Mechanistic Insights in “CO-free” Carbonylation Reactions as Revealed by Quantitative 2D Correlation X-ray and Infrared Spectroscopy

该研究项目涉及催化反应的表征，特别是利用X射线吸收光谱和振动光谱表征“无CO”羰基化反应。一种新的定量方法来评估二维相关光谱，为表征提供了支持。涉及甲醛或甲酸等一氧化碳替代物的羰基化反应可以成为碳中和循环经济的重要垫脚石。循环经济描述了一个封闭的生产周期，其中资源多次转换为不同的产品。对于化学过程，这种方法意味着燃烧产物如二氧化碳（CO2）和一氧化碳（CO）的活化和再循环。不幸的是，CO是剧毒和易燃的。因此，它是适当的，从更无害的CO替代品，如甲醛开始的合成路线。为了充分了解参与“无CO”羰基化反应的原子反应途径，重要的是要研究在原位或operando条件下使用复杂的光谱技术的催化反应。这些可用的技术之一是X射线吸收光谱法。通过将X射线吸收光谱与振动光谱相结合，可以观察氧化态和局部环境的变化以及分子结构的变化。这种表征的结果可用于设计能源和资源高效的化学过程中的未来。二维相关光谱是一种分析技术，分析的扰动依赖行为的光谱变化。不幸的是，2D相关谱通常通过查看2D相关模式以高度主观的方式进行分析。这种分析方法完全抛弃了二维相关分析的定量结果。在拟议项目中，应开发一种新的二维相关光谱定量分析方法。2D相关光谱的定量分析方法将能够深入评估已建立的理论，并且还将能够量化例如另外的配体系统对催化反应的（去）稳定化影响的影响。总之，目前的研究项目将一方面处理的光谱表征的“无CO”羰基化反应，利用X射线吸收和振动光谱，另一方面，它将处理一个新的定量2D相关分析方法的发展。该项目将导致催化反应特性的创新方法。

The research project deals with the characterization of catalytic reactions in particular with the characterization of “CO-free” carbonylation reactions utilizing X-ray absorption spectroscopy and vibrational spectroscopy. The characterization is supported by a new quantitative way to evaluate 2D correlation spectra.Carbonylations reactions involving carbon monoxide surrogates like formaldehyde or formic acid can be a vital stepping stone to a carbon neutral circular economy. A circular economy describes a closed production cycle where resources are converted multiple times to different products. For a chemical process this approach implies an activation and recycling of combustion products like carbon dioxide (CO2) and carbon monoxide (CO). Unfortunately, CO is highly toxic and flammable. Thus, it is appropriate to start the synthesis route from more harmless CO surrogates like formaldehyde.To fully understand the atomic reaction pathways involved in “CO-free” carbonylation reactions it is important to study the catalytic reaction during in-situ or operando conditions using sophisticated spectroscopic techniques. One of these available techniques is X-ray absorption spectroscopy. By combining X-ray absorption spectroscopy with vibrational spectroscopy it is possible to look into changes in oxidation states and local environments as well as in changing molecular structures. The results of this characterization can be used to design energy and resource efficient chemical processes in the future.2D correlation spectroscopy is an analysis technique to analyze the perturbation-dependent behavior of spectral changes. Unfortunately, 2D correlation spectra are usually analyzed in a highly subjective way by looking at the 2D correlation patterns. This analysis approach completely discards the quantitative results from the 2D correlation analysis. Within the proposed project a new quantitative analysis approach for 2D correlation spectra shall be developed. A quantitative analysis approach for 2D correlation spectra will enable an in-depth evaluation of established theories and will also enable a quantification of the influence of e.g. the (de-)stabilizing influence of an additional ligand system to the catalytic reaction. In summary, the present research project will on one hand deal with the spectroscopic characterization of “CO-free” carbonylation reactions utilizing X-ray absorption and vibrational spectroscopy and on the other hand it will deal with the development of a new quantitative 2D correlation analysis approach. The project will lead to innovative ways in the characterization of catalytic reactions.