Self-supported metal sulphide nanocrystals-assembled nanosheets on carbon paper as efficient counter electrodes for quantum-dot-sensitized solar cells

Developing efficient counter electrodes (CEs) and quantum dots made of earth-abundant and non-toxic elements is essential but still challenging for quantum dot-sensitized solar cells (QDSSCs). Here, we report a facile strategy to prepare self-supported and robust CoS₂ and NiS nanocrystals-assembled nanosheets directly grown on carbon paper (MSx NS@CP) as efficient counter electrodes for QDSSCs. Such CEs integrate the merits of fast electron transfer from interconnected conductive scaffold, efficient mass transfer from hierarchically vertical nanosheet on 3D open substrate, as well as abundant highly active catalytic sites from metal sulphide nanocrystal units. As a result, QDDSCs based on such CoS₂ NS@CP and NiS NS@CP CEs achieve a PCE of 8.88% and 7.53%, respectively. The detailed analyses suggest that CoS₂ NS@CP has the highest catalytic activity and shows the lowest charger transfer resistance, leading to the highest PCE. These findings may inspire the design and exploration of other self-supported efficient CEs by integrating highly active catalysts onto 3D conductive networks for efficient QDSSCs.     

Structure and further fragmentation of significant [a3 + Na − H]+ ions from sodium‐cationized peptides

A good understanding of gas‐phase fragmentation chemistry of peptides is important for accurate protein identification. Additional product ions obtained by sodiated peptides can provide useful sequence information supplementary to protonated peptides and improve protein identification. In this work, we first demonstrate that the sodiated a₃ ions are abundant in the tandem mass spectra of sodium‐cationized peptides although observations of a₃ ions have rarely been reported in protonated peptides. Quantum chemical calculations combined with tandem mass spectrometry are used to investigate this phenomenon by using a model tetrapeptide GGAG. Our results reveal that the most stable [a₃ + Na ? H]⁺ ion is present as a bidentate linear structure in which the sodium cation coordinates to the two backbone carbonyl oxygen atoms. Due to structural inflexibility, further fragmentation of the [a₃ + Na ? H]⁺ ion needs to overcome several relatively high energetic barriers to form [b₂ + Na ? H]⁺ ion with a diketopiperazine structure. As a result, low abundance of [b₂ + Na ? H]⁺ ion is detected at relatively high collision energy. In addition, our computational data also indicate that the common oxazolone pathway to generate [b₂ + Na ? H]⁺ from the [a₃ + Na ? H]⁺ ion is unlikely. The present work provides a mechanistic insight into how a sodium ion affects the fragmentation behaviors of peptides. Copyright © 2015 John Wiley & Sons, Ltd.     

Optically Active Helical Vinylterphenyl Polymers: Chiral Teleinduction in Radical Polymerization and Tunable Stereomutation

Helical vinyl aromatic polymers are emerging as interesting chiral materials due to their dynamic tailorability, synthetic simplicity, and outstanding chemical and physical stabilities. This Personal Account discusses long‐range chirality transfer in the radical polymerization of vinylterphenyl monomers and tunable stereomutation of the resultant polymers. It begins with a general introduction to the design, synthesis, and characterization of helical poly{(+)‐2,5‐bis[4′‐((S)‐2‐methylbutyloxy)phenyl]styrene}, the first one of this series of polymers. Then, long‐range chirality transfer during radical polymerization of terphenyl‐based vinyl monomers is explained. After that, the chiroptical property control of the resultant polymers by means of the transition from kinetically controlled conformation to thermodynamically controlled conformation and external stimulus is described. This Personal Account concludes by discussing the advantages and disadvantages of the strategy of using vinylterphenyls to obtain optically active helical polymers and providing a short outlook, especially emphasizing the importance of tacticity on the chiroptical properties of polymers.     

微生物铁氧化还原作用对水中砷锑去除影响的研究进展

砷锑污染在全球领域广泛存在,与常规的铁氧化物相比,微生物铁氧化生成的含Fe(Ⅲ)矿物对水中砷/锑(As/Sb)具有更强的吸附能力,并因其高效、实用和环境友好而具有广阔的应用前景,但微生物铁还原也可能导致被吸附的As/Sb再次释放。本文综述了微生物铁氧化还原作用对As/Sb去除影响的研究进展,归纳了铁矿物“合成-溶解-转化”的微生物循环过程以及该循环伴随的水中As/Sb固定、溶解与转化机理,整合了微生物合成Fe(Ⅲ)矿物的矿物学性质、对As/Sb固定的热动力学规律和络合机制,总结了微生物合成Fe(Ⅲ)矿物对As/Sb去除的影响因素,基于该研究的现存问题展望了利用微生物铁氧化还原作用去除As/Sb的发展方向。     

