Zhang Qiyang, Xiao Tianci, Liu Chengyuan, Otroshchenko Tatiana, Kondratenko Evgenii V
Department of Advanced methods for applied catalysis, Leibniz-Institut für Katalyse e.V. (LIKAT), Albert-Einstein-Str. 29a, 18059, Rostock, Germany.
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, Anhui, P. R. China.
Angew Chem Int Ed Engl. 2023 Oct 2;62(40):e202308872. doi: 10.1002/anie.202308872. Epub 2023 Aug 4.
The metathesis of ethylene with 2-butenes to propene is an established large-scale process. However, the fundamentals behind in situ transformation of supported WO , MoO , or ReO species into catalytically active metal-carbenes and the intrinsic activity of the latter as well as the role of metathesis-inactive cocatalysts are still unsolved. This is detrimental for catalyst development and process optimization. In this study, we provide the required essentials derived from steady-state isotopic transient kinetic analysis. For the first time, the steady-state concentration, the lifetime, and the intrinsic reactivity of metal carbenes were determined. The obtained results can be directly used for the design and the preparation of metathesis-active catalysts and cocatalysts, thereby opening up possibilities for optimizing propene productivity.
乙烯与2-丁烯复分解生成丙烯是一个成熟的大规模工艺。然而，负载型WO、MoO或ReO物种原位转化为催化活性金属卡宾背后的基本原理、后者的本征活性以及复分解惰性助催化剂的作用仍然没有解决。这不利于催化剂开发和工艺优化。在本研究中，我们提供了从稳态同位素瞬变动力学分析中获得的必要要素。首次测定了金属卡宾的稳态浓度、寿命和本征反应活性。所得结果可直接用于设计和制备复分解活性催化剂和助催化剂，从而为优化丙烯生产率开辟了可能性。
