Plasmonic photoelectrochemical reactions on noble metal electrodes of nanostructures

Rani, Karuppasamy Kohila; Devasenathipathy, Rajkumar; Wang, Jiazheng; Hui, Xiao-Yuan; Lin, Jiande; Zhang, Yi-Miao; Zhao, Liu−Bin; Zhou, Jian-Zhang; Wu, De‐Yin; Zhang, Tian

doi:10.1016/j.coelec.2022.100985

Cited by 6 publications

(3 citation statements)

References 50 publications

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“…In comparison to the band position of the NO 2 group of NTP acquired during conventional Raman and SERS measurements ( Table 1 ), one can then safely assume that the reaction of ATP in HCl aq (under plasmonic conditions) leads to the formation of a new compound, most likely due to the presence of active hot carriers in the strong electromagnetic field, as hot carriers-induced reactions can strongly influence SERS spectra. 31 Although the redox reactions of ATP and NTP have been the subject of numerous studies, 32 the intermediates formed within the monomer pathway have not been characterized in detail, yet. As detailed above, the NO 2 and ring stretching modes enable a clear distinction between the compounds formed in the reaction.…”

Section: Resultsmentioning

confidence: 99%

Mechanism of Plasmon-Induced Catalysis of Thiolates and the Impact of Reaction Conditions

Yao,

Ehtesabi,

Höppener

et al. 2024

J. Am. Chem. Soc.

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The conversion of the thiols 4-aminothiophenol (ATP) and 4-nitrothiophenol (NTP) can be considered as one of the standard reactions of plasmon-induced catalysis and thus has already been the subject of numerous studies. Currently, two reaction pathways are discussed: one describes a dimerization of the starting material yielding 4,4′dimercaptoazobenzene (DMAB), while in the second pathway, it is proposed that NTP is reduced to ATP in HCl solution. In this combined experimental and theoretical study, we disentangled the involved plasmon-mediated reaction mechanisms by carefully controlling the reaction conditions in acidic solutions and vapor. Motivated by the different surfaceenhanced Raman scattering (SERS) spectra of NTP/ATP samples and band shifts in acidic solution, which are generally attributed to water, additional experiments under pure gaseous conditions were performed. Under such acidic vapor conditions, the Raman data strongly suggest the formation of a hitherto not experimentally identified stable compound. Computational modeling of the plasmonic hybrid systems, i.e., regarding the wavelengthdependent character of the involved electronic transitions of the detected key intermediates in both reaction pathways, confirmed the experimental finding of the new compound, namely, 4-nitrosothiophenol (TP*). Tracking the reaction dynamics via timedependent SERS measurements allowed us to establish the link between the dimer-and monomer-based pathways and to suggest possible reaction routes under different environmental conditions. Thereby, insight at the molecular level was provided with respect to the thermodynamics of the underlying reaction mechanism, complementing the spectroscopic results.

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Section: Resultsmentioning

confidence: 99%

Mechanism of Plasmon-Induced Catalysis of Thiolates and the Impact of Reaction Conditions

Yao,

Ehtesabi,

Höppener

et al. 2024

J. Am. Chem. Soc.

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“…In spite of different models and several contradictions, all the studies agree in considering the presence of plasmonic nanoparticles as mandatory for driving the photoreaction. [5] More generally, even when the reaction was run by applying an external voltage or by adding oxidants (AgNO 3 , FeCl 3 , H 2 O 2 ), metal nanoparticles have always been present. [3,6] Here, I unexpectedly discovered that PATP can undergo photodimerization in the absence of any metal mediators, by direct irradiation with a low power 633 nm laser (1.96 eV).…”

Section: Introductionmentioning

confidence: 99%

4‐Aminothiophenol Photodimerization Without Plasmons**

Alessandri

2022

Angewandte Chemie

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The photodimerization of 4-aminothiophenol (PATP) into 4,4'-dimercaptobenzene (DMAB) has been extensively utilized as a paradigm reaction to probe the role of surface plasmons in nanoparticle-mediated lightdriven processes. Here I report the first observation of the PATP-to-DMAB photoreaction in the absence of any plasmonic mediators. The reaction was observed to occur with different kinetics either for PATP adsorbed on non-plasmonic nanoparticles (TiO 2 , ZnO, SiO 2 ) or deposited as macroscopic droplets. Confocal microRaman spectroscopy enabled to investigate the reaction progress in different plasmon-free contexts, either aerobic or anaerobic, suggesting a new interpretation of the photodimerization process, based on direct laser-induced activation of singlet oxygen species. These results provide new insights in light-driven redox processes, elucidating the role of sample morphology, light and oxygen.

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“…Although the redox reaction of ATP and NTP has been the subject of numerous studies, 17 the monomer pathway intermediates have not yet been well explored experimentally. Currently, the investigation of potential intermediates is mainly limited to theoretical studies.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of plasmon-induced catalysis of thiols and the impact of reaction conditions

Yao

Ehtesabi

Höppener

et al. 2022

Preprint

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Plasmon-induced catalysis of the thiols 4-aminothiophenol (ATP) and 4-nitrothiophenol (NTP) has been investigated in numerous studies. Currently, two reaction pathways are discussed in the literature, one leading to dimerization to 4,4’-dimercaptoazobenzene (DMAB), and the other, depending on experimental conditions, resulting in a monomer commonly assigned to ATP. In this joint experimental-theoretical study, we disentangle the involved photo-/plasmon-mediated reaction mechanisms by thorough control of the reaction conditions, particularly the involved surface-enhanced Raman scattering (SERS) substrates. The Raman spectra experimentally and strongly suggest that the formation of a new stable intermediate plays a crucial role. Tracking the reaction with time-dependent SERS experiments allows us to build the connection between the dimer (DMAB) and monomer pathways and to propose potential reaction pathways for different environmental conditions. Furthermore, theoretical modelling addressing the excited-states properties of key intermediates involved in both reaction pathways and the respective thermodynamics allows to investigate the underlying reaction mechanism in more detail – complementing the spectroscopic results.

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Plasmonic photoelectrochemical reactions on noble metal electrodes of nanostructures

Cited by 6 publications

References 50 publications

Mechanism of Plasmon-Induced Catalysis of Thiolates and the Impact of Reaction Conditions

Mechanism of Plasmon-Induced Catalysis of Thiolates and the Impact of Reaction Conditions

4‐Aminothiophenol Photodimerization Without Plasmons**

Mechanism of plasmon-induced catalysis of thiols and the impact of reaction conditions

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