Engineering the Au‐Cu₂O Crystalline Interfaces for Structural and Catalytic Integration

Abstract

Precise structural control has attracted tremendous interest in pursuit of the tailoring of physical properties. Here, this work shows that through strong ligand‐mediated interfacial energy control, Au‐Cu2O dumbbell structures where both the Au nanorod (AuNR) and the partially encapsulating Cu2O domains are highly crystalline. The synthetic advance allows physical separation of the Au and Cu2O domains, in addition to the use of long nanorods with tunable absorption wavelength, and the crystalline Cu2O domain with well‐defined facets. The interplay of plasmon and Schottky effects boosts the photocatalytic performance in the model photodegradation of methyl orange, showing superior catalytic efficiency than the AuNR@Cu2O core–shell structures. In addition, compared to the typical core–shell structures, the AuNR‐Cu2O dumbbells can effectively electrochemically catalyze the CO2 to C2+ products (ethanol and ethylene) via a cascade reaction pathway. The excellent dual function of both photo‐ and electrocatalysis can be attributed to the fine physical separation of the crystalline Au and Cu2O domains.

Strong Ligand Control for Noble Metal Nanostructures

“…47,64 The spatially isolated domains of Au−Cu 2 O and Au−C 60 Janus NPs promote charge separation and prevent charge recombination (Figure 10c). 2,52,77 The forest of ultrathin NWs provide large surface area, open diffusion channels, and interconnected circuits, promoting efficiency in catalysis and flexible electronics (Figure 10d). 57,78−82 The chiral nanostructures via active surface growth give strong chiral-optical responses.…”

“…(c) Photocatalytic and electrocatalytic properties of AuNR–Cu 2 O dumbbell structures: time-resolved transient fluorescence decay spectra and the plot of the photocatalytic conversion rate of methyl orange (MO) against the reaction times by using different catalysts; the Faradaic efficiency from CO 2 reduction and in situ ATR-SEIRAS spectra by AuNR–Cu 2 O dumbbell structures. Reprinted with permission from ref . Copyright 2023 Wiley-VCH GmbH.…”

“…The noble metal NPs with sophisticated structures have great potential in many applications. Briefly, the embedding of ligands gives rise to strong SERS signals for sensing and monitoring (Figure a). ,, The appendant islands, branches, and complex hat morphologies on AuNPs lead to strong NIR absorption for photothermal therapy and photoacoustic imaging (Figure b). , The spatially isolated domains of Au–Cu 2 O and Au–C 60 Janus NPs promote charge separation and prevent charge recombination (Figure c). ,, The forest of ultrathin NWs provide large surface area, open diffusion channels, and interconnected circuits, promoting efficiency in catalysis and flexible electronics (Figure d). ,− The chiral nanostructures via active surface growth give strong chiral-optical responses. , And the nano-saw-teeth (Figure ) could be potentially used for building nanoscale cutting tools . It should be noted that the adsorption of strong ligands on metal surfaces can have various other effects, − in addition to the control of morphological features.…”

Gaining Deep Understanding of Electrochemical CO2RR with In Situ/Operando Techniques

“…[185] Copyright 2022, American Chemical Society. c) Operando FTIR for Cu (100) in the presence of 13 CO and with D 2 O as electrolyte in a 0.1 m LiOH solution from 0.1 V to −0.2 V versus RHE, where peaks at 1145 and 1584 cm −1 represent 13 C─OH stretching and 12 C═O stretching. Reproduced with permission.…”

Nanocomposites of Cu2O with plasmonic metals (Au, Ag): design, synthesis, and photocatalytic applications

“…Janus and dumbbell structures are better than core–shell structures in avoiding charge buildup and in facilitating charge separation. 87,92 A major downside of a core–shell structure is that the encapsulating shell causes charge carriers to accumulate in the core component, and this negatively impacts the photocatalytic efficiency as only the charge carriers on the surface can partake in photocatalytic reactions. A full shell also limits the core in absorbing incoming photons.…”