斯蒂芬酸氢铷的制备，晶体结构和热分解机理

A new compound,[RbHTNR]_∞[HTNR:C_6H(NO_2)_3(OH)O],was synthesized by the reaction of rubidium ni-trate and styphnic acid.The molecular structure was characterized using X-ray diffraction analysis,elementalanalysis and FTIR spectroscopy.The crystalline is monoclinic with space group P2_1/n and the empirical formulaC_6H_2N_3O_8Rb.The unit cell parameters are:a=0.4525 nm,b=1.0777 nm,c=1.9834 nm,β=90.47(2)°,V=0.96725 nm~3,Z=4,D_c=2.263 g/cm~3,Mr=329.58,F(000)=640,μ(Mo Kα)=5.165 mm~(-1).The thermal decompo-sition mechanism of the complex was studied by differential scanning calorimetry(DSC),thermogravimetry-derivative thermogravimetry(TG-DTG)and FTIR techniques.At the linear rate of 10 ℃/min,the thermaldecomposition of the complex showed three mass reducing processes between 60 and 500 ℃,and finally evolvedRbCN and some gaseous products.     

超声波处理对球形β-Ni(OH)2结构及电化学性能的影响

A method of ultrasonic treatment （UST） was first used to modify the structure and electrochemical performance of nickel hydroxide for the active material of nickel series alkaline batteries. The experimental results showed that UST was an effective method to improve the electrochemical performance of β-Ni（OH）2 such as specific discharge capacity, discharge potential, electrochemical reversibility and oxygen evolution over-potential. The results of electrochemical impedance spectroscopy, powder X-ray diffraction and particle size distribution indicated that the improvement of the performance of β-Ni（OH）2 through UST was attributed to the reduction of the charge-transfer resistance （Rt） and the diffusion impedance （Zw）, which resulted from the decrease of the crystallite and particle size and the increase of interlayer spacing. Diffusion coefficient of proton DH of ultrasonic treated β-Ni（OH）2 gained by CV tests was 1.13 × 10^-11 cm^2/s, and the average discharge specific capacity of ultrasonic treated β-Ni（OH）2 electrode was 301 mAh/g.     

方酸染料在远红光区／近红外区对纳米晶二氧化钛电极的高效敏化作用

Four para-dialkylaminophenyl （PDAAP1-PDAAP4） bearing carboxyl groups were studied for application to the dye-sensitized solar cells （DSC）. It was found the short spacer CH2 between carboxyl and dialkylaminophenyl chromophore in PDAAP3 and PDAAP4 led to highly efficient monochromatic incident photon-to-current conversion efficiencies （IPCE）, however the long alkyl group C4H9 attached on aniline moieties in PDAAP2 and PDAAP4 favored improvement of open-circuit photovoltage. Thus, the solar cell sensitized by PDAAP4, having both short carboxyl groups CH2COOH and long alkyl groups C4H9, exhibited the IPCE maximum of 73% at 670 nm and overall energy conversion efficiency η of 3.06%, representing the highest IPCE and η values so far in dialkylaminophenyl-based organic dye-sensitized semiconductor solar cells. Taking advantage of the highly efficient sensitizing ability of PDAAP4 in far-red region, the data of IPCE above 630 nm of the solar cells were improved greatly by cosensitization with both N3 and PDAAP4. The influences of the TiO2 film thickness and the concentration of 4-tert-butylpyridine （TBP） in electrolyte were also investigated.     

3-氨基环己基甲酸和cis-3-氨基环己烯基-5-甲酸立体异构体的合成

通过手性胺拆分方法，从3-环己烯基甲酸出发分别合成得到了3-氨基环己基甲酸（ACHC）的四个立体异构体，以及cis-5-氨基-3-环己烯基甲酸（ACHEC）的二个立体异构体。     

新型一维梯状双链配位聚合物{[Cu(malate)(2,2'-bipy)]•3H2O}∞的合成、晶体结构与表征

合成了铜(II)与羟基丁二酸和2,2'-联吡啶形成的配位聚合物{[Cu(malate)(2,2'-bipy)]•3H₂O}_∞ (其中malate＝羟基丁二酸根, 2,2'-bipy＝2,2'-联吡啶), 通过X射线衍射测定了单晶结构, 并进行了元素分析、红外光谱、紫外光谱、热分析等研究. 配合物属单斜晶系, 空间群P2(1)/c; 晶胞参数: a＝0.70132(10) nm, b＝1.9730(3) nm, c＝1.18998(16) nm, β＝94.551(3)°; Z＝2; 最终偏离因子R＝0.0483. 配合物中每个铜(II)原子与来自2,2'-联吡啶的两个氮原子和两个羟基丁二酸根的三个氧原子配位, 形成畸变的三角双锥结构单元. 每个羟基丁二酸根以R构型方式桥联两个三角双锥结构单元, 沿a轴方向无限延伸形成一维链. 两条平行链以面对面的方式重叠, 彼此吡啶环之间存在强的(-(相互作用, 加之C_吡啶环—H…O_羧基弱相互作用形成新颖的梯状双链结构, 比邻的梯状双链又通过分子间O_羟基-H…O_羧基氢键沿a轴方向共同构筑了具有隧道的三维结构.     