ZIF-8衍生的具有可控氧空位的ZnO对光催化去除NO的增强及毒性NO2形成的抑制

氧化锌作为一种半导体材料,具有合适的能带结构位置,高催化效率,低成本和环境可持续性,因而广泛用于光催化领域.然而,由于氧化锌的宽带隙,可见光吸收能力差以及光生电子-空穴对的快速复合,极大地影响了其光催化效率.通过引入氧空位调控光催化剂的结构被证明是一种可以改善光生载流子的分离,从而提高光催化性能的有效方法.本文以ZIF-8为前驱体,采用两步煅烧法合成了具有不同浓度氧空位分布的ZnO纳米光催化剂,通过X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、紫外-可见漫反射光谱(UV-Vis DRS)、X射线光电子能谱(XPS)、电子顺磁共振(EPR)、荧光光谱仪(PL)等手段系统地分析了合成的光催化剂的理化性质,并评价了它们在可见光下光催化氧化去除NO反应性能.EPR结果表明,样品中氧空位的浓度取决于温度处理的过程.通过两步煅烧法得到氧化锌中氧空位的含量高于一步直接煅烧法所得的样品.此外,随着煅烧温度升高,合成的氧化锌晶格越完好,其氧空位含量越少.UV-Vis DRS结果表明,两步煅烧法合成的ZnO与商业的ZnO及一步法直接煅烧合成的ZnO相比,其吸光范围从紫外光拓展到了可见光,表现出了更加优异的吸光性能.光催化反应结果表明,与商业氧化锌和一步直接煅烧法所得样品相比,两步煅烧法合成的样品表现出了更优异的光催化去除NO性能,并抑制了中间产物毒性NO2的产生,促进了NO的深度氧化.具体反应路径为:在光照过程中,光生电子很容易被氧空位俘获,与O2反应产生更多的超氧自由基(·O2^-),从而将NO氧化成最终的产物硝酸盐.尤其有趣的是,先在350 ℃煅烧2小时再400℃煅烧1小时的两步法样品Z 350-400的NO去除效率分别比一步法样品Z 400(400℃煅烧)和商用ZnO高出1.5和4.6倍.这表明以MOF材料衍生的具有适当量氧空位的金属氧化物为一种高效去除NO的光催化剂具有很好的应用前景.     

等达因图象的自动采集与识别

文中提出了一种机机械扫描系统．小功率激光器、图象板、相移元件、微机和程序软件组成的等达因图象自动采集与处理系统，用灰度值比较的思想实现了等达因图象的跟踪采集。提出了四幅图象相移法实现等达因图象的自动识别。系统能快速、实时、精确和全自动地实现等达因图象的记录和分析。给出与物体内各点应力状态一一对应的位相图。并用来研究了其他实验方法困难的局部三维效应问题。     

高温封隔器胶筒与套管接触压力的实验研究

本文利用所研制的高温封隔器测试装置,应用高温电阻应变测试技术与有限元相结合的方法,研究了油井高温封隔器胶筒与石油套管内壁接触压力大小和分布规律,为优化高温封隔器的设计,提供有价值的数据。     

ANALYSIS OF FRICTION INDUCED VIBRATION UNDER THE ACTIVE DISTURBANCE REJECTION CONTROL FRAMEWORK 1)

自抗扰控制(active disturbance rejection control, ADRC)是一种具有两自由度控制结构的工程化方法, 由于其能够直观有效地处理多种扰动, 近些年来在许多机电系统上得到了成功应用. 当采用ADRC对带有摩擦力的机电系统进行调节时, 可能会产生极限环振动. 目前, 还没有ADRC框架下摩擦力振动精确分析的相关工作. 因此, 本文采用非线性动力学系统的分析工具对这一问题进行研究. 首先, 考虑两种典型摩擦力模型, 静态切换模型和动态LuGre 模型, 对一类二阶运动系统设计不同阶次的ADRC, 得到控制器的等效形式, 并揭示出与比例积分微分(proportional-integral-derivative, PID)控制之间的联系. 然后, 采用打靶法结合拟弧长延拓方法求解系统中的极限环, 并根据Floquet理论判断极限环的稳定性、可能出现的分岔以及分岔类型. 此外, 通过雅克比矩阵和近似数值方法对系统平衡点集的局部稳定性进行了分析. 最后, 通过数值计算研究了摩擦力模型和参数、ADRC阶次和参数对极限环和平衡点集的影响. 计算结果表明, 决定摩擦力Stribeck效应负斜率的参数$\beta$作用较大. 当$\beta>1$时, 两种摩擦力模型下的闭环系统呈现出相同的特性, 极限环会出现环面折叠分岔(cyclic fold bifurcation, CFB)且平衡点集是局部稳定的. 然而当$\beta<1$时, 两种闭环系统呈现出完全不同的特性. 此外, 不同阶次的ADRC在极限环的存在性和稳定性、平衡点集的稳定性上面的结论是相同的, 而低阶次的ADRC能够更好地解决摩擦力补偿和稳定鲁棒性之间的矛盾问题. 这些结论对实际现象的理解、ADRC阶次的选择以及参数整定提供了一定指导.     

Ⅰ—Ⅲ混合型裂纹相变增韧分析

本文采用压力敏感准则和权函数法对相变增韧陶瓷Ⅰ－Ⅲ混合型裂纹的增韧效应进行了理论预测。分别给出了静止裂纹和定长扩展裂纹相变塑性屏蔽的理论表达式，结果表明：相变对静止裂纹有负屏蔽效应，并随ＫⅢ／ＫⅠ比值的增大而趋于零，对扩展裂纹的增韧结果除与材料的弹性模量，相变尾区高度和相变体积分数有关外，还与ＫⅢ／ＫⅠ的比值有关。