Highly Efficient Low-loaded PdOx/AlSiOx for Ethylene Dimerization.

Ethylene dimerization is an industrial process that is currently carried out using homogeneous catalysts. Here we present a highly active heterogeneous catalyst containing minute amounts of atomically dispersed Pd. It requires no co-catalyst(s) or activator(s) and significantly outperforms previously reported catalysts tested under similar reaction conditions. The selectivity to C4- and C6-hydrocarbons was about 80% and 10% at 42% ethylene conversion at 200°C using an industrially relevant feed containing 50 vol% ethylene, respectively. Our kinetic and catalyst characterization experiments complemented by density functional theory calculations provide molecular insights into the local environment of isolated Pd(II)Ox species and their role in achieving high activity in the target reaction. When the developed catalyst was rationally integrated with a Mo-containing olefin metathesis catalyst in the same reactor, the formed butenes reacted with ethylene to propylene with a selectivity of 98% at about 24% ethylene conversion.

Performance Descriptors for Catalysts Based on Molybdenum, Tungsten, or Rhenium Oxides for Metathesis of Ethylene with 2-Butenes to Propene.

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.

Highly efficient Bi-promoted ZrO2-based materials for non-oxidative propane dehydrogenation.

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.

Current status and perspectives in oxidative, non-oxidative and CO2-mediated dehydrogenation of propane and isobutane over metal oxide catalysts.

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.

Mechanism for O-O Bond Formation via Radical Coupling of Metal and Ligand Based Radicals: A New Pathway.

Artificial photosynthesis carries promise to deliver abundant clean energy for the needs of a growing population. Deep mechanistic understanding is required to achieve rational design of fast and durable water oxidation catalysts. Here we provided first evidence for a new mechanism of the O-O bond formation via radical coupling of the oxidized metal═oxo of radicaloid character (RuIV═O) and ligand based radical ([ligand-NO]+• cation radical). O-O bond formation is facilitated via spin alignment and takes place via a virtually barrier less pathway inside the single metal complex. In situ reactive intermediate conversion was monitored by mass spectrometry, resonance Raman (RR) and EPR. Computational analysis have shown that the formation of [ligand-NO]+• happens at a lower overpotential than the formation of the [RuV═O(ligand)]3+ intermediate. Overall, the presented paradigm for O-O bond formation opens new opportunities for rational catalyst design.

Control of coordinatively unsaturated Zr sites in ZrO2 for efficient C-H bond activation.

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.