Revising Model Reactions in Plasmonic Chemistry: From Nitrothiophenol Coupling to Alkoxyamine Homolysis

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-06-13 DOI:10.1021/acscatal.5c01129

Alina Gorbunova, Daria E. Votkina, Oleg Semyonov, Dmitry Kogolev, Jean-Patrick Joly, Sylvain R. A. Marque, Junais Habeeb Mokkah, Soniya Gahlawat, Markus Valtiner, Odile Chevalier, Pavel S. Postnikov, Olga Guselnikova

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Abstract

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.

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修正等离子体化学模型反应：从亚硝基苯酚偶联到烷氧胺均解

等离子体化学的进步需要对能量传递、机制和材料发现进行研究。在这方面，已有3000篇论文将4-亚硝基苯酚（PNTP）偶氮偶联作为模型反应。在这里，我们挑战了该反应作为模型的地位，因为实验证据表明，使用x射线光电子能谱（XPS）作为分析技术监测激光照射在等离子激元激发过程中硫醇解吸。用PNTP包覆常用的金纳米粒子（NPs）进行偶氮偶联，并通过拉曼光谱和XPS进行了验证。n1s和s2p光谱区域的变化表明Au-S键的断裂伴随着硫醇氧化。基于XPS数据，我们假设了一种化学途径和动力学模型，其复杂性超过了之前使用的简单模型，因此很难得出可靠的结论。Au-S键的解离是由等离子体加热触发的，实验和理论确定的局部温度超过硫醇解吸温度。偶氮偶联反应不符合模型一的要求，模型一应简单，并以结构证明的产物进行。由于产物已知，且动力学模型简单，我们建议采用电子顺磁共振谱法跟踪烷氧胺均解反应。合适的模型反应的应用加速了等离子体催化的发现。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.