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Lecture

Van Marum Colloquium: Death and life of homogeneous carbonyl reduction catalysts: navigating condition space towards superior catalytic performance

Date
Wednesday 21 December 2022
Time
Location
T.B.A.

Abstract

Catalytic reduction of carbonyl moieties in ketones and esters to their corresponding alcohols are fundamental to the production of high value fine-chemicals. In recent years, traditional Ru and Ir catalysts have been complemented by novel first-row transition metal catalysts due to their favorable sustainability, economics, and reduced toxicity.[1] The practical implementation of such catalysts based on e.g. Fe or Mn is often hampered by their limited stability under the catalytic conditions. Understanding the catalytic and deactivation paths for such systems is key to tailoring their properties towards enhanced and sustained catalytic performance. In this lecture, I will discuss the importance and challenges of understanding the chemistry of catalyst deactivation for the development of practical catalytic technologies with the examples of our recent studies on Mn catalysis for selective reduction of carbonyl-containing compounds. [2,3] 

Conventionally, the performance of homogeneous catalyst is interpreted in terms of the molecular structures and electronic properties of the organometallic compounds they originate from. In practice, the catalyst systems are highly complex, multicomponent, and intrinsically multifunctional. Their behaviour is only partially controlled by the chemistry of “catalyst molecule” (e.g., nature of the metal site, ligand structure and composition, intrinsic reactivity of the complex). It should rather be viewed as a complex function of a much wider range of parameters such as the activation procedure, the presence of promotors, solvent type, and the selected conditions (T, p, medium composition). [3] The position within such a complex condition space defines the preference of the catalytic species to live and drive the catalytic cycles of the desired chemical transformations or to die via one of the competing deactivation channels. An insight into the underlying mechanisms and their condition-dependencies could be obtained through the combination of operando spectroscopy, kinetic studies [3] and automated expert-bias free computational mechanistic analysis [4], which would help navigate this vast condition space and boost the efficiency and lifetime of the 3d metal-based catalyst systems.

References

  1. G.A. Filonenko, R. van Putten, E.J.M. Hensen, E.A. Pidko, Chem. Soc. Rev. 2018, 47, 1459.
  2. R. van Putten, E.A. Uslamin, M. Garbe, C. Liu, A. Gonzalez-de-Castro, M. Lutz, K. Junge, E.J.M. Hensen, M. Beller, L. Lefort, E.A. Pidko, Angew. Chem. Int. Ed. 2017,  129, 7639; W. Yang, I. Yu. Chernyshov, R. K. A. van Schendel, M. Weber, C. Müller, G. Filonenko, E. Pidko, Nat. Commun. 2021, 12, 12
  3. C. Liu, R. van Putten, P.O. Kulayev, G.A. Filonenko, E.A. Pidko, J. Catal. 2018, 363, 136; A. Krieger, P. Kulyaev, F. Armstrong Hall, D. Sun, E.A. Pidko, J. Phys. Chem. C 2020, 124, 26990; W. Yang, T. Kalavalapalli, A. Krieger, T.A. Khvorost, I. Yu. Chernyshov, M. Weber, E.A. Uslamin, E.A. Pidko, G. Filonenko, J. Am. Chem. Soc. 2022,  144, 8129
  4. K. D. Vogiatzis, M. V. Polynski, J. K. Kirkland, J. Townsend, A. Hashemi, C. Liu, E. A. Pidko, Chem. Rev. 2019, 119, 2453; A. Hashemi, S. Bougueroua, M.P. Gaigeot, E.A. Pidko, J. Chem. Theory Comput. 2022, DOI: 10.1021/acs.jctc.2c00404

Biography

Evgeny Pidko (Moscow, Russia, 1982) received his Ph.D. from Eindhoven University of Technology in 2008, where in 2011-2017, he was an Assistant Professor of Catalysis for Sustainability. In 2016 he obtained an ERC Consolidator grant “DeLiCat” to learn, understand and control the deactivation phenomena in hydrogenation catalysis. In September 2017, he moved to Delft Univeristy of Technology to become an Associate Professor and head of the Inorganic Systems Engineering group at the Chemical Engineering Department, where he was promoted to Full Professor in 2020. He is a member of the advisory boards of ChemCatChem and Catal. Sci. Technol. journals, and an editorial board member of Kin. Catal. and Mend. Commun. journals. He is an author of >200 publications on various topics of computational, physical, inorganic, supramolecular chemistry, catalysis, and chemical engineering. In his research, he successfully combines experiments and theory to understand molecular mechanisms underlying the behaviour of various chemical systems ranging from heterogeneous and homogeneous catalysis to inorganic functional materials and use these fundamental insights to guide the development of new, more sustainable and efficient chemical technologies.

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