Designer Gold‐Framed Palladium Nanocubes for Plasmon‐Enhanced Electrocatalytic Oxidation of Ethanol

Abstract

Surface plasmon of coinage metal nanostructures has been employed as a powerful route in boosting the performances in heterogenous catalysis. Development of efficient plasmonic nanocatalysts with high catalytic performance and efficient light harvesting properties is of vital importance. Herein, we rationally designed and synthesized a plasmonic nanocatalyst composed of Au-framed Pd nanocubes by an Ag(I)-assisted seed-mediated growth method. In the synthesis, the incorporation of Ag(I) suppresses the reduction of Au on the {100} surface of cubic Pd seeds and leads to the formation of Au nanoframes on the Pd nanocubes. The unique Au-framed Pd nanocubes can integrate the superior electrocatalytic of Pd and the outstanding plasmonic properties of Au. Thus, these nanostructures were employed as plasmonic nanocatalysts for plasmon-enhanced electrocatalytic oxidation of ethanol with improved stability.

Metallic Heterostructures for Plasmon‐Enhanced Electrocatalysis

“…These heterostructures with emergent properties could be employed to applications that are not accessible otherwise (Figure 3m–p). [45–46] For example, Nam et al. reported Au@Cu core‐shell‐Ag hybrids, which uniquely integrate the architectural features of core–shell and dimers topologies [44] .…”

“…Recently, various plasmonic metallic heterogeneous nanostructures have been reported to enhance electrooxidation activity via charge transfer mechanism [61] . For example, Au‐framed Pd nanocubes (AFPNs) with exposed Pd and Au surface exhibit an enhanced ethanol electrocatalytic activity under LSPR‐matched light irradiation [46] . AFPNs with large size possess a high percentage of Au content, which exhibit the best plasmon‐enhanced performance owing to the highest light harvesting ability via the indirect charge transfer mechanism.…”

“…These heterostructures with emergent properties could be employed to applications that are not accessible otherwise (Figure 3m-p). [45][46] For example, Nam et al reported Au@Cu core-shell-Ag hybrids, which uniquely integrate the architectural features of core-shell and dimers topologies. [44] In another complicated heterostructures, tetraphase heterostructured nanoparticles composed of Au, CoNi, NiSn, and PdSn phases are synthesized.…”

“…(o) Au-framed Pd nanocubes, Reproduced from Ref. [46], Copyright (2022), with permission from Wiley-VCH. (p) tetraphase heterostructured nanoparticles with six interfaces, Adapted with permission from Ref.…”

“…[61] For example, Au-framed Pd nanocubes (AFPNs) with exposed Pd and Au surface exhibit an enhanced ethanol electrocatalytic activity under LSPR-matched light irradiation. [46] AFPNs with large size possess a high percentage of Au content, which exhibit the best plasmon-enhanced performance owing to the highest light harvesting ability via the indirect charge transfer mechanism. Thus, the holes left on AFPNs participate in ethanol electrocatalytic reactions, while hot electrons transfer to the external circuit (Figure 5b, c).…”