氧化钛负载脱硝催化剂的碱中毒过程：氧化钒的保留和氧化钨的牺牲

V2O5-WO3/TiO2催化剂目前已广泛用于电厂和工业锅炉燃烧废气脱硝,但燃烧原料煤及石油中含有的杂质元素碱金属与碱土金属元素可吸附在催化剂上,不仅会减少催化剂酸性位的数量,还会与催化活性元素结合生成惰性物种,导致催化剂失活。因此,已有许多有关钒钨钛催化剂碱中毒的研究,从催化剂的氧化还原能力、酸性位损失及表面孔结构等方面进行了讨论。但这些研究大多集中在碱中毒对活性组分V2O5的影响及中毒催化剂的活性变化,很少涉及催化剂中WO3的作用,也缺乏有关不同活性元素与钾盐反应的实验证据。本文采用过量浸渍法制备了不同钒和钨含量的钒钨钛催化剂,研究了氯化钾对其氨法选择性催化还原(NH3-SCR)活性的失活效应。利用感应耦合等离子体、N2吸附、拉曼光谱、H2程序升温还原、NH3吸附红外光谱和NH3氧化活性等手段对新鲜和中毒催化剂的性质进行了表征,特别探讨了V2O5和WO3对催化剂抗碱中毒能力的贡献。
　　催化剂活性测试结果表明, V2O5含量越高,活性温度窗口越宽,而且含有WO3的三元催化剂活性高于V2O5/TiO2二元催化剂。催化剂的BET比表面积和孔结构取决于TiO2载体,随活性组分配比变化不大,说明催化剂物理结构性质并非影响活性的主要因素。原位红外光谱及H2程序升温还原测试结果表明,随V2O5含量提高,催化剂表面Br?nsted酸性位数量及氧化还原能力提高。作为反应的主要活性物种, V2O5在碱中毒处理后变成惰性的偏钒酸钾KVO3,使催化剂中Br?nsted酸性位减少,热稳定性下降,并削弱了催化剂的氧化还原能力,因此低钒含量的催化剂容易严重中毒失活。在高钒负载量(3%)时,部分V2O5在碱中毒后得以保留,从而使催化剂保持了一定的脱硝催化活性。
　　另外, WO3能给催化剂表面提供热稳定的酸性位,虽然WO3自身的氧化还原能力差,但其能改善V2O5的分散性,从而提高V2O5-WO3/TiO2催化剂的活性。除此之外, WO3在催化剂碱中毒过程中还能扮演牺牲剂,与钾反应生成钨酸钾(K2WO4),即在V2O5与钾离子结合形成KVO3的同时,部分WO3也会与钾反应形成K2WO4,可以使三元催化剂保留更多的活性V物种。因此,在所研究的催化剂中,高钒负载量的V2O5-WO3/TiO2催化剂表现出最好的抗碱中毒能力。
　　活性影响因素分析表明,对于新鲜催化剂,其表面吸附的NH3量足够多,催化剂活性与表面酸性相关度不大,脱硝效率主要取决于催化剂的氧化还原能力。但是,对于碱中毒处理后的催化剂,其表面吸附NH3的能力大大削弱,这时脱硝效率除了受催化剂氧化还原能力影响,在很大程度上也依赖于催化剂的表面酸性。     

镥晶体的绝热量热法测试和热力学函数

文章合成了Lu(NO₃)₃(C₂H₅O₂N)_4.H₂O,用红外和元素分析对其进行了表征。用高精度全自动绝热量热仪,测定了该配合物80-382 K温区的热容, 利用实验热容数据, 根据热容与焓、熵的热力学关系, 求出了配合物85-350 K温区内每隔5 K相对于298.15K的标准热力学函数(HT - H298.15)m和(ST - S298.15)m.在80-350 K温度区间内,配合物的热容随温度升高而增大,没有相转移点和热力学吸收峰的出现,该配合物在此温度区间内是稳定存在的。     

Probing Bis‐FeIV MauG: Experimental Evidence for the Long‐Range Charge‐Resonance Model

The biosynthesis of tryptophan tryptophylquinone, a protein‐derived cofactor, involves a long‐range reaction mediated by a bis‐Fe^IV intermediate of a diheme enzyme, MauG. Recently, a unique charge‐resonance (CR) phenomenon was discovered in this intermediate, and a biological, long‐distance CR model was proposed. This model suggests that the chemical nature of the bis‐Fe^IV species is not as simple as it appears; rather, it is composed of a collection of resonance structures in a dynamic equilibrium. Here, we experimentally evaluated the proposed CR model by introducing small molecules to, and measuring the temperature dependence of, bis‐Fe^IV MauG. Spectroscopic evidence was presented to demonstrate that the selected compounds increase the decay rate of the bis‐Fe^IV species by disrupting the equilibrium of the resonance structures that constitutes the proposed CR model. The results support this new CR model and bring a fresh concept to the classical CR theory.     

