一步硫/磷热处理制备空心Co9S8/CoP/C纳米复合材料及其储钠性能研究

低成本、高性能的钠离子电池有望成为代替锂离子电池的下一代核心器件.但是开发出高比容量、高倍率的钠离子电池负极材料依然是瓶颈.本文通过水热/溶剂热法制备了Co基前驱体,然后将其一步硫/磷热处理制得具有空心多孔结构的h-Co₉S₈/CoP/C纳米复合材料.通过X-射线粉末衍射(XRD)、拉曼光谱(Raman)、扫描电镜(SEM)、透射电镜(TEM)和X-射线光电子能谱(XPS)等表征以确定纳米复合物的物相以及形貌特征.当h-Co₉S₈/CoP/C作为钠离子电池负极材料时,该电极材料展示了高的比容量(561 mAh g^-1@0.1 Ag^-1)、较好的循环性能(可逆比容量200 mAh g^-1@2 Ag^-1)和倍率性能.h-Co₉S₈/CoP/C之所以显示出良好的储钠性能,主要得益于其空心多孔结构不仅提供更多的空间缓解钠在反复嵌入和脱出过程造成的体积膨胀效应,而且可以缩短离子/电荷扩散途径以加快反应动力学,此外,Co₉S₈、CoP和C独特的电子结构优势得以共同发挥.     

A 2D Copper(Ⅱ) Complex with Half Paddlewheel-like Building Block Controlled by 1,2,4,5-Benzenetetracarboxylic Acid: Synthesis,Crystal Structure and Luminescence Property

Self-assembly reaction of 1,2,4,5-benzenetetracarboxylic acid(H_4 btc) with CuCl_2 in mixed N,N-dimethylformamide(DMF), methanol and aqueous solution at room temperature generated a 2D complex, [Cu(btc)_(0.5)(DMF)(H_2 O)]_n(1) which was further characterized by X-ray diffraction, IR spectrum, elemental analysis and TG-DTA experiments. The structure determination reveals that the fundamental unit of complex 1 contains one Cu(Ⅱ) ion, half a btc~(4–), one DMF molecule and one water molecule, forming a half paddlewheel-like building block [Cu_2(btc)(DMF)_2(H_2 O)_2] which is different from those previous Cu-btc(Ⅱ) polymers obtained either in water or other media without water. It crystallizes in monoclinic system, space group C2/c with a = 22.8209(14), b = 9.2244(6), c = 10.8876(7) ?, b = 117.5210(10)o, V = 2032.6(2) ?~3, Z = 2, C_8 H_(10) CuNO_6, M_r = 279.71, D_c = 1.828 g/cm~3, μ = 2.162 mm-1, F(000) = 1136, the final R = 0.0225 and wR = 0.0652 with I 2s(I). Furthermore, the thermal stability of complex 1 is observed to be dependent on the polymeric structure nature. And the luminescent measurements show that complex 1 produces strong emission at room temperature.     

三唑-芳香多羧酸类混配金属配合物的结构与磁性能研究

以三唑为主配体的过渡金属配合物以其结构多样性及在磁性、吸附等功能材料中的潜在应用而成为众多科研工作者的研究热点内容之一．本文从三唑一芳香多羧酸混配配合物的合成以及芳香酸对配合物中金属一三唑次级结构的调节角度,总结了近年来报道的该类混配金属配合物的结构多样性．在此基础上,初步关联了该类混合配体顺磁金属配合物的磁一构关系．     

4-(1,2,4-三唑-1-基)苯酚铜(Ⅱ)/镍(Ⅱ)配合物的晶体结构及荧光性质（英文）

合成并通过单晶和粉末X射线衍射、元素分析、红外光谱、热失重以及荧光光谱技术表征了含有4-(1,2,4-三唑-1-基)苯酚(hptrz)配体的2个过渡金属配合物{[Ni(H_2O)_2(hptrz)_2(tp)]·2DMF}_n(1)和[Cu(hptrz)_2(SCN)_2]·2H_2O (2)(H_2tp为对苯二甲酸)。配合物1中八面体的Ni(Ⅱ)离子由tp~(2-)阴离子拓展形成线性的一维链状结构;而配合物2则呈现中心对称的单核结构。配合物中,中性的hptrz配体呈现端基配位模式,并通过形成O-H…O氢键相互作用将低维结构拓展为高维超分子网络。此外,配体内的电荷转移使这2个配合物均在紫外区发射出强的荧光发射峰。     

