Research Progress in the Field of Adsorption and Catalytic Degradation of Sewage by Hydrotalcite‐Derived Materials

With the rapid development of industry and agriculture and the greatly improved living conditions, the resultant gradually deteriorated environments threaten the human beings. Refractory or even toxic pollutants, which are from different industries such as printing and dyeing, pesticides, chemicals, petrochemicals, plastics and rubber, seriously threat the ecosystems and human health. Having the advantages of flexible composition, unique structure, high stability, memory effect, easy preparation and low cost, hydrotalcite compounds have a great potential in sewage degradation and environmental protection. This study focuses on the adsorption and catalytic properties (such as photocatalysis, electrocatalysis and photoelectrocatalysis) of hydrotalcite‐derived materials for treating organic, inorganic and heavy metal ion sewage. The types of adsorption and catalysis, and the effects of various influencing factors on the degradation efficiency were discussed as well.     

Comprehensive separation of iridoid glycosides and triterpenoid saponins from Dipsacus asper with salt‐containing solvent by high‐speed countercurrent chromatography coupled with recycling mode

The roots of Dipsacus asper Wall as a commonly used traditional Chinese medicine are used for tonifying liver and kidney and strengthening bones and muscles. However, an effective separation strategy for comprehensive and rapid separation of the main active compounds from the roots of D. asper is nonexistent. This investigation provided an effective separation method based on AB‐8 macroporous resin column chromatography using different ratios of ethanol in water and two different modes of high‐speed countercurrent chromatography with salt‐containing solvent system for rapid enrichment and separation from the roots of D. asper. The macroporous resin column chromatography was performed on AB‐8 resin using ethanol in water ratios of 10, 30, 40, 50, and 80% as the optimized enrichment conditions for iridoid glycosides and triterpenoid saponins with different polarities. For high‐speed countercurrent chromatography separation, the conventional and recycling modes were combined together to develop a strategy for 12 compounds ( 1 – 12 ) from the enriched parts of 30, 40, and 80% ethanol, including six high‐polarity iridoid glycosides ( 1 – 6 ) using inorganic salt‐containing solvent system and six triterpenoid saponins ( 7 – 12 ). Recycling high‐speed countercurrent chromatography separation was successfully applied to separate two isomers ( 9 and 10 ) after 11 cycles.     

Photocatalysis: an overview of recent developments and technological advancements

Photocatalysis,which is the catalyzation of redox reactions via the use of energy obtained from light sources,is a topic that has garnered a lot of attention in recent years as a means of addressing the environmental and economic issues plaguing society today.Of particular interest are photosynthesis can potentially mimic a variety of vital reactions,many of which hold the key to develop sustainable energy economy.In light of this,many of the technological and procedural advancements that have recently occurred in the field are discussed in this review,namely those linked to:(1)photocatalysts made from metal oxides,nitride,and sulfides;(2)photocatalysis via polymeric carbon nitride(PCN);and(3)general advances and mechanistic insights related to TiO2-based catalysts.The challenges and opportunities that have arisen over the past few years are discussed in detail.Basic concepts and experimental procedures which could be useful for eventually overcoming the problems associated with photocatalysis are presented herein.     

Unique Thia‐Baeyer–Villiger‐Type Oxidation of Dibenzothiophene Sulfoxides Derivatives

The present research has demonstrated that selective C?S bond cleavages of dibenzothiophene and its derivatives are feasible by thia‐Baeyer–Villiger type oxidation, i. e. the oxygen insertion process within a sulfoxide‐carbon linkage, in the presence of porphyrin iron (III) and by ultraviolet irradiation originating from sunlight, high pressure Hg‐lamp or residentially germicidal ultraviolet lamp under very mild conditions. This reaction with tert‐butylhydroperoxide at 30.0 °C leads to dibenzo[1,2]oxathiin‐6‐oxide ( PBS ) in 83.2 % isolated yield or its hydrated products, 2‐(2‐hydroxyphenyl)‐benzenesulfinic derivatives ( HPBS ) in near 100 % yield based HPLC data. PBS and HPBS are a type of biological products detected on the C?S bond cleavage step through various oxidative biodesulfurization ( OBDS ) pathways, and are useful synthetic intermediates and fine chemicals. These observations may contribute on understanding delicately molecular aspect of OBDS in the photosynthesis system, expanding the C‐S cleavage chemistry of S‐heterocyclic compounds and approaching toward biomemic desulfurization with respect to converting sulfur contaminants to chemically beneficial blocks as needed and performing under the ambient conditions.     

