芳基四硫富瓦烯与溴化铜电荷转移复合物的合成及晶体结构

采用溶液扩散的方法合成了硫原子桥联芳基取代四硫富瓦烯1~4与CuBr₂的4种电荷转移复合物（1^+·）（Cu₂Br₆）_0.5、（2^+·）（Cu₂Br₆）_0.5、（3^+·）（Cu₂Br₆）_0.5和（4^+·）（CuBr₂）。晶体结构研究表明,复合物中阴离子呈现2种构型：八面体型（Cu^Ⅱ₂Br₆）^2-和直线型（Cu^ⅠBr₂）^-,并且4种复合物呈现不同的堆积结构。通过调控芳基上卤素原子取代位置和大小,实现了对电荷转移复合物堆积结构和阴离子构型的有效调控。     

掺杂和取代对红色荧光材料SrAl12O19:Mn4+发光性能的影响

SrAl₁₂O₁₉：Mn⁴⁺是一种用于高显色性白光发光二极管的候选红色荧光材料。本论文研究了Mg²⁺、Zn²⁺和Ge⁴⁺离子的掺杂效应以及Ga³⁺、Ca²⁺和Ba²⁺离子的取代效应对SrAl₁₂O₁₉：Mn⁴⁺荧光材料性能的影响。样品通过高温固相反应制备,焙烧温度在1 250~1 500 ℃之间。利用X射线衍射技术表征了材料的相纯度,用荧光激发光谱和发射光谱表征了材料的荧光性能。研究结果指出,与未进行Mg²⁺或Zn²⁺掺杂的样品相比,Mg²⁺或Zn²⁺离子对Al³⁺格位的掺杂可以使材料的发光强度提高~60%,其原因被认为是掺杂促进了激活剂Mn⁴⁺离子进入晶格,其过程可以表示为：MO+MnO₂⇔M_Al^''+M_Al^·+3O_O^×（M=Mg,Zn）,电子顺磁共振谱支持这一结果。Ge⁴⁺离子的掺杂使材料的发光性能明显下降。Ga³⁺离子可以取代Al³⁺离子形成全范围的固溶体,其中少量Ga³⁺离子的掺杂可以使材料的荧光发射强度提高~13%,而掺杂量进一步提高使材料的荧光性能下降。Ca²⁺和Ba²⁺对Sr²⁺的取代仅形成有限范围的固溶体。Ca²⁺的取代使材料的发光性能提高;而 Ba²⁺的取代使材料的发光强度下降。     

基于2-(4'-羧基苯基)咪唑-4,5-二羧酸构筑的三个镉/锌配位聚合物的合成、拓扑结构、荧光光谱及DNA作用

以2-（4''-羧基苯基）咪唑-4,5-二羧酸（H₄CPhIDC,C₁₂H₈N₂O₆）为配体,用溶剂热合成了3种配位聚合物{[Cd₂（CPhIDC）（bimb）]·H₂O}_n（1）、{[Cd₂（CPhIDC）（phen）₂]·3H₂O}_n（2）、{[Zn₂（CPhIDC）（bpp）]·1.5H₂O}_n（3）（bimp=1,4-双咪唑基-丁烷,phen=1,10-菲咯啉,bpp=1,3-双（4-吡啶基）-丙烷）。用元素分析、红外光谱、粉末X射线衍射和单晶X射线衍射对配合物进行了表征和结构分析。结构分析表明,主配体以完全去质子化CPhIDC^4-的形式与中心金属离子形成以μ₄和μ₅为配位模式的二维及三维聚合物。配合物1和3是三维网络结构,同时呈现（3,4,5）-连接的（5·6·7）（4·5²·6·7²）（4·5²·6·7⁴·8²）拓扑结构,两者的不同之处是中心离子和辅助配体。配合物2是二维波纹状渔网结构,呈现4⁴·6²拓扑结构,在其空间填充上又类似于DNA双螺旋链的单螺旋结构。测定了产物的固体荧光光谱;用EtBr荧光探针法研究了配体及配合物与ct-DNA的相互作用。     

CdS柱撑钛铌酸介孔复合材料的制备与光解水制氢活性

以钛铌酸纳米片层为主体,CdS纳米颗粒为客体,通过剥离-重堆积法合成了不同投料比的CdSTiNbO₅介孔复合材料,材料的层间距为1.19nm,比表面积约为93m₂·g^-1.CdSTiNbO₅复合材料表现出良好的光解水制氢活性,当投料比n_CdS/n_HTiNbO5=1:2时,复合材料在模拟太阳光和可见光下的产氢速率分别为231和184μmol·h^-1·g^-1,是CdS的8.6和9.7倍.复合材料光催化活性的提高归因于比表面积的增加和光生载流子的有效分离.     