一个对2,4,6-三硝基苯酚和Fe3+离子具有双重荧光传感行为的层状镉(Ⅱ)-有机配位聚合物

通过水热法合成了一个由三连接的2,3-喹啉二甲酸桥联扭曲的Cd²⁺八面体形成的二维层状配位聚合物[Cd（QDA）]_n（1）。该配合物发射出较强的蓝色荧光并具有很高的热稳定性和化学稳定性。更为重要的是,该配合物在乙醇分散体系中可快速识别痕量的2,4,6-三硝基苯酚和Fe³⁺离子,其对2,4,6-三硝基苯酚的淬灭常数（K_sv）和检测限（LOD）分别为6.61×10⁴ L·mol^-1和0.83 μmol·L^-1,对Fe³⁺离子的淬灭常数和检测限分别为1.74×10⁴ L·mol^-1和2.70 μmol·L^-1。     

Synthesis,Structure and Photocatalytic Activity of Two 4-(2,6-Di(pyrazin-2-yl)pyridin-4-yl)benzoate-Based Chain Complexes

Two new one-dimensional chains extended by alternate benzenedicarboxylate(BDC) and 4-(2,6-di(pyrazin-2-yl)pyridin-4-yl)benzoate(L~-) connectors, {[Cu(L)(BDC)_(0.5)]·3.5 H_2 O}_n (1) and {[Zn(L)(BDC)_(0.5)] ·H_2 O}_n (2), were solvothermally synthesized. Complex 1 is in triclinic system, space group P1 with a = 9.6456(14), b = 11.1160(16), c = 12.0414(18) ?, α = 106.266(3), β = 92.277(3), γ =108.104(3)°, V = 1166.6(3) ?~3, D_c = 1.603 g·cm~(-3), Mr = 563.00, Z = 2, F(000) = 578, μ = 0.996 mm~(-1), the final R = 0.0575 and wR = 0.1386 for 3704 observed reflections with I 2σ(I). Complex 2 crystallizes in monoclinic, space group C2/c with a = 28.607(5), b = 8.9767(16), c = 19.705(4) ?, β = 125.396(3)°, V = 4125.0(13) ?~3, D_c = 1.674 g·cm~(-3), Mr = 519.79, Z = 8, F(000) = 2120, μ = 1.242 mm~(-1), the final R = 0.0487 and w R = 0.0907 for 2944 observed reflections with I 2σ(I). Resulting from the narrower band gap and broader response to visible light, the CuII-chain exhibits better photocatalytic performance towards the degradation of rhodamine B and methylene blue than those of ZnII-chain.     

自制亥姆霍兹线圈的设计与应用研究

电磁学是高中物理教学的重点和难点,有效地开展实验教学是解决难点的重要手段. 电磁学演示实验 中经常需要磁场,而常规的实验器材因为提供的磁场范围小、不均匀,影响了演示效果. 自制可旋转亥姆霍兹线圈, 结合教学进行应用研究,是提高这类实验演示效果的一个途径     

C_8芳烃异构体+异丙醇体系在333.15K时的过量摩尔Gibbs自由能

采用CP-I型汽液平衡双循环釜,测定了333.15 K时乙苯+异丙醇、邻二甲苯+异丙醇、间二甲苯+异丙醇、对二甲苯+异丙醇四个体系的汽液平衡数据,计算了该温度下四个体系的过量摩尔Gibbs自由能,并对所测数据进行了恒温下热力学一致性检验。用Wilson方程关联了实验数据,拟合精度令人满意。     

Synthesis,Structure and Magnetic Property of a New MOF with Triazolate and Azido Heterobridges

A new magnetic MOF with cyclic triazolate and linear azido mediators, [Co2(trz)3(N3)]n 1(trz- = 1,2,4-triazolate), was hydrothermally synthesized and structurally and magnetically characterized. 1 crystallizes in the rhombohedral P63/mmc space group with a = b = 10.0716(17), c = 7.5860(14) , V = 666.4(2) 3, Dc = 1.814 g/cm3, Mr = 364.09, Z = 2, F(000) = 360, μ = 2.499 mm1, the final R = 0.0676 and wR = 0.1952 for 229 observed reflections with I 2σ(I). Complex 1 consists of linear {Co(trz)3}n chains passing through a C6 rotation axis, which are interconnected with tetrahedral CoⅡ ion by u3-trz- ligands into a hexagonal three-dimensional antiferromagnetic framework.     

6-(5''-(8''-羟基喹啉)亚甲基)-1,4,8,11-四氮杂十一烷-5,7-二酮·5-取代邻菲罗啉合铜(Ⅱ)-铜(Ⅱ)或钴(Ⅱ)双核混配体系的稳定性研究

本文合成了8-羟基喹啉取代的二氧四胺开链配体L并进行了红外、元素分析、核磁和质谱表征。在(25±0.1)℃,I=0.1mol·dm