Herein we describe a reaction of ortho‐carbonylated alkynyl‐substituted arylaldehydes with common primary amines that can provide functionalized isoindolinone and 3‐hydroxylindenamine products in high yields. Depending on the substituent size of primary amines, two distinct reaction pathways were exploited selectively, that are, an initial aza‐conjugate addition followed by hydrogen transfer to access isoindolinone framework and a unique oxa‐conjugate addition followed by Petasis–Ferrier rearrangement to afford indenamine derivatives. In the presence of Et3N, the reaction property of small primary amines was changed, proceeding to afford 3‐hydroxylindenamine derivatives efficiently. These products contain interesting substructures that exist in many natural products and bioactive molecules. The reaction features contain the use of transition‐metal‐free catalysts, simple operation, broad substrate scope, and product diversity. 相似文献
Mesoporous carbon (m‐C) has potential applications as porous electrodes for electrochemical energy storage, but its applications have been severely limited by the inherent fragility and low electrical conductivity. A rational strategy is presented to construct m‐C into hierarchical porous structures with high flexibility by using a carbon nanotube (CNT) sponge as a three‐dimensional template, and grafting Pt nanoparticles at the m‐C surface. This method involves several controllable steps including solution deposition of a mesoporous silica (m‐SiO2) layer onto CNTs, chemical vapor deposition of acetylene, and etching of m‐SiO2, resulting in a CNT@m‐C core–shell or a CNT@m‐C@Pt core–shell hybrid structure after Pt adsorption. The underlying CNT network provides a robust yet flexible support and a high electrical conductivity, whereas the m‐C provides large surface area, and the Pt nanoparticles improves interfacial electron and ion diffusion. Consequently, specific capacitances of 203 and 311 F g?1 have been achieved in these CNT@m‐C and CNT@m‐C@Pt sponges as supercapacitor electrodes, respectively, which can retain 96 % of original capacitance under large degree compression. 相似文献
This paper presents the bifurcation behaviors of a modified railway wheelset model to explore its instability mechanisms of hunting motion. Equivalent conicity data measured from China high-speed railway vehicle are used to modify the wheelset model. Firstly, the relationships between longitudinal stiffness, lateral stiffness, equivalent conicity and critical speed are taken into account by calculating the real parts of the eigenvalues of the Jacobian matrix and Hurwitz criterion for the corresponding linear model. Secondly, measured equivalent conicity data are fitted by a nonlinear function of the lateral displacement rather than are considered as a constant as usual. Nonlinear wheel–rail force function is used to describe the wheel–rail contact force. Based on these modifications, a modified railway wheelset model with nonlinear equivalent conicity and wheel–rail force is set up, and then, some instability mechanisms of China high-speed train vehicle are investigated based on Hopf bifurcation, fold (limit point) bifurcation of cycles, cusp bifurcation of cycles, Neimark–Sacker bifurcation of cycles and 1:1 resonance. In particular, fold bifurcation of cycles can produce a vast effect on the hunting motion of the modified wheelset model. One of the main reasons leading to hunting motion is due to the fold bifurcation structure of cycles, in which stable limit cycles and unstable limit cycles may coincide, and multiple nested limit cycles appear on a side of fold bifurcation curve of cycles. Unstable hunting motion mainly depends on the coexistence of equilibria and limit cycles and their positions; if the most outward limit cycle is stable, then the motion of high-speed vehicle should be safe in a reasonable range. Otherwise, if the initial values are chosen near the most outward unstable limit cycle or the system is perturbed by noises, the high-speed vehicle will take place unstable hunting motion and even lead to serious train derailment events. Therefore, in order to control hunting motions, it may be the easiest way in theory to guarantee the coexistence of the inner stable equilibrium and the most outward stable limit cycle in a wheelset system.
The top-down fabrication of catalytically active molecular metal oxide anions, or polyoxometalates, is virtually unexplored, although these materials offer unique possibilities, for catalysis, energy conversion and storage. Here, we report a novel top-down route, which enables the scalable synthesis and deposition of sub-nanometer molybdenum-oxo clusters on electrically conductive mesoporous carbon. The new approach uses a unique redox-cycling process to convert crystalline MoIVO2 particles into sub-nanometer molecular molybdenum-oxo clusters with a nuclearity of ∼1–20. The resulting molybdenum-oxo cluster/carbon composite shows outstanding, stable electrocatalytic performance for the oxygen reduction reaction with catalyst characteristics comparable to those of commercial Pt/C. This new material design could give access to a new class of highly reactive polyoxometalate-like metal oxo clusters as high-performance, earth abundant (electro-)catalysts.The top-down synthesis and deposition of polyoxometalate-like clusters on porous carbon is reported together with the high electrocatalytic oxygen reduction reactivity of the composite.相似文献
We report the design and synthesis of a titanium catecholate framework, MOF-217, comprised of 2,4,6-tri(3,4-dihydroxyphenyl)-1,3,5-triazine (TDHT) and isolated TiO6 clusters, with 2-fold interpenetrated srs topology. The dynamics of the organic linker, breaking the C3h symmetry, allowed for reversible twist and sliding between interpenetrated frames upon temperature change and the inclusion of small molecules. Introduction of 28 wt% imidazole into the pores of MOF-217, 28% Im-in-MOF-217, resulted in four orders of magnitude increase in proton conductivity, due to the appropriate accommodation of imidazole molecules and their proton transfer facilitated by the H-bond to the MOF structure across the pores. This MOF-based proton conductor can be operated at 100 °C with a proton conductivity of 1.1 × 10−3 S cm−1, standing among the best performing anhydrous MOF proton conductors at elevated temperature. The interframe dynamics represents a unique feature of MOFs that can be accessed in the future design of proton conductors.Twist and sliding dynamics observed in a titanium catecholate MOF induced by imidazole for efficient proton conduction.相似文献
New integrable B_2 model with off-diagonal boundary reflections is proposed. The general solutions of the reflection matrix for the B_2 model are obtained by using the fusion technique. Wefind that the reflection matrix has 7 free boundary parameters, which are used to describe the degree of freedom of boundary couplings, without breaking the integrability of the system. The new quantization conditions will induce the novel structure of the energy spectrum and the boundary states. The corresponding boundary effects can be studied based on the results in this paper. Meanwhile, the reflection matrix of high rank models associated with Bnalgebra can also be obtained by using the method suggested in this paper. 相似文献
Atomic regulation of metal catalysts has emerged as an intriguing yet challenging strategy to boost product selectivity. Here, we report a density functional theory‐guided atomic design strategy for the fabrication of a NiGa intermetallic catalyst with completely isolated Ni sites to optimize acetylene semi‐hydrogenation processes. Such Ni sites show not only preferential acetylene π‐adsorption, but also enhanced ethylene desorption. The characteristics of the Ni sites are confirmed by multiple characterization techniques, including aberration‐corrected high‐resolution scanning transmission electron microscopy and X‐ray absorption spectrometry measurements. The superior performance is also confirmed experimentally against a Ni5Ga3 intermetallic catalyst with partially isolated Ni sites and against a Ni catalyst with multi‐atomic ensemble Ni sites. Accordingly, the NiGa intermetallic catalyst with the completely isolated Ni sites shows significantly enhanced selectivity to ethylene and suppressed coke formation. 相似文献