一种含吡啶酮结构分散染料的从头算研究

采用限制的Hartree-Fock方法和中等基组6-31G,计算了一种含吡啶酮结构的分散染料。通过几何结构优化,得到了其醌式结构和偶氮式结构能量最小化时所对应的结构及其能量值,对较稳定的醌式结构振动光谱也进行了计算,并与文献报道的实验值进行了比较,对特征明显的红外振动吸收进行了振动分析。此外,还计算了醌腙式和偶氮式结构在互变过程中,反应路径、正逆反应活化能以及化学平衡常数。结果表明,醌腙式结构的能量比偶氮结构能量低约67.7kJ/mol;3266.9cm-1为腙基上H在分子平面的伸缩振动频率,893.8cm-1为腙基上H离开分子平面的摇摆振动频率;由偶氮式到醌腙式过程的ΔT,pG小于零,是热力学自发过程;异构反应的标准平衡常数为7.07×10-13。     

量子化学计算方法与GPU应用综述

本文从量子化学计算的诞生出发,简述了常用的3种计算方法的优缺点和适用范围;从量子化学计算与计算机技术的关联出发,介绍了量子化学计算处理器对量子化学计算的贡献,以及GPU引发的新一轮量子化学革命,最后对量子化学计算的前景做了展望。     

Understanding the atomic and electronic origin of mechanical property in thaumasite and ettringite mineral crystals

Ettringite and thaumasite are 2 of the relevant secondary products in portland cement minerals. They are rare crystals with high water content. Two density functional theory based ab initio packages VASP and the OLCAO were used for exploring the geometry structure, electronic, and mechanical properties of ettringite and thaumasite. The calculations focus on the comparison of their structures and properties to gain insights that can reveal the minute difference in properties due to differences in their structure, composition and water content. Detailed analysis of interatomic bonding shows the similarities and subtle difference between them even though thaumasite has the Si tetrahedron as the backbone unit in contrast to ettringite with Al‐columns and no Si atoms. Moreover, thaumasite has strong C–O bonds that are absent in ettringite, and ettringite has far more water molecules with a substantial contribution from the hydrogen bonding. It is shown that the role played by relatively strong S–O bonds in both crystals has a large impact on the hydration in these crystals. On the basis of calculated total bond order density, it is concluded that thaumasite is slightly more cohesive than ettringite consistent with the calculated mechanical properties. The detailed comparative results for these 2 important minerals we obtained in this paper, many of them for the first time, will pave the way to understanding the structure and electronic structure origin of other more complex cement crystals.     

玻璃中Fe2+和Fe3+测试方法的Tobit模型估计

快速准确地测定浮法玻璃中Fe^2＋和Fe^3＋的含量对生产过程中气泡缺陷的控制、稳定生产、提高质量、减少损失具有十分重要的意义。研究发现,利用Fe^2＋和Fe^3＋离子对不同波长光的吸收特性可以建立快速测定Fe^2＋和Fe^3＋含量的方法,并采用Tobit模型进行回归分析标准曲线,很好地解决了在低Fe含量的高质量超白及超薄浮法玻璃生产过程中使用最小二乘法回归标准曲线造成较大误差的问题,满足了生产需要。     

Fe2O3掺杂TiO2催化超声降解糠醛废水的研究

采用Fe2O3掺杂TiO2为催化剂,超声辐照为主要手段对实际糠醛废水进行了降解试验研究,考察了各种反应参数对糠醛废水降解效果的影响.结果表明,Fe2O3掺杂TiO2对糠醛废水的超声降解效果具有明显的辅助和提高.当超声波频率为40 kHz,功率为160 W,初始COD为1 128 mg·L-1,超声反应时间为1.5 h的务件下,糠醛废水的COD去除率为67%,而同样条件下,按质量浓度750mg·L-1加入1.0%Fe2O3掺杂量的催化剂TiO2,其超声降解废水COD去除率可达95%.     

