铈基催化剂的密度泛函理论研究进展

铈基催化剂是重要的汽车尾气三元转化(TWCs)及挥发性有机废气(VOCs)氧化催化剂,从理论上系统研究载体、活性组分的性质及其相互作用,反应物在铈基催化剂上吸附与反应行为,可认识催化现象的电子本质,加深反应机制的理解,为催化剂的设计提供理论参考与依据。本文通过CeO2体相、表面、氧空位、团簇性质,探针分子在CeO2表面吸附反应行为,金属铈基催化剂性质及探针分子在其表面吸附与反应等4个方面对近年来的研究工作进行了综述,指出了铈基催化剂研究的方向与前景。     

海萤荧光素衍生物发光反应关键步骤的理论研究

用不同取代基对化学发光物质6-芳基-2-甲基咪唑[1,2-α]吡嗪-3-(7H)酮环(海萤发光的类似物)的芳基位进行取代,形成系列海萤荧光素类似物MIPa-MIPd;并采用B3LYP/6-311+G(d,p)方法,通过电子抽取能(EEP)的计算和自然电荷布居分析(NPA),研究了在气相、二甲亚砜(DMSO)和二甘醇二甲醚(DG)中海萤发光的类似物从阴离子变化到自由基过程中取代基的作用.结果表明:在这个过程中,吲哚在DG中作为取代基(MIPb)时的EEP最小,电荷变化最大,说明这种取代基有利于反应的进行.     

Kinetic simulation of oxidative coupling of methane over perovskite catalyst by genetic algorithm： Mechanistic aspects

The reaction kinetics of oxidative coupling of methane catalyzed by perovskite was studied in a fixed bed flow reactor. At atmospheric pressure, the reactions were carried out at 725, 750 and 775 ℃, inlet methane to oxygen ratios of 2 to 4.5 and gas hourly space velocity (GHSV) of 100 min-1. Correlation of the kinetic data has been performed with the proposed mechanisms. The selected equations have been regressed with experimental data accompanied by genetic algorithm (GA) in order to obtain optimized parameters. After investigation the Langmuir-Hinshelwood mechanism was selected as the best mechanism, and Arrhenius and adsorption parameters of this model were obtained by linear regression. In this research the Marquardt algorithm was also used and its results were compared with those of genetic algorithm. It should be noted that the Marquardt algorithm is sensitive to the selection of initial values and there is possibility to trap in a local minimum.     

Kinetics of the water-gas shift reaction in Fischer-Tropsch synthesis over a nano-structured iron catalyst

Based on formate and direct oxidation mechanisms, three Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic models of the water-gasshift (WGS) reaction over a nano-structured iron catalyst under Fischer-Tropsch synthesis (FTS) reaction conditions were derived and compared with those over the conventional catalyst. The conventional and nanostructured Fe/Cu/La/Si catalysts were prepared by co-precipitation of Fe and Cu nitrates in aqueous media and water-oil micro-emulsion, respectively. The WGS kinetic data were measured by experiments over a wide range of reaction conditions and comparisons were also made for various rate equations. WGS rate expressions based on the formate mechanism with the assumption that the formation of formate is rate determining step were found to be the best.     

层状复合氢氧化物的药物控释动力学机制

以层状复合氢氧化物(LDH)为载体组装乙酰苯甲酸(ASP)的插层复合物LDH-ASP,以pH2.48~6.89的磷酸盐溶液为介质进行药物释放动力学实验,通过对不同时间药物释放度的测定及释放药物后载体结构变化分析研究了LDH对层间药物的控制释放机制。结果表明粉末状LDH-ASP能在较宽的pH范围表现明显缓控释作用,药物释放度积分方程与Higchi方程、Ritger-Peppas方程、Bhaskar方程及一级动力学方程等经验模型吻合。复合物与溶出介质的反应机制研究表明,药物释放速率及释放度大小取决于交换配比n(ASP)/n[HnPO4(3-n)-]所决定的LDH层间通道畅阻情况。     

《仿生材料化学》专辑序言——向大自然学习构筑新材料与新体系

从工业4.0到中国制造2025,材料——作为人类社会进步的基石,每一次的重大突破都改变着人类的生产生活方式.每一种新材料的诞生,都有可能颠覆以往的技术手段,加速人类文明的历史进程.因而,设计开发具有独特性能的新材料成为材料、化学、物理等领域科学家们的共同目标.20世纪60年代,"仿生"一词开始出现和使用,标志着仿生学作...     

基于有监督对比学习的遥感图像场景分类

针对遥感场景图像中复杂背景以及类内多样性和类间相似性影响场景分类性能的问题,提出一种基于有监督对比学习的遥感场景分类方法。该方法包含判别性特征学习和线性分类两个阶段。在判别性特征学习阶段,引入有监督对比损失以拉近同类场景间的距离并增大不同类场景间的距离,提高类内多样性和类间相似性场景的判别能力;然后引入门控自注意模块对无用的背景信息进行过滤且聚焦关键场景区域,提高复杂背景的场景识别;最后引入一个预训练的Inception V3语义分支,把语义分支和原始模型提取的特征进行融合增强特征判别能力,以提高场景分类的整体性能。线性分类阶段通过对特征学习阶段训练的模型进行微调获得分类结果。在AID和NWPU-RESISC45数据集上的综合实验证明了所提方法的有效性。     

Mg-PSZ陶瓷在不同环境温度下的摩擦磨损行为与机制研究

研究了氧化镁部分稳定氧化锆陶瓷（Ｍｇ－ＰＳＺ）在不同环境温度下的摩擦磨损行为与机制．结果表明：室温时,Ｍｇ－ＰＳＺ陶瓷的磨损机制主要是微观犁削和微观断裂;温度为２００ ℃时,陶瓷磨损表面形成的针（轴）状磨屑呈现“滚动轴承”效应,表现出最低的摩擦系数和磨损率;随着温度的进一步升高磨损率增大;４００ ℃以上时可使偶件的磨损率急剧上升,其磨损机制则转变为脆性断裂和晶粒剥落．     

Ni—W—Co／SiC复合材料磨损特性与磨损机制

研究了ＳｉＣ颗粒和ＳｉＣ晶须为复合第二相的Ｎｉ－Ｗ－Ｃｏ合金基复合材料的磨损特性和磨损机制。结果表明,复合相含量、几何主载荷和滑动速度对复合材料的耐磨性影响很大。其原因在于ＳｉＣ颗粒与ＳｉＣ晶须以不同的形式发生流失。     

Metric Expansion from Microscopic Dynamics in an Inhomogeneous Universe

Theories with ingredients like the Higgs mechanism, gravitons, and inflaton fields rejuvenate the idea that relativistic kinematics is dynamically emergent. Eternal inflation treats the Hubble constant H as depending on location. Microscopic dynamics implies that H is over much smaller lengths than pocket universes to be understood as a local space reproduction rate. We illustrate this via discussing that even exponential inflation in TeV-gravity is slow on the relevant time scale. In our on small scales inhomogeneous cosmos, a reproduction rate H depends on position. We therefore discuss Einstein-Strauss vacuoles and a Lindquist-Wheeler like lattice to connect the local rate properly with the scaling of an expanding cosmos. Consistency allows H to locally depend on Weyl curvature similar to vacuum polarization. We derive a proportionality constant known from Kepler＇s third law and discuss the implications for the finiteness of the cosmological constant.