Nanosheets of Ni-SAPO-34 Molecular Sieve for Selective Oxidation of Cyclohexanone to Adipic Acid.

Nanosheets of nickel doped SAPO-34 molecular sieves in thickness of ∼10 nm (denoted as NS-Ni-SAPO-34) has been successfully prepared through a morphology-reserved method of synthesis. A special aluminum phosphate in two-dimensional layered structure is used as precursor and converts to crystallized SAPO-34 molecular sieve, in nanosheet morphology reserved from the aluminum phosphate precursor, under hydrothermal conditions with tetraethyl orthosilicate and templates of mixed amines added. It is found that adequate amount of nickel, ∼5 wt %, added to the synthetic system is a key factor for the morphology-reserved synthesis. By characterization, the nickel is proved to be doped in the framework of the molecular sieve, which more likely helps to balance the high surface energy of nanosheet products. The NS-Ni-SAPO-34 shows excellent catalytic performance for oxidation of cyclohexanone to adipic acid by gaseous oxygen.

Crystal-Facet Modulated CrOx/γ-Al2O3: Quasi-Liquid Surface Modification by Bonded Polydimethylsiloxane for Catalytic Oxidation of Propene.

The crystal-facet effect of catalytic supports plays a crucial role in tailoring the physicochemical properties of active sites and the surface chemically bonded polymer can also regulate the local environment around active sites for optimizing catalytic performance. Herein, we report the effect of exposed facets of γ-Al2O3 supports and further modification by surface bonded long-chain polydimethylsiloxane (PDMS) on the properties of CrOx/γ-Al2O3 catalysts for selective oxidation of propene. The {111} facets of γ-Al2O3 stabilize "non-redox Cr3+" and promote the overall oxidation rates compared with catalysts on {110} facets of γ-Al2O3. The surface bonded PDMS, with grafting density being about 0.13 chains/nm2, endows a hydrophobic environment to facilitate the enrichment of the hydrophobic substrate and the desorption of hydrophilic products and occupies some acid sites on catalysts to limit acid-catalyzed side reactions. The inherent liquidlike nature of bonded PDMS also forms a setting that can regulate the redox ability of surface Cr species, that lead to modified activation of oxygen toward more surface adsorbed species. As a result, the modified catalysts enhance the whole oxidation process with favorable formation of epoxide product at low reaction temperatures (<225 °C). Our findings highlight the impact of surface chemically bound polydimethylsiloxane (PDMS) upon tailoring the surroundings of the catalyst surface, and that combined with facet-effect of supports can tune the reaction process toward selective ones.

Appropriate aggregation is needed for highly active Pt/Al2O3 to enable hydrogenation of chlorinated nitrobenzene.

The atomic dispersion of a noble metal with a reducible support has been reported to be beneficial for catalytic hydrogenation reactions. Conversely, we found that Pt particles (3-5 nm) could be obtained on the non-reducible support Al2O3 by weakening the interaction between the metal and support using oleic acid, and the turnover frequency of catalyzing the hydrogenation of chlorinated nitrobenzene could reach 3700 h-1, which is three orders of magnitude higher than that of atomic platinum species.