ZnIn2S4/Au纳米片阵列的制备及其可见光响应光电化学固氮特性

采用简单的水热法合成出单晶ZnIn₂S₄纳米片阵列以实现可见光响应光电化学固氮。并采用光沉积法将超细Au纳米颗粒（5 nm）沉积于ZnIn₂S₄纳米片的棱角位置处,实现了可见光俘获和载流子分离能力的同时增强。当负载合适含量的Au纳米颗粒,ZnIn₂S₄纳米片阵列的光电固氮活性由1.092 μg·cm^-2·h^-1提升至2.262 μg·cm^-2·h^-1。我们还提出一个简单模型用以阐明其性能增强机制,这也被光致发光（PL）谱和光电化学（PEC）性能结果所证实。     

芳基四硫富瓦烯与碘电荷转移复合物的合成及其晶体结构

采用缓慢挥发溶剂的方法合成了硫原子桥联芳基取代四硫富瓦烯（Ar-S-TTF）与碘的3种电荷转移复合物（1^+·）（I₃）·I₂、（2^+·）（I₅）·I₂和（3²⁺）（I₃）₂,采用单晶X射线衍射、紫外可见光谱、循环伏安对其进行了表征。复合物（1^+·）（I₃）·I₂为C2/c空间群,1^+·呈椅式构型。化合物1与碘之间在溶液中和复合物中电荷转移一致。复合物（2^+·）（I₅）·I₂为P1空间群,2^+·呈椅式构型。复合物（3²⁺）（I₃）₂为Pbca空间群,3²⁺呈独特的平面构型。化合物2和3与碘之间在溶液中和复合物中呈现不同的电荷转移。复合物中聚碘阴离子呈现不同的堆积结构：由I₃^-或I₅^-/I₂组成的一维链状和I₃^-/I₂组成的二维网格状。     

γ-AlOOH/Al2O3修饰硅藻土的制备与Cs+、Pb2+吸附性能

以结晶氯化铝(AlCl₃·6H₂O)作为铝源,十二烷基苯磺酸钠(SDBS)为模板剂,采用水热法在硅藻土盘上制备了束状纳米结构γ-AlOOH/Al₂O₃复合吸附剂。采用XRD、SEM、TEM、TG/DSC、N₂吸脱附等对样品进行了表征。研究了样品对¹³³Cs⁺及Pb²⁺的吸附能力。研究表明,样品γ-AlOOH/硅藻土、γ-Al₂O₃/硅藻土对Cs⁺及Pb²⁺均具有良好的吸附性能,两者对Cs⁺的去除率分别为98.9%和99.6%;对Pb²⁺的最大吸附量分别为357.1、416.7mg·g^-1。两种样品对Pb²⁺的吸附均符合Langmuir吸附模型。     

碳酸盐共沉淀法可控制备超高倍率锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2

采用碳酸盐共沉淀法通过调节NH₃·H₂O用量来实现可控制备超高倍率纳米结构LiNi_1/3Co_1/3Mn_1/3O₂正极材料。NH₃·H₂O用量会对颗粒的形貌、粒径、晶体结构以及材料电化学性能产生较大的影响。X射线衍射（XRD）分析和扫描电镜（SEM）结果表明,随着NH₃·H₂O用量的降低,一次颗粒形貌由纳米片状逐渐过渡到纳米球状,且n_NH3·H2O：（n_Ni+n_Co+n_Mn）=1：2样品晶体层状结构最完善、Li⁺/Ni²⁺阳离子混排程度最低。电化学性能测试结果也证实了n_NH3·H2O：（n_Ni+n_Co+n_Mn）=1：2样品具有最优异的循环稳定性和超高倍率性能。具体而言,在2.7~4.3 V,1C下循环300次后的放电比容量为119 mAh·g^-1,容量保持率为81%,中值电压基本无衰减（保持率为97%）。在100C（18 Ah·g^-1）的超高倍率下,放电比容量还能达到56 mAh·g^-1,具有应用于高功率型锂离子电池的前景。此NH₃·H₂O比例值对于共沉淀法制备其他高倍率、高容量的正/负极氧化物材料具有一定的工艺参考价值。     