Fe_2O_3可见光光催化降解水中腐殖酸的研究

采用均相沉淀法制备了Fe2O3光催化剂,并用XRD对其晶型进行了表征。研究了Fe2O3催化剂在可见光照射下对水中腐殖酸的降解行为,考察了催化剂用量、初始pH值、腐殖酸初始浓度等因素对光催化氧化过程的影响。结果表明,当Fe2O3用量为0.4 g/L,腐殖酸溶液的初始浓度为10 mg/L,pH为3.0,20 W黄色荧光灯(Em ax=548 nm)照射下反应150 m in,腐殖酸的降解率达到94.1%,说明所制备的Fe2O3光催化剂在可见光照射下对水中腐殖酸有较好的降解效果,并可多次重复使用。     

乙基硅橡胶的耐热性研究

研究了2种耐热助剂对乙基硅橡胶耐热性的影响.热空气老化试验结果表明,经200 ℃×24 h热空气老化后,空白样和添加Fe2O3的试样已经脆化,失去弹性;而添加有机抗氧剂4,4'-双(α,α-二甲基苄基)二苯胺(KY-405)的试样的扯断伸长率仍达186%,比初期减少39%,保持良好的弹性,且其-75 ℃下的压缩耐寒系数为0.58.TG-DSC试验分析也表明,添加KY-405将乙基硅橡胶的初始分解温度从279 ℃提高到了336 ℃,有机抗氧剂通过有效防护乙基硅橡胶中乙基侧链的氧化交联提高了乙基硅橡胶的耐热空气老化性能.     

Fe2O3/泡沫镍复合材料电磁屏蔽效能研究

本文以电沉积法制备了泡沫镍材料,并在泡沫镍材料空隙内生长了纳米棒状Fe2O3,制备了Fe2O3/泡沫镍复合材料,测试了复合材料在Ku(12.4～18 GHz)频段的介电常数和电磁屏蔽效能.实验结果表明:复合材料具有较高的介电常数,介电常数的实部和虚部最大值可分别达到51和100.该复合材料的电磁屏蔽效能则随频率的增大而增加,并在20～33 dB范围内变化,表明该材料具有潜在的实际应用价值.     

PVA/Fe2O3磁敏感性水凝胶的制备及性能

采用循环冷冻-解冻方法制备了聚乙烯醇(PVA)/Fe2O3磁敏感性水凝胶. 考察了水凝胶的力学性能、溶胀性能和磁敏感性,并用扫描电镜观察了其表面形貌. 结果表明,当Fe2O3含量为1%(w)时,水凝胶的力学性能最好;水凝胶的溶胀度和脱水率随时间增加有相似的变化趋势,都随磁性粒子含量升高而降低;溶胀性能降低其交联程度增加;PVA和Fe2O3相容性较好;水凝胶在3000 Oe的磁场强度下达到饱和,呈现出很强的顺磁性,磁滞损耗较多,表明具有较好的磁敏感性.     

Fe2O3改性电石渣高温固硫性能的研究

利用工业废弃物电石渣,经适当预处理,并掺入适量的Fe2O3对电石渣进行改性,配制成新型复合固硫剂。在高温条件下进行了固硫实验,达到了较为理想的固硫效果。研究了影响改性电石渣高温固硫效果的因素,分析了该改性电石渣的固硫机理。结果表明,改性电石渣高温固硫的适宜条件为:煤燃烧温度1200℃、Ca/S=2.2、改性电石渣的粒径为100目。在该条件下,对实验用烟煤(含硫量2.92%)燃烧20min,其高温固硫率高达88.5%,较相同条件下的普通钙基固硫剂的固硫率提高30%以上。     

碳化硅微粉中除铁方法的研究

本文主要研究了除去碳化硅微粉中Fe2O3的方法及最佳条件。     

探究本地资源优势浮法玻璃质量达新标

通过对浮法玻璃成分和原料配方的调整,合理使用本地原料,降低了玻璃成分中Fe2O3的含量,改善玻璃颜色,使生产的浮法玻璃透光率等指标达到新国标的要求。     

Fe2O3对CaO-SiO2玻璃和微晶玻璃性能的影响

利用溶胶-凝胶法制得Fe2O3-CaO-SiO2系基础玻璃,研究不同含量的Fe2O3对CaO-SiO2玻璃和微晶玻璃性能的影响.经分析,不同组分的玻璃凝结时间不同,处于低共熔点的样品凝结时间最短,而离低共熔点最远的样品凝结时间最长.样品的密度并不随成分而变化.溶胶凝胶转变过程中,不同组分所得的凝胶玻璃有一定的耐酸碱性.而微晶玻璃的耐酸碱性比玻璃都略有增强.微晶玻璃的饱和磁化强度和磁铁矿在玻璃中所占的体积分数有关.随着玻璃中Fe2O3含量的增加,饱和磁化强度增大.     

