Dealloyed nanoporous Au membranes and spongy Au nanoparticles exhibit a set of unique structural features highly desirable for heterogeneous catalysis and electrocatalysis. In this Focus Review, we present the state‐of‐the‐art understanding of the complex mechanisms dictating the nanoscale porosity evolution during percolation dealloying of alloys and the structure‐composition‐performance correlations underpinning the catalytic behaviors of dealloyed nanoporous Au. We focus on several fundamentally intriguing but widely debated topics concerning the nature of the active sites, the dynamic surface reconstruction under reaction conditions, and the origin of catalytic selectivity toward certain reactions. We also provide perspectives on versatile dealloying‐based synthetic approaches for precise architectural tailoring of metallic nanocatalysts as well as exciting opportunities of harnessing the combined optical and catalytic properties of dealloyed nanoporous Au to drive or enhance unconventional interfacial chemical transformations.

Galvanic exchange occurring within the confinement by nanoparticulate templates provides a unique pathway to controllably transform solid metallic nanoparticles into architecturally more sophisticated multimetallic hollow nanostructures under facile reaction conditions. In this Minireview, we elaborately discuss how the nanoparticle-templated galvanic exchange can be deliberately coupled with redox manipulation to synthesize a large library of complex multimetallic hollow nanostructures with precisely tailored architectures and compositions, with a particular emphasis on important mechanistic insights concerning the dynamic interplay among multiple structure-remodeling processes that synergistically dictate the versatile structure-transforming behaviors of metallic nanoparticles during kinetically and regioselectively modulated galvanic exchange reactions. Guangfang Grace Li received her B.S. degree in Chemistry from Wuhan Institute of Technology in China in 2009 and her Ph.D. degree in Physical Chemistry from the University of South Carolina in 2018. Her Ph.D. work, supervised by Hui Wang, was focused on the structure-controlled synthesis and electrocatalytic properties of multimetallic nanostructures. After a postdoc stint with John C.