Tuning Magnetic Anisotropy in a Class of Co(II) Bis(hexafluoroacetylacetonate) Complexes

Tuning the magnetic anisotropy of metal ions remains highly interesting in the design of improved single‐molecule magnets (SMMs). We herein report synthetic, structural, magnetic, and computational studies of four mononuclear Co^II complexes, namely [Co(hfac)₂(MeCN)₂] ( 1 ), [Co(hfac)₂(Spy)₂] ( 2 ), [Co(hfac)₂(MBIm)₂] ( 3 ), and [Co(hfac)₂(DMF)₂] ( 4 ) (MeCN=acetonitrile, hfac=hexafluoroacetylacetone, Spy=4‐styrylpyridine, MbIm=5,6‐dimethylbenzimidazole, DMF=N,N‐dimethylformamide), with distorted octahedral geometry constructed from hexafluoroacetylacetone (hfac) and various axial ligands. By a building block approach, complexes 2 – 4 were synthesized by recrystallization of the starting material of 1 from various ligands containing solution. Magnetic and theoretical studies reveal that 1 – 4 possess large positive D values and relative small E parameters, indicating easy‐plane magnetic anisotropy with significant rhombic anisotropy in 1 – 4 . Dynamic alternative current (ac) magnetic susceptibility measurements indicate that these complexes exhibit slow magnetic relaxation under external fields, suggesting field‐induced single‐ion magnets (SIMs) of 1 – 4 . These results provide a promising platform to achieve fine tuning of magnetic anisotropy through varying the axial ligands based on Co(II) bis(hexafluoroacetylacetonate) complexes.     

Hyperbranched Poly(ester‐enamine) from Spontaneous Amino‐yne Click Reaction for Stabilization of Gold Nanoparticle Catalysts

Hyperbranched polymers have garnered much attention due to attractive properties and wide applications, such as drug‐controlled release, stimuli‐responsive nano‐objects, photosensitive materials and catalysts. Herein, two types of novel hyperbranched poly(ester‐enamine) (hb‐PEEa) were designed and synthesized via the spontaneous amino‐yne click reaction of A₂ monomer (1, 3‐bis(4‐piperidyl)‐propane (A_2a) or piperazine (A_2b)) and B₃ monomer (trimethylolpropanetripropiolate). According to Flory's hypothesis, gelation is an intrinsic problem in an ideal A₂+B₃ polymerization system. By controlling the polymerization conditions, such as monomer concentration, molar ratio and rate of addition, a non‐ideal A₂+B₃ polymerization system can be established to avoid gelation and to synthesize soluble hb‐PEEa. Due to abundant unreacted alkynyl groups in periphery, the hb‐PEEa can be further functionalized by different amino compounds or their derivates. The as‐prepared amphiphilic PEG‐hb‐PEEa copolymer can readily self‐assemble into micelles in water, which can be used as surfactant to stabilize Au nanoparticles (AuNPs) during reduction of NaBH₄ in aqueous solution. As a demonstration, the as‐prepared PEG‐hb‐PEEa‐supported AuNPs demonstrate good dispersion in water, solvent stability and remarkable catalytic activity for reduction of nitrobenzene compounds.     

A twofold interpenetrating two‐dimensional zinc(II) coordination polymer: synthesis,crystal structure and physical properties

A novel twofold interpenetrating two‐dimensional (2D) Zn^II coordination framework, poly[[(μ‐1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene‐κ²N³:N³)(μ‐naphthalene‐2,6‐dicarboxylato‐κ²O²:O⁶)zinc(II)] dimethylformamide monosolvate], {[Zn(C₁₂H₆O₄)(C₁₄H₁₄N₄)]·C₃H₇NO}_n or {[Zn(1,3‐BMIB)(NDC)]·DMF}_n (I), where H₂NDC is naphthalene‐2,6‐dicarboxylic acid, 1,3‐BMIB is 1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene and DMF is dimethylformamide, was prepared and characterized through IR spectroscopy, elemental analysis, thermal analysis and single‐crystal X‐ray diffraction. Single‐crystal X‐ray diffraction analysis revealed that (I) exhibits an unusual twofold interpenetrating 2D network. In addition, it displays strong fluorescence emissions and a high photocatalytic activity for the degradation of Rhodamine B (RhB) under UV‐light irradiation.     

