Rotaxanes and molecular knots exhibit particular properties resulting from the presence of a mechanical bond within their structure that maintains the molecular components interlocked in a permanent manner. On the other hand, the disassembly of the interlocked architecture through the breakdown of the mechanical bond can activate properties which are masked in the parent compound. Herein, we present the development of stimuli-responsive CuI-complexed [2]catenanes as OFF/ON catalysts for the copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction. The encapsulation of the CuI ion inside the [2]catenanes inhibits its ability to catalyze the formation of triazoles. In contrast, the controlled opening of the two macrocycles induces the breaking of the mechanical bond, thereby restoring the catalytic activity of the CuI ion for the CuAAC reaction. Such OFF/ON catalysts can be involved in signal amplification processes with various potential applications. 相似文献
We have made a comparative study of CO/H2 reactions over the nickel catalysts supported on X- and Y-zeolites, prepared by incipient-wetness impregnation (W) and ion-exchange (E) methods. The catalysts were characterized by surface area and volumetric chemisorption measurements, temperature programmed reduction profiles, and x-ray diffraction analysis. The results show that the turnover frequency decreases in the order; NiX(W)>NiY(W)>NiY(E)>NiX(E). The metal dispersion and catalytic activity of the catalyst are mainly affected by the support materials, the preparation methods, and the activation procedures. The high activity of NiX(W) was due to its higher reducibility, smaller nickel crystalline size, and better nickel dispersion. The low activity of NiX(E) was attributed to the poor ion-exchange of Ni with NaX, the poor reducibility, the large crystalline size, and the poor nickel dispersion. 相似文献
Steam-reforming reactions of methanol over NiO/Al2O3 and CuO/ZnO have been investigated. Over the nickel catalyst, the reaction rate is of zero kinetic order with respect to either methanol or steam, and the activation energy is 12.4 kJmol?1, whereas with copper catalyst, the rate is expressed according to the literature as kPa/(1 + KaPa + Kb+Pb) in which “a” and “b” are methanol and steam, respectively. The rate-controlling step of the reaction is assigned to the dissociation of O-H bond with dehydrogenation of C-H bond proceed rapidly to form carbon oxides. With copper catalyst the intrinsic participation of a water molecule during the dehydrogenation of C-H bond leads to the formation of carbon dioxide. With nickel catalyst, the dehydrogenation proceed more rapidly than the migration of a water molecule from an alumina site to a nickel site and causes almost exclusively the formation of carbon monoxide and hydrogen at a lower reaction temperature. 相似文献
Summary: The azaferrocenyliminonickel dibromide complexes 1 bearing a pentaphenylcyclopentadienyl group and a wide range of N‐aryl groups were synthesized and examined as catalysts for ethylene polymerization. Both the ortho‐ (R1) and para‐substituents (R2) of the N‐aryl groups in 1 were found to strongly influence both the polymerization activity and the properties of the obtained polyethylenes. The effect of changing the polymerization conditions, such as temperature, ethylene pressure, and cocatalyst, was also examined.