计算材料科学中桥域多尺度方法的若干进展

材料科学中存在固有的多尺度特性,桥域多尺度方法是在宏观尺度(如连续介质力学)中引入不同的细微观尺度的计算区域,乃至纳米尺度的分子动力学、量子力学计算区域,将不同尺度的研究方法通过一定的数学模型耦合在一起。该方法既能节约计算成本,又能保证所研究问题的物理特性。本文对多尺度方法的基本概念、跨尺度桥域多尺度方法的发展、基本原理、耦合方法和离散方程进行了讨论,给出了几个应用算例,并在最后进行了总结,展望了今后的可能发展方向。     

Dynamics and trajectory planning of a planar flipping robot

In this paper, a new planar one-legged robot model is firstly proposed, which, unlike previous one-legged robot with springy legs, consists of three revolute joints. Then a novel manner of one-legged locomotion (i.e., ballistic flip) is designed for this robot. A complete flipping gait cycle is composed of four phases: two stance phases and two flight phases. During flight phases, no active control is needed on the knee joint. Rotational motion and translational motion is decoupled from each other in flight phases. Landing of the robot is regarded as an inelastic impulsive impact. During stance phases, the robot model can be simplified as a two-degree-of-freedom rigid manipulator. Based on analysis of kinematics and dynamics of the flip robot, trajectory planning of cyclic flip gait is formulized as a problem of numerical optimization subject to nonlinear constraints such as positive reaction force of ground and finite torque of the joints. One potential application of the flipping robot is space exploration, which urgently requires the legged locomotive robots to be light-weighted and energy efficient.     

斜交连续梁桥数值分析研究

在分析了矩阵位移法和传递矩阵法的理论基础上，将二者组合而成矩阵混合法。矩阵混合法的实质就是将结构物的一端未知向量通过矩阵的简单乘法传递到另一端，再将已知条件代入求解的过程。在矩阵传递的过程中引入位移法中的前进代入的概念，即将未知向量不断地以新的未知向量替换，可以防止误差的传递和积累。将矩阵混合法运用于斜交连续梁桥内力计算，完成了矩阵混合法在斜交连续梁桥内力计算中的理论推导和程序的设计，给出了实际算例并与有限元法进行了比较。     

Initial‐Boundary Value Problems for the Coupled Nonlinear Schrödinger Equation on the Half‐Line

Initial‐boundary value problems for the coupled nonlinear Schrödinger equation on the half‐line are investigated via the Fokas method. It is shown that the solution can be expressed in terms of the unique solution of a matrix Riemann–Hilbert problem formulated in the complex k‐plane, whose jump matrix is defined in terms of the matrix spectral functions and that depend on the initial data and all boundary values, respectively. If there exist spectral functions satisfying the global relation, it can be proved that the function defined by the above Riemann–Hilbert problem solves the coupled nonlinear Schrödinger equation and agrees with the prescribed initial and boundary values. The most challenging problem in the implementation of this method is to characterize the unknown boundary values that appear in the spectral function . For a particular class of boundary conditions so‐called linearizable boundary conditions, it is possible to compute the spectral function in terms of and given boundary conditions by using the algebraic manipulation of the global relation. For the general case of boundary conditions, an effective characterization of the unknown boundary values can be obtained by employing perturbation expansion.     

广义sine-Gordon方程高精度隐式紧致差分方法

本文研究一类二维非线性的广义sine-Gordon(简称SG)方程的有限差分格式.首先构造三层时间的紧致交替方向隐式差分格式,并用能量分析法证明格式具有二阶时间精度和四阶空间精度.然后应用改进的Richardson外推算法将时间精度提高到四阶.最后,数值算例证实改进后的算法在空间和时间上均达到四阶精度.