ambient conditions by electrochemical dealloying. The low melting point of PdBi2 corresponds to low vacancy formation energies, which enables the facile removal of the Bi from the surface while simultaneously enabling interdiffusion of the constituent atoms via a vacancy diffusion mechanism under ambient conditions. The resulting phase-converted ordered intermetallic Pd3Bi exhibits 11 times and 3.5 times higher mass activity and high methanol tolerance for the oxygen reduction reaction compared with Pt/C and Pd/C, respectively, which is the highest reported for a Pd-based catalyst, to the best of our knowledge. These results establish a key development in the synthesis of noble-metal-rich ordered intermetallic phases with high catalytic activity and set forth guidelines for the design of ordered intermetallic compounds under ambient conditions.

Liquid metal dealloying (LMD) has recently emerged as a novel technique to fabricate bulk nanostructures using a bottom-up self-organization method, but the literature lacks fundamental studies of this kinetic process. In this work, we conduct an in-depth study of the kinetics and fundamental microstructure evolution mechanisms during LMD using Ti-Ta alloys immersed in molten Cu as a model system. We develop a model of LMD kinetics based on a quantitative characterization of the effects of key parameters in our system including alloy composition, dealloying duration, and dealloying temperature. This work demonstrates that the dealloying interface is at or near equilibrium during LMD, and that the rate-limiting step is the liquidstate diffusion of dissolving atoms away from the dealloying interface (diffusion-limited kinetics). The quantitative comparison between theoretically predicted and measured dealloying rates further reveals that convective transport and rejection of the dissolving element during coarsening of the structure also influence the dealloying kinetics.

Electroreduction of small molecules in aqueous solution often competes with the hydrogen evolution reaction (HER), especially if the reaction is driven even moderately hard using a large overpotential. Here, the oxygen reduction reaction (ORR) was studied under proton diffusion-limited conditions in slightly acidic electrolytes: a model system to study the relative transport kinetics of protons and reactants to an electrocatalyst and the relationship between transport and catalytic performance. Using dealloyed nanoporous nickel-platinum (np-NiPt) electrodes, we find the hydrogen evolution reaction can be completely suppressed even at high overpotentials (-400 mV vs RHE). In addition, the mechanism of oxygen reduction can be changed by using buffered versus unbuffered solutions, suggesting the reaction selectivity is associated with a transient rise (or lack thereof) in the interface pH at the np-NiPt surface. Independently controlling reactant transport to electrocatalyst surfaces at high overpotentials exhibited a surprisingly rich phenomenology that may offer a generalizable strategy to increase activity and selectivity during electroreduction reactions.

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We describe the basic thermodynamic and kinetic aspects that govern the growth of Si and Ge nanowires directly on bulk metal films. We illustrate essential differences between the vapour-solid-solid and the conventional vapour-liquid-solid nanowire growth. Ge and Si nanowires were formed on a select set of metal films including Ag, Al, Au, Cr, Cu and Ni. Metals that form silicides or germanides (Cr, Cu, and Ni) generally yield higher quality nanowires compared to nanowires grown on metal films whose equilibrium phases are defined by alloyed phases below eutectic temperatures (Al, Ag, Au). Combinatorial experiments presented here provide new basic insights into nanowire formation in the context of metal germanide and silicide formation rates. The mechanism established from our experiments successfully predicts the nanowire growth under a broad range of conditions and also predicts the nanowire growth on other metals to provide guidance to future progress in nanowire synthesis.

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