Adsorption Site Regulation to Guide Atomic Design of Ni–Ga Catalysts for Acetylene Semi‐Hydrogenation

Atomic regulation of metal catalysts has emerged as an intriguing yet challenging strategy to boost product selectivity. Here, we report a density functional theory‐guided atomic design strategy for the fabrication of a NiGa intermetallic catalyst with completely isolated Ni sites to optimize acetylene semi‐hydrogenation processes. Such Ni sites show not only preferential acetylene π‐adsorption, but also enhanced ethylene desorption. The characteristics of the Ni sites are confirmed by multiple characterization techniques, including aberration‐corrected high‐resolution scanning transmission electron microscopy and X‐ray absorption spectrometry measurements. The superior performance is also confirmed experimentally against a Ni₅Ga₃ intermetallic catalyst with partially isolated Ni sites and against a Ni catalyst with multi‐atomic ensemble Ni sites. Accordingly, the NiGa intermetallic catalyst with the completely isolated Ni sites shows significantly enhanced selectivity to ethylene and suppressed coke formation.     

A Simplified Parallel Two-Level Iterative Method for Simulation of Incompressible Navier-Stokes Equations

Based on two-grid discretization, a simplified parallel iterative finite element method for the simulation of incompressible Navier-Stokes equations is developed and analyzed. The method is based on a fixed point iteration for the equations on a coarse grid, where a Stokes problem is solved at each iteration. Then, on overlapped local fine grids, corrections are calculated in parallel by solving an Oseen problem in which the fixed convection is given by the coarse grid solution. Error bounds of the approximate solution are derived. Numerical results on examples of known analytical solutions, lid-driven cavity flow and backward-facing step flow are also given to demonstrate the effectiveness of the method.     

非定常Navier-Stokes方程基于完全重叠型区域分解的有限元并行算法

基于完全重叠型区域分解技巧,提出三种求解非定常Navier-Stokes方程的有限元并行算法.其基本思想是首先对空间施行完全重叠区域分解,然后各个处理器使用向后Euler格式独立并行求解关于时间t的常微分方程;对于非线性的对流项,分别采用半隐格式和全隐格式进行处理.算法中每个处理器所负责的子问题是一个全局问题,它定义在整个求解区域上,但绝大部分自由度来自其所负责的子区域,从而使得算法实现简单,通信需求少.数值算例验证了算法的有效性及其良好的并行性能.     

不可压缩流的并行两水平稳定有限元算法

提出一种数值求解定常不可压缩Stokes方程的并行两水平Grad-div稳定有限元算法。首先在粗网格中求解Grad-div稳定化的全局解, 再在相互重叠的细网格子区域上并行纠正。通过对稳定化参数、粗细网格尺寸恰当的选取, 该方法可得到最优收敛率, 数值结果验证了算法的高效性。     

Adsorption Site Regulation to Guide Atomic Design of Ni–Ga Catalysts for Acetylene Semi-Hydrogenation

Atomic regulation of metal catalysts has emerged as an intriguing yet challenging strategy to boost product selectivity. Here, we report a density functional theory-guided atomic design strategy for the fabrication of a NiGa intermetallic catalyst with completely isolated Ni sites to optimize acetylene semi-hydrogenation processes. Such Ni sites show not only preferential acetylene π-adsorption, but also enhanced ethylene desorption. The characteristics of the Ni sites are confirmed by multiple characterization techniques, including aberration-corrected high-resolution scanning transmission electron microscopy and X-ray absorption spectrometry measurements. The superior performance is also confirmed experimentally against a Ni₅Ga₃ intermetallic catalyst with partially isolated Ni sites and against a Ni catalyst with multi-atomic ensemble Ni sites. Accordingly, the NiGa intermetallic catalyst with the completely isolated Ni sites shows significantly enhanced selectivity to ethylene and suppressed coke formation.     

