Plasmonic Hot Electron-Mediated Hydrodehalogenation Kinetics on Nanostructured Ag Electrodes

Liu, Jia; Cai, Zhuan-Yun; Sun, Wei-Xin; Wang, Jiazheng; Shen, Xiao-Ru; Zhan, Chao; Devasenathipathy, Rajkumar; Zhou, Jian-Zhang; Wu, De‐Yin; Mao, Bing‐Wei; Tian, Zhong‐Qun

doi:10.1021/jacs.0c07027

Cited by 62 publications

(63 citation statements)

References 70 publications

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“…This involves a favorable one-electron transfer reaction to the hole that occurs at a potential of 0.10 V vs SHE (−4.54 eV) 48 with respect to the Fermi energy of 0.36 V vs SHE (−4.80 eV). 13 This would result in the formation of photosensitive AgBr on the Ag surface ( eq 12 ) which has also been reported by Xie et al in one of their seminal works. 31 …”

Section: Resultssupporting

confidence: 58%

“… 9 , 11 , 12 On a similar ground, an initial report from our group demonstrates the C–Br bond cleavage in 8-bromoadenine (BrAde) adsorbed on aggregates of Au and Ag via hot electron transfer based on the DEA model. 8 Along this line, an understanding over controlling and increasing the efficiency of the same plasmon-induced reaction was laid forward by Liu et al 13 using different applied potentials and laser light. In principle, a three-step mechanism based on DEA has been proposed which is generalized as follows: 3 , 8 , 13 The first step involves the generation of hot electrons upon laser illumination at a selected wavelength described by eq 1 .…”

Section: Introductionmentioning

confidence: 99%

“… 8 Along this line, an understanding over controlling and increasing the efficiency of the same plasmon-induced reaction was laid forward by Liu et al 13 using different applied potentials and laser light. In principle, a three-step mechanism based on DEA has been proposed which is generalized as follows: 3 , 8 , 13 The first step involves the generation of hot electrons upon laser illumination at a selected wavelength described by eq 1 . The next step involves the transfer of generated primary hot electrons to the lowest unoccupied molecular orbital (LUMO) of adsorbed bromonucleobases (BrNBs) resulting in the formation of TNI (BrNB *– ) described by eq 2 .…”

Section: Introductionmentioning

confidence: 99%

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Kinetics and Mechanism of Plasmon-Driven Dehalogenation Reaction of Brominated Purine Nucleobases on Ag and Au

et al. 2021

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Plasmon-driven photocatalysis is an emerging and promising application of noble metal nanoparticles (NPs). An understanding of the fundamental aspects of plasmon interaction with molecules and factors controlling their reaction rate in a heterogeneous system is of high importance. Therefore, the dehalogenation kinetics of 8-bromoguanine (BrGua) and 8-bromoadenine (BrAde) on aggregated surfaces of silver (Ag) and gold (Au) NPs have been studied to understand the reaction kinetics and the underlying reaction mechanism prevalent in heterogeneous reaction systems induced by plasmons monitored by surface enhanced Raman scattering (SERS). We conclude that the time-average constant concentration of hot electrons and the time scale of dissociation of transient negative ions (TNI) are crucial in defining the reaction rate law based on a proposed kinetic model. An overall higher reaction rate of dehalogenation is observed on Ag compared with Au, which is explained by the favorable hot-hole scavenging by the reaction product and the byproduct. We therefore arrive at the conclusion that insufficient hole deactivation could retard the reaction rate significantly, marking itself as rate-determining step for the overall reaction. The wavelength dependency of the reaction rate normalized to absorbed optical power indicates the nonthermal nature of the plasmon-driven reaction. The study therefore lays a general approach toward understanding the kinetics and reaction mechanism of a plasmon-driven reaction in a heterogeneous system, and furthermore, it leads to a better understanding of the reactivity of brominated purine derivatives on Ag and Au, which could in the future be exploited, for example, in plasmon-assisted cancer therapy.