钒掺杂对正极材料LiFePO4/C的电化学性能影响

以LiH₂PO₄和廉价的Fe₂O₃为原料,葡萄糖为有机碳源,通过选择高价V⁵⁺进行铁位掺杂固相合成碳包覆复合改性的LiFe_1-xV_xPO₄/C（x=0,0.01,0.03,0.05,0.07,0.1）材料。700℃下处理得到结晶性好、电化学性能良好、较高振实密度ρ=1.2g·cm^-3的材料。X射线光电子能谱（XPS）测试结果表明掺入的钒为高价态V⁵⁺,能产生更多的过剩电子,从而提高了电子电导率,且V⁵⁺的掺入没有改变Fe的价态。交流阻抗测试结果进一步证明了V⁵⁺的掺入降低了电荷迁移阻抗,提高了材料的电子电导率。其中优化的材料LiFe_0.95V_0.05PO₄显示了不同倍率下良好的充放电比容量,在0.1C、1C、2C和5C倍率的放电比容量分别为155、146.5、135.3和125.9mAh·g^-1,5C循环500次后容量为119.5mAh·g^-1,容量保持率为94.9%,材料循环性能较好,具有良好的实际应用价值。     

芳基四硫富瓦烯与碘电荷转移复合物的合成及其晶体结构

采用缓慢挥发溶剂的方法合成了硫原子桥联芳基取代四硫富瓦烯(Ar-S-TTF)与碘的3种电荷转移复合物(1^+·)(I₃)·I₂、(2^+·)(I₅)·I₂和(3²⁺)(I₃)₂,采用单晶X射线衍射、紫外可见光谱、循环伏安对其进行了表征。复合物(1^+·)(I₃)·I₂为C2/c空间群,1^+·呈椅式构型。化合物1与碘之间在溶液中和复合物中电荷转移一致。复合物(2^+·)(I₅)·I₂为P1空间群,2^+·呈椅式构型。复合物(3²⁺)(I₃)₂为Pbca空间群,3²⁺呈独特的平面构型。化合物2和3与碘之间在溶液中和复合物中呈现不同的电荷转移。复合物中聚碘阴离子呈现不同的堆积结构：由I₃^-或I₅^-/I₂组成的一维链状和I₃^-/I₂组成的二维网格状。     

Strain of 2D materials via substrate engineering

Two-dimensional(2D) materials have received extensive attention in the fields of electronics, optoelectronics, and magnetic devices attributed to their unique electronic structures and physical properties. The application of strain is a simple and effective strategy to change the lattice structure of 2D materials thus modulating their physical properties, which further facilitate their applications in carrier mobility transistor, magnetic sensor, single-photon emitter etc. In this short review, ...     

二维过渡金属硫属化合物的大面积制备与应用研究进展

二维过渡金属硫属化合物(TMDs)因具有可调带隙、 谷电子学性质和高催化活性等优点, 在电子学、 光电子学和能源相关领域受到广泛关注. 为了实现以上应用, 实现大面积、 厚度均匀TMDs薄膜的批量制备至关重要. 化学气相沉积法(CVD)是制备大面积均匀、 高质量二维材料普遍使用的方法. 本文从前驱体的供给和衬底的设计两个角度, 总结了目前合成大面积TMDs薄膜的CVD方法, 并讨论了高质量TMDs的生长机制和参数优化方法; 介绍了高质量TMDs在电子学、 光电子学和电/光催化等方面的应用; 讨论了目前合成大面积均匀、 高质量TMDs所面临的挑战, 并对该领域的发展方向进行了展望.     

非生理活性蛋白质的研究进展及其在材料领域中的应用

介绍了自然界产量最丰富、研究最深入的几种非生理活性蛋白质,如胶原蛋白、丝素蛋白和大豆蛋白,包括它们的基本结构和最新研究进展以及在材料领域的应用情况.     

Progress on the optoelectronic functional organic crystals

Organic crystals constructed by pi-conjugated molecules have been paid great attention to in the field of organic optoelectronic materials. The superiorities of these organic crystal materials, such as high thermal stability, highly ordered structure, and high carrier mobility over the amorphous thin film ma-terials, make them attractive candidates for optoelectronic devices. Single crystal with definite struc-ture provides a model to investigate the basic interactions between the molecules (supramolecular interaction), and the relationship between molecular stacking modes and optoelectronic performance (luminescence and carrier mobility). Through modulating molecular arrangement in organic crystal, the luminescence efficiency of organic crystal has exceeded 80% and carrier mobility has been up to the level of 10 cm2·V?1·s?1. Amplified stimulated emission phenomena have been observed in many crys-tals. In this paper, we will emphatically introduce the progress in optoelectronic functional organic crystals and some correlative principle.     