Synthesis of α-arylalkylferrocenes through cesium fluoride-promoted coupling of arylboronic acids with N-tosylhydrazones

A cesium fluoride-promoted reductive coupling reaction of acylferrocene tosylhydrazones with arylboronic acids has been developed, producing highly substituted α-arylalkylferrocenes in moderate to excellent yields. The reaction employs anionic fluorine to facilitate the cleavage of C–B bond. The developed methodology demonstrates a wide substrate scope and high functional groups tolerance. Moreover, the α-arylalkylferrocenes compounds were also obtained on a multi-gram scale.     

Local and parallel finite element algorithms based on two-grid discretizations for the transient Stokes equations

Based on two-grid discretizations, some local and parallel finite element algorithms for the d-dimensional (d = 2,3) transient Stokes equations are proposed and analyzed. Both semi- and fully discrete schemes are considered. With backward Euler scheme for the temporal discretization, the basic idea of the fully discrete finite element algorithms is to approximate the generalized Stokes equations using a coarse grid on the entire domain, then correct the resulted residue using a finer grid on overlapped subdomains by some local and parallel procedures at each time step. By the technical tool of local a priori estimate for the fully discrete finite element solution, errors of the corresponding solutions from these algorithms are estimated. Some numerical results are also given which show that the algorithms are highly efficient.     

Spontaneous Agglomeration of Silver Nanoparticles Deposited on Carbon Film Surface

The spontaneous aggregation of silver nanoparticles on a two-dimensional surface at room temperature is investigated. The nanoparticles were deposited on a carbon film and have been observed by a transmission electron microscope (TEM) for over one year. These particles were about 10nm, spherical and well dispersed initially, and an obviously spontaneous agglomeration was observed at the 12th day, the values, coverage rate of the silver particles on carbon film, were increased with time (before 40th day), but reduced with time (after 40th day). These show that the aggregates of the particles tend to have the smallest surface to reduce their surface free energy and are compact three-dimensional cluster in which the most size is above 100nm. Agglomerating is a successively slow diffusion-limited aggregation (DLA) growth. Another phenomenon, a big aggregate gathering some particles and a small aggregate to form a still bigger one, is observed. This indicates that the aggregating processes are controlled by migration of the particles on carbon film surface and surface energy of the particles.     

Properties of Ferrofluid Nanoparticles Prepared by Coprecipitation and Acid Treatment

A new stable acid water-based CoFe₂O₄ ferrofluid is prepared by coprecipitation and acid treatment. The properties of the nanoparticles forming the ferrofluid are examined by means of X-ray diffraction, vibrating sample magnetometer, scanning tunneling microscopy, transmission electron microscopy and annihilation technique. The results show that the particles are cubic CoFe₂O₄ nanoparticles, which have an average diameter of 12.2nm and are coated with a low density porous amorphous layer. The CoFe₂O₄ particles in an acid aqueous medium exist in two kinds of forms, one is a single spherical particle and another is an aggregation of several spherical particles.     

New Prediction Model of Surface and Interfacial Energies Based on COSMO-UCE**

The nature and strength of intermolecular and surface forces are the key factors that influence the solvation, adhesion and wetting phenomena. The universal cohesive energy prediction equation based on conductor-like screening model (COSMO-UCE) was extended from like molecules (pure liquids) to unlike molecules (dissimilar liquids). A new molecular-thermodynamic model of interfacial tension (IFT) for liquid-liquid and solid-liquid systems was developed in this work, which can predict the surface free energy of solid materials and interfacial energy directly through cohesive energy calculations based on COSMO-UCE. The applications of this model in prediction of IFT for water-organic, solid (n-hexatriacontane, polytetrafluoroethylene (PTFE) and octadecyl-amine monolayer)-liquid systems have been verified extensively with successful results; which indicates that this is a straightforward and reliable model of surface and interfacial energies through predicting intermolecular interactions based on merely molecular structure (profiles of surface segment charge density), the dimensionless wetting coefficient R_A/C can characterize the wetting behavior (poor adhesive (non-wetting), wetting, spreading) of liquids on the surface of solid materials very well.