A Corrole‐Based Covalent Organic Framework Featuring Desymmetrized Topology

Herein, for the first time, we present the successful synthesis of a novel two‐dimensional corrole‐based covalent organic framework (COF) by reacting the unusual approximately T‐shaped 5,10,15‐tris(p‐aminophenyl)corrole H₃TPAPC with terephthalaldehyde, which adopts desymmetrized hcb topology and consists of a staggered AB stacking structure with elliptical pores. The resultant corrole‐based COF, TPAPC‐COF , exhibits high crystallinity and excellent chemical stability. The combination of extended π‐conjugated backbone and interlayer noncovalent π–π interactions endows TPAPC‐COF with excellent absorption capability in the entire visible‐light and even near‐infrared regions. Moreover, this work suggests the promise of TPAPC‐COF as a new class of photoactive material for efficient singlet‐oxygen generation with potential photodynamic therapy application as demonstrated by in vitro anticancer studies.     

Engineering Active Sites of Polyaniline for AlCl2+ Storage in an Aluminum‐Ion Battery

The reversible capacity of AlCl₄^? intercalation/de‐intercalation in conventional cathodes of aluminum‐ion batteries (AIBs) is difficult to improve due to the large size of AlCl₄^? anions. Therefore, it is highly desirable to realize the intercalation/de‐intercalation of smaller Al‐based ions. Here, we fabricated polyaniline/single‐walled carbon nanotubes (PANI/SWCNTs) composite films and protonated the PANI nanorods. The protonation endows PANI with more active sites and enhanced conductivity. Hyper self‐protonated PANI (PANI(H⁺)) exhibits reversible AlCl₂⁺ intercalation/de‐intercalation during the discharge/charge process. As a result, the discharge capacity of the Al/PANI(H⁺) battery is twice as high as that of the initial composite films. PANI(H⁺)@SWCNT electrodes also have a stable cycling life with only 0.003 % capacity decay per cycle over 8000 cycles. Owing to the excellent mechanical properties, PANI(H⁺)@SWCNT composite films can act as the electrodes of flexible AIBs.     

Thermal‐Gated Polymer Electrolytes for Smart Zinc‐Ion Batteries

Smart self‐protection is essential for addressing safety issues of energy‐storage devices. However, conventional strategies based on sol‐gel transition electrolytes often suffer from unstable self‐recovery performance. Herein, smart separators based on thermal‐gated poly(N‐isopropylacrylamide) (PNIPAM) hydrogel electrolytes were developed for rechargeable zinc‐ion batteries (ZIBs). Such PNIPAM‐based separators not only display a pore structure evolution from opened to closed states, but also exhibit a surface wettability transition from hydrophilic to hydrophobic behaviors when the temperature rises. This behavior can suppress the migration of electrolyte ions across the separators, realizing the self‐protection of ZIBs at high temperatures. Furthermore, the thermal‐gated behavior is highly reversible, even after multiple heating/cooling cycles, because of the reversibility of temperature‐dependent structural evolution and hydrophilic/hydrophobic transition. This work will pave the way for designing thermal‐responsive energy‐storage devices with safe and controlled energy delivery.     

Supramolecular Assembly Based on Octamolybdate and Triazole Derivative: Crystal Structure and Catalytic Application in Olefin Epoxidation

A novel polyoxometalate-based compound, [H(atrz)]₄[(atrz)₂(Mo₈O₂₆)]·2H₂O (1) (atrz = 3-amino-1,2,4-triazole), has been synthesized by traditional hydrothermal method, and characterized by means of elemental analysis, FT-IR spectroscopy, Powder X-ray diffraction and single-crystal X-ray. The compound 1 contains a 2D supramolecualr layer which is constructed from [(atrz)₂(γ-Mo₈O₂₆)]^4? units via intermolecular hydrogen-bonding interactions. Furthermore, the adjacent 2D layers are packed together through the aromatic π?π stacking interactions and exhibits a 3D supramolecular structure. The catalytic properties of 1 were investigated in olefin epoxidation with tert-butylhydroperoxide (t-BuOOH) as the oxidant. It was found that compound 1 could serve as active and stable heterogeneous catalyst for the epoxidation of cyclooctene and 1-octence. Besides, introducing copper ions into compound 1 could further improve the catalytic activity for olefin epoxidation.     

