Plasmon-driven protodeboronation reactions in nanogaps

Huynh, Ly Thi Minh; Trinh, Hoa Duc; Lee, Sungwoon; Yoon, Sangwoon

doi:10.1039/d0nr07023h

Cited by 19 publications

(25 citation statements)

References 40 publications

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“…Several snapshot SERS spectra captured at various reaction times are shown in Figure E, and the temporal evolutions of the relative intensities of several characteristic SERS modes are plotted in Figure F. The Raman modes of 1000 and 1022 cm –1 were the spectral signatures of the mono-substituted benzene ring of TP, ,,, both of which progressively increased in intensity as TP was produced. The SERS peak at 1420 cm –1 was assigned to the vibrational mode of COO – , ν(COO – ), − whose intensity decreased over time during the reactions.…”

Section: Results and Discussionmentioning

confidence: 99%

Hot-Hole-Induced Molecular Scissoring: A Case Study of Plasmon-Driven Decarboxylation of Aromatic Carboxylates

Chen

Wang

2021

J. Phys. Chem. C

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Optically excited plasmonic nanostructures may function as molecular scissors with unique capabilities to cleave specific chemical bonds in molecular adsorbates through either plasmon-enhanced intramolecular electronic excitations or injection of photoexcited hot electrons into adsorbate orbitals. Here we chose plasmon-driven decarboxylation of aromatic carboxylates as a model reaction system to demonstrate that plasmonic hot holes, instead of electrons, could also be effectively harnessed to trigger regioselective bond cleavage in molecular adsorbates. We used surfaceenhanced Raman scattering as an in situ spectroscopic tool to precisely monitor the decarboxylation reactions in real time and further correlate the reaction kinetics to local-field enhancements. The apparent rate constants were proportional to the fourth power of the local-field enhancements and exhibited a superlinear dependence on the excitation powers. Such a non-linear power dependence of reaction rates was a hallmark of hot-carrier-driven reactions involving multiphoton absorption rather than photothermally triggered processes, as inferred by the results of Raman thermometry. The decarboxylation reactions took place only at the surface sites with local-field intensities exceeding a certain threshold value, whereas the molecules experiencing weaker local fields below the threshold remained essentially unreactive. With the aid of density functional theory calculations, we were able to further relate the experimentally observed pH dependence of reaction kinetics to the frontier orbital energies of the hole-accepting adsorbates and the redox potentials of the electron-accepting protons, both of which could be modulated by adjusting the pH of the reaction medium.

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Section: Results and Discussionmentioning

confidence: 99%

Hot-Hole-Induced Molecular Scissoring: A Case Study of Plasmon-Driven Decarboxylation of Aromatic Carboxylates

Chen

Wang

2021

J. Phys. Chem. C

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“…This attribute may be due to the lateral electron confinement in the ribbons which opens a band-gap in graphene. These elongated strips of graphene have recently attracted both theoretical and experimental studies due to their immense potential as basic building blocks in nano-devices and spin electronics [54][55][56][57]. This was reported by a study on scrolled graphene nanoribbon (sGNR) which were generated by means of CVD method by Park and co-workers, especially discovered by NPoM-SERS experiment in Figure 8a,b.…”

Section: Surface-enhanced Raman Spectroscopy (Sers) Of Cvd-mg With Nanoparticle-on Mirror (Npom) Systemmentioning

confidence: 93%

“…Furthermore, the unique metallic structure of NPoM, composed of Au NP/CVD-MG/Au film in this article, could be a good candidate in terms of studying out-of-plane vibrational modes thanks to strongly generated z-polarized electromagnetic (EM) field contribution in comparison with in-plane vibrational modes such as G-and 2D-modes [20,21]. As a result of the NPoM-SERS experiment, Radial Breathing Like Mode (RBLM) associated with surface-to-normal directional (z-axis) vibrational phonon modes from the spaced CVD-MG could be exclusively observed (or enhanced) by dipole-dipole interaction between Au NP and Au film in the low frequency region at ~150 cm −1 [22], which was quite similar to the Raman shift position of Radial Breathing Mode (RBM) from single-walled carbon nanotubes (SWCNTs) [55]. In this part, both xy-plane (in-plane) and upward z-directional (out-of-plane) phonon vibration of CVD-MG spaced between an Au NP and Au film junction are simultaneously used, which could make a pivotal contribution to the quantitative assessment of the role played by the z-polarized (or localized) electromagnetic (EM) field in this experiment.…”

Section: Surface-enhanced Raman Spectroscopy (Sers) Of Cvd-mg With Nanoparticle-on Mirror (Npom) Systemmentioning

confidence: 98%

“…This problem is still being overcome by methods such as by producing self-assembled nanoparticle-molecule monolayer-film junctions, called the Nanoparticle-on-Mirror (NPoM) system [18][19][20][21][22][23][24][25][26] that generates significantly reproducible SERS signals at the single-junction level. Moreover, exploring catalytic chemical reactions probed by plasmon-driven coupling has been done by Yoon and colleagues via NPoM system [53][54][55]. Furthermore, the unique metallic structure of NPoM, composed of Au NP/CVD-MG/Au film in this article, could be a good candidate in terms of studying out-of-plane vibrational modes thanks to strongly generated z-polarized electromagnetic (EM) field contribution in comparison with in-plane vibrational modes such as G-and 2D-modes [20,21].…”

