重审人类赖以生存的科学——化学的定义

当代高科技飞速发展与当今地球环境日趋恶化，赋现代化学以新的机遇与挑战。为协调人与自然的关系、明确化学学科肩负的使命，重新审视化学学科意义已成为人们日益关注的热点。本文尝试的哲学观社会观，企求赋化学定义以较为完善的时代表述

柠檬酸镍(Ⅱ)配合物的合成、光谱和晶体结构

在弱酸性介质中，氯化镍和柠檬酸铵反应可得到镍水合离子与二聚柠檬酸镍配离子的加合配合物（ＮＨ４）［Ｎｉ（Ｈ２Ｏ）６］［Ｎｉ（Ｈｃｉｔ）（Ｈ２Ｏ）２］４·１０Ｈ２Ｏ１。该配合物的晶体属三斜晶系，空间群为Ｐ１，晶胞参数：ａ＝９．７２７３（９），ｂ＝１２．０３４（２），ｃ＝１３．３４８（２），α＝６３．５４（２），β＝８８．４５（１），γ＝８６．２８（１）°，Ｖ＝１３９５．９（３）３，Ｚ＝１，配合物的阳离子为两个铵离子和一个六水合镍离子，阴离子由两个二聚柠檬酸镍［Ｎｉ（Ｈｃｉｔ）（Ｈ２Ｏ）２］２－２组成。在不对称的配阴离子中，两个柠檬酸分别以羟基、α－羧基和一个β－羧基同第一个镍配位，剩下的β－羧基作为桥基同另一个镍配位形成二聚体

Basis study on quantum catalysis & molecular dynamics : Ab initio calculation of coordinationadsorption clusters on gas-solid clusters & rempi spectra of allene

要在原子与分子水平上对固体催化剂表面的多相催化反应得到微观的理解，气相反应分子在固体表面的分子反应动态学的研究是至关重要的。表面微区配位吸附态是固体表面多相催化的微观基础，现有的可用于原位动态研究的分子光谱如拉曼和红外等所提供的表面反应信息可以说还只是半微观的，不能提供态－态反应的细节。而激光与分子束技术的发展虽已使化学研究达到了态－态反应水平，但由于实验技术和数学处理上的困难，目前还基本上局限于气相的范畴，关于气－固界面微观信息的许多细节还只能借助于量子化学的理论方法和计算来预言。另一方面，对于固体表面配位吸附态的研究以往多着重于被吸附分子（或离子、原子）的活化过程，而忽略了在这一过程中固体...The interaction of gas-surface is much important for the study of the heterogeneous catalysis. The adsorption of small molecules on the micro metal surface is the basis of the solid surface catalysis. Many experiment techniques can give more and more informations of the catalytic reactions, but most of them only offer the semi-micro informations. Some micro details only can be described and predic...学位：理学硕士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：19962502

DFT Study on Coordination Clusters of N_xH_y-Fe (x=0 - 2, y=0 - 3)

采用杂化密度泛函（ＤＦＴ）之Ｂ３ＬＹＰ／６－３１１Ｇ方法研究了ＮｘＨｙ－Ｆｅ（ｘ＝０～２，ｙ＝０～３）配位簇的几何结构和振动光谱。讨论了在纯铁催化剂上，氮分子和氢分子逐步合成氨的反应机理。结果表明，合成氨过程可能经历Ｎ２和Ｎ２Ｈ２物种。在优化结构的基础上，计算了各个模型的振动频率并解释了有关实验结果。The geometries, energetics and spectroscopic properties of the coordination clusters of NxHy- Fe (x= 0 -2, y = 0 -3) were investigated using B3LYP/6 - 311G method. The mechanism of hydrogenation of nitrogen into ammonia was discussed on the pure iron surface. It was suggested that the ammonia synthesis may pass a way via N2 and N2H2, species. Also, the calculated frequencies are in good agreement with the experiments.国家自然科学基金;; 固体表面物理化学国家重点实验室资助项

The Effect of Supporters and Ruthenium Contents on the Reaction Activity for Ammonia Synthesis

传统的熔铁型合成氨催化剂的使用条件相当苛刻（450℃，1.5~3.5x105PA），近20年来国外一直致力于开发温和条件下使用的钌基合成氨催化剂［1，2］，并已取得了相当的进展［3］，可望在不久的将来完全实现工业化，代替铁基合成氨催化剂，成为一种高效...The effects of different supporters, such as active carbon, γ Al 2O 3、NaX molecular sieve, silica gel, Sm 2O 3, CeO 2, Y 2O 3 and C 60 (6%), and contents (2%￣6%) of ruthenium on reaction activity of ruthenium based catalysts for ammonia synthesis have been studied.The activity for ammonia synthesis of Ru based catalysts supported by different supporters decreased in the sequence of C 60 >Sm 2O 3>CeO 2>Y 2O 3>γ Al 2O 3>NaX>AC>silica gel, and the optimum content of ruthenium is 4 %, under 1×10 5 Pa; the Ru K/C 60 catalyst has the highest activity for ammonia synthesis at 350 ℃.Also, the Ru based catalysts have been characterized by SEM.国家自然科学基金;固体表面物理化学国家重点实验室资

