Nanoscale Surface Redox Chemistry Triggered by Plasmon‐Generated Hot Carriers

Yin, Hao; Lan, Jinggang; Goubert, Guillaume; Wang, Yaohui; Li, Jianfeng; Zenobi, Renato

doi:10.1002/smll.201903674

Cited by 15 publications

(19 citation statements)

References 44 publications

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“…As noted above, electron capture can yield radicals, trigger redox processes, and generate molecular fragments in plasmonic systems. 4 , 24 , 31 , 33 , 43 Of particular interest was the report that radicals can exhibit increased Raman scattering. 32 …”

Section: Results and Discussionmentioning

confidence: 99%

“…One of the first reports illustrated how H 2 gas could be dissociated on gold nanoparticles when the plasmon resonance was excited . This has led to an increasing number of reports illustrating how the electrons and electric fields associated with plasmon resonances can be captured for chemical conversion. ,, Additional work has addressed the relative contributions of hot electrons versus thermalized electrons that arise from plasmon excitation, helping understanding of the mechanisms driving reactivity on the nanoparticle …”

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confidence: 99%

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Spectrally Resolved Surface-Enhanced Raman Scattering Imaging Reveals Plasmon-Mediated Chemical Transformations

et al. 2021

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Challenges investigating molecules on plasmonic nanostructures have limited understanding of these interactions. However, the chemically specific information in the surface-enhanced Raman scattering (SERS) spectrum can identify perturbations in the adsorbed molecules to provide insight relevant to applications in sensing, catalysis, and energy conversion. Here, we demonstrate spectrally resolved SERS imaging, to simultaneously image and collect the SERS spectra from molecules adsorbed on individual nanoparticles. We observe intensity and frequency fluctuations in the SERS signal on the time scale of tens of milliseconds from n -mercaptobenzoic acid (MBA) adsorbed to gold nanoparticles. The SERS signal fluctuations correlate with density functional theory calculations of radicals generated by the interaction between MBA and plasmon-generated hot electrons. Applying localization microscopy to the data provides a super-resolution spectrally resolved map that indicates the plasmonic-induced molecular charging occurs on the extremities of the nanoparticles, where the localized electromagnetic field is reported to be most intense.

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Section: Results and Discussionmentioning

confidence: 99%

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confidence: 99%

Spectrally Resolved Surface-Enhanced Raman Scattering Imaging Reveals Plasmon-Mediated Chemical Transformations

et al. 2021

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“…Importantly, hot electron transfer through an inelastic tunneling process can also occur in physisorbed MLs (Fig. 3d ), even without strong interaction between the surface and MLs 64 . When the LSP is aligned with the molecular LUMO energy level near the metal Fermi level (Fig.…”

Section: Resultsmentioning

confidence: 98%

In-situ nanospectroscopic imaging of plasmon-induced two-dimensional [4+4]-cycloaddition polymerization on Au(111)

et al. 2021

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Plasmon-induced chemical reactions (PICRs) have recently become promising approaches for highly efficient light-chemical energy conversion. However, an in-depth understanding of their mechanisms at the nanoscale still remains challenging. Here, we present an in-situ investigation by tip-enhanced Raman spectroscopy (TERS) imaging of the plasmon-induced [4+4]-cycloaddition polymerization within anthracene-based monomer monolayers physisorbed on Au(111), and complement the experimental results with density functional theory (DFT) calculations. This two-dimensional (2D) polymerization can be flexibly triggered and manipulated by the hot carriers, and be monitored simultaneously by TERS in real time and space. TERS imaging provides direct evidence for covalent bond formation with ca. 3.7 nm spatial resolution under ambient conditions. Combined with DFT calculations, the TERS results demonstrate that the lateral polymerization on Au(111) occurs by a hot electron tunneling mechanism, and crosslinks form via a self-stimulating growth mechanism. We show that TERS is promising to be plasmon-induced nanolithography for organic 2D materials.

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“…Other applications of TERS in bioscience include the study of biological systems, such as RNA, DNA, proteins, collagen, bacteria and viruses [ 28 , 31 , 32 , 33 , 34 ], as well as the in vivo characterization of the protein uptake by yeast cell envelopes [ 35 ]. Very recently, the implementation of new detection schemes has made it possible to measure TERS in liquid environment with the development of the first electrochemical TERS setup [ 36 ], paving the way for the study and the control of chemical and/or physical processes at a local level [ 37 , 38 ]. Nevertheless, a major scientific field for the TERS technique is still represented by material science.…”

Section: Introductionmentioning

confidence: 99%

Comparing Commercial Metal-Coated AFM Tips and Home-Made Bulk Gold Tips for Tip-Enhanced Raman Spectroscopy of Polymer Functionalized Multiwalled Carbon Nanotubes

et al. 2022

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Tip-enhanced Raman spectroscopy (TERS) combines the high specificity and sensitivity of plasmon-enhanced Raman spectroscopy with the high spatial resolution of scanning probe microscopy. TERS has gained a lot of attention from many nanoscience fields, since this technique can provide chemical and structural information of surfaces and interfaces with nanometric spatial resolution. Multiwalled carbon nanotubes (MWCNTs) are very versatile nanostructures that can be dispersed in organic solvents or polymeric matrices, giving rise to new nanocomposite materials, showing improved mechanical, electrical and thermal properties. Moreover, MWCNTs can be easily functionalized with polymers in order to be employed as specific chemical sensors. In this context, TERS is strategic, since it can provide useful information on the cooperation of the two components at the nanoscale for the optimization of the macroscopic properties of the hybrid material. Nevertheless, efficient TERS characterization relies on the geometrical features and material composition of the plasmonic tip used. In this work, after comparing the TERS performance of commercial Ag coated nanotips and home-made bulk Au tips on bare MWCNTs, we show how TERS can be exploited for characterizing MWCNTs mixed with conjugated fluorene copolymers, thus contributing to the understanding of the polymer/CNT interaction process at the local scale.

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Nanoscale Surface Redox Chemistry Triggered by Plasmon‐Generated Hot Carriers

Cited by 15 publications

References 44 publications

Spectrally Resolved Surface-Enhanced Raman Scattering Imaging Reveals Plasmon-Mediated Chemical Transformations

Spectrally Resolved Surface-Enhanced Raman Scattering Imaging Reveals Plasmon-Mediated Chemical Transformations

In-situ nanospectroscopic imaging of plasmon-induced two-dimensional [4+4]-cycloaddition polymerization on Au(111)

Comparing Commercial Metal-Coated AFM Tips and Home-Made Bulk Gold Tips for Tip-Enhanced Raman Spectroscopy of Polymer Functionalized Multiwalled Carbon Nanotubes

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