多孔有机含BINAP聚合物负载Rh催化剂在苯乙烯不对称氢甲酰化中的应用:柔性手性口袋对产物对映体选择性的提高作用

不对称氢甲酰化是合成具有单一光学活性物质(如光学活性的醛、α-氨基酸和醇等)最为重要的反应之一.尽管不对称氢甲酰化反应的研究超过40年,但仍然是催化体系中具有挑战性的课题.该反应涉及到产物的化学选择性、立体选择性和对映体选择性的优化.目前,在Rh催化体系中,使用磷-亚磷酸酯手性配体或双亚磷酸酯配体可以在不对称氢甲酰化反应中取得优异的催化性能.然而在Rh/手性双膦配体催化体系中,不对称氢甲酰化反应性能通常很低.以BINAP配体为例,负载Rh金属后,在催化苯乙烯不对称氢甲酰化反应中,产物的ee值只有25％.同时,由于均相催化体系存在催化剂回收和产物提纯等问题,因此有必要研究多相不对称氢甲酰化反应催化剂.本文使用乙烯基修饰的BINAP配体5,5'-divinyl-BINAP与具有不同结构的共聚单体二乙烯基苯或1,3,5-三乙烯基苯基苯共聚,得到具有不同孔结构的聚合物Poly-1和Poly-2.为了比较,利用线性共聚单体乙二醇二甲基丙烯酸甲酯与乙烯基BINAP共聚得到聚合物Poly-3.上述三种聚合物材料负载金属Rh后,用作苯乙烯不对称氢甲酰化反应的催化剂.固体13C核磁分析表明,三种聚合物材料负载金属后仍然保持较为稳定的C骨架结构.通过31p核磁可以看到,嵌入在材料骨架中的BIANP仍然保持未被氧化的状态.N2物理吸附结果发现Poly-1和Poly-2具有较大的比表面积和孔体积,而Poly-3的比表面积最小.热重分析显示,这些材料具有较高的热稳定性.在不同反应溶剂中催化剂活性差异较大.通过优化反应温度和合成气压力后,催化剂Rh/Poly-1在80℃和0.2 MPa下产物的对映体选择性可高达58.9％,支链醛与直链醛的比值为8.5;而在相同反应条件下,均相催化剂Rh-BINAP的ee值仅为35.3％,但高于Rh/Poly-3.这是由于三个多相催化剂骨架中BINAP周围环境不同所致.前两个催化剂中,BINAP与空间位阻较大的单体相连接,使得反应底物按照特定方向与催化活性位点接触,形成了类似于手性口袋的结构.而Rh/Poly-3中,BIANP周围是线性的共聚单体,不能形成有效的手性口袋结构.Rh/Poly-1重复使用7次后,催化活性没有显著下降.拓展X射线吸收精细结构表征结果表明,Rh/Poly-1催化剂使用前没有Rh-Rh键存在,但经重复使用后,Rh金属部分聚集,生成了Rh-Rh键.球差电镜照片也证实了这一点.     

ZnO/BiOI微球的合成及其光催化性能

通过一步溶剂热法合成ZnO/BiOI纳米复合材料,在Bi（NO₃）₃·6H₂O、KI、ZnO和乙二醇（EG）溶剂中,制备出的样品尺寸和形貌采用X射线粉末衍射（XRD）、场发射扫描电镜（FESEM）、高分辨透射电镜（HRTEM）、紫外-可见漫反射光谱（DRS）、X射线光电子能谱（XPS）、N₂吸附-脱附等,对实验所得产物的组成、结构及光学性质等进行表征。以染料罗丹明B（RhB）水溶液和气态乙醛作为降解对象,采用BiOI、ZnO/BiOI和ZnO微纳材料作为光催化剂,通过对BiOI、ZnO/BiOI和ZnO微纳材料在可见光下光催化降解染料罗丹明B（RhB）水溶液和气态乙醛,结果表明多孔微纳材料的ZnO/BiOI具有更高的降解效率,实验表明多孔微纳材料的ZnO/BiOI具有更高的氧空位浓度,因此使其催化活性增强,讨论了其可能的催化活性机理。     

Porous Medium Flow with Both a Fractional Potential Pressure and Fractional Time Derivative

The authors study a porous medium equation with a right-hand side. The operator has nonlocal diffusion effects given by an inverse fractional Laplacian operator.The derivative in time is also fractional and is of Caputo-type, which takes into account"memory". The precise model isD_t~αu- div(u(-Δ)~(-σ)u) = f, 0 σ 1/2.This paper poses the problem over {t ∈ R~+, x ∈ R~n} with nonnegative initial data u(0, x) ≥0 as well as the right-hand side f ≥ 0. The existence for weak solutions when f, u(0, x)have exponential decay at infinity is proved. The main result is H¨older continuity for such weak solutions.     

