We present a comprehensive experimental study of the formation and activity of dealloyed nanoporous Ni/Pt alloy nanoparticles for the cathodic oxygen reduction reaction. By addressing the kinetics of nucleation during solvothermal synthesis we developed a method to control the size and composition of Ni/Pt alloy nanoparticles over a broad range while maintaining an adequate size distribution. Electrochemical dealloying of these size-controlled nanoparticles was used to explore conditions in which hierarchical nanoporosity within nanoparticles can evolve. Our results show that in order to evolve fully formed porosity, particles must have a minimum diameter of ∼15 nm, a result consistent with the surface kinetic processes occurring during dealloying. Nanoporous nanoparticles possess ligaments and voids with diameters of approximately 2 nm, high surface area/mass ratios usually associated with much smaller particles, and a composition consistent with a Pt-skeleton covering a Ni/Pt alloy core. Electrochemical measurements show that the mass activity for the oxygen reduction reaction using carbon-supported nanoporous Ni/Pt nanoparticles is nearly four times that of commercial Pt/C catalyst and even exceeds that of comparable nonporous Pt-skeleton Ni/Pt alloy nanoparticles.

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.

Dealloying is currently used to tailor the morphology and composition of nanoparticles and bulk solids for a variety of applications including catalysis, energy storage, sensing, actuation, supercapacitors, and radiation damage resistant materials. The known morphologies, which evolve on dealloying of nanoparticles, include core-shell, hollow core-shell, and porous nanoparticles. Here we present results examining the fixed voltage dealloying of AgAu alloy particles in the size range of 2-6 and 20-55 nm. High-angle annular dark-field scanning transmission electron microcopy, energy dispersive, and electron energy loss spectroscopy are used to characterize the size, morphology, and composition of the dealloyed nanoparticles. Our results demonstrate that above the potential corresponding to Ag(+)/Ag equilibrium only core-shell structures evolve in the 2-6 nm diameter particles. Dealloying of the 20-55 nm particles results and in the formation of porous structures analogous to the behavior observed for the corresponding bulk alloy. A statistical analysis that includes the composition and particle size distributions characterizing the larger particles demonstrates that the formation of porous nanoparticles occurs at a well-defined thermodynamic critical potential.

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.

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.

Abstract

One way of expediting materials development is to decrease the need for new experiments by making greater use of published literature. Here, we use data mining and automated image analysis to gather new insights on nanoporous gold (NPG) without conducting additional experiments or simulations. NPG is a three-dimensional porous network that has found applications in catalysis, sensing, and actuation. We assemble and analyze published images from among thousands of publications on NPG. These images allow us to infer a quantitative description of NPG coarsening as a function of time and temperature, including the coarsening exponent and activation energy. They also demonstrate that relative density and ligament size in NPG are not correlated, indicating that these microstructure features are independently tunable. Our investigation leads us to propose improved reporting guidelines that will enhance the utility of future publications in the field of dealloyed materials.

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