不同细料含量土石混合料塑性行为离散元模拟

土石混合料是指由大粒径的块石和作为填充成分的细粒土组成的二元混合料, 其塑性行为与细料含量密切相关. 目前对细粒含量如何影响土石混合料塑性行为及其细观机制的研究尚不充分, 为此本文开展了不同细料含量土石混合料的二维离散元数值模拟, 基于二阶功失稳准则与细观力学理论, 探究了细料含量对石料骨架土石混合料失稳特性与非关联流动特性的影响, 并揭示了细料含量影响土石混合料塑性力学行为的细观机制. 研究结果表明, 细颗粒可通过限制集合体塑性变形从而起到促进集合体整体稳定的作用; 细颗粒控制颗粒集合体塑性变形的方向(即塑性势面法方向), 随着细料含量增大, 土石混合料的塑性势面法方向和屈服面法方向之间的夹角减小, 非关联流动性减弱, 材料分岔失稳区域变窄; 尽管加入到石颗粒中的部分细颗粒与石颗粒共同承担骨架作用, 但是细颗粒的加入不影响颗粒集合体的力学状态, 不改变材料屈服面法方向. 相关研究结果可为建立考虑细料含量的土石混合料弹塑性本构模型提供理论依据.      

基于FDM-DEM耦合的冲击损伤大理岩静态断裂力学特征研究

为探究循环冲击损伤后大理岩的静态断裂力学特征,基于有限差分（finite difference method,FDM）-离散元（discrete element method,DEM）耦合的建模技术构建了三维分离式霍普金森压杆（split Hopkinson pressure bar,SHPB）数值模型,其中杆件系统和岩石试件分别采用FLAC3D和PFC3D程序建模。利用该模型对中心直切槽半圆盘（NSCB）试样进行了恒定子弹速度下的循环冲击,随后对受损试样进行静态三点弯曲断裂实验。通过编写Fish程序,提取试样断裂面数据,对断裂面进行重构并定量计算表面粗糙度。通过与相关室内实验结果的对比分析,验证了本文数值分析的合理性与可靠性。模拟结果表明,随着循环冲击次数的增加,试样内部微裂纹、破碎颗粒均增加。连接力场分布混乱,部分力链发生断裂。力链的变化是试样力学性能劣化的根本原因。在静态三点弯曲断裂实验中,冲击5次后试样的静态断裂韧度较天然试样产生一定程度的降低。试样在静载过程中产生的微裂纹和碎块的数量随循环冲击次数的增加而增加,断裂面粗糙度随循环冲击次数的增加而增加。     

并行FDTD和IBM BlueGene/L巨型计算机结合求解电大尺寸的电磁问题

高性能巨型计算机的快速发展正在改变着人们在计算电磁学方面的一些传统观念,特别是IBM BlueGene/L巨型计算机的出现使计算电磁学所解决的问题尺寸和时间发生了巨大的变化.IBM BlueGene/L巨型计算机可以包括多达65,536处理器和 32 TB 内存,更重要的是由于它所使用的特殊体系结构使它在4000个处理器时时域有限差分程序的并行效率仍然在百分之九十左右.测试显示,在单个CPU速度接近的情况下,一台奔腾4计算机上运行五十二天的工作量在一个包含有4000个处理器的BlueGene/L巨型计算机上仅需10min左右.虽然普通的PC机群与单个处理器相比也能快速地求解相对大的问题,但是无论是使用千兆 Ethernet、Foundry、Myrinet或者Infiniband,普通PC机群的效率都会在处理其数量超过几十个的时候快速下降.为了验证并行时有预先差分程序的正确性,我们使用并行时域有限差分程序在巨型计算机IBM BlueGene/L上模拟一个144单元的对偶极化Vivaldi阵列的抛物面天线馈源.