Complementing Nanoscale Galvanic Exchange with Redox Manipulation toward Architectural Control of Multimetallic Hollow Nanostructures

Abstract

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.

Galvanic Restructuring of Exsolved Nanoparticles for Plasmonic and Electrocatalytic Energy Conversion

“…[ 2d,7 ] Among them, GRR stands out due to its simplicity and versatility in engineering the metallic nanostructures in terms of composition, morphology, structure, etc. [ 8 ] GRR is a chemical process in which one metal often referred to as the sacrificial template is oxidized by the ions of another metal. The standard reduction potential difference between the sacrificial and depositing metals provides the driving force for the galvanic deposition of the desired metallic element.…”

“…These new and otherwise impossible to form exotic nanostructures supported on perovskite oxides (SrTiO 3 ) have tunable catalytic functionalities and are prepared with minimal engineering requirements. [ 8b,11 ] Specifically, we deposit through the galvanic replacement reaction plasmonic Au nano‐islands on exsolved Ni NPs and both experimental evidence and modeling data correlate the improved PEC water splitting performance to the localized surface plasmon resonance of Au, as well as to the synergetic effect between Ni and Au in the form of antenna–reactor. We shift the catalytic activity of the parent compound by galvanically depositing Pt that forms Pt nano‐needles with superior hydrogen evolution rate (HER) activity, approaching that of commercial Pt/C in alkaline media, with considerably lower Pt loadings.…”

The Synergistic Effect of Oxygen Vacancy and Carbon Interface Engineering in Hollow Cerium Oxide to Achieve Enhanced Oxygen Reduction Performance

“…Hollow CeO 2 has a wide application prospect in the field of energy storage and conversion because of its abundant internal space. 25 By adjusting the external geometry, chemical composition, shell structural units, and the internal spatial structure of hollow materials, the electrochemical performance of hollow materials can be improved to meet the increasing energy demands. For the ZAB, the larger internal space of hollow CeO 2 can effectively relieve the structural stress caused by ion insertion/desorption or surface Faradaic reaction during repeated charge and discharge, thus maintaining the electrode stability.…”

“…In recent years, the design and synthesis of hollow nanostructures have become important research fields in chemistry and materials science. Hollow CeO 2 has a wide application prospect in the field of energy storage and conversion because of its abundant internal space . By adjusting the external geometry, chemical composition, shell structural units, and the internal spatial structure of hollow materials, the electrochemical performance of hollow materials can be improved to meet the increasing energy demands.…”

Palladium-rich plasmonic nanorattles with enhanced LSPRs via successive galvanic replacement mediated by co-reduction

“…[21][22][23][24][25][26] Besides the conventional wet-chemistry approaches for the fabrication of the multicomponent hybrid nanostructures, such as core-shell nanoparticles, [27][28][29][30][31][32] nanoscale galvanic replacement reaction (GRR) has emerged as an alternative yet extremely versatile method to produce multi-metallic hollow particles with tailored interior architectures and enhanced optical and catalytic properties via a heterogeneous electrochemical redox process thermodynamically driven by the differences in the reduction potentials of a pair of metals. 33 Nevertheless, the most majority of the work has focused on the transformation of solid sacricial template of Ag nanoparticles into Au-Ag hollow nanostructures through the process of galvanic replacement reaction, including nanoboxes, nanocages and nanoframes. [34][35][36][37][38][39][40][41][42] Despite the rapid advancement in mechanistic studies of hollow Ag-Pd nanostructures with increased architectural complexity, [43][44][45][46][47][48][49] very few are the examples found in the literature reporting such Pd-containing hollow particles with robust extinction peaks across the broad spectral ranges, 50 primarily due to the strong plasmon damping when incorporating Pd into the nanoparticles.…”