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1.
Research on Chemical Intermediates - Owing to the simultaneous utilization of photogenerated electrons and holes, coupling light-driven hydrogen (H2) evolution reaction (HER) and biomass-derived...  相似文献   
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At present, the reactivity of cyclic alkanes is estimated by comparison with acyclic hydrocarbons. Due to the difference in the structure of cycloalkanes and acycloalkanes, the thermodynamic data obtained by analogy are not applicable. In this study, a molecular beam sampling vacuum ultraviolet photoionization time-of-flight mass spectrometer (MB-VUV-PI-TOFMS) was applied to study the low-temperature oxidation of cyclopentane (CPT) at a total pressure range from 1–3 atm and low-temperature range between 500 and 800 K. Low-temperature reaction products including cyclic olefins, cyclic ethers, and highly oxygenated intermediates (e. g., ketohydroperoxide KHP, keto-dihydroperoxide KDHP, olefinic hydroperoxides OHP and ketone structure products) were observed. Further investigation of the oxidation of CPT – electronic structure calculations – were carried out at the UCCSD(T)-F12a/aug-cc-pVDZ//B3LYP/6-31+ G(d,p) level to explore the reactivity of O2 molecules adding sequentially to cyclopentyl radicals. Experimental and theoretical observations showed that the dominant product channel in the reaction of CPT radicals with O2 is HO2 elimination yielding cyclopentene. The pathways of second and third O2 addition – the dissociation of hydroperoxide – were further confirmed. The results of this study will develop the low-temperature oxidation mechanism of CPT, which can be used for future research on accurately simulating the combustion process of CPT.  相似文献   
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Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.  相似文献   
4.
Copper-catalyzed divergent annulations between α-diketones and alkynyl α-diketones have been achieved, delivering a series of highly functionalized and biologically important cis-hexahydro-2Hcyclopenta[b]furan(HCPF) and 2-hydroxydihydrofuran-3(2H)-one(HDFO) products with high levels of stereoselectivity under identical conditions. The protocol features the use of earth-abundant copper catalyst, mild conditions, shortening synthetic routes in constructing different molecular frameworks, and reduc...  相似文献   
5.
To improve the numerical evaluation of weakly singular integrals appearing in the boundary element method, a logarithmic Gaussian quadrature formula is usually suggested in the literature. In this formula the singular function is expressed in terms of the distance between source point and field point, which is a real variable. When an anisotropic elastic solid is considered, most of the existing fundamental solutions are written in terms of complex variables. When the problems with holes, cracks, inclusions, or interfaces are considered, to suit for the shape of the boundaries usually a mapping function is introduced and then the solutions are expressed in terms of mapped complex variables. To deal with the trouble induced by the complex variables, in this study through proper change of variables we develop a simple way to improve the evaluation of weakly singular integrals, especially for the problems of anisotropic elastic solids containing holes, cracks, inclusions, or interfaces. By simple matrix expansion, the proposed method is extended to the problems with piezoelectric or magneto-electro-elastic solids. By using the dual reciprocity method, the proposed method employed for the elastostatic fundamental solution can also be applied to the elastodynamic analysis.  相似文献   
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The singularly perturbed boundary value problem for nonlinear higher order ordinary differential equation involving two small parameters has been considered. Under appropriate assumptions, for the three cases:ε/μ2→0(μ→0),μ2/ε→0 (ε→0) andε=μ2, the uniformly valid asymptotic solution is obtained by using the expansion method of two small parameters and the theory of differential inequality.  相似文献   
9.
In this paper, by using qualitative analysis, we investigate the number of limit cycles of perturbed cubic Hamiltonian system with perturbation in the form of (2n+2m) or (2n+2m+1)th degree polynomials . We show that the perturbed systems has at most (n+m) limit cycles, and has at most n limit cycles if m=1. If m=1, n=1 and m=1, n=2, the general conditions for the number of existing limit cycles and the stability of the limit cycles will be established, respectively. Such conditions depend on the coefficients of the perturbed terms. In order to illustrate our results, two numerical examples on the location and stability of the limit cycles are given.  相似文献   
10.
研究了制备的掺钕螯合物Nd(DBM)3Phen材料的吸收光谱、激发光谱、荧光光谱,应用Judd-Ofelt理论计算了该材料的强度参量.分析了钕离子激发态4F3/2的辐射寿命(631 μs)和4F3/2→4IJ′跃迁的受激发射截面和荧光分支比.  相似文献   
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