MCNOs/CdS双效光催化剂的制备及其性能研究

水热合成法制备了不同磁性纳米洋葱碳(MCNOs)负载量(0%、1%、3%、5%)的MCNOs/CdS光催化剂。并通过X射线衍射分析(XRD)、扫描电子显微镜(SEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)、紫外可见光光谱(UV-Vis)、磁滞回线测定仪(VSM)对其进行表征,探究了MCNOs负载比例对催化剂在可见光下降解RhB性能及机理的影响。结果表明,MCNOs能有效提高CdS的光催化效果,复合3%MCNOs后降解率为96%,与纯CdS相比降解率提高了30%,磁性分析表明,其具有良好的顺磁性并能实现催化剂的有效回收。MCNOs/CdS在可见光下催化降解RhB的一级反应动力学直线有较好的拟合度,表明制备的催化剂有较好的催化活性。     

气相输运沉积制备c轴择优取向的碘化铋薄膜

铋基卤化物材料因其无毒和优良的光电性能而显示出巨大的应用潜力。BiI₃作为一种层状重金属半导体,已被用于X射线检测、γ射线检测和压力传感器等领域,最近其作为一种薄膜太阳能电池吸收材料备受关注。本文采用简单的气相输运沉积(VTD)法,以BiI₃晶体粉末作为蒸发源,在玻璃基底上得到高质量c轴择优取向的BiI₃薄膜。并通过研究蒸发源温度和沉积距离对薄膜物相和形貌的影响,分析了BiI₃薄膜择优生长的机理。结果表明VTD法制备的BiI₃薄膜属于三斜晶系,其光学带隙为~1.8 eV。沉积温度对薄膜的择优取向有较大影响,在沉积温度低于270 ℃时,沉积的薄膜具有沿c轴择优取向生长的特点,超过此温度,c轴择优取向生长消失。在衬底温度为250 ℃、沉积距离为15 cm时制备的薄膜结晶性能最好,晶体形貌为片状八面体。     

Current trends in the description of lanthanum strontium manganite oxygen electrode reaction mechanism in a high-temperature solid oxide cell

This review summarizes recent progress in understanding the oxygen reduction and evolution reactions at the lanthanum strontium manganite electrode of a high-temperature solid oxide cell. Information provided here is put into the perspective of the defect chemistry of lanthanum strontium manganite and its impact on the electrode reaction mechanisms itself. After summarizing recent views on the oxygen reduction reaction mechanism, the focus turns to the oxygen evolution reaction, which is significantly less treated in the literature. A combination of the information in the literature on both reactions was the basis for modified reaction mechanism of the oxygen evolution reaction to be proposed under consideration of recent experimental observations and theoretical findings.     

1,3-丁二烯选择性加氢催化剂的设计策略以及构效关系

催化裂化是石油化工的核心单元之一.从催化裂化尾气中分离出来的碳四馏分富含许多的不饱和烯烃,如1-丁烯、顺、反式-2-丁烯以及少量的1,3-丁二烯,这些不饱和烯烃可以通过后续聚合反应,生成合成橡胶和工程塑料的重要原料,具有重要的应用价值.上述工艺过程对原料中1,3-丁二烯的含量(<100~200 ppm)有严苛的要求.采用选择性加氢技术对碳四馏分中的1,3-丁二烯进行选择性加氢,将其转化为更高附加值的单烯烃是一个理想的解决方案.然而,1,3-丁二烯加氢反应得到的单烯烃可能发生深度加氢得到副产物丁烷.因此,开发高效选择性加氢催化剂对碳四资源的利用具有重要的现实意义.另一方面,1,3-丁二烯加氢反应可以作为模型反应,用来考察选择性加氢催化剂的性能.基于此,该反应无论在工业界还是学术界均受到广泛关注.尽管如此,有关1,3-丁二烯加氢催化剂研究进展方面的综述极少.仅有关于1,3-丁二烯加氢作为模型反应的综述报道.本文对过去半个世纪以来1,3-丁二烯加氢反应中不同催化剂的发展历程进行系统综述,特别是包括Pd,Pt和Au等的单一贵金属催化剂.重点介绍以下内容:(1)固体催化剂构效关系,包括活性金属尺寸效应、晶面和形貌效应以及载体效应(晶相、孔道和酸碱性);(2)高性能催化剂的设计新策略,如单原子催化剂、核壳结构催化剂、金属-离子液复合催化体系以及载体的形貌调控;(3)催化剂的反应机理和失活机理.提出了1,3-丁二烯选择性加氢高性能催化剂开发面临的挑战,并对潜在的发展方向进行了展望.本文认为随着纳米技术和金属纳米材料合成方法的快速发展,对贵金属活性组分进行原子层面上的调控(包括形貌、尺寸以及单原子配位环境等)已成为可能.这将有助于研制出一类新型高性能选择性加氢催化材料,从而实现高转化率条件下高附加值单烯烃的定向转化.此外,载体的酸碱性和孔道结构的调控有助于进一步调节催化剂的抗积炭性能,也是未来发展的一个重要方向.     

