Co(H_2O)_6~(2 /3 )体系电子转移反应动力学的理论研究

电子转移过程在化学、生命科学、材料科学等领域普遍存在,几十年来一直受到国际学术界的广泛关注,是当前化学研究的前沿课题之一[1－6].过渡金属络合物间的电子转移是一类重要的电子转移过程,其动力学行为是理论和实验研究的热点[7－12].根据过渡态理论,这类自交换反应速率可表示为ket=κeZeffexp(－ΔE/RT)(1)其中,Zeff为核频率因子,对于溶液中的双分子反应其值约为1011dm3·mol－1·s－1[11];ΔE是活化能;κe称为电子因子,对于绝热反应κe=1.显然,活化能和电子因子是影响电子转移速率的两个关键因素.根据络合物的结构特点,一…     

Eu3+和Tb3+的2,3-吡啶二甲酸配合物的发光研究

合成了一系列Eu3+和Tb3+与 2 ,3-吡啶二甲酸 (简称H2 QUI)的单核、同多核及它们分别与非荧光性稀土离子La3+,Gd3+,Y3+的异多核配合物 ,并对单核配合物分别引入含氮配体 1,10-邻菲咯啉 (简称 phen)和 2 ,2’ -联吡啶 (简称 2 ,2’ -bipy)生成三元配合物。对这些配合物进行了红外     

DFT研究掺杂和电场条件下2,6-二氯苯并-2,4-二氯苯胺在石墨烯表面的吸附

本工作采用密度泛函理论详细探讨了2,6-二氯苯并-2,4-二氯苯胺（2,6-DBDA）氯代有机二噁英与纯的, Fe和Ti掺杂石墨烯之间的吸附机理, 并考虑了外加电场对吸附的影响. 结果表明掺杂 Fe和Ti原子增强了2,6-DBDA 在石墨烯表面的吸附, 这是因为Fe和Ti掺杂石墨烯与2,6-DBDA间形成了metal-N和metal-Cl共价相互作用. 此外, 在外加电场的作用下, 不同原子掺杂的石墨烯对2,6-DBDA的吸附影响不同. 2,6-DBDA-Ti-G体系, 在添加0.010 au的外电场时有最大相互作用, 而2,6-DBDA-Fe-G体系, 相互作用随着电场的施加反而有所减小. 金属掺杂及电场可以灵活调控2,6-DBDA在石墨烯表面的吸附, 此研究有望为氯代有机二噁英的检测及去除提供有价值的理论指导.     

Synthesis, characterization of the pentacene and fabrication of pentacene field-effect transistors

A comprehensive understanding of the organic semiconductor material pentacene is meaningful for organic fieldeffect transistors （OFETs）. Thin films of pentacene are the most mobile molecular films known to date. This paper reported that the pentacene sample was successfully synthesized. The purity of pentacene is up to 95%. The results of a joint experimental investigation based on a combination of infrared absorption spectra, mass spectra （MS）, element analysis, x-ray diffraction （XRD） and atom force microscopy （AFM）. The authors fabricated OFET with the synthesized pentacene. Its field effect mobility is about 1.23 cm^2/（V·s） and on-off ratio is above 10^6.     

高指数晶面和梯度组成的PtCu3@Pt3Cu@Pt纳米枝晶氧还原电催化剂性能

燃料电池作为一种清洁、高效的能量转换装置,其大规模应用受到阴极氧还原反应(ORR)动力学缓慢以及铂资源稀缺和价格高昂等的极大制约.尽管研究人员在过去几十年中付出了巨大努力,但研制高效、耐用的低Pt合金催化剂仍亟待突破.近年的研究表明,Pt的一些高指数晶面能够表现出比Pt(111)晶面更高的ORR活性,尤其是Pt(332...     