UO22＋•nH2O和PuO22＋•nH2O (n＝2, 4, 5, 6)密度泛函理论研究

首先用密度泛函理论(DFT)方法研究了铀酰和钚酰离子的几何与电子结构, 计算结果与实验基本符合, 表明DFT方法也能用于含铀和钚重原子的化合物计算. 然后对铀酰和钚酰水合离子的几何构型、Mulliken集居数分布以及铀酰(钚酰)与配体水分子的结合能进行计算, 计算结果表明UO₂^2＋•5H₂O和PuO₂^2＋•5H₂O分别为铀酰和钚酰系列水合离子中最稳定的配合物.     

用分子轨道理论研究NO气体在TiO2表面吸附

根据一氧化氮(NO)气体在二氧化钛(TiO₂)表面吸附和脱附的实验结果, 揭示了气体脱附量的变化规律. 利用MOPAC 和GAUSSIAN分子轨道理论计算了在TiO₂(110)表面上吸附NO分子的原子簇模型, 电荷分布以及原子簇的能级, 推断了NO在TiO₂(110)表面吸附的稳定性.     

TiO2/Eu-MCM纳米超分子材料的组装和光催化性能

利用有机相-水相界面共沉淀溶胶支持自组装方法制备粒径为15 nm、孔径为8 nm的分子筛Eu-MCM, 它拥有734 m²/g的比表面积和1.49 cm³/g的比孔容. 把TiO₂组装到Eu-MCM的孔道中, 组装成TiO₂/Eu-MCM纳米复合材料. XRD, RAMAN和选区电子衍射花样分析表明纳米复合材料中的TiO₂为锐钛型. TiO₂/Eu-MCM的发光表现为Eu^3＋离子的特征光谱, 激发峰分别为342 (⁵L₁₀), 358 (⁵L₉), 378 (⁵L₇), 390 (⁵L₆), 411 (⁵D₃), 462 (⁵D₂)和524 (⁵D₁) nm; 发射峰为579, 592, 613, 653和701 nm, 归属于⁵D₀→⁷F_J (J＝0, 1, 2, 3, 4)组态间的跃迁. 纳米复合材料的发光强度都要比Eu-MCM的发光强, 其中43%TiO₂/Eu-MCM的发光最强. 荧光和紫外漫反射结果表明客体TiO₂对主体分子筛存在能量传递效应. 在微弱的紫外灯光照射下, TiO₂/Eu-MCM纳米复合材料对苯酚的光催化氧化性能和其发光强度具有一定的相关性. 29%TiO₂/Eu-MCM的纳米复合材料拥有的比表面积、孔容和孔径分别为204 m²/g, 0.24 cm³/g和4.7 nm. 29%TiO₂/Eu- MCM对苯酚具有68%的最高光催化氧化产率和85%催化氧化选择性.     

BF分子X1Σ＋, A1P和B1Σ＋态的势能函数

使用SAC/SAC-CI和D95＋＋, 6-311＋＋g, 6-311＋＋g**及D95(d)基组, 分别对BF分子的基态X¹Σ^＋、第一简并激发态A¹Π和第二激发态B¹Σ^＋的平衡结构和谐振频率进行优化计算. 对所有计算结果进行比较, 得出6-311＋＋g**基组为最优基组. 运用6-311＋＋g**基组和SAC方法对基态X¹Σ^＋, SAC-CI方法对激发态A¹Π和B¹Σ^＋进行单点能扫描计算, 并用正规方程组拟合Murrell-Sorbie函数, 得到相应电子态的势能函数解析式, 由得到的势能函数计算了与X¹Σ^＋, A¹Π和B¹Σ^＋态相对应的光谱常数, 结果与实验数据较为一致.     

可见光响应的镍硅共掺杂二氧化钛及其光催化性能

为了更好地利用太阳光和提高二氧化钛的光催化性能,以钛酸四正丁酯、正硅酸乙酯、六水合硝酸镍为原料,在高压釜中140℃非水溶剂热反应,所得材料经400℃焙烧制得镍硅共掺杂的二氧化钛光催化剂.所得材料用X射线衍射、氮吸附、透射电镜、X射线光电子能谱、傅里叶变换红外光谱、紫外漫反射等测试手段分析,结果显示所有样品均为锐钛矿型二氧化钛,Si和Ni均掺杂到TiO2体相中,样品具有较大的比表面积,其最大达303.3m2·g-1.在可见光照射下,以降解罗丹明-B为探针反应研究其可见光催化性能,与未掺杂和镍掺杂的二氧化钛相比较,共掺杂的二氧化钛具有更高的可见光催化性能,当Ni/Ti和Si/Ti的物质的量的比分别为0.01和0.20时,可见光催化性能最好.可见光催化性能的提高归因于镍和硅的协同作用.