Synthesis and Properties of Glass-Forming Hydrazones II [1]. Hydrazones Containing Bicarbazolyl Units

 A series of new glass-forming hydrazones containing bicarbazolyl units were synthesized starting from 9-(2-(9H-carbazol-9-yl)-cyclobutyl)-9H-carbazole and 9-(6-(9H-carbazol-9-yl)-hexyl)-9H-carbazole, and their thermal properties were studied. The correlation between their inclination to form glasses and their chemical structures are discussed. The results of a preliminary investigation of the photoelectric properties of amorphous films of the title compounds are briefly reported. The highest hole drift mobility was observed for 9-(2-(9H-carbazol-9-yl)-cyclobutyl)-9H-carbazole-3-carbaldehyde N,N-diphenylhydrazone; at high electric fields, it approaches 1 · 10⁻³ cm²/Vs.     

Comparable charge transport property based on S…S interactions with that of π-π stacking in a bis-fused tetrathiafulvalene compound

Compact molecular packing with short π-π stacking and large π-overlap in organic semiconductors is desirable for efficient charge transport and high carrier mobility.Thus charge transport anisotropy along different directions is commonly observed in organic semiconductors.Interestingly,in this article,we found that comparable charge transport property were achieved based on the single crystals of a bis-fused tetrathiafulvalene derivative(EM-TTP) compound along two interaction directions,that is,the multiple strong S…S intermolecular interactions and the π-π stacking direction,with the measured electrical conductivity and hole mobility of 0.4 S cm~(-1),0.94 cm~2 V~(-1) s~(-1) and 0.2 S cm~(-1),0.65 cm2 V~(-1) s~(-1),respectively.This finding provides us a new molecular design concept for developing novel organic semiconductors with isotropic charge transport property through the synergistic effect of multiple intermolecular interactions(such as S…S interactions) and π-π stacking.     

Synthesis and Properties of Glass-Forming Hydrazones II [1]. Hydrazones Containing Bicarbazolyl Units

Summary.  A series of new glass-forming hydrazones containing bicarbazolyl units were synthesized starting from 9-(2-(9H-carbazol-9-yl)-cyclobutyl)-9H-carbazole and 9-(6-(9H-carbazol-9-yl)-hexyl)-9H-carbazole, and their thermal properties were studied. The correlation between their inclination to form glasses and their chemical structures are discussed. The results of a preliminary investigation of the photoelectric properties of amorphous films of the title compounds are briefly reported. The highest hole drift mobility was observed for 9-(2-(9H-carbazol-9-yl)-cyclobutyl)-9H-carbazole-3-carbaldehyde N,N-diphenylhydrazone; at high electric fields, it approaches 1 · 10⁻³ cm²/Vs. Received September 17, 2001. Accepted (revised) October 16, 2001     

铁基普鲁士蓝正极的制备及电化学储钠性能

通过引入抗氧化剂(抗坏血酸)和配位剂(柠檬酸钠),采用共沉淀法在室温下制备出了高钠含量、低缺陷的铁基普鲁士蓝材料。由于高的钠含量和低的晶体缺陷,该材料在0.1C时容量可达110.0 mAh·g^-1。除了普鲁士蓝材料独特的开放框架结构,其多边界结构和低的缺陷,使该材料表现出优异的倍率性能和循环稳定性。在10C大电流下,容量仍有86.6 mAh·g^-1,1C电流下经过1300次循环,容量保持在90.1 mAh·g^-1,容量保持率达到86.9%。     

氧-硼共修饰多壁碳纳米管载铂催化剂的制备及氧还原活性

采用一种简便的方法,合成了氧-硼共修饰的多壁碳纳米管材料,以此为载体制备的铂基催化剂具有更小的铂粒径、更高的电化学表面积(40 m²·g_Pt^-1)和更高的氧还原活性(0.3 A·mg_Pt^-1)。氧、硼在提高碳纳米管的载体分散性、控制铂颗粒的均匀性和粒径、促进氧还原反应的氧吸附/解离方面发挥着重要的作用。     

First-Principles Study on Electronic and Optical Properties of Graphene-Like Boron Phosphide Sheets

Two-dimensional semiconducting materials with moderate band gap and high carrier mobil-ity have a wide range of applications for electronics and optoelectronics in nanoscale. On the basis of first-principles calculations, we perform a comprehensive study on the electronics and optical properties of graphene-like boron phosphide (BP) sheets. The global structure search and first-principles based molecular dynamic simulation indicate that two-dimensional BP sheet has a graphene-like global minimum structure with high stability. BP monolayer is semiconductor with a direct band gap of 1.37 eV, which reduces with the number of layers. Moreover, the band gaps of BP sheets are insensitive to the applied uniaxial strain.= The calculated mobility of electrons in BP monolayer is as high as 10⁶ cm²/(V·s). Lastly, the MoS₂/BP van der Waals heterobilayers are investigated for photovoltaic applications, and their power conversion efficiencies are estimated to be in the range of 17.7%－19.7%. This study implies the potential applications of graphene-like BP sheets for electronic and optoelectronic devices in nanoscale.