Properties of the Reactants and Their Interactions within and with the Enzyme Binding Cavity Determine Reaction Selectivities. The Case of Fe(II)/2-Oxoglutarate Dependent Enzymes

Fe(II)/2-oxoglutarate dependent dioxygenases (ODDs) share a double stranded beta helix (DSBH) fold and utilise a common reactive intermediate, ferryl species, to catalyse oxidative transformations of substrates. Despite the structural similarities, ODDs accept a variety of substrates and facilitate a wide range of reactions, that is hydroxylations, desaturations, (oxa)cyclisations and ring rearrangements. In this review we present and discuss the factors contributing to the observed (regio)selectivities of ODDs. They span from inherent properties of the reactants, that is, substrate molecule and iron cofactor, to the interactions between the substrate and the enzyme's binding cavity; the latter can counterbalance the effect of the former. Based on results of both experimental and computational studies dedicated to ODDs, we also line out the properties of the reactants which promote reaction outcomes other than the “default” hydroxylation. It turns out that the reaction selectivity depends on a delicate balance of interactions between the components of the investigated system.     

Key Role of a-Top CO on Terrace Sites of Metallic Pd Clusters for CO Oxidation

Pd-based catalysts are the most widely used for CO oxidation because of their outstanding catalytic activity and thermal stability. However, fundamental understanding of the detailed catalytic processes occurring on Pd-based catalysts under realistic conditions is still lacking. In this study, we investigated CO oxidation on metallic Pd clusters supported on Al₂O₃ and SiO₂. High-angle annular dark-field scanning transmission electron microscopy revealed the formation of similar-sized Pd clusters on Al₂O₃ and SiO₂. In contrast, CO chemisorption analysis indicated a gradual change in the dispersion of Pd (from 0.79 to 0.2) on Pd/Al₂O₃ and a marginal change in the dispersion (from 0.4 to 0.24) on Pd/SiO₂ as the Pd loading increased from 0.27 to 5.5 wt %; these changes were attributed to differences in the metal-support interactions. Diffuse reflectance infrared Fourier-transform spectroscopy revealed that fewer a-top CO species were present in Pd supported on Al₂O₃ than those in Pd supported on SiO₂, which is related to the morphological differences in the metallic Pd clusters on these two supports. Despite the different dispersion profiles and surface characteristics of Pd, O₂ titration demonstrated that linearly bound CO (with an infrared signal at 2090 cm⁻¹) reacted first with oxygen in the case of CO-saturated Pd on Al₂O₃ and SiO₂, which suggests that a-top CO on the terrace site plays an important role in CO oxidation. The experimental observations were corroborated by periodic density functional calculations, which confirmed that CO oxidation on the (111) terrace sites is most plausible, both kinetically and thermodynamically, compared to that on the edge or corner sites. This study will deepen the fundamental understanding of the effect of Pd clusters on CO oxidation under reaction conditions.     

新型暂堵酸化用自降解暂堵剂的制备及现场应用

针对传统暂堵酸化用暂堵剂颗粒耐酸性差、降解性差和除堵工艺复杂等问题，本研究通过水溶液自由基聚合法制备了一种新型的自降解暂堵剂CQZDJ。考察了单体加量、交联剂加量、引发剂加量对CQZDJ凝胶强度和降解性的影响；通过FT-IR、TGA、SEM对其结构进行表征；并对其降解机理进行了探讨；最后在长8区块的环平81-8实验井进行了现场实践。结果表明：CQZDJ凝胶强度及降解时间与单体加量、交联剂加量、引发剂加量成正比关系，且降解时间可控；降解性实验表明CQZDJ在(1%~10%)HCl溶液、水、（2%~10%）NaCl溶液中均可在4 d内完全降解，具备良好的降解性能，对地层伤害小；SEM照片显示CQZDJ的降解过程是从初始三维网状结构逐渐崩解为层状结构，最终降解为无规则线性小分子链的过程；暂堵后现场流压上升6.3 MPa，日产油由3.87 t/d增产至5.22 t/d，实现了储层的有效改造，增产效果显著。      

硫化丁苯橡胶纳观界面耐磨机理及参数影响分析

硫化橡胶因其良好的力学和物理化学性能而被广泛作为摩擦副的基础材料. 本文提出了一种硫化交联算法, 实现了C—C键的硫化互交联和自交联, 构建了硫化丁苯橡胶的分子动力学磨损模型, 从微观摩擦学的角度阐明了硫化交联结构对改善丁苯橡胶磨损性能的机理, 研究了不同界面参数对硫化橡胶微观磨损性能的影响. 结果发现 硫化使丁苯橡胶分子链的界面黏附能力和活动能力更弱, 拉伸和解缠能力更低, 磨损过程中界面累积能量更低, 更不容易脱离橡胶基体, 因此可以表现出更好的摩擦学性能, 更强的抗磨损性能; 随着速度的增大, 硫化橡胶的磨损率降低, 与宏观实验结果一致, 原因是硫化橡胶的原子分布函数和相互作用能随着速度增大而降低, 说明橡胶分子链的黏附能力和活动能力随着速度增加趋弱, 温升更低, 导致较低的磨损率; 压入深度对磨损率的影响规律则呈现相反的结果和趋势.     

基于电化学老化衰退模型的锂离子动力电池外特性

当前锂离子动力电池电化学模型存在模型复杂、建模难度大、计算效率低、老化评估效果差的问题,本文提出一种考虑电池衰退老化的机理模型(ADME).本文首先通过有限差分法对伪二维(P2D)电化学模型进行离散降阶处理,得到简化伪二维(SP2D)模型.在SP2D模型的基础上,基于阴阳两极发生的副反应导致的衰退老化现象,提出一种考虑电池衰退老化的机理模型.其次,使用多变量偏差补偿最小二乘法实现模型参数辨识.最后通过动力电池衰退老化性能循环实验,对比分析了恒流、脉冲工况下SP2D模型和ADME模型的终端电压输出.结果表明:ADME模型较为简单、计算效率和估算精度高,可以有效评估电池容量老化衰退,得到理想的锂离子动力电池外特性曲线.