Single-Particle Spectroelectrochemistry: Revealing the Electrochemical Tuning Mechanism of Chemical Interface Damping in 1,2-Benzenedithiol-Adsorbed Single Gold Nanorods

IF 6.7 1区化学 Q1 CHEMISTRY, ANALYTICAL Analytical Chemistry Pub Date : 2024-10-30 DOI:10.1021/acs.analchem.4c03511

Mukunthan Ramasamy, Ji Won Ha

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Abstract

Chemical interface damping (CID) is a newly proposed plasmon damping pathway based on interfacial hot-electron transfer from metal to adsorbate molecules. However, achieving in situ tunability of CID in single gold nanorods (AuNRs) remains a considerable challenge. Here, we present the CID effect induced by benzene 1,2-dithiol (BDT) molecule adsorption on single AuNRs and the effective electrochemical tunability of CID in BDT-adsorbed AuNRs immobilized on an indium tin oxide (ITO) surface. Manipulations of the electrochemical potential alter the electron density of AuNRs, thereby influencing and tuning the localized surface plasmon resonance (LSPR) spectrum, with cathodic potential blueshifting and anodic potential redshifting. The strong adsorption of BDT on Au induced CID in single AuNRs. The potential-induced LSPR scattering spectra of BDT-adsorbed AuNRs for linear potential sweep showed a stable LSPR spectral response, irrespective of the concentrations of BDT molecules. Due to the involvement of two Au–S bonds, BDT molecules have a higher free adsorption energy and a lower desorption rate on the Au surface. This resulted in a stable LSPR spectral response for a linear electrochemical potential sweep. Furthermore, a constant anodic and cathodic potential application showed the tunability of the CID at the BDT-Au interface.

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单颗粒光谱电化学：揭示 1,2-苯二硫醇吸附单金纳米棒化学界面阻尼的电化学调谐机制

化学界面阻尼（CID）是一种新提出的等离子体阻尼途径，它基于从金属到吸附分子的界面热电子转移。然而，在单个金纳米棒（AuNRs）中实现 CID 的原位可调性仍然是一个相当大的挑战。在此，我们介绍了苯 1,2-二硫醇（BDT）分子在单个 AuNRs 上吸附所诱导的 CID 效应，以及固定在铟锡氧化物（ITO）表面的 BDT 吸附 AuNRs 中 CID 的有效电化学可调性。操纵电化学势会改变 AuNRs 的电子密度，从而影响和调整局部表面等离子体共振 (LSPR) 光谱，阴极电势会蓝移，阳极电势会红移。BDT 在金上的强烈吸附诱导了单个 AuNRs 的 CID。线性电位扫描时，吸附了 BDT 的 AuNRs 的电位诱导 LSPR 散射光谱显示出稳定的 LSPR 光谱响应，与 BDT 分子的浓度无关。由于两个 Au-S 键的参与，BDT 分子在金表面具有较高的自由吸附能和较低的解吸率。因此，在线性电化学势扫描时，LSPR 光谱响应稳定。此外，恒定的阳极和阴极电位应用显示了 BDT-Au 界面上 CID 的可调性。

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来源期刊

Analytical Chemistry 化学-分析化学

CiteScore

12.10

自引率

12.20%

发文量

1949

审稿时长

1.4 months

期刊介绍： Analytical Chemistry, a peer-reviewed research journal, focuses on disseminating new and original knowledge across all branches of analytical chemistry. Fundamental articles may explore general principles of chemical measurement science and need not directly address existing or potential analytical methodology. They can be entirely theoretical or report experimental results. Contributions may cover various phases of analytical operations, including sampling, bioanalysis, electrochemistry, mass spectrometry, microscale and nanoscale systems, environmental analysis, separations, spectroscopy, chemical reactions and selectivity, instrumentation, imaging, surface analysis, and data processing. Papers discussing known analytical methods should present a significant, original application of the method, a notable improvement, or results on an important analyte.