H-SAPO-18催化甲醇制烯烃反应的芳烃烃池机理：基于范德华校正的密度泛函理论研究

由于可以从非石油资源如煤、天然气、生物质等出发制备低碳烯烃,分子筛催化甲醇制烯烃(MTO)反应在学术界和工业界引起了广泛的研究兴趣. H-SAPO-34是目前表现优异性能的分子筛催化剂之一,其双烯(乙烯+丙烯)的选择性在80%以上,已经实现了工业化应用.为了提升MTO反应的选择性,以及调控乙烯丙烯的选择性之比,非常有必要从反应机理出发来优化设计新的催化剂.然而,由于MTO催化反应产物复杂多样,对MTO反应机理的认识还存在很大的争议.目前基本能够接受的是MTO催化反应沿着烃池机理进行.在此反应机理中,无机分子筛和有机烃池活性中心形成共催化剂,甲醇进攻有机活性中心生成烷基链,此烷基链断裂得到烯烃产物.目前提出的烃池活性中心主要包括多甲基苯和烯烃自身,它们分别沿着各自的循环反应网络(芳烃循环和烯烃循环)生成烯烃产物.有文献指出在H-ZSM-5分子筛中芳烃循环主要生成乙烯,而烯烃循环主要生成丙烯等产物.因此,系统研究分子筛结构对两条循环网络相对贡献程度的影响规律,从而阐述分子筛结构和MTO催化性能之间的关系具有重要的意义. H-SAPO-18是一类结构上与H-SAPO-34相类似的分子筛,其笼由八元环孔道互联.实验研究指出,其也具有优异的MTO催化性能.在本工作中,我们利用包含范德华相互作用校正的交换相关泛函(BEEF-vdW),系统研究了H-SAPO-18分子筛中的芳烃循环反应机理.所有计算用VASP程序包完成, H-SAPO-18用48T周期性结构模型表示.利用静态吸附和相互转化的自由能变化情况,我们首先确认了反应条件下H-SAPO-18中最稳定的多甲基苯的结构.计算结果指出,1,2,4,5-四甲基苯的吸附能最强,而六甲基苯是主要存在的多甲基苯组分.多甲基苯在分子筛孔道内的稳定性主要由两个相反的作用共同影响：范德华相互作用引起的吸引,以及分子筛孔道结构引起的排斥.在芳烃循环路线中,乙基侧链的增长是反应的关键基元步.吉布斯自由能分析指出芳烃循环路线中,在反应温度673 K下H-SAPO-18中的六甲基苯并不比五甲基苯,四甲基苯的活性高,这与H-SAPO-34分子筛中的结果相一致. H-SAPO-18中的四甲基苯、五甲基苯和六甲基苯的总吉布斯自由能垒分别是208,215,239 kJ/mol.六甲基苯循环路线所表现出的高反应能垒的一个原因,是由于分子筛几何限域效应引起的熵增加所致.通过与烯烃循环路线的动力学进行比较,本文芳烃循环路线动力学的工作可以为MTO催化反应机理的研究提供一些启示.     

THERMODYNAMIC AND PARTICLE-DYNAMIC STUDIES ON SYNTHESIS OF SILICA NANOPARTICLES USING MICROWAVE-INDUCED PLASMA CVD

1. Introduction1.1 Silica nanoparticles and synthesis methods Silica (SiO2) nanoparticles are widely used in industry asan active filler for polymer reinforcement, a rheologicaladditive in fluids, a free flow agent in powders, and anagent for chemical mechanical polishing during IC (inte-grated circuit) fabrication (Sniegowski & de Boer, 2000).Silica powder is also used for producing silicon carbide(Koc & Cattamanchi, 1998) or opaque silica aerosols (Leeet al., 1995). Many methods can …     

OFDMA中继系统中基于QoS保证的资源分配算法

研究了 OFDMA 中继下行链路通信系统中的动态资源分配问题,提出了一种可以保证用户最低 QoS 需求的资源分配算法.首先在简化资源优化问题的过程中,采用等功率分配方法以降低算法复杂度,然后通过拉格朗日松弛优化方法推导出了子载波分配和中继选择最优解,并在此基础上引入用户速率权衡因子,根据速率权衡因子越大的用户,越具有选择子载波和中继的优先权这一准则进行子载波分配和中继选择.仿真结果表明:新算法能够获得较高的系统容量,同时也能很好地保证不同用户的最低速率需求.     

Synthesis and gelation behaviors of five new dimeric cholesteryl derivatives

Five new diacid amides of di-cholesteryl L-glycinates were designed and prepared.The compounds with linkers containing 0,1, 2,3,or 4 methylene units are denoted as 1,2,3,4,and 5,respectively.Their gelation behaviors in 25 solvents were tested as novel low-molecular-mass organic gelators(LMOGs).It was shown that the length of the linker connecting the two-cholesteryl residues in a gelator plays a crucial role in the gelation behavior of the compound.1 gels 11 of the 25 solvents tested at a concentration lowe...     

CHARACTERIZATIONS AND RELATIONSHIPS BETWEEN OUTDOOR AND INDOOR BIOAEROSOLS IN AN OFFICE BUILDING

1.IntroductionBioaerosolsaremicroorganismsorparticles,gases,vapors,orfragmentsofbiologicalorigin(i.e.,aliveorreleasedfromalivingorganism)thatexistintheair.Bioaerosolsareeverywhereintheenvironment.Underfavorableconditions,bioaerosolsareabletogrowandpropagateonavarietyofbuildingmaterialsandindoorsurfaces,causingindoorairpollution.Therefore,owingtotheirubiquitouspresenceinnature,bioaerosolsasapollutionsourcearealmostinevitableinarangeofenclosedenvironmentsandincommunityair(Kodama&McGee,1986;Lig…     

Synthesis and Crystal Structure of Triethyl 1,2,2-triphenylpyrrolidine-3,4,5-tricarboxylate,A Proline Derivative

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Two New Diterpene Alkaloids from the Roots of Spiraea japonica var. Acuta

Spiraea japonica L. (Rosaceae) is widely distributed in Yunnan Provence, P. R. China. Previous chemical investigations on S. japonica and its varieties have led to the report of 7 new atisane-type diterpenoids and 38 new diterpene alkaloids of atisine- and hetisine-type1-11. This paper describes the isolation and structure elucidation of two new diterpene alkaloids named spiratines A and B (1-2). Their structures were elucidated on the basis of 1D and 2D NMR experiments (HMQC, HMBC, 1…