Nanostructured BiVO4 Derived from Bi-MOF for Enhanced Visible-light Photodegradation

BiVO4,a promising visible-light responding photocatalyst,has aroused extensive research interest because of inexpensiveness and excellent chemical stability.However,its main drawback is the poor photoinduced charge-transfer dynamics.Building nanostructures is an effective way to tackle this problem.Herein,we put forward a new method to prepare nanostructured BiVO4 from Bi-based metal-organic frameworks[Bi-MOF(CAU-17)]precursor.The as-prepared material has a rod-like morphology inherited from the Bi-MOF sacrificial template and consists of small nanoparticle as building blocks.Compared with its counterparts prepared by conventional methods,MOF-derived nanostructured BiVO4 shows better light absorption ability,narrower bandgap,and improved electrical conductivity as well as reduced recombination.Consequently,BiVO4 nanostructure demonstrates high photocatalytic activity under visible light towards the degradation of methylene blue.Methylene blue can be degraded up to 90%within 30 min with a reaction rate constant of 0.058 min-1.Moreover,the cycling stability of the catalyst is excellent to withstand unchanged degradation efficiency for at least 5 cycles.     

星载海洋激光雷达最佳工作波长分析

星载激光雷达是实现海洋垂直剖面探测的有效工具,也是目前迫切需求的海洋光学遥感手段。对星载海洋激光雷达的波长参数进行评估对保证探测有效性具有重要意义。本文从探测深度和信噪比两方面分析了星载海洋激光雷达探测全球海洋的最佳波长。利用MODIS 10个波段的水体光学特性数据,估算全球海水探测深度及相应的最优波长;并根据太阳夫琅禾费暗线特性,对信号信噪比进行优化。结果表明:在探测深度方面,最优探测波长在488 nm波段的海洋占全球海洋面积的70%左右,并且全球95%以上的海域在488 nm波段的探测深度优于0.8倍的真光层深度;在信噪比方面,相对于488 nm波段,486.134 nm夫琅禾费暗线处采用0.1 nm带宽的滤光片可以将背景光强度降低70%,相应地回波信噪比整体提升了约5.0%。就全球海洋探测来说,使用486.134 nm作为探测波长可以提高探测深度,有效抑制太阳背景光,提高信噪比,因此,486.134 nm是星载海洋激光雷达的最佳工作波长。     

d-Orbital Reconstructions Forced by Double Bow-Shaped Deformations and Second Coordination Sphere Effects of Cu(II) Heme Analogs in HER**

Both geometric architecture and electronic configurations of heme proteins contribute to its activity. In this work we designed and synthesized a series of four copper(II) porphyrin complexes ( 4 -, 3 -, 2 - and 1 -Cu) where the molecular conformations are modulated by a pair of stepwise shortened straps on the same porphyrin side (cis-ortho) to give double bow-shaped skeletons. Single crystal structures demonstrate that the straps gradually increase the saddle deformation and the deviation of the metal centers, which is in accordance with two, unusual d-orbital reconstructions of two different ground states, as revealed by 4 K EPR and DFT calculations. In the study of the electrocatalytic hydrogen evolution reaction (HER), 1 -Cu, with the shortest straps, showed the most apparent improvement of activity. Second coordination sphere (SCS) effects created by the double bow-shaped architecture and the strong saddle porphyrin core in 1 -Cu are found to play key roles in proton trapping during the catalytic process. The work contributes a novel strategy to improve the catalytic performance of heme analogs through ligand geometric modulation.     

A Novel Energetic Ionic Salt: Hydroxylammonium Potassium 3,3’-Dinitro-5,5’-bis-1,2,4-triazole-1,1’-diolate Dihydrate

A novel energetic ionic salt,hydroxylammonium potassium 3,3?-dinitro-5,5?-bis-1,2,4-triazole-1,1?-diolate dihydrate[(NH3OH)2K(DNOBT)1.5?2H2O],was synthesized and structurally characterized by elemental analysis,IR spectra,13C NMR and single-crystal X-ray diffraction.(NH3OH)2K(DNOBT)1.5?2H2O crystallizes in triclinic system,space group P with a=7.9212(6),b=9.1924(7),c=14.2549(15)?,a=103.917(2)°,β=99.736(2)°,g=104.8110(10)°,V=944.16(14)?^3,Z=2,Dc=1.855 g/cm^3,F(000)=538,μ=0.386 mm^-1,S=1.070,the final R=0.0525 and wR(I>2s(I))=0.1593.Thermal decomposition of(NH3OH)2K(DNOBT)1.5?2H2O and its intermediate potassium 1?-hydroxy-3,3?-dinitro-5,5?-bis-1,2,4-triazole-1-olate monohydrate[K(HDNOBT)?H2O]was studied by using DSC and TG-DTG.It was found that(NH3OH)2K(DNOBT)1.5?2H2O,which has primarily one exothermic decomposition process at 248.2℃,has better thermal stability than K(HDNOBT)?H2O which is decomposed at 210.9℃.     