Crystal Engineering of an nbo Topology Metal–Organic Framework for Chemical Fixation of CO2 under Ambient Conditions

Crystal engineering of the nbo metal–organic framework (MOF) platform MOF‐505 with a custom‐designed azamacrocycle ligand (1,4,7,10‐tetrazazcyclododecane‐N,N′,N′′,N′′′‐tetra‐p‐methylbenzoic acid) leads to a high density of well‐oriented Lewis active sites within the cuboctahedral cage in MMCF‐2, [Cu₂(Cu‐tactmb)(H₂O)₃(NO₃)₂]. This MOF demonstrates high catalytic activity for the chemical fixation of CO₂ into cyclic carbonates at room temperature under 1 atm pressure.     

The Molecular Structure of Alzheimer β‐Amyloid Fibrils Formed in the Presence of Phospholipid Vesicles

β‐amyloid (Aβ) fibrils are the major species involved in Alzheimer’s disease (AD). An atomic‐resolution molecular structure of Aβ40 fibrils formed in the presence of lipid vesicles was obtained by using magic angle spinning (MAS) solid‐state NMR spectroscopy. The fibril structures formed in the presence of the lipid vesicles are remarkably different from those formed in solution. These results provide insights into the molecular mechanism of Aβ aggregation in the presence of lipid vesicles.     

An Energy Investigation into 1D/2D Oriented‐Attachment Assemblies of 1D Ag Nanocrystals

In the field of oriented‐attachment crystal growth, one‐dimensional nanocrystals are frequently employed as building blocks to synthesize two‐dimensional or large‐aspect‐ratio one‐dimensional nanocrystals. Despite recent extensive experimental advances, the underlying inter‐particle interaction in the synthesis still remains elusive. In this report, using Ag as a platform, we investigate the van der Waals interactions associated with the side‐by‐side and end‐to‐end assemblies of one‐dimensional nanorods. The size, aspect ratio, and inter‐particle separation of the Ag precursor nanorods are found to have dramatically different impacts on the van der Waals interactions in the two types of assemblies. Our work facilitates the fundamental understanding of the oriented‐attachment assembling mechanism based on one‐dimensional nanocrystals.     

Tetradecacobalt(II)‐Containing 36‐Niobate [Co14(OH)16(H2O)8Nb36O106]20− and Its Photocatalytic H2 Evolution Activity

A gigantic Co₁₄‐containing 36‐niobate, Na₁₂K₈[Co₁₄(OH)₁₆(H₂O)₈Nb₃₆O₁₀₆] ? 71H₂O ( 1 ), has been prepared by the hydrothermal method and structurally characterized. Polyanion [Co₁₄(OH)₁₆(H₂O)₈Nb₃₆O₁₀₆]^20? ( 1 a ) comprises a central Co₇ core, surrounded by another seven isolated Co²⁺ ions and six Lindqvist‐type (Nb₆O₁₉) hexaniobate fragments. This is the first example of a high‐nuclear cobalt‐cluster‐containing polyoxoniobate. The photocatalytic H₂ evolution activity of Pt‐loaded 1 was observed in methanol solution under irradiation using a 300 W Xe lamp.     

Synthesis and electrochromic properties of polybismaleimides containing triphenylamine units

The bismaleimide (BMI) monomer containing triphenylamine was prepared firstly. Then BMI was reacted with different diamines by Michael addition to obtain prepolymers, respectively. Finally, polyimides (PIs) were obtained through melting procedure. The effects of the structure of BMI moiety and thermal curing condition on thermal stability of PIs were studied by thermogravimetric analysis. PIs have excellent processing properties for film casting. Cyclic voltammetry of PI films was carried out on an indium-doped tin oxide-coated glass substrate. Results which exhibit two reversible oxidations at 0.71–0.78 and 1.06–1.16 V vs Ag/AgCl. The electrochromic performance was investigated by spectroelectrochemical methods. These anodically coloring polymer films not only showed good electrochromic properties but also exhibited high optical contrast ratio of transmittance with a color changing from yellow to green. After 100 cyclic switches, the polymer films still retained excellent redox and electrochromic activity.     