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Abstract: Industrial olefin metathesis catalysts generally suffer from low reaction rates and require harsh reaction conditions for moderate activities. This is due to their inability to prevent metathesis active sites (MAS) from aggregation and their intrinsic poor adsorption and activation of olefin molecules. Here, isolated tungstate species as single molecular MAS is immobilized inside zeolite pores by Brønsted acid sites (BAS) on the inner surface. It is demonstrated for the first time that unoccupied BAS in atomic proximity to MAS enhance olefin adsorption and greatly facilitate the formation of metallocycle intermediates in a stereospecific manner. Thus, effective cooperative catalysis takes place over the BAS-MAS pair. In consequence, for the cross-metathesis of ethene and trans-2-butene to propene, under the same mild reaction conditions, the propene production rate over WOx/USY is ca. 7,300 times that over the industrial WO3/SiO2 based catalyst. A propene yield up to 79% (80% selectivity) without observable deactivation was obtained over WOx/USY for a wide range of reaction conditions.

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Abstract: In the past decades, many efforts have been devoted to characterizing {001} platelet defects in type Ia diamond. It is known that N is concentrated at the defect core. However, an accurate description of the atomic structure of the defect and the role that N plays in it is still unknown. Here, by using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy we have determined the atomic arrangement within platelet defects in a natural type Ia diamond and matched it to a prevalent theoretical model. The platelet has an anisotropic atomic structure with a zigzag ordering of defect pairs along the defect line. The electron energy-loss near-edge fine structure of both carbon K- and nitrogen K-edges obtained from the platelet core is consistent with a trigonal bonding arrangement at interstitial sites. The experimental observations support an interstitial aggregate mode of formation for platelet defects in natural diamond.

Open Access

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Abstract: Unsupported and SiO 2 ‐supported Ni nanoparticles (NPs), were synthesised via hot‐injection colloidal route using oleylamine (OAm) and trioctylphosphine (TOP) as reducing and protective agents, respectively. By adopting a multi‐length scale structural characterization, it was found that by changing equivalents of OAM and TOP not only the size of the nanoparticles is affected but also the Ni electronic structure. The synthetized NPs were modified with ( R , R )‐tartaric acid (TA) and investigated in the asymmetric hydrogenation of methyl acetoacetate to chiral methyl‐3‐hydroxy butyrate. The comparative analysis of structure and catalytic performance for the synthetized catalysts has enabled us to identify a Ni metallic active surface, whereby the activity increases with the size of the metallic domains. Conversely, at the high conversion obtained for the unsupported NPs there was no impact of particle size on the selectivity. ( R )‐selectivity was very high only on catalysts containing positively charged Ni species such as over the SiO 2 ‐supported NiO NPs. This work shows that the chiral modification of metallic Ni NPs with TA is insufficient to maintain high selectivity towards the ( R )‐enantiomer at long reaction time and provide guidance for the engineering of long‐term stable enantioselective catalysts.

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Abstract: Although molecular dinitrogen (N2) is widely used as a carrier or inert gas for many catalytic reactions, it is rarely considered as a catalytic promoter. Here, we report that N2 could be used to reduce the activation energy for catalytic hydrodeoxygenation over ruthenium-based catalysts. Specifically, we report a 4.3-fold activity increase in the catalytic hydrodeoxygenation of p-cresol to toluene over a titanium oxide supported ruthenium catalyst (Ru/TiO2) by simply introducing 6 bar N2 under batch conditions at 160 °C and 1 bar hydrogen. Detailed investigations indicate that N2 can be adsorbed and activated on the metallic ruthenium surface to form hydrogenated nitrogen species, which offer protic hydrogen to lower the activation energy of direct carbonaromatic–oxygen bond scission and the hydrogenation of hydroxy groups. Thus, by employing different ruthenium catalysts, including Ru/TiO2, Ru/Al2O3, Ru/ZrO2 and Ru/C, we demonstrate that N2 promotion of hydrodeoxygenation can be regarded as a general strategy.

Open Access

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Abstract: Wet impregnation is broadly applied for the synthesis of carbon-supported metal/metal oxide nanostructures because of its high flexibility, simplicity and low cost. By contrast, impregnated catalysts are typified by a usually undesired nanostructural and morphological heterogeneity of the supported phase resulting from a poor stabilization at the support surface. This study on graphite-supported Fe-based materials from Fe nitrate precursor is concerned with the understanding of the chemistry that dictates during the multistep synthesis, which is key to designing structurally homogeneous catalysts. By means of core-level X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy and atomic resolution electron microscopy, we found not only a large variety of particles sizes and morphologies but also chemical phases. Herein, thermally stable single atoms and few atoms clusters are identified together with large agglomerates of an oxy-hydroxide ferrihydrite-like phase. Moreover, the thermally induced phase transformation of the initially poorly ordered oxy-hydroxide phase into several oxide phases is revealed, together with the existence of thermally stable N impurities retained in the structure as Fe–N–O bonds. The nature of the interactions with the support and the structural dynamics induced by the thermal treatment rationalize the high heterogeneity observed in these catalysts.