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A prerequisite for the development or optimization of heterogeneous catalysts is a comprehensive understanding of the reaction mechanism and kinetics at the level as elementary as possible. In comparison with steady‐state catalytic tests typically used for this purpose, non‐steady‐state (transient) studies provide deeper insights due to higher time resolution. For several decades, temporal analysis of products (TAP) and steady‐state isotopic transient kinetic analysis (SSITKA) have been successfully applied to the analysis of various heterogeneous reactions. In this review, we highlight the contributions made by TAP and SSITKA studies between 2017 and 2023 to the understanding of reaction mechanisms and to the derivation of microkinetics. The versatility of these methods is illustrated by the examples of oxidative coupling of methane, CO/CO2 hydrogenation to hydrocarbons or methanol, metathesis of ethylene with 2‐butenes to propene, acrolein oxidation to acrylic acid, methanol conversion to olefins and non‐oxidative propane dehydrogenation to propene. We also provide our personal views on possible developments in this area. [ABSTRACT FROM AUTHOR]

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The metathesis of ethylene with 2‐butenes to propene is an established large‐scale process. However, the fundamentals behind in situ transformation of supported WOx, MoOx, or ReOx 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. [ABSTRACT FROM AUTHOR]

Surface or bulk promotion of ZrO2-based catalysts with Bi2O3 facilitates the removal of lattice oxygen from ZrO2 under reductive conditions resulting in the formation of coordinatively unsaturated Zr cations. The catalysts demonstrated an industrially relevant propene yield at 600 °C. The results highlight the importance of the usage of suitable promoters for controlling catalyst performance. [ABSTRACT FROM AUTHOR]

We investigated the effect of supports based on ZrO2, TiO2, Al2O3, and SiO2 on the rate of propene formation in the metathesis of ethylene with 2-butene at 50 °C over Mo-containing catalysts possessing highly dispersed MoOx. Large improvements in this rate were achieved when using supports composed of mixed oxides (ZrO2–SiO2, ZrO2–PO4, TiO2–SiO2; Al2O3–SiO2) rather than of individual oxides (ZrO2, TiO2, Al2O3, SiO2). Although previous literature studies dealing with the metathesis reaction over Al2O3- or SiO2-suppported catalysts at higher temperatures suggest the importance of redox or acidic properties of supported MoOx species for catalyst activity, we were not able to establish any general direct correlation in this regard. Contrarily, the rate of propene formation can be significantly enhanced when promoting supports with an oxide promoter. We suggest that the created support lattice defects may facilitate the transformation of MoOx to Mo carbenes under reaction conditions or improve the intrinsic activity of the latter. [ABSTRACT FROM AUTHOR]

Conversion of propane or butanes from natural/shale gas into propene or butenes, which are indispensable for the synthesis of commodity chemicals, is an important environmentally friendly alternative to oil-based cracking processes. Herein, we critically analyse recent developments in the non-oxidative, oxidative, and CO2-mediated dehydrogenation of propane and isobutane to the corresponding olefins over metal oxide catalysts. Particular attention is paid to (i) comparing the developed catalysts in terms of their application potential, (ii) structure–activity–selectivity relationships for tailored catalyst design, and (iii) reaction-engineering aspects for improving product selectivity and overall process efficiency. On this basis, possible directions for further research aimed at the development of inexpensive and environmentally friendly catalysts with industrially relevant performance were identified. In addition, we provide general information regarding catalyst preparation and characterization as well as some recommendations for carrying out non-oxidative and CO2-mediated dehydrogenation reactions to ensure unambiguous comparison of catalysts developed in different studies. [ABSTRACT FROM AUTHOR]

Keywords: 2-Buten; Ethen; Metathese; Propen; SSITKA DE 2-Buten Ethen Metathese Propen SSITKA 1 1 1 09/27/23 20231002 NES 231002 B Heterogeneous Catalysis b . In their Communication (e202308872), Tatiana Otroshchenko, Evgenii V. Kondratenko et al. report performance descriptors for catalysts based on molybdenum, tungsten, or rhenium oxides for ethylene metathesis with 2-butenes to propene. [Extracted from the article]

Frontispiece: Performance Descriptors for Catalysts Based on Molybdenum, Tungsten, or Rhenium Oxides for Metathesis of Ethylene with 2-Butenes to Propene Keywords: 2-Butene; Ethylene; Metathesis; Propene; SSITKA EN 2-Butene Ethylene Metathesis Propene SSITKA 1 1 1 09/27/23 20231002 NES 231002 B Heterogeneous Catalysis b . In their Communication (e202308872), Tatiana Otroshchenko, Evgenii V. Kondratenko et al. report performance descriptors for catalysts based on molybdenum, tungsten, or rhenium oxides for ethylene metathesis with 2-butenes to propene. [Extracted from the article]

Due to the complexity of heterogeneous catalysts, identification of active sites and the ways for their experimental design are not inherently straightforward but important for tailored catalyst preparation. The present study reveals the active sites for efficient C-H bond activation in C1-C4 alkanes over ZrO2 free of any metals or metal oxides usually catalysing this reaction. Quantum chemical calculations suggest that two Zr cations located at an oxygen vacancy are responsible for the homolytic C-H bond dissociation. This pathway differs from that reported for other metal oxides used for alkane activation, where metal cation and neighbouring lattice oxygen form the active site. The concentration of anion vacancies in ZrO2 can be controlled through adjusting the crystallite size. Accordingly designed ZrO2 shows industrially relevant activity and durability in non-oxidative propane dehydrogenation and performs superior to state-of-the-art catalysts possessing Pt, CrOx, GaOx or VOx species. Identifying active sites and designing rationally heterogeneous catalysts are not inherently straightforward due to their complexity. Here, the authors reveal the nature of active sites for efficient C-H bond activation in C1-C4 alkanes over bare ZrO2 and provide fundamentals for controlling their concentration. [ABSTRACT FROM AUTHOR]