Revising Model Reactions in Plasmonic Chemistry: From Nitrothiophenol Coupling to Alkoxyamine Homolysis; ACS Catalysis; Vol. 15, iss. 13
| Parent link: | ACS Catalysis.— .— Washington: American Chemical Society Vol. 15, iss. 13.— 2025.— P. 11163-11176 |
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| מחברים אחרים: | Gorbunova A. Alina, Votkina D. E. Darjya Evgenjevna, Semyonov O. V. Oleg Vladimirovich, Kogolev D. A. Dmitry Anatoljevich, Joly J. P. Jean-Patrick, Marque S. R. A. Sylvain Remon Alber, Mokkah J. H. Junais Habeeb, Gahlawat S. Soniya, Valtiner M. Markus, Chevalier O. Odile, Postnikov P. S. Pavel Sergeevich, Guselnikova O. A. Olga Andreevna |
| סיכום: | Title screen The progress in plasmonic chemistry requires research on energy transfer, mechanisms, and materials discovery. In this pursuit, there are >3000 papers applying the azo coupling of 4-nitrothiophenol (PNTP) as a model reaction. Here, we challenge the status of this reaction as a model due to experimental evidence of thiol desorption during plasmon excitation using laser irradiation monitored by X-ray photoelectron spectroscopy (XPS) as an analytic technique. The azo coupling was performed on commonly used Au nanoparticles (NPs) coated with PNTP and confirmed by Raman spectroscopy and XPS. Changes in the N 1s and S 2p spectral regions indicated the cleavage of the Au–S bond, accompanied by thiol oxidation. Based on XPS data, we hypothesized a chemical pathway and a kinetic model that surpasses previously used simple models in complexity, making it challenging to draw reliable conclusions. The dissociation of the Au–S bond is triggered by plasmonic heating, supported by experimentally and theoretically determined local temperatures exceeding the thiol desorption temperature. The azo coupling reaction does not fit within the requirements of the model one, which should be simple and proceed with structurally evidenced products. As one of the alternative reactions, we suggest alkoxyamine homolysis tracked by electron paramagnetic resonance spectroscopy because of known products and the simple kinetic model. Applications of suitable model reactions accelerate discoveries in plasmon catalysis Текстовый файл AM_Agreement |
| שפה: | אנגלית |
| יצא לאור: |
2025
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| נושאים: | |
| גישה מקוונת: | https://doi.org/10.1021/acscatal.5c01129 |
| פורמט: | אלקטרוני Book Chapter |
| KOHA link: | https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=681246 |
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Uncovering the Role of Chemical and Electronic Structures in Plasmonic Catalysis: The Case of Homolysis of Alkoxyamines; ACS Catalysis; Vol. 13, iss. 5
יצא לאור: (2023) -
The Role of Geometric Parameters of Palladium Nanoparticles in the Plasmon-Activated Suzuki–Miyaura Reaction; Russian Journal of General Chemistry; Vol. 96, iss. 4
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יצא לאור: (2026) -
From batch to flow plasmon catalysis: revealing mass transport limits in Au@Pd nanocatalysts for Suzuki coupling; Nanoscale; Vol. 18, iss. 10
יצא לאור: (2026) -
Plasmon-Assisted Chemistry Using Chiral Gold Helicoids: Toward Asymmetric Organic Catalysis; ACS Catalysis; Vol. 13, iss. 19
יצא לאור: (2023) -
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