A Simple and Highly Stable Porous Gold‐based Electrochemical Sensor for Bisphenol A Detection

A porous gold electrode with a uniform pore size was prepared by a simple single potential step method. It provided around 19 times more surface area than a bare gold electrode. The porous gold electrode, without any modification, exhibited good electrocatalytic activity towards the oxidation of bisphenol A (BPA). The effect of the pH and scan rate, on the porous gold electrode was studied and discussed. Under optimum conditions of the flow system, the calibration plot of BPA was linear over a wide range of concentration, from 2.0 nM to 800 nM (R²=0.999), and the detection limit was 2.0 nM (s/n=3). It was of interest that, the porous gold electrode showed an exceptional result in minimizing the fouling from the oxidation product of BPA and led to a very high operational stability of the electrode for the detection of BPA (560 consecutive times). The porous gold electrode showed good fabrication reproducibility and can be used to detect bisphenol A that leached from baby bottles and drinking water bottles. The obtained results were in good agreement with the GC‐MS method (P >0.05).     

Flow through a laboratory sediment sample by computer simulation modeling

A laboratory sediment sample is digitized by X-ray computed tomography system to obtain a host matrix of size 100³${100}^3$ of porosity 0.282. Flow through the porous medium is studied by an interacting lattice gas model for fluid driven by pressure bias. The bias H(0?H?1)$H(0?H?1)$ is implemented via soft and hard pressure constraints in selecting the stochastic movement of fluid particles. The response of fluid flux density to bias H is nearly linear with soft pressure; it becomes nonmonotonic with the hard pressure.     

测量土、岩石介质中的动态应力用的压电式应力计

本文介绍一种压电式应力计,它的主要性能是:测量量程为10-1000kgf/cm~2;响应时间小于7μs;线性误差小于士1％;综合应力测量误差小于±10％,该应力计可用于测量土、岩石和混凝土介质中的动态应力,也可用于测量动态力和流体介质中的动态压力。     

新型甲醛多孔硅复合传感器的制备

构建了一种简便、快速检测甲醛的新型钯-多孔硅(Pd-PS)复合传感器.采用水热腐蚀法制备多孔硅,通过扫描电镜表征其表面微结构.对多孔硅腐蚀条件进行了优化,得出多孔硅的最佳制备条件.多孔硅经化学浸渍法在其表面掺杂金属钯,进而制成了钯-多孔硅复合传感器.当此传感器被置于含甲醛的混合气体中时,可高选择性结合甲醛气体分子,并产生电信号,其强度与甲醛浓度相关,通过万用表检测其电信号,进而分析其气敏性能.检测结果表明,此传感器对甲醛气体敏感,且表现出良好的选择性,对乙醇、氨气、甲醇和丙酮不敏感.此传感器对甲醛浓度的检测范围在0.1～ 6.0 mg/m3之间,检出限为0.1 mg/m3,检测时间为3 min.     

Highly-sensitive electrochemical sensing platforms for food colourants based on the property-tuning of porous carbon

It is very challenging to develop highly-sensitive analytical platforms for toxic synthetic colourants that widely added in food samples. Herein, a series of porous carbon (PC) was prepared using CaCO₃ nanoparticles (nano-CaCO₃) as the hard template and starch as the carbon precursor. Characterizations of scanning electron microscopy and transmission electron microscopy indicated that the morphology and porous structure were controlled by the weight ratio of starch and nano-CaCO₃. The electrochemical behaviours of four kinds of widely-used food colourants, Sunset yellow, Tartrazine, Ponceau 4R and Allura red, were studied. On the surface of PC samples, the oxidation signals of colourants enhanced obviously, and more importantly, the signal enhancement abilities of PC were also dependent on the starch/nano-CaCO₃ weight ratio. The greatly-increased electron transfer ability and accumulation efficiency were the main reason for the enhanced signals of colourants, as confirmed by electrochemical impedance spectroscopy and chronocoulometry. The prepared PC-2 sample by 1:1 starch/nano-CaCO₃ weight ratio was more active for the oxidation of food colourtants, and increased the signals by 89.4-fold, 79.3-fold, 47.3-fold and 50.7-fold for Sunset yellow, Tartrazine, Ponceau 4R and Allura red. As a result, a highly-sensitive electrochemical sensing platform was developed, and the detection limits were 1.4, 3.5, 2.1 and 1.7 μg L⁻¹ for Sunset yellow, Tartrazine, Ponceau 4R and Allura red. The practical application of this new sensing platform was demonstrated using drink samples, and the detected results consisted with the values that obtained by high-performance liquid chromatography.     

Determination of Nitrates in Water Samples by In‐Electrode Coulometric Titration in Copper Coated Porous Vitreous Carbon Electrode

Nitrate in water samples was determined by in‐electrode coulometric titration in porous electrode made of vitreous carbon particles coated with copper. The sample was mixed with diluted sulfuric acid containing 1 mmol/L hydrochloric acid, the solution was filled into the cell and electrode and the nitrate ions were directly reduced by constant current to ammonium ions. The stoichiometry of the electrode reaction was found by coulometric and photometric measurements. The detection limit and precision were found to be 0.2 mg/L and 1.7 %, respectively. The interfering effect of high chloride contents was eliminated by precipitating chlorides with silver sulfate. The method was applied for the analysis of various water samples and beverages. The results were in good agreement with data from isotachophoretic and photometric measurements.