from first principles PP-I-1

PL-5From Mechanistic and Kinetic Understanding of HeterogeneouslyCatalyzed Reactions to Tuning Catalysts PerformanceKondratenko E.V.Leibniz-Institut für Katalyse e. V. an der Universität Rostock,Albert-Einstein-Str. 29 A, D-18059 Rostock, Germanyevgenii.kondratenko@catalysis.deHeterogeneous catalysis is the basis of the majority of chemical processes in modern industryand affects our life in myriad ways. It helps to convert readily available raw materials tohigher value-added products. Due to the scarcity of these materials and the requirements fortreating/removal of side products, there is a high demand for more efficient andenvironmentally benign catalytic technologies. Yet, catalytic materials are too complex topredict their behaviour and to develop novel catalysts with desired performance (activity,selectivity, time-on-stream stability). Therefore it is highly desired to elaborate fundamentalprinciples enabling to couple molecular knowledge about the structure and functioning ofcatalytically active sites with the reaction kinetics on the level as elementarily as possible.The relationships between the individual rate constants and catalytic sites can provideguidelines for the rational catalyst design and for the optimization of reactor operation.To accomplish these objectives, various approaches are applied. This paper demonstrates thepotential of steady-state, transient methods operating with sub-millisecond time resolution,time-resolved operando catalyst characterization and DFT calculations for monitoring andmolecular understanding of various heterogeneously catalyzed reactions. The importance ofmicro-kinetic analysis will be especially highlighted. Finally, it will be shown that thesophisticated fundamental knowledge does really enable to tune catalysts performance for anumber of gas-phase catalytic reactions such as functionalization of natural gas, Fischer-Tropsch, Ostwald and Deacon processes. This was, however, possible owing to thedevelopment of methods for controlled synthesis of catalysts with the uniformity ofcatalytically active species and their distribution on the support surface. Particularly the roleof well-defined metal nanoparticles for establishing explicit structure-performancerelationships will be discussed in this contribution.11