In this work, we present a novel experimental tool that integrates in situ Raman spectroscopy and an annular reactor for the operando-Raman kinetic analysis of heterogeneous catalytic reactions. The proposed configuration can monitor via Raman spectroscopy the catalytic surface under kinetically limited reaction conditions, with reliable product analysis, thus retaining the main features of both Raman spectroscopy and kinetic investigation in an annular reactor. We report a thorough description of the key constraints in developing online Raman spectroscopic tools for kinetic investigations. These constraints are considered in the design, assembly and testing of the experimental method by minimizing the mutual invasiveness of the Raman spectroscopy and of the annular reactor configurations. Show-cases of dry reforming and partial oxidation of CH₄ on Rh catalysts are used to establish proof of concept of the method, demonstrating the acquisition of time-resolved Raman spectroscopic data under kinetically relevant conditions. Experiments both on clean and coked Rh surfaces reveal that well-structured graphitic deposits are likely to form during DR. During CPO, instead, the presence of O₂ and H₂O limits the formation of organized graphitic-like carbonaceous species. On a more general basis, this reactor allows a detailed structural characterization of a catalyst material during the reaction and at conditions of temperature, pressure and composition relevant to catalysis. Therefore, it is an important breakthrough for the simultaneous collection of spectroscopic and kinetically relevant data for the investigation of the structure–activity relationship in heterogeneous catalysis.

中文翻译：

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用于非均相催化动力学研究的全拉曼环形反应器的设计和测试†

在这项工作中，我们提出了一种新颖的实验工具，该工具集成了原位拉曼光谱和环形反应器，用于非均相催化反应的拉曼动力学分析。建议的配置可以通过以下方式进行监控拉曼光谱法在动力学受限的反应条件下催化表面具有可靠的产物分析，因此保留了环形反应器中拉曼光谱法和动力学研究的主要特征。我们报告了开发动力学研究在线拉曼光谱工具的关键约束条件的详尽描述。通过最小化拉曼光谱法和环形反应器配置的相互侵入性，在实验方法的设计，组装和测试中考虑了这些限制。CH ₄的干重整和部分氧化的展示Rh催化剂上的NaCl用于建立该方法的概念证明，证明了在动力学相关条件下对时间分辨拉曼光谱数据的获取。在干净和结焦的Rh表面上进行的实验表明，在DR期间可能形成结构良好的石墨沉积物。相反，在CPO期间，存在O ₂和H ₂O限制了有组织的石墨状碳质物质的形成。在更一般的基础上，该反应器允许在反应期间以及在与催化有关的温度，压力和组成的条件下对催化剂材料进行详细的结构表征。因此，这是同时收集光谱和动力学相关数据以研究非均相催化中结构与活性关系的重要突破。