Etherification of Isoamylenes with Methanol in Reactive Distillation Collumn

研究异戊烯和甲醇在反应蒸馏柱中以苯磺酸阳离子交换树脂为催化剂 ,在 40～ 80℃醚化的转化率随反应条件的变化。结果表明 ,在 6 9℃、n(异戊烯 ) /n(甲醇 ) =1/1.2时 ,异戊烯醚化反应的转化率最高 ;反应压力对异戊烯醚化反应的转化率影响不大The change of etherification conversions against reaction conditions has been studied in reactive distillation columns at temperatures of 40～80 ℃.A benzene sulfonate cationexchange resin was used as catalyst.Results show that the conversion is the highest at a temperature of 69 ℃ and a molar ratio of methanol to isoamylenes of 1.2. The etherification conversion of isoamylenes is less dependent on the reaction pressure.These results are of significant importance in the comprehensive utilization of isoamylenes in FCC factory

STUDIES ON CATALYTIC ETHERIFICATION of ISOPENTENE

为了适应环保的要求，世界各国已纷纷明令不准使用含铅汽油，而代之以掺有汽油添加剂的无铅汽油，汽油添加剂主要是一些含氧有机化合物。醚类具有可替代汽油组份、不溶于水、调合辛烷值高、蒸气压低和不污染环境等优点，适合作为汽油添加剂。目前已开发了甲基叔丁基醚（M...The etherification of isopentene by catalyst,benzol sulfonic acid cation exchange resin,has been studied.The results indicats that the resin is an effective catalyst with total conversion of over 97% at 55℃ to 70℃ and CH 3OH/C 5=1.2.The influences of temperature,pressure and CH 3OH/C 5 ratio have also been investigated.国家自然科学基金;固体表面物理化学国家重点实验室;福建炼油厂资

BOC MP Study For Ammonia Synthesis

用键级守恒莫尔势函数法（bOC-MP）研究了铁催化剂表面氨合成反应的缔合式和解离式两种机理，计算表明缔合式机理速控步骤的活化能垒n2，Ad＋HAd→nHAd＋n（92kJMOl-1）低于解离式机理速控步骤nAd＋HAd→nHAd（163kJMOl-1）的活化能垒，但反应n2，Ad→nAd＋nAd（50kJMOl-1）的活化能垒又明显低于缔合式途径速控步骤的活化能垒.由此可推断，在铁催化剂表面存在着两种氨合成竞争反应途径，但缔合式机理在反应能量学上较为有利.Both mechanisms of ammonia synthesis, the associative and the dissociative, on iron catalysts are studied with the Bond order conservation Morse potential (BOC MP) approach.The calculations indicated that the activation barrier of the rate(determining step, N 2,ad +H ad NH ad +N ad (92 kJ mol -1 ) For the associative pathway is lower than that of the N ad +H ad NH ad (163 kJ mol -1 ) For the dissociative pathway.Howerver, the activation barrier For reaction, N 2,ad N ad +N ad (50 kJ mol -1 ) is lower more much than that of rate determining step, N 2,ad +H ad NH ad +N ad For the associative pathway.It is shown that there are two competitive reaction pathways For ammonia synthesis on iron catalysts but the associative pathway is more Favorable in catalytic reaction energy.国家自然科学基金;福建省自然科学基金;国家教委留学回国人员科研资

BOC-MP Study on the Mechanism of Reactions of Methanol on Transition Metals

运用键级守恒莫尔势函数法（bOC-MP）对CH3OH在过渡金属Ag（110）、Cu（111）、Pd（111）、nI（111）、PT（111）面上的解离和临氧条件正气反应机理进行了探讨。结果表明CH3OH在清洁过渡金属表面可能发生C-O键或C-H键的断裂，生成CHX（X＝2，3）物种。在临氧条件下，CH3OH直接氧化生成HCOH。The mechanism of dissociation of methanol and its reactions with oxygen on transition metal surFaces,Ag(111),Cu(111),Pd(111),Ni(111)and Pt(111),are analyzed by the Bond-Order-Conservation-Morse-Potential(BOC-MP)approach.It is shown that the cleavage of the C-O bond or C-H bond of methanol may takes place,resulting the Formation of the CH x(x=2,3)species.However,in the presence of oxygen,the methanol is directly oxidized to Formaldehyde.The calculation values of activation barrier by BOC-MP approach are in good agreement with the experimental values.The results showed that the HCOH is very easy oxidized into CO or CO_2 on the surFace of Ni,Pd,Pt,Cu and Ag.So,the very small amount of oxygen must be controlled For the system oxidizing mathanol to Formaldehyde by transition metal catalysts.The easy order is Ni>Pd>Pt>Cu>Ag For dissociation of mathanol over transition metal catalysts.However,in very low oxygen content,the carbon deposition is more easy on Ni,Pd and Pt than Cu adn Ag surFace.TherFore,The Cu and Ag rather than Ni,Pd and Pt are used in the commercial catalysts For the oxidation of mathanol to Formaldehyde.国家自然科学基金;国家教委留学回国人员科研资

Preperation and Activity of Ni catalyst for Selective Hydrogenation of 4 n butylbenzoic Acid

正丁基苯甲酸选择加氢催化剂的制备及其催化性能陈鸿博廖代伟黑美军林贻基洪琦于腊佳蔡启瑞（厦门大学化学系物理化学研究所厦门361005）液晶具有独特的光学、电学、光电和热性质，近几年来被广泛用作液晶显示器，与光发射显示器相比，它具有功耗低，体积小，携带方...The preperation of Nickel catalyst and determination of activity for selective hydrogenation of 4 n butylbenzoic acid to 4 n butylcyclohexanal carboxlic acid have been done.The results showed that the operation conditions employed for hydrogenation are much more moderate than Raney Ni catalyst and cheaper than PtO 2.Therefore, the catalyst prepared by this method is especially suitable for the medium manufactories