参外联合激励下的簇发振荡及其机理

当周期激励频率远小于系统固有频率时，会存在快慢耦合效应，与单项激励不同，参外联合激励不仅会导致快子系统平衡曲线和分岔行为的复杂化，也会产生一些特殊的非线性现象，为此，本文以两耦合Hodgkin-Huxley细胞模型为例，引入周期参外联合激励，探讨在频域不同尺度耦合时该系统的簇发振荡的特点及其分岔机制．通过建立相应的快慢子系统，得到慢变参数变化下的快子系统的各种分岔模式以及相应的分岔行为，结合转换相图，揭示耦合系统随激励幅值变化时的动力学行为及其机理．研究表明，在激励幅值较小时，系统表现为概周期振荡，两频率分别近似于快子系统平衡曲线由Hopf分岔引起的两稳定极限环的振荡频率．概周期解随激励幅值的增加进入簇发振荡，导致这些簇发振荡的主要原因是在慢变参数变化的部分区间内，存在唯一稳定的平衡曲线，使得系统的轨迹逐渐趋向该平衡曲线，产生沉寂态，并随着慢变参数的变化，由分岔进入激发态．同时，快子系统中参与簇发振荡的稳定吸引子随激励幅值的变化也会不同，导致不同形式的簇发振荡．另外，与单项激励下的情形不同，联合激励时快子系统的部分稳定吸引子掩埋在其它稳定吸引子内，从而失去对簇发振荡的影响．     

Mechanism of N-to-S acyl transfer of N-(2-hydroxybenzyl) cysteine derivatives and origin of phenol acceleration effect

The mechanism of N-to-S acyl transfer of N-(2-hydroxybenzyl) cysteine derivatives and the origin of acceleration effect of phenol substitutes were investigated by DFT methods.     

从“概念转变”到“概念理解”——科学概念学习研究的转向

当前国际科学概念学习研究显示了从“概念转变”到“概念理解”的转向。通过分析概念转变教学研究的结果,得出影响概念转变的关键因素在于学生对科学概念的理解。阐释了概念理解的内涵、特征,探讨了概念理解与高级思维的关系、概念理解水平、概念理解的教学和评价等内容。     

NaOH后处理对多级孔Hβ分子筛上木质素催化热解性能的影响

采用碱性条件下"后处理"脱硅的方法,制备了一系列多级孔Hβ分子筛,考察了Na OH浓度对Hβ分子筛上木质素催化热解性能的影响。结果表明,当Na OH浓度小于0.2 mol/L时,碱处理后的多级孔Hβ分子筛的介孔数量增加,木质素热解液体产物的收率随着Na OH浓度提高而显著增加。当Na OH浓度小于0.5 mol/L时,碱处理可以保持多级孔Hβ分子筛的微孔结构基本不被破坏,木质素催化热解具有较好的脱氧效果;产物以芳烃为主,含氧化合物的收率始终小于3%。当Na OH的浓度增加到1 mol/L时,会造成Hβ分子筛过度脱硅,骨架坍塌;由于Hβ分子筛的多级孔结构被破坏,此时不仅木质素热解液体产物的收率降低,而且脱氧效果变差。     

Fe3O4@HTlc的制备及其对甲基橙的吸附研究

采用液相非稳态共沉淀法制备了磁性镁铝类水滑石(Fe3O4@HTlc),采用透射电子显微镜、粉末X射线衍射仪、傅里叶变换红外光谱仪、振动样品磁强计、比表面分析仪、微电泳仪等对样品的形貌和结构进行了表征,并比较了 Fe3O4@HTlc和HTlc对甲基橙的吸附性能。结果表明,Fe3O4@HTlc为顺磁性、具有核-壳结构和较大比表面积、带有正电荷的近球状颗粒。甲基橙在Fe3O4@HTlc和HTlc上的吸附动力学曲线均符合准一级动力学方程;吸附等温线均符合Langmuir吸附等温式;298 K时Fe3O4@HTlc和HTlc对甲基橙的饱和吸附量分别为138.89和147.06 mg/g,但Fe3O4@HTlc对甲基橙有较强吸附推动力和较短的吸附平衡时间。二者对甲基橙的吸附量均随温度的升高和pH (5~11)的增加而降低。     

Modular One‐Step Three‐Component Synthesis of Tetrahydroisoquinolines Using a Catellani Strategy

Reported is a modular one‐step three‐component synthesis of tetrahydroisoquinolines using a Catellani strategy. This process exploits aziridines as the alkylating reagents, through palladium/norbornene cooperative catalysis, to enable a Catellani/Heck/aza‐Michael addition cascade. This mild, chemoselective, and scalable protocol has broad substrate scope (43 examples, up to 90 % yield). The most striking feature of this protocol is the excellent regioselectivity and diastereoselectivity observed for 2‐alkyl‐ and 2‐aryl‐substituted aziridines to access 1,3‐cis‐substituted and 1,4‐cis‐substituted tetrahydroisoquinolines, respectively. Moreover, this is a versatile process with high step and atom economy.