The catalyst support 3DOM LaFeO3 contains highly ordered macropores that are connected with each other by small windows. 3DOM LaFeO3 supported gold catalysts, which combine the advantages of good contact by the macroporous support and highly active sites for activation of O2 by gold clusters, exhibit super catalytic performance for soot oxidation.
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.
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.
Conversion of propane or isobutane from natural/shale gas into propene or isobutene, which are indispensable for the synthesis of commodity chemicals, is an important environmentally friendly alternative to oil-based cracking processes.
A series of catalysts of three-dimensionally ordered macroporous (3DOM) Ce 0.8 Zr 0.2 O 2 -supported gold nanoparticles with controllable sizes were successfully synthesized by the facile method of gas bubbling-assisted membrane reduction (GBMR). All the catalysts possess well-defined 3DOM structures, which consist of interconnected networks of spherical voids, and the Au nanoparticles are well dispersed and supported on the inner wall of the uniform macropore. The relationship between Au particle sizes and the ability to adsorb and activate oxygen was characterized by means of O 2 -TPD and XPS. The results show that the active oxygen species (O À ) and gold ions with oxidation state of Au + are essential for soot oxidation reaction. 3DOM Au 0.04 /Ce 0.8 Zr 0.2 O 2 catalyst with Au particle size of 2-3 nm has the strong capability of adsorption and activation of oxygen. Thus, it exhibits super-catalytic activity for diesel soot oxidation, especially at low temperature. The reaction pathways of catalytic soot oxidation in the presence or absence of NO can be outlined as follows: at low temperature (<250 C), the catalytic performance of supported Au catalyst is dependent on the Au particle sizes. At relatively high temperature (>250 C), the catalytic activity is strongly related to the NO gas, because NO 2 derived from NO oxidation is used as intermediate to catalyze soot oxidation.
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