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In Situ XAS Diagnostics of Reductive Hydroformylation Reaction in Segmented Flow Under Elevated Pressure and Temperature
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2024-07-17 , DOI: 10.1021/acs.iecr.4c01487 Mahmoud E. A. Eid 1, 2 , Dmitry N. Gorbunov 3 , Viktor V. Shapovalov 1 , Maria V. Nenasheva 3 , Bogdan O. Protsenko 1 , Evgeny Khramov 4 , Aleksei N. Bulgakov 1 , Sergey V. Abrosimov 1 , Sergei V. Chapek 1 , Alexander A. Guda 1 , Alexander V. Soldatov 1
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2024-07-17 , DOI: 10.1021/acs.iecr.4c01487 Mahmoud E. A. Eid 1, 2 , Dmitry N. Gorbunov 3 , Viktor V. Shapovalov 1 , Maria V. Nenasheva 3 , Bogdan O. Protsenko 1 , Evgeny Khramov 4 , Aleksei N. Bulgakov 1 , Sergey V. Abrosimov 1 , Sergei V. Chapek 1 , Alexander A. Guda 1 , Alexander V. Soldatov 1
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Homogeneous hydroformylation is an important industrial reaction for the production of aldehydes and alcohols. Rh metal complexes modified with tertiary amine ligands allow tandem one-pot reactions for converting olefins directly into alcohols, and more often, such reactions are performed in microfluidic flow regimes relevant to both academic research and industrial automatization. The reaction yield depends on the coordination of Rh atoms or the formation of Rh clusters; therefore, knowledge about the local atomic and electronic structure of active sites under industrial conditions is important. Rh K-edge X-ray absorption spectroscopy (XAS) is a unique tool to probe Rh coordination; however, to date, there have been no reports of the application of this methodology to hydroformylation in microfluidic biphasic flow. Our work demonstrates the experimental setup and transmission cell developed for segmented flow operando measurements. Quantitative analysis of XAS data was performed with the library of theoretical spectra computed for relevant monomeric, dimeric, and small cluster species. As found recently by EXAFS analysis for autoclave, we demonstrate that under segmented flow, the presence of amine species in the reaction prevents the formation of Rh clusters in favor of Rh dimers.
中文翻译：
高温高压分段流还原加氢甲酰化反应的原位 XAS 诊断
均相加氢甲酰化是生产醛和醇的重要工业反应。用叔胺配体修饰的 Rh 金属配合物允许串联一锅反应将烯烃直接转化为醇，并且更常见的是，此类反应在与学术研究和工业自动化相关的微流体流态中进行。反应产率取决于Rh原子的配位或Rh簇的形成；因此，了解工业条件下活性位点的局部原子和电子结构非常重要。 Rh K 边 X 射线吸收光谱 (XAS) 是探测 Rh 配位的独特工具；然而，迄今为止，还没有将该方法应用于微流体双相流中的加氢甲酰化的报道。我们的工作展示了为分段流量操作测量而开发的实验装置和传输单元。使用针对相关单体、二聚体和小簇物种计算的理论光谱库对 XAS 数据进行定量分析。最近通过高压釜的 EXAFS 分析发现，我们证明在分段流动下，反应中胺类物质的存在阻止了 Rh 簇的形成，有利于 Rh 二聚体。
更新日期：2024-07-17
中文翻译：
高温高压分段流还原加氢甲酰化反应的原位 XAS 诊断
均相加氢甲酰化是生产醛和醇的重要工业反应。用叔胺配体修饰的 Rh 金属配合物允许串联一锅反应将烯烃直接转化为醇，并且更常见的是，此类反应在与学术研究和工业自动化相关的微流体流态中进行。反应产率取决于Rh原子的配位或Rh簇的形成；因此，了解工业条件下活性位点的局部原子和电子结构非常重要。 Rh K 边 X 射线吸收光谱 (XAS) 是探测 Rh 配位的独特工具；然而，迄今为止，还没有将该方法应用于微流体双相流中的加氢甲酰化的报道。我们的工作展示了为分段流量操作测量而开发的实验装置和传输单元。使用针对相关单体、二聚体和小簇物种计算的理论光谱库对 XAS 数据进行定量分析。最近通过高压釜的 EXAFS 分析发现，我们证明在分段流动下，反应中胺类物质的存在阻止了 Rh 簇的形成，有利于 Rh 二聚体。
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