Zichittella Guido, Polyhach Yevhen, Tschaggelar René, Jeschke Gunnar, Pérez-Ramírez Javier
Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland.
Laboratory of Physical Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 2, 8093, Zurich, Switzerland.
Angew Chem Int Ed Engl. 2021 Feb 15;60(7):3596-3602. doi: 10.1002/anie.202013331. Epub 2020 Dec 15.
Identification and quantification of redox-active centers at relevant conditions for catalysis is pivotal to understand reaction mechanisms and requires development of advanced operando methods. Herein, we demonstrate operando EPR spectroscopy as an important technique to quantify the oxidation state of representative CrPO and EuOCl catalysts during propane oxychlorination, an attractive route for propylene production. In particular, we show that the space-time-yield of C H correlates with the amount of Cr and Eu ions generated over the catalysts during reaction. These results provide a powerful strategy to gather quantitative understanding of selective alkane oxidation, which could potentially be extrapolated to other functionalization approaches and operating conditions.
在催化相关条件下识别和定量氧化还原活性中心对于理解反应机理至关重要,并且需要开发先进的原位方法。在此,我们展示了原位电子顺磁共振光谱作为一种重要技术,用于定量代表性的CrPO和EuOCl催化剂在丙烷氧氯化反应(一种有吸引力的丙烯生产途径)过程中的氧化态。特别地,我们表明C₃H₆的时空产率与反应过程中催化剂上生成的Cr和Eu离子量相关。这些结果提供了一个强有力的策略,以获得对选择性烷烃氧化的定量理解,这有可能推广到其他官能团化方法和操作条件。