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Alkali metal promoters have been widely employed for preparation of heterogeneous catalysts used in many industrially important reactions. However, the fundamentals of their effects are usually difficult to access. Herein, we unravel mechanistic and kinetic aspects of the role of alkali metals in CO2 hydrogenation over Fe‐based catalysts through state‐of‐the‐art characterization techniques, spatially resolved steady‐state and transient kinetic analyses. The promoters affect electronic properties of iron in iron carbides. These carbide characteristics determine catalyst ability to activate H2, CO and CO2. The Allen scale electronegativity of alkali metal promoter was successfully correlated with the rates of CO2 hydrogenation to higher hydrocarbons and CH4 as well as with the rate constants of individual steps of CO or CO2 activation. The derived knowledge can be valuable for designing and preparing catalysts applied in other reactions where such promoters are also used. [ABSTRACT FROM AUTHOR]

Alkalimetallpromotoren werden in großem Umfang für die Herstellung heterogener Katalysatoren eingesetzt, die in vielen industriell wichtigen Reaktionen verwendet werden. Die Ursachen für ihre Wirkung sind jedoch in der Regel nur schwer zu ergründen. In dieser Arbeit werden die mechanistischen und kinetischen Aspekte der Wirkung von Alkalimetallen bei der CO2‐Hydrierung an Fe‐haltigen Katalysatoren mithilfe modernster Charakterisierungstechniken sowie räumlich aufgelöster stationärer und instationärer kinetischer Analysen aufgeklärt. Die Promotoren beeinflussen die elektronischen Eigenschaften von Eisen in Eisenkarbiden. Diese Karbideigenschaften bestimmen die Fähigkeit des Katalysators, H2, CO und CO2 zu aktivieren. Die Elektronegativität des Alkalimetallpromoters nach der Allen‐Skala wurde erfolgreich mit der Reaktionsgeschwindigkeit der CO2‐Hydrierung zu höheren Kohlenwasserstoffen und CH4 sowie mit den Geschwindigkeitskonstanten der einzelnen Schritte der CO‐ oder CO2‐Aktivierung korreliert. Die gewonnenen Erkenntnisse können für die Entwicklung und Herstellung von Katalysatoren für andere Reaktionen, bei welchen derartige Promotoren ebenfalls verwendet werden, von Nutzen sein. [ABSTRACT FROM AUTHOR]

Propane dehydrogenation (PDH) to propene is an important alternative to oil-based cracking processes, to produce this industrially important platform chemical1,2. The commercial PDH technologies utilizing Cr-containing (refs. 3,4) or Pt-containing (refs. 5–8) catalysts suffer from the toxicity of Cr(vi) compounds or the need to use ecologically harmful chlorine for catalyst regeneration9. Here, we introduce a method for preparation of environmentally compatible supported catalysts based on commercial ZnO. This metal oxide and a support (zeolite or common metal oxide) are used as a physical mixture or in the form of two layers with ZnO as the upstream layer. Supported ZnOx species are in situ formed through a reaction of support OH groups with Zn atoms generated from ZnO upon reductive treatment above 550 °C. Using different complementary characterization methods, we identify the decisive role of defective OH groups for the formation of active ZnOx species. For benchmarking purposes, the developed ZnO–silicalite-1 and an analogue of commercial K–CrOx/Al2O3 were tested in the same setup under industrially relevant conditions at close propane conversion over about 400 h on propane stream. The developed catalyst reveals about three times higher propene productivity at similar propene selectivity.Propene is obtained through propane dehydrogenation using catalysts that are toxic, expensive or demanding to regenerate with ecologically harmful compounds, but the ZnO-based alternative reported here is cheap, clean and scalable. [ABSTRACT FROM AUTHOR]

The Front Cover depicts the main products of the oxidative coupling of methane reaction over MnOx‐Na2WO4/support catalysts. In their Research Article, G. Jian, E. V. Kondratenko and co‐workers established that low catalyst surface area and low reactivity of support lattice oxygen are advantageous for achieving high selectivity to C2H6 and C2H4. The TiO2 support fulfills these requirements, whereas the use of Al2O3‐ or ZrO2‐containing supports leads to the predominant formation of CO or CO2. In addition, the selectivity to the desired products over TiO2‐supported catalysts can be improved by replacing O2 with N2O and/or through co‐fed H2O due to reducing the concentration of adsorbed diatomic oxygen species. More information can be found in the Research Article by G. Jian, E. V. Kondratenko and co‐workers. [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]