Comparison of free energy surfaces calculations from ab initio molecular dynamic simulations at the example of two transition metal catalyzed reactions

We carried out ab initio molecular dynamic simulations in order to determine the free energy surfaces of two selected reactions including solvents, namely a rearrangement of a ruthenium oxoester in water and a carbon dioxide addition to a palladium complex in carbon dioxide. For the latter reaction we also investigated the gas phase reaction in order to take solvent effects into account. We used two techniques to reconstruct the free energy surfaces: thermodynamic integration and metadynamics. Furthermore, we gave a reasonable error estimation of the computed free energy surface. We calculated a reaction barrier of ΔF = 59.5 ± 8.5 kJ mol(-1) for the rearrangement of a ruthenium oxoester in water from thermodynamic integration. For the carbon dioxide addition to the palladium complex in carbon dioxide we found a ΔF = 44.9 ± 3.3 kJ mol(-1) from metadynamics simulations with one collective variable. The investigation of the same reactions in the gas phase resulted in ΔF = 24.9 ± 6.7 kJ mol(-1) from thermodynamic integration, in ΔF = 26.7 ± 2.3 kJ mol(-1) from metadynamics simulations with one collective variable, and in ΔF = 27.1 ± 5.9 kJ mol(-1) from metadynamics simulations with two collective variables.     

H9P2W15V3/C催化1,4-丁二醇环化脱水制备四氢呋喃

以活性炭为载体,通过浸渍法制备了H9P2W15V3/C催化剂,对催化剂进行FT-IR表征。以催化1,4-丁二醇脱水制备四氢呋喃为探针反应,考察催化剂的酸催化性能。通过正交实验得出了最佳条件反应：w（催化剂）=3.93%（相对1,4丁二醇质量）,反应温度为185～190 ℃,反应时间为40 min,四氢呋喃平均收率达93.30%,催化剂重复使用3次,产率仍可达90.94%。本工艺具有绿色、安全、操作简单、收率高等优点。     

Ab initio energy calculations and macroscopic rate modeling of hydroformylation of higher alkenes by Rh‐based catalyst

Ab initio quantum chemical computations have been done to determine the energetics and reaction pathways of hydroformylation of higher alkenes using a rhodium complex homogeneous catalyst. Calculation of fragments of the potential energy surfaces of the HRh(CO)(PPh₃)₃‐catalyzed hydroformylation of 1‐decene, 1‐dodecene, and styrene were performed by the restricted Hartree‐Fock method at the second‐order MØller‐Plesset (MP2) level of perturbation theory and basis set of 6‐31++G(d,p). Geometrically optimized structures of the intermediates and transition states were identified. Three generalized rate models were developed on the basis of above reaction path analysis as well as experimental findings reported in the literature. The kinetic and equilibrium parameters of the models were estimated by nonlinear least square regression of available literature data. The model based on H₂‐oxidative addition fitted the data best; it predicts the conversion of all the alkenes quite satisfactorily with an average deviation of 7.6% and a maximum deviation of 13%. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Fe~(3+)改性TiO_2薄膜的制备、表征及光催化性能研究

采用溶胶-凝胶法,制备了纳米Fe3+/TiO2薄膜,利用XRD、TEM等测试手段进行了样品的表征分析,以降解含阿奇霉素废水为反应模型,研究了纳米Fe3+/TiO2薄膜的紫外光照射催化活性及薄膜的重复使用效果。结果表明,纳米Fe3+/TiO2薄膜不易失活,其催化活性寿命较粉体纳米Fe3+/TiO2的强,且再生性能好,薄膜重复使用4次,仍有明显的降解效果。