Interaction of 4-nitrothiophenol with low energy electrons: Implications for plasmon mediated reactions

Schürmann, Robin; Luxford, Thomas F. M.; Vinklárek, Ivo S.; Kočišek, Jaroslav; Zawadzki, Mateusz; Bald, Ilko

doi:10.1063/5.0018784

Cited by 13 publications

(8 citation statements)

References 59 publications

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“…As recently shown, low energy carriers (with energies on the order of ∼0.15 eV) can initiate this reaction . Considering that the maximum (theoretical) energy that a hot-carrier can harvest is the same as that of the incident wavelength, , this low energy barrier reaction serves as a perfect probe to test a broadband absorber catalyst as this one.…”

Section: Resultsmentioning

confidence: 87%

“…As recently shown, low energy carriers (with energies on the order of ∼0.15 eV) can initiate this reaction. 65 Considering that the maximum (theoretical) energy that a hot-carrier can harvest is the same as that of the incident wavelength, 9,66 this low energy barrier reaction serves as a perfect probe to test a broadband absorber catalyst as this one. In this reaction, the hot electron can be directly injected into the adsorbed pNTP molecules to drive the −NO 2 group to react with the water absorbed on the silver surface to dimerize into a DMAB molecule.…”

Section: Resultsmentioning

confidence: 99%

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Self-Constructed Multiple Plasmonic Hotspots on an Individual Fractal to Amplify Broadband Hot Electron Generation

et al. 2021

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Plasmonic nanoparticles are ideal candidates for hot-electron-assisted applications, but their narrow resonance region and limited hotspot number hindered the energy utilization of broadband solar energy. Inspired by tree branches, we designed and chemically synthesized silver fractals, which enable self-constructed hotspots and multiple plasmonic resonances, extending the broadband generation of hot electrons for better matching with the solar radiation spectrum. We directly revealed the plasmonic origin, the spatial distribution, and the decay dynamics of hot electrons on the single-particle level by using ab initio simulation, dark-field spectroscopy, pump–probe measurements, and electron energy loss spectroscopy. Our results show that fractals with acute tips and narrow gaps can support broadband resonances (400–1100 nm) and a large number of randomly distributed hotspots, which can provide unpolarized enhanced near field and promote hot electron generation. As a proof-of-concept, hot-electron-triggered dimerization of p-nitropthiophenol and hydrogen production are investigated under various irradiations, and the promoted hot electron generation on fractals was confirmed with significantly improved efficiency.

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Section: Resultsmentioning

confidence: 87%

Section: Resultsmentioning

confidence: 99%

Self-Constructed Multiple Plasmonic Hotspots on an Individual Fractal to Amplify Broadband Hot Electron Generation

et al. 2021

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“…[44] Dissociative electron attachment was also observed in gas phase experiments. [45] Determining the yield of a reaction from Raman spectra is generally difficult, as the precise Raman scattering cross-section of a single molecule is usually not known. The situation is even more complicated in SERS measurements due to very inhomogeneous amplification of the Raman signal in plasmonic hot spots.…”

Section: Selectivity Of the Plasmon Driven Dimerizationmentioning

confidence: 99%

The Role of Structural Flexibility in Plasmon‐Driven Coupling Reactions: Kinetic Limitations in the Dimerization of Nitro‐Benzenes

Koopman

Titov

Sarhan

et al. 2021

Adv Materials Inter

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molecules simultaneously, which facilitates coupling reactions of two or more molecules. [7][8][9] On the other hand, nanoscale heating can increase the speed of molecular reorganization and surface diffusion, thereby increasing the rate of favorable reactive encounters. Several important examples of plasmon-driven bond formation were demonstrated in recent years, [10,11] including CC bond formation in hydrocarbons, [7,12] Suzuki-Miyaura type reactions, [13] and molecular dimerization reactions by NN bond formation. [7,14,15] Until recently, the question if the dominating effect of plasmonic nanoparticles is to act as charge donors [16,17] or heat sources [14,18] has been heavily debated. Nowadays, most authors agree that depending on the reaction, one or the other effect can dominate. [19] For example, the dissociation of diatomic compounds on gold-particles, in particular of H 2 [1,20] and O 2 , [21,22] is likely determined by the transfer of energetic electrons, while the fragmentation of organic molecules, such as the decomposition of dicumyl-peroxide, [18] is rather dominated by the plasmon-mediated photo-heating. Although much progress has been made in understanding such dissociation reactions, our understanding of plasmon-driven multistep bond-formation processes is still in its infancy. In these reactions, different reaction steps might profit from the presence of plasmonic excitations. As a prominent example, the dimerization reaction of 4-nitrothiophenol (4NTP) to 4-4′-dimercaptoazobenzene (DMAB) was confirmed by many

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“…Dissociative electron attachment was also observed in gas phase experiments. 40 Determining the yield of a reaction from Raman spectra is generally difficult, as the precise Raman scattering cross-section of a single molecule is usually not known. The situation is even more complicated in SERS measurements due to very inhomogeneous amplification of the Raman signal in plasmonic hot spots.…”

Section: Selectivity Of the Plasmon Driven Dimerizationmentioning

confidence: 99%

The Role of Structural Flexibility in Plasmon-Driven Coupling Reactions: Kinetic Limitations in the Dimerization of Nitro-Benzenes

Koopman¹,

Titov²,

Sarhan³

et al. 2021

Preprint

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<div>The plasmon-driven dimerization of 4-nitrothiophenol (4NTP) to 4-4’-dimercaptoazobenzene (DMAB) has become a testbed for understanding bimolecular photoreactions enhanced by nanoscale metals, in particular, regarding the relevance of electron transfer and heat transfer from the metal to the molecule. By adding a methylene group between the thiol bond and the nitrophenyl, we add structural flexibility to the reactant molecule. Time-resolved surface-enhanced Raman-spectroscopy proves that this (4-nitrobenzyl)mercaptan (4NBM) molecule has a larger dimerization rate and dimerization yield than 4NTP and higher selectivity towards dimerization. X-ray photoelectron spectroscopy and density functional theory calculations show that the electron transfer would prefer activation of 4NTP over 4NBM. We conclude that the rate limiting step of this plasmonic reaction is the dimerization step, which is dramatically enhanced by the additional flexibility of the reactant. This study may serve as an example for using nanoscale metals to simultaneously provide charge carriers for bond activation and localized heat for driving bimolecular reaction steps. The molecular structure of reactants can be tuned to control the reaction kinetics.<br></div>

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Interaction of 4-nitrothiophenol with low energy electrons: Implications for plasmon mediated reactions

Cited by 13 publications

References 59 publications

Self-Constructed Multiple Plasmonic Hotspots on an Individual Fractal to Amplify Broadband Hot Electron Generation

Self-Constructed Multiple Plasmonic Hotspots on an Individual Fractal to Amplify Broadband Hot Electron Generation

The Role of Structural Flexibility in Plasmon‐Driven Coupling Reactions: Kinetic Limitations in the Dimerization of Nitro‐Benzenes

The Role of Structural Flexibility in Plasmon-Driven Coupling Reactions: Kinetic Limitations in the Dimerization of Nitro-Benzenes

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