Small gold clusters catalyzing oxidant-free dehydrogenation of glycerol initiated by methene hydrogen atom transfer

We report a finding of feasible oxidant-free dehydrogenation of glycerol over small Au clusters, with a low-energy barrier of transition state initiated by hydrogen atom transfer from methene, which differs from the general reaction mechanism based on hydroxyl.     

In Situ Corrosion Fabrication of NaNbO3/Nb3O7F Heterojunctions with Optimized Band Realignment for Enhanced Photocatalytic Hydrogen Evolution

Heterostructured photocatalysis is a significant issue owing to the unique band alignment, improved spectrum absorption, and enhanced photocatalytic activity. However, the construction of uniform, controllable, and effective heterojunctions is still a huge challenge. Herein, NaNbO₃/Nb₃O₇F heterojunctions are fabricated through an in situ corrosion technique for the first time. The influence of phase transformation on the hydrogen evolution reaction (HER) activity is investigated systematically in terms of photocatalytic water splitting for H₂ production. Interestingly, the band realignment and good interfacial contact endow the NaNbO₃/Nb₃O₇F heterojunctions with a high HER activity (43.3 mmol g⁻¹ h⁻¹), which is about 2.4 times that of pure Nb₃O₇F and 1.36 times that of pure NaNbO₃. The results may provide some new insights into the corrosion technique and HER activity of novel heterostructured catalysts.     

某型探测器冷却组件的研制

介绍了一种探测器冷却组件的研制背景及设计方案,采用仿真的设计手段对组件的制冷系统进行了优化设计,实践证明其设计是成功的。同时说明了该型组件所具有的特点及应用场合。     

HAMILTON-JACOBI-BELLMAN方程的混合元方法

0　引　　言考虑下列随机微分方程 :ｄＸｔｄｔ =σ(Ｘｔ,αｔ) ζｔ+ｂ(Ｘｔ,αｔ)　ｔ≥ 0 ( 1 .1ａ)　　　　Ｘ0 =ｘ ∈ＲＮ ( 1 .1ｂ)　　此处 ,σ和ｂ分别是定义在ＲＮ×Ａ上的矩阵值和向量值函数 ,Ａ是给定的可分空间 ,αｔ值位于Ａ中的随机过程 更严格地 ,方程 ( 1 .1ａ)可写成下列形式 :Ｘｔ =ｘ + ∫ｔ0 σ(Ｘｓ,αｓ)ｄＢｓ+ ∫ｔ0 ｂ(Ｘｓ,αｓ)ｄｓ　ｔ≥ 0 ( 1 .2 )此外 ,Ｂｔ 是ｍ 维Ｂｒｏｗｎ运动 ,使得 :Ｅ(Ｂｔ) =0 ,Ｅ(Ｂ2 ｔ) =ｔ;∫ｔ0 σ(Ｘｓ,αｓ)ｄＢｓ 是随机积分 我们知道 ,σ ,ｂ若足够光滑 ,则保证了对每一…     

Front-fixing FEMs for the pricing of American options based on a PML technique

In this paper, efficient numerical methods are developed for the pricing of American options governed by the Black–Scholes equation. The front-fixing technique is first employed to transform the free boundary of optimal exercise prices to some a priori known temporal line for a one-dimensional parabolic problem via the change of variables. The perfectly matched layer (PML) technique is then applied to the pricing problem for the effective truncation of the semi-infinite domain. Finite element methods using the respective continuous and discontinuous Galerkin discretization are proposed for the resulting truncated PML problems related to the options and Greeks. The free boundary is determined by Newton’s method coupled with the discrete truncated PML problem. Stability and nonnegativeness are established for the approximate solution to the truncated PML problem. Under some weak assumptions on the PML medium parameters, it is also proved that the solution of the truncated PML problem converges to that of the unbounded Black–Scholes equation in the computational domain and decays exponentially in the perfectly matched layer. Numerical experiments are conducted to test the performance of the proposed methods and to compare them with some existing methods.     

Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer–Villiger Reaction of 3‐Substituted Cyclobutanones with H2O2 as the Oxidant

The mechanism of the chiral phosphoric acid catalyzed Baeyer–Villiger (B–V) reaction of cyclobutanones with hydrogen peroxide was investigated by using a combination of experimental and theoretical methods. Of the two pathways that have been proposed for the present reaction, the pathway involving a peroxyphosphate intermediate is not viable. The reaction progress kinetic analysis indicates that the reaction is partially inhibited by the γ‐lactone product. Initial rate measurements suggest that the reaction follows Michaelis–Menten‐type kinetics consistent with a bifunctional mechanism in which the catalyst is actively involved in both carbonyl addition and the subsequent rearrangement steps through hydrogen‐bonding interactions with the reactants or the intermediate. High‐level quantum chemical calculations strongly support a two‐step concerted mechanism in which the phosphoric acid activates the reactants or the intermediate in a synergistic manner through partial proton transfer. The catalyst simultaneously acts as a general acid, by increasing the electrophilicity of the carbonyl carbon, increases the nucleophilicity of hydrogen peroxide as a Lewis base in the addition step, and facilitates the dissociation of the OH group from the Criegee intermediate in the rearrangement step. The overall reaction is highly exothermic, and the rearrangement of the Criegee intermediate is the rate‐determining step. The observed reactivity of this catalytic B–V reaction also results, in part, from the ring strain in cyclobutanones. The sense of chiral induction is rationalized by the analysis of the relative energies of the competing diastereomeric transition states, in which the steric repulsion between the 3‐substituent of the cyclobutanone and the 3‐ and 3′‐substituents of the catalyst, as well as the entropy and solvent effects, are found to be critically important.     

Investigation of annealing‐induced oxygen vacancies in the Co‐doped ZnO system by Co K‐edge XANES spectroscopy

To clarify the mechanism of the observed room‐temperature ferromagnetism (RTF), many studies have been focused on dilute magnetic semiconductor systems. Several investigations have demonstrated that oxygen vacancies play a significant role in mediating the RTF behavior so that much effort has been devoted to confirm their presence. In this investigation, X‐ray absorption spectroscopy was combined with ab initio calculations of the electronic structure of Co and Zn in the Zn_0.9Co_0.1O system before and after annealing, which has been recognized as an effective method of originating oxygen vacancies. A feature at about 20 eV after the rising edge of the Co K‐edge XANES that disappears after annealing has been associated with the presence of an oxygen vacancy located in the second shell surrounding the Co atom. Moreover, Zn K‐edge XANES spectra point out that this oxygen vacancy affects the electronic structure near the Fermi level, in agreement with density functional theory calculations.     

An adaptive least-squares mixed finite element method for nonlinear parabolic problems

A least-squares mixed finite element method for nonlinear parabolic problems is investigated in terms of computational efficiency. An a posteriori error estimator, which is needed in an adaptive refinement algorithm, was composed with the least-squares functional, and a posteriori errors were effectively estimated.     

RPM-2: a recyclable porous material with unusual adsorption capability: self assembly via structural transformations

Structural transformation via deliberate and partial topological changes in a grid network structure has led to a three-dimensional, fully recyclable porous material (RPM-2) with a very high sorption capability.     

Synthesis and crystal structure of As-synthesized and calcined pure silica zeolite ITQ-12

The small-pore pure silica zeolite ITQ-12 has been synthesized with fumed silica as the silica source in the presence of 1,3,4-trimethylimidazolium hydroxide and hydrofluoric acid under hydrothermal conditions at 448 K. Rietveld refinement using synchrotron X-ray diffraction data of the calcined ITQ-12 product taken at 298 K confirms the proposed topology, framework type code ITW, which can be described by a monoclinic unit cell [Si(24)O(48)] having Cm symmetry. Unit cell parameters are a = 10.3360(4), b = 15.0177(6), and c = 8.8639(4) A, beta = 105.356(3) degrees, and cell volume V = 1326.76(9) A(3). For as-synthesized ITQ-12, the occluded fluoride anion is located inside the double four-membered ring, while the flat 1,3,4-trimethylimidazolium cation lies on the equatorial plane of the slit-shaped [4(4)5(4)6(4)8(4)] cage, with its longest dimension in the [010] direction. The monoclinic unit cell |(C(6)N(2)H(11))(+)(2)F(-)(2)|[Si(24)O(48)], having Cm symmetry, has parameters a = 10.4478(3), b = 14.9854(4), and c = 8.8366(3) A, beta = 105.935(2) degrees, and cell volume V = 1330.34(7) A(3) at 298 K. Cooperative structure-directing effects during the crystallization of ITQ-12 are discussed in terms of the structure of the as-made material.