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”的羰基化反应。这一表征得到了一种新的定量方法的支持，该方法可以评估2D关联光谱。涉及一氧化碳替代品(如甲醛或甲酸)的羰化反应可能是实现碳中性循环经济的重要踏脚石。循环经济描述了一个封闭的生产周期，资源多次转化为不同的产品。对于化学过程，这种方法意味着二氧化碳(CO2)和一氧化碳(CO)等燃烧产物的活化和回收。不幸的是，一氧化碳是剧毒和易燃的。因此，从更无害的CO替代物如甲醛开始合成路线是合适的。为了全面了解无CO羰化反应中涉及的原子反应路径，用复杂的光谱技术研究原位或操作条件下的催化反应是很重要的。其中一种可用的技术是X射线吸收光谱分析。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。这一表征结果可用于未来设计能源和资源高效的化学过程。二维相关光谱是一种分析技术，用于分析光谱变化的微扰相关行为。不幸的是，2D相关谱通常通过查看2D相关模式来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。在拟议的项目中，将开发一种新的二维相关谱定量分析方法。2D相关光谱的定量分析方法将使对已有理论的深入评估成为可能，也将使对额外配体系统对催化反应的(去)稳定影响的影响能够量化。综上所述，本研究项目一方面将利用X射线吸收和振动光谱对“无CO”的羰基化反应进行光谱表征，另一方面将研究开发一种新的定量二维相关分析方法。该项目将导致在催化反应表征方面的创新方法。

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.