Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review.     

季戊四醇的超分子化学

介绍季戊四醇的超分子化学,包括超分子网状结构、螺环冠醚、非常规液晶、富勒烯衍生物、固相光催化反应、Janus树枝状分子等等。     

Towards an Environmentally Acceptable Heterogeneous Catalytic Method of Producing Adipic Acid by the Oxidation of Hydrocarbons in Air

A survey is given of the catalytic methods potentially available for the production of adipic acid by the oxidation of readily available hydrocarbon precursors under environmentally benign conditions. Encouraging results are reported using H₂O₂ as oxidant and microporous FeAlPO-5 as catalyst at moderate temperatures.     

Understanding heterogeneous catalysis on an atomic scale: a combined surface science and reactivity investigation for the dehydrogenation of ethylbenzene over iron oxide catalysts

In order to study the dehydrogenation of ethylbenzene to styrene, epitaxial iron oxide model catalyst films with Fe₃O₄(111), -Fe₂O₃(0001) and KFe _x O _y (111) stoichiometry were prepared in single crystal quality on Pt(111). They were investigated using surface science techniques before and after atmospheric pressure reaction experiments in a newly designed single crystal flow reactor. As expected from low-pressure measurements, Fe₃O₄(111) is catalytically inactive. The catalytic activity of -Fe₂O₃(0001) starts after an activation period of about 45 min. After that, the surface is essentially clean but shows a high concentration of defects. On the potassium-promoted films, however, the activation period is much longer, the activity then is higher and the surface gets covered completely with carbon and oxygen during reaction. This indicates a different reaction pathway on the promoted films with a carbon–oxygen species as catalytically active species.     

湍流化学反应的分形数值模拟

基于涡串唯象概念和分形理论,建立了能够表达湍流多尺度结构物理特性的分形湍流化学反应模型,针对Steckler室内燃烧过程进行了数值模拟研究.湍流流动采用浮力修正的κ-ε双方程模型来模拟,辐射由Rosseland模型描述,整个模拟过程由ANSYS-CFX10.0实现.将模拟结果与Steckler的燃烧实验数据进行对比,并与EDC燃烧模型及文献中EBU燃烧模型的模拟结果进行对比.结果表明,FM燃烧模型模拟得出的温度、速度场分布与实验数据能够较好地吻合,是一种有前途的湍流化学反应模拟方法.     

淀粉分子磁化修饰及其再生膜材料制备

以高直链淀粉（HS）为原料，通过“还原胺化-点击化学法”在其还原性端的潜在醛基上进行磁化分子修饰，得到具有磁性的变性淀粉（MMS），并在外磁场作用下制备再生淀粉膜。具体包括在HS分子唯一的潜在醛基上引入炔基，对四氧化三铁粒子（MNP）进行硅烷包覆得到叠氮化磁体粒子（azide-MNPs），两者经点击化学反应得到分子链末端带磁的变性淀粉。借助XRD、FTIR、NMR和MALDI-TOF MS对产物进行结构表征，结果表明，磁体粒子精准接枝到高直链淀粉分子还原末端，得到目标产物MMS。再生淀粉膜性能测试结果表明，在外磁场诱导条件下MMS逐渐趋于分子有序排列，制得的再生淀粉膜较纯CMS淀粉膜断裂伸长提升49.5%，断裂强度提升88.3%，短程有序程度提高。该文为基于外加磁场下的淀粉再生膜结构设计和力学性能调控提供了新思路。     

磷钨酸催化合成丁酮乙二醇缩酮

以磷钨酸H3 PW12 O40 为催化剂 ,通过丁酮和乙二醇反应合成丁酮乙二醇缩酮。探讨了H3 PW12 O40 对缩酮反应的催化活性 ,较系统地研究了酮醇物质的量比、催化剂用量、反应时间等因素对产品收率的影响。实验表明 :H3 PW12 O40 是合成丁酮乙二醇缩酮的良好催化剂 ,在n(酮 )∶n(醇 ) =1∶1.75 ,催化剂用量为反应物料总质量的 1.2 5 % ,环己烷为带水剂 ,反应时间 2 .0h ,反应温度 72～ 96℃的优化条件下 ,丁酮乙二醇缩酮的收率可达 5 9.5 %。     

二氧化氯的生产和应用评述

详细评述了 2 0世纪二氧化氯的主要生产工艺和制备方法及二氧化氯作为漂白剂、消毒杀菌剂、水处理剂等在多种行业中的应用 ,分析展望了 2 1世纪二氧化氯的生产和应用前景 ,认为应在我国大力发展二氧化氯的生产并促进其应用。     

固体推进剂燃烧机理诊断方法的研究进展

介绍和评述了诊断含能材料热分解和推进剂燃烧波结构的方法、仪器和研究进展,以及含能材料和推进剂热分解和燃烧波结构的研究结果,探讨了燃烧机理研究方法的发展方向。提出需要不断完善和更新推进剂燃烧的诊断方法,以获得更为全面的接近真实条件下推进剂燃烧的有效信息。附参考文献14篇。     

环糊精及其包合物的研究与应用

介绍了环糊精及其包合物的合成、结构、包合物形成的热力学与动力学等的研究概况，着重叙述了环糊精的包合作用与环糊精的修饰，描绘了环糊精化学的应用与发展前景。