Er3+单掺与Er3+/Yb3+共掺NBT-CT无铅压电陶瓷的上转换发光性能研究

采用固相烧结法制备一系列Er³⁺单掺与Er³⁺/Yb³⁺共掺0.96Na_0.5Bi_0.5TiO₃-0.04CaTiO₃(NBT-CT∶xEr³⁺/yYb³⁺,x=0.002~0.015,y=0.010)无铅压电陶瓷。通过X射线衍射仪和荧光光谱仪分别对样品的物相结构和上转换发光特性进行表征和分析。结果表明,样品的主晶相为NBT晶相。在波长为980 nm的近红外光激发下,Er³⁺单掺与Er³⁺/Yb³⁺共掺NBT-CT陶瓷均呈现强的以绿光为主的Er³⁺特征上转换发光。在NBT-CT∶xEr³⁺中,当x=0.010时上转换发光性能最佳;Yb³⁺能够起到敏化作用,明显增强Er³⁺的上转换发光强度。     

基于群表示论的微波等离激元谐振器模式响应研究

作为光频段局域表面等离激元的低频对应物,人工局域表面等离激元因其深亚波长局域场增强和高Q值谐振的特点而受到广泛关注。微波等离激元谐振器是产生人工局域表面等离激元的典型器件,其特点是具有多重离散旋转对称性和镜面反射对称性。以往的研究提出了等效媒质法和等效色散法分析微波等离激元谐振器的模式响应,但这两种方法都未能充分考虑谐振器的几何对称性从而未能全面揭示其模式特性。本文针对谐振器的几何对称性提出了群表示论方法分析其模式响应。通过对称性分析,发现谐振器的几何对称性所构成的群的不可约表示数等于谐振器所能支持的人工局域表面等离激元模式的数目。以对称性构成C_7v群的谐振器为例,C_7v群的5个不可约表示数对应了5种人工局域表面等离激元模式,分别为零阶模式(也即磁偶极子)、偶极子、四极子、六极子和十四极子。受限于几何对称性,谐振器将不能支持更多阶的模式。为验证群表示论方法,设计了对称性构成C_7v群的微波等离激元谐振器,全波仿真结果很好地证明了上述理论。本文提出的群表示论方法也可推广到其他频段如光频,因而具有广泛的适用性。     

Cobalt porphyrin immobilized on the TiO_2 nanotube electrode for CO_2 electroreduction in aqueous solution

Herein we report CO₂ electrochemical reduction reaction(CO₂ ERR)on the cobalt tetraphenylporphyrin(Co TPP)modified TiO₂ nanotube(TNT)electrode.It was found the axial coordination of drop-casting solvent to Co TPP and the porphyrin structure are the major factors that have significant effects on the catalytic performance of the electrode.As confirmed by spectrophotometric titration,pyridine has a stronger coordination bond to Co TPP than DMF and THF thus leading to the highest efficiency among the dropcasting solvents tested in the study.Based on the spectrophotometric analysis,possible coordination mechanism between drop-casting solvents and Co TPP is put forward.On the other hand,introduction of-COOMe substituents in phenyl rings of Co TPP weakens the coordination bond between pyridine and Co TPP as clearly evidenced by deuterium NMR spectra,resulting in a detrimental effect on CO₂ ERR.Therefore,the manipulation of the coordination environment around the metal center of immobilized catalyst is crucial in designing an efficient electrocatalytic system.     

Institution Publication Feature Analysis Based on Time-Series Clustering

Based on the time series of articles obtained from the literature, we propose three analysis methods to deeply examine the characteristics of these articles. This method can be used to analyze the construction and development of various disciplines in institutions, and to explore the features of the publications in important periodicals in the disciplines. By defining the concepts and methods relevant to research and discipline innovation, we propose three methods for analyzing the characteristics of agency publications: numerical distribution, trend, and correlation network analyses. The time series of the issuance of articles in 30 important journals in the field of management sciences were taken, and the new analysis methods were used to discover some valuable results. The results showed that by using the proposed methods to analyze the characteristics of institution publications, not only did we find similar levels of discipline development or similar trends in institutions, achieving a more reasonable division of the academic levels, but we also determined the preferences of the journals selected by the institutions, which provides a reference for subject construction and development.