Section: Surface-enhanced Raman Spectroscopy (Sers) Of Cvd-mg With Nanoparticle-on Mirror (Npom) Systemmentioning

confidence: 99%

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Nano-Physical Characterization of Chemical Vapor Deposition-Grown Monolayer Graphene for High Performance Electrode: Raman, Surface-Enhanced Raman Spectroscopy, and Electrostatic Force Microscopy Studies

Park

2021

Nanomaterials

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To achieve high-quality chemical vapor deposition of monolayer graphene electrodes (CVD-MG), appropriate characterization at each fabrication step is essential. In this article, (1) Raman spectroscopy/microscopy are employed to unravel the contact effect between the CVD-MG and Cu foil in suspended/supported formation. (2) The Surface-Enhanced Raman spectroscopy (SERS) system is described, unveiling the presence of a z-directional radial breathing-like mode (RBLM) around 150 cm−1, which matches the Raman shift of the radial breathing mode (RBM) from single-walled carbon nanotubes (SWCNTs) around 150 cm−1. This result indicates the CVD-MG located between the Au NPs and Au film is not flat but comprises heterogeneous protrusions of some domains along the z-axis. Consequently, the degree of carrier mobility can be influenced, as the protruding domains result in lower carrier mobility due to flexural phonon–electron scattering. A strongly enhanced G-peak domain, ascribed to the presence of scrolled graphene nanoribbons (sGNRs), was observed, and there remains the possibility for the fabrication of sGNRs as sources of open bandgap devices. (3) Electrostatic force microscopy (EFM) is used for the measurement of surface charge distribution of graphene at the nanoscale and is crucial in substantiating the electrical performance of CVD-MG, which was influenced by the surface structure of the Cu foil. The ripple (RP) structures were determined using EFM correlated with Raman spectroscopy, exhibiting a higher tapping amplitude which was observed with structurally stable and hydrophobic RPs with a threading type than surrounding RPs. (4) To reduce the RP density and height, a plausible fabrication could be developed that controls the electrical properties of the CVD-MG by tuning the cooling rate.

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“…4,5 Plasmonic nanocatalysis was shown to initiate novel reaction pathways described either via the generation of hot electrons or by a thermally-induced mechanism. [6][7][8][9] The dimerization of 4-nitrothiophenol and 4aminothiophenol have been considered as the first examples of plasmonic chemistry, followed by other reactions that are driven by plasmonic effects. [10][11][12][13][14][15] Plasmonic nanostructures made from gold, silver and copper nanoparticles exhibit a strong absorption in the visible and near-infrared range of the solar spectrum, unlike the traditional semiconductors that catalyze chemical reactions only with the high energetic UV light.…”

Section: Introductionmentioning

confidence: 99%

Colloidal black gold with broadband absorption for photothermal conversion and plasmon-assisted crosslinking of thiolated diazonium compound

Sarhan

Kogikoski

Schürmann

et al. 2022

Preprint

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Broadband light absorbers are very attractive for many applications, including solar energy conversion, photothermal therapy, and plasmonic nanocatalysis. Black gold nanoparticles are an excellent example of broadband light absorbers in the visible and near-infrared (NIR) ranges; however, their synthesis typically requires multi-step deposition and/or high temperatures. Herein, we report the synthesis of black gold via a facile, one-step green method using commonly known precursors (chloroauric acid and sodium citrate) performed at room temperature. The formation of the black gold particles is driven by self-assembly of in-situ formed small nanoparticles (~ 5 nm) followed by a fusion step forming extensive networks of nanowires. These assemblies form intense hotspots for enhancing the electric field as well as the local temperature. Thus, the nanowires exhibit a strong photothermal effect and a good SERS performance. A high temperature up to 47 °C was recorded in the colloidal solution upon NIR irradiation, while the high SERS signal enhancement is used to monitor the kinetics of plasmon-assisted de-nitrogenation and cross-linking of designed thiolated benzenediazonium molecules. Our work offers new possibility to design efficient light absorbing materials to achieve good solar-to-chemical/thermal energy conversion.

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Plasmon-driven protodeboronation reactions in nanogaps

Abstract: Hot charge carriers created by plasmons break the C–B bond of 4-mercaptophenylboronic acid, transforming it into benzenethiol in nanogaps.

Cited by 19 publications

References 40 publications

Hot-Hole-Induced Molecular Scissoring: A Case Study of Plasmon-Driven Decarboxylation of Aromatic Carboxylates

Hot-Hole-Induced Molecular Scissoring: A Case Study of Plasmon-Driven Decarboxylation of Aromatic Carboxylates

Nano-Physical Characterization of Chemical Vapor Deposition-Grown Monolayer Graphene for High Performance Electrode: Raman, Surface-Enhanced Raman Spectroscopy, and Electrostatic Force Microscopy Studies

Colloidal black gold with broadband absorption for photothermal conversion and plasmon-assisted crosslinking of thiolated diazonium compound

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