Pt含量及活化温度对固体超强酸催化剂异构化性能的影响

本文制备了固体超强酸Pt- S2O82-/ZrO2-Al2O3催化剂,采用XRD、TPR、TG-DTA 、FT-IR等表征手段对催化剂进行了表征,并在高压微反－色谱联合装置上,考察了Pt质量分数和活化温度对催化剂正戊烷异构化性能的影响. 结果表明,Pt能使催化剂的还原温度降低;增强载体表面氢气的溢流效应,提高酸强度;Pt质量分数0.10%、活化温度300℃的催化剂异构化活性最高,在反应温度220℃、压力2.0MPa、氢烃摩尔比4:1、质量空速1.0h-1时,异戊烷产率达62.3%. 在100h内异戊烷收率可稳定在55%左右,选择性在98.0％以上.     

电解水金属单原子催化剂的研究进展

氢能因其能量密度高、清洁无污染等特点,作为替代化石燃料的能源载体得到了广泛的研究.如何清洁高效地制备氢气受到了大量研究者的关注.当前,以化石能源的热反应所得副产氢气是主要来源.然而,采用该类方法不仅不能摆脱化石能源的使用以及温室气体的排放,还会造成生产氢气的纯度不高,碳氧化物杂质浓度过高的问题,严重影响氢气的后续使用.采用可再生能源(太阳能、风能等)所产富余电,进行电解水制氢,产生的氢气不含碳氧化合物杂质,纯度很高,可以真正实现碳的零排放,被认为是未来氢气来源的重要方式.目前,电解水制氢在制氢市场的所占份额较小,而造成这样局面的主要因素是该过程中的高能耗问题.为了降低能耗,开发高效催化剂加速两个电极上的电解反应的动力学尤为重要.近年,金属单原子催化剂(SACs)因其独特的结构,在很多研究中被用作电解水催化剂,进而开发出大量高性能的金属单原子电解水催化剂.本文综述了近年SACs在电解水催化方面的应用.首先,针对电解水反应本身,总结了阴阳极两侧的电极反应机制以及影响电极催化性能的关键吸附中间物种;然后,根据载体的不同,即合金、碳以及其它化合物将SACs分为三类,总结了相关电解水催化研究现状,并且针对不同类型SACs目前的发展情况,提出了它们各自存在的问题.其次,进一步总结了影响SACs电解水催化活性的因素,提出了四种决定SACs催化性能的影响因子,分别为金属原子的固有元素性质、配位环境、几何结构和负载量;同时讨论了这四类影响因素对SACs催化活性的影响机制,总结了调控各类影响因素的方法,为SACs的设计提出了一些建议.最后,展望了SACs在电解水催化中的应用,探讨了SACs在催化剂设计及催化机制研究方面的问题,提出了SACs在电解水催化中的未来发展方向.     

误差非线性回归模型基于几何方法的若干二阶渐近性质

该文用微分几何方法对AR(q)误差非线性回归模型若干二 阶渐近性质进行了研究. 作者基于Fisher信息阵在欧氏空间定义了内积，并在期望参数空间建立了几何结构. 基于上述几何结构，给出了AR(q)误差非线性回归模型若干二阶渐近性质的曲率表示. 将前人的一些结果推广到AR(q)误差非线性回归模型.      

A probabilistic analysis of a discrete-time evolution in recombination

We study the discrete-time evolution of a recombination transformation in population genetics. The transformation acts on a product probability space, and its evolution can be described by a Markov chain on a set of partitions that converges to the finest partition. We describe the geometric decay rate to this limit and the quasi-stationary behavior of the Markov chain when conditioned on the event that the chain does not hit the limit.     

Variational Analysis of Toda Systems

The author surveys some recent progress on the Toda system on a two-dimensional surface Σ,arising in models from self-dual non-abelian Chern-Simons vortices,as well as in differential geometry.In particular,its variational structure is analysed,and the role of the topological join of the barycentric sets of Σ is shown.     

Synthesis of aspergillide A via proline-catalyzed trans-to-cis isomerization of a substituted tetrahydropyran

The transformation of a common synthetic intermediate of aspergillides B and C into aspergillide A, a cytotoxin produced by a marine-derived fungus, has been accomplished in an eleven-step sequence involving an efficient proline-catalyzed isomerization of a 2,6-trans-substituted tetrahydropyran-2-acetaldehyde intermediate into the corresponding cis isomer and the Yamaguchi macrolactonization as the key steps.     

Relaxation oscillations and canard explosion in a predator–prey system of Holling and Leslie types

We give a geometric analysis of relaxation oscillations and canard cycles in a singularly perturbed predator–prey system of Holling and Leslie types. We discuss how the canard cycles are found near the Hopf bifurcation points. The transition from small Hopf-type cycles to large relaxation cycles is also discussed. Moreover, we outline one possibility for the global dynamics. Numerical simulations are also carried out to verify the theoretical results.     

Quantum phases for a generalized harmonic oscillator

An effective Hamiltonian for the generalized harmonic oscillator is determined by using squeezed state wavefunctions. The equations of motion over an extended phase space are determined and then solved perturbatively for a specific choice of the oscillator parameters. These results are used to calculate the dynamic and geometric phases for the generalized oscillator with this choice of parameters.      

The ?-positive center figure

Based on Gage's notion of a “positive center” of a planar convex set, an ε-positive center figure is defined, constructed, and illustrated through example. The existence of an ε-positive center point, and the convexity of the ε-positive center figure, is conjectured.