The role of the plasmon in interfacial charge transfer.

The lack of a detailed mechanistic understanding for plasmon-mediated charge transfer at metal-semiconductor interfaces severely limits the design of efficient photovoltaic and photocatalytic devices. A major remaining question is the relative contribution from indirect transfer of hot electrons generated by plasmon decay in the metal to the semiconductor compared to direct metal-to-semiconductor interfacial charge transfer. Here, we demonstrate an overall electron transfer efficiency of 44 ± 3% from gold nanorods to titanium oxide shells when excited on resonance. We prove that half of it originates from direct interfacial charge transfer mediated specifically by exciting the plasmon. We are able to distinguish between direct and indirect pathways through multimodal frequency-resolved approach measuring the homogeneous plasmon linewidth by single-particle scattering spectroscopy and time-resolved transient absorption spectroscopy with variable pump wavelengths. Our results signify that the direct plasmon-induced charge transfer pathway is a promising way to improve hot carrier extraction efficiency by circumventing metal intrinsic decay that results mainly in nonspecific heating.

d-Band Holes React at the Tips of Gold Nanorods.

Reactive hot spots on plasmonic nanoparticles have attracted attention for photocatalysis as they allow for efficient catalyst design. While sharp tips have been identified as optimal features for field enhancement and hot electron generation, the locations of catalytically promising d-band holes are less clear. Here we exploit d-band hole-enhanced dissolution of gold nanorods as a model reaction to locate reactive hot spots produced from direct interband transitions, while the role of the plasmon is to follow the reaction optically in real time. Using a combination of single-particle electrochemistry and single-particle spectroscopy, we determine that d-band holes increase the rate of gold nanorod electrodissolution at their tips. While nanorods dissolve isotropically in the dark, the same nanoparticles switch to tip-enhanced dissolution upon illimitation with 488 nm light. Electron microscopy confirms that dissolution enhancement is exclusively at the tips of the nanorods, consistent with previous theoretical work that predicts the location of d-band holes. We, therefore, conclude that d-band holes drive reactions selectively at the nanorod tips.

Mechanism for plasmon-generated solvated electrons.

Solvated electrons are powerful reducing agents capable of driving some of the most energetically expensive reduction reactions. Their generation under mild and sustainable conditions remains challenging though. Using near-ultraviolet irradiation under low-intensity one-photon conditions coupled with electrochemical and optical detection, we show that the yield of solvated electrons in water is increased more than 10 times for nanoparticle-decorated electrodes compared to smooth silver electrodes. Based on the simulations of electric fields and hot carrier distributions, we determine that hot electrons generated by plasmons are injected into water to form solvated electrons. Both yield enhancement and hot carrier production spectrally follow the plasmonic near-field. The ability to enhance solvated electron yields in a controlled manner by tailoring nanoparticle plasmons opens up a promising strategy for exploiting solvated electrons in chemical reactions.

Single-Particle Hyperspectral Imaging Reveals Kinetics of Silver Ion Leaching from Alloy Nanoparticles.

Gold-silver alloy nanoparticles are interesting for multiple applications, including heterogeneous catalysis, optical sensing, and antimicrobial properties. The inert element gold acts as a stabilizer for silver to prevent particle corrosion, or conversely, to control the release kinetics of antimicrobial silver ions for long-term efficiency at minimum cytotoxicity. However, little is known about the kinetics of silver ion leaching from bimetallic nanoparticles and how it is correlated with silver content, especially not on a single-particle level. To characterize the kinetics of silver ion release from gold-silver alloy nanoparticles, we employed a combination of electron microscopy and single-particle hyperspectral imaging with an acquisition speed fast enough to capture the irreversible silver ion leaching. Single-particle leaching profiles revealed a reduction in silver ion leaching rate due to the alloying with gold as well as two leaching stages, with a large heterogeneity in rate constants. We modeled the initial leaching stage as a shrinking-particle with a rate constant that exponentially depends on the silver content. The second, slower leaching stage is controlled by the electrochemical oxidation potential of the alloy being steadily increased by the change in relative gold content and diffusion of silver atoms through the lattice. Interestingly, individual nanoparticles with similar sizes and compositions exhibited completely different silver ion leaching yields. Most nanoparticles released silver completely, but 25% of them appeared to arrest leaching. Additionally, nanoparticles became slightly porous. Alloy nanoparticles, produced by scalable laser ablation in liquid, together with kinetic studies of silver ion leaching, provide an approach to design the durability or bioactivity of alloy nanoparticles.

Nanoelectrode-emitter spectral overlap amplifies surface enhanced electrogenerated chemiluminescence.

Electrogenerated chemiluminescence (ECL) is a promising technique for low concentration molecular detection. To improve the detection limit, plasmonic nanoparticles have been proposed as signal boosting antennas to amplify ECL. Previous ensemble studies have hinted that spectral overlap between the nanoparticle antenna and the ECL emitter may play a role in signal enhancement. Ensemble spectroscopy, however, cannot resolve heterogeneities arising from colloidal nanoparticle size and shape distributions, leading to an incomplete picture of the impact of spectral overlap. Here, we isolate the effect of nanoparticle-emitter spectral overlap for a model ECL system, coreaction of tris(2,2'-bipyridyl)dichlororuthenium(ii) hexahydrate and tripropylamine, at the single-particle level while minimizing other factors influencing ECL intensities. We found a 10-fold enhancement of ECL among 952 gold nanoparticles. This signal enhancement is attributed exclusively to spectral overlap between the nanoparticle and the emitter. Our study provides new mechanistic insight into plasmonic enhancement of ECL, creating opportunities for low concentration ECL sensing.

Hot Holes Assist Plasmonic Nanoelectrode Dissolution.

Strong light-absorbing properties allow plasmonic metal nanoparticles to serve as antennas for other catalysts to function as photocatalysts. To achieve plasmonic photocatalysis, the hot charge carriers created when light is absorbed must be harnessed before they decay through internal relaxation pathways. We demonstrate the role of photogenerated hot holes in the oxidative dissolution of individual gold nanorods with millisecond time resolution while tuning charge-carrier density and photon energy using snapshot hyperspectral imaging. We show that light-induced hot charge carriers enhance the rate of gold oxidation and subsequent electrodissolution. Importantly, we distinguish how hot holes generated from interband transitions versus hot holes around the Fermi level contribute to photooxidative dissolution. The results provide new insights into hot-hole-driven processes with relevance to photocatalysis while emphasizing the need for statistical descriptions of nonequilibrium processes on innately heterogeneous nanoparticle supports.