Propane dehydrogenation (PDH) to propene is an important alternative to oil-based cracking processes, to produce this industrially important platform chemical^1,2. 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 ZnO_x 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 ZnO_x species. For benchmarking purposes, the developed ZnO–silicalite-1 and an analogue of commercial K–CrO_x/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.

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)O_x 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.

Die Ethylen‐Dimerisierung ist ein industrieller Prozess, der derzeit mit homogenen Katalysatoren durchgeführt wird. Hier stellen wir einen hochaktiven heterogenen Katalysator vor, der winzige Mengen von atomar dispergiertem Pd enthält. Er erfordert keine Cokatalysatoren oder Aktivatoren und übertrifft die Leistung früherer Katalysatoren, die unter ähnlichen Reaktionsbedingungen getestet wurden. Die Selektivität für C₄‐ und C₆‐Kohlenwasserstoffe betrug bei 200 °C etwa 80 % bzw. 10 % bei 42 % C₂H₄‐Umsatz unter Verwendung eines industriell relevanten Reaktionsgemisches mit 50 Vol.‐% Ethylen. Unsere Experimente zur Kinetik und Katalysatorcharakterisierung, ergänzt durch Dichtefunktionaltheorie‐Berechnungen, liefern molekulare Einblicke in die lokale Umgebung isolierter Pd(II)O_x‐Spezies und ihre Rolle bei der Erzielung einer hohen Aktivität in der Zielreaktion. Als der entwickelte Katalysator rationell mit einem Mo‐haltigen Olefinmetathesekatalysator im gleichen Reaktor integriert wurde, reagierten die gebildeten Butene mit Ethylen zu Propylen mit einer Selektivität von 98 % bei etwa 24 % C₂H₄‐Umsatz.