The Origin of Shape Sensitivity in Palladium‐Catalyzed Suzuki–Miyaura Cross Coupling Reactions

The shape sensitivity of Pd catalysts in Suzuki–Miyaura coupling reactions is studied using nanocrystals enclosed by well‐defined surface facets. The catalytic performance of Pd nanocrystals with cubic, cuboctahedral and octahedral morphologies are compared. Superior catalytic reactivity is observed for Pd NCs with {100} surface facets compared to {111} facets. The origin of the enhanced reactivity associated with a cubic morphology is related to the leaching susceptibility of the nanocrystals. Molecular oxygen plays a key role in facilitating the leaching of Pd atoms from the surface of the nanocrystals. The interaction of O₂ with Pd is itself facet‐dependent, which in turn gives rise to more efficient leaching from {100} facets, compared to {111} facets under the reaction conditions.     

丙烯直接环氧化Cu基催化剂的研究进展与挑战

作为一种重要的化工原料,环氧丙烷年产量近千万吨,然而目前工业上制备环氧丙烷的方法仍然面临着成本高、副产物多以及污染严重等问题。直接氧气氧化法进行丙烯环氧化因为具有原子经济、环保等优点受到了越来越多的关注。但是,催化过程中丙烯的α-H和环氧丙烷都具有很高的活性,使得在高转化率的条件下提升环氧丙烷选择性成为一个巨大的挑战。研究者们发现相较于其他币族金属,Cu基催化剂表现出更优异的丙烯直接环氧化反应性能。本综述总结梳理了近年来关于Cu基催化剂催化丙烯直接环氧化反应的研究成果,聚焦于Cu基催化剂改性方法,并对Cu基催化剂依然存在的问题和挑战进行深入探讨。     

高指数晶面纳米催化剂的电化学制备及应用

催化剂的性能与其表面结构及组成密切相关,高指数晶面纳米晶的表面含有高密度的台阶原子等活性位点而表现出较高的催化活性. 本文综述了电化学方波电位方法用于Pt、Pd、Rh等贵金属高指数晶面结构纳米晶催化剂的制备、形成机理及其电催化性能的研究. 针对贵金属利用率问题,还着重介绍了具有较高质量活性的小粒径Pt二十四面体的制备. 在此基础上,还介绍了电化学方波电位方法用于低共熔溶剂中制备高指数晶面纳米晶,以及高指数晶面纳米催化剂的表面修饰及应用;最后对高指数晶面纳米催化剂的发展做出了展望.     

室温下制备以{211}晶面为主的Ti1-xVxO2薄膜及其可见光催化性能

以金属Ti和V作为靶材,采用直流反应共溅射技术在室温下制备了以{211}晶面为主的锐钛矿相Ti_1-xV_xO₂薄膜,研究了不同V靶功率对Ti_1-xV_xO₂薄膜的薄膜成分、晶相结构和可见光催化性能的影响。研究表明,Ti_1-xV_xO₂薄膜的晶相结构为锐钛矿相,择优取向为(211),而结晶度受V靶功率的影响。随着V靶功率的增加,薄膜中V元素含量逐渐增加,同时,晶粒和沉积速率也逐渐增加。另外,当V靶功率为150 W时,薄膜的表面粗糙度值有一个最大值。V的掺杂导致薄膜的能带间隙变窄,对光的吸收向可见光区偏移,从而有效地改善了薄膜的可见光催化能力。当V靶功率为150 W时,Ti_1-xV_xO₂薄膜的能带间隙值为 2.82 eV,其在2 h的可见光照射下分解了80%的RhB染料。这被归结于能带间隙窄,高能晶面{211}和结晶度高的共同作用。     

具有主导晶面的BiOIO3/BiOCl异质结制备与光催化性能

分别以乙二醇/去离子水为溶剂,通过溶剂热/水热法分别制备了具有不同主导晶面的BiOIO₃/{110}BiOCl和BiOIO₃/{001}BiOCl异质结。采用X射线衍射、扫描电子显微镜、能量色散谱和紫外可见漫反射光谱对制备的BiOIO₃/BiOCl光催化剂进行了表征。在可见光照射下,通过对罗丹明 B和苯酚水溶液的光催化降解,考察了 BiOIO₃/BiOCl异质结的光催化活性。结果显示25% BiOIO₃/{110}BiOCl异质结具有最高的光催化效率。BiOIO₃/{110}BiOCl较好的光催化性能是由于其在可见光区较强的光吸收,以及异质结结构和BiOCl所具有的(110)主导晶面有利于光生载流子的分离。超氧自由基(·O₂^-)和空穴(h⁺)是光催化过程中的主要活性物质。此外,根据实验结果探讨了光催化性能增强的机理。     

非水溶剂热法制备(001)面暴露的F/TiO2纳米晶及其光催化活性

采用非水体系溶剂热法制备了(001)面暴露的锐钛矿相F/TiO2纳米光催化剂.结果表明,F的掺杂对TiO2纳米单晶的形成影响很大.一方面,F离子作为晶面导向剂稳定(001)晶面,形成(001)面暴露的锐钛矿相TiO2;另一方面,F离子也起到稳定剂作用,抑制纳米粒子的快速生长.以光催化降解甲基橙为模型反应比较了不同F/T...     

行NA随机变量三角阵列的完全收敛性

令{Xm;1≤i≤n,n≥1}是行NA的随机变量三角阵列．利用NA随机变量序列的一个矩不等式,讨论了行NA的随机变量三角阵列在被随机变量X弱平均控制的条件下的完全收敛性．所得到的结果推广了行独立的随机变量三角阵列相应的结果．     

A monotone finite element scheme for convection-diffusion equations

A simple technique is given in this paper for the construction and analysis of a class of finite element discretizations for convection-diffusion problems in any spatial dimension by properly averaging the PDE coefficients on element edges. The resulting finite element stiffness matrix is an -matrix under some mild assumption for the underlying (generally unstructured) finite element grids. As a consequence the proposed edge-averaged finite element scheme is particularly interesting for the discretization of convection dominated problems. This scheme admits a simple variational formulation, it is easy to analyze, and it is also suitable for problems with a relatively smooth flux variable. Some simple numerical examples are given to demonstrate its effectiveness for convection dominated problems.

     

Large deviations for heavy-tailed random sums of independent random variables with dominatedly varying tails

We prove large deviation results on the partial and random sums Sn = ∑i=1n Xi,n≥1; S(t) = ∑i=1N(t) Xi, t≥0, where {N(t);t≥0} are non-negative integer-valued random variables and {Xn;n≥1} are independent non-negative random variables with distribution, Fn, of Xn, independent of {N(t); t≥0}. Special attention is paid to the distribution of dominated variation.     

Growth kinetics of metastable (3 3 1) nanofacet on Au and Pt(1 1 0) surfaces

A theoretical epitaxial growth model with realistic barriers for surface diffusion is investigated by means of kinetic Monte Carlo simulations to study the growth modes of metastable (3 3 1) nanofacets on Au and Pt(1 1 0) surfaces. The results show that under experimental atomic fluxes, the (3 3 1) nanofacets grow by 2D nucleation at low temperature in the submonolayer regime. A metastable growth phase diagram that can be useful to experimentalists is presented and looks similar to the one found for the stationary growth of the bcc(0 0 1) surface in the kinetic 6-vertex model.