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Section: Resultssupporting

confidence: 58%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Kinetics and Mechanism of Plasmon-Driven Dehalogenation Reaction of Brominated Purine Nucleobases on Ag and Au

et al. 2021

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“…An activation of the carbon-halogen (C-X) bond that leads to elimination of halogen is very important chemical reactions used in organic synthesis. Tian's group used 8-bromoadenine (8BrAd) as a molecular reporter to study the effect of the electrode potential, laser wavelength, and power on plasmon-mediated chemical reactions (PMCR) kinetics on AgNP-modified silver electrodes [50]. The researchers combined both experimental methods (in situ electrochemical SERS) and theory (DFT calculation) to investigate the plasmonic-driven cleavage of C-Br bond in 8BrAd, Figure 5.…”

Section: Plasmon-driven Scissoring and Elimination Reactionsmentioning

confidence: 99%

Nanoscale structural characterization of plasmon-driven reactions

Kurouski

2021

Nanophotonics

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Illumination of noble metal nanostructures by electromagnetic radiation induces coherent oscillations of conductive electrons on their surfaces. These coherent oscillations of electrons, also known as localized surface plasmon resonances (LSPR), are the underlying physical cause of the electromagnetic enhancement of Raman scattering from analytes located in a close proximity to the metal surface. This physical phenomenon is broadly known as surface-enhanced Raman scattering (SERS). LSPR can decay via direct interband, phonon-assisted intraband, and geometry-assisted transitions forming hot carriers, highly energetic species that are responsible for a large variety of chemical transformations. This review critically discusses the most recent progress in mechanistic elucidation of hot carrier-driven chemistry and catalytic processes at the nanoscale. The review provides a brief description of tip-enhanced Raman spectroscopy (TERS), modern analytical technique that possesses single-molecule sensitivity and angstrom spatial resolution, showing the advantage of this technique for spatiotemporal characterization of plasmon-driven reactions. The review also discusses experimental and theoretical findings that reported novel plasmon-driven reactivity which can be used to catalyze redox, coupling, elimination and scissoring reactions. Lastly, the review discusses the impact of the most recently reported findings on both plasmonic catalysis and TERS imaging.

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“…On the other hand, a concomitant rise in peak at 765 cm -1 corresponding to adenosine vibration can be observed with time. Recently Liu et al 36 proposed a very interesting mechanism for the plasmon-mediated hydrodehalogenation reaction of 8bromo-adenine and the many reaction steps. One of the most interesting properties of DNA is the possibility to transfer charges along the double helix.…”

Section: Decomposition Of 8brda In Dnamentioning

confidence: 99%

Spatial Separation of Plasmonic Hot Electron Generation and a Hydrodehalogenation Reaction Center Using a DNA Wire

Kogikoski¹,

Dutta²,

Bald³

2021

Preprint

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<p>Using hot charge carriers far from a plasmonic nanoparticle surface is very attractive for many applications in catalysis and nanomedicine, and will lead to a better understanding of plasmon-induced processes, such as hot charge carrier or heat driven chemical reactions. Herein we show that DNA is able to transfer hot electrons generated by a silver nanoparticle over several nanometers to drive a chemical reaction in a molecule non-adsorbed on the surface. For this we use 8-bromo-adenosine introduced in different positions within a double stranded DNA oligonucleotide. The DNA is also used to assemble the nanoparticles into superlattices enabling the use of surface enhanced Raman scattering to track the decomposition reaction. To prove the DNA mediated transfer, the probe molecule was insulated from the charge carriers source, which hindered the reaction. The results indicate that DNA can provide an attractive platform to study the transfer of hot electrons, leading to the future development of more advanced plasmonic catalysts. </p>

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Plasmonic Hot Electron-Mediated Hydrodehalogenation Kinetics on Nanostructured Ag Electrodes

Cited by 62 publications

References 70 publications

Kinetics and Mechanism of Plasmon-Driven Dehalogenation Reaction of Brominated Purine Nucleobases on Ag and Au

Kinetics and Mechanism of Plasmon-Driven Dehalogenation Reaction of Brominated Purine Nucleobases on Ag and Au

Nanoscale structural characterization of plasmon-driven reactions

Spatial Separation of Plasmonic Hot Electron Generation and a Hydrodehalogenation Reaction Center Using a DNA Wire

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