This paper demonstrates the potential of Eu2O3 and Gd2O3 as catalysts for non-oxidative propane dehydrogenation to propene. They reveal a higher activity than the state-of-the-art bare ZrO2-based catalysts due to the higher intrinsic activity of Gdcus or Eucus in comparison with that of Zrcus (cus = coordinatively unsaturated). [ABSTRACT FROM AUTHOR]

The article titled "Back Cover: Controlling Metal-Oxide Reducibility for Efficient C-H Bond Activation in Hydrocarbons" discusses the challenge of designing metal oxide catalysts and proposes a method to control their structural properties. The authors, Bingsen Zhang, Evgenii V. Kondratenko, Zhong-Wen Liu, and others, suggest that catalyst post-treatment in an NH3⋅H2O solution can dissolve and precipitate individual catalyst components, allowing for the tailoring of catalyst reducibility. This is important for C-H bond activation in hydrocarbons. The article provides valuable insights for researchers interested in catalyst design and C-H bond activation. [Extracted from the article]

In the article titled "Control of the Reducibility of Metal Oxides for Efficient Activation of C-H Bonds in Hydrocarbons," the authors discuss the challenge of designing metal oxide catalysts. They propose a method of controlling the structural properties of supported/bulk metal oxides through post-treatment in an NH3⋅H2O solution. This treatment allows for the dissolution and simultaneous precipitation of individual catalyst components, resulting in the ability to tailor catalyst reducibility. The authors highlight the importance of catalyst reducibility in the activation of C-H bonds in hydrocarbons. [Extracted from the article]

Au/TiO2 and Au/SiO2 catalysts containing 2 wt % Au and different amounts of K or Cs were tested for alcohol synthesis from CO2, H2, and C2H4/C3H6. 1‐Propanol or 1‐butanol/isobutanol were obtained in the presence of C2H4 or C3H6. Higher yields of the corresponding alcohols were obtained over TiO2‐based catalysts in comparison with their SiO2‐based counterparts. This is caused by an enhanced ability of the TiO2‐based catalysts for CO2 activation, as concluded from in situ fourier‐transform infrared (FTIR) spectroscopy and temporal analysis of products (TAP) studies. The synthesized carbonate and formate species adsorbed on the support do not hamper CO2 conversion into CO and the hydroformylation reaction. The transformation of Auδ+ to active Au0 sites proceeds during an activation procedure. As reflected by CO adsorption and scanning transmission electron microscopy, the accessible Au0 sites are influenced by the amount of alkali dopants and the support. FTIR data and TAP tests reveal a very weak interaction of C2H4 with the catalyst, suggesting its quick reaction with CO and H2 after activation on Au0 sites to form propanol and propane. Au NPs and alkali dopants—an effective team: In situ FTIR spectroscopy and temporal analysis of products reveal the importance of the type of support and alkali‐metal dopant on the performance of Au NPs for CO2 adsorption and its conversion with H2 into C3 or C4 alcohols in the presence of C2H4 or C3H6. The active Au0 sites required for the activation of all feed components are generated by in situ reduction of Auδ+ during an activation process. [ABSTRACT FROM AUTHOR]

Non-oxidative dehydrogenation of propane to propene is an established large-scale process that, however, faces challenges, particularly in catalyst development; these are the toxicity of chromium compounds, high cost of platinum, and catalyst durability. Herein, we describe the design of unconventional catalysts based on bulk materials with a certain defect structure, for example, ZrO2 promoted with other metal oxides. Comprehensive characterization supports the hypothesis that coordinatively unsaturated Zr cations are the active sites for propane dehydrogenation. Their concentration can be adjusted by varying the kind of ZrO2 promoter and/or supporting tiny amounts of hydrogenation-active metal. Accordingly designed Cu(0.05 wt%)/ZrO2-La2O3 showed industrially relevant activity and durability over ca. 240 h on stream in a series of 60 dehydrogenation and oxidative regeneration cycles between 550 and 625°C. [ABSTRACT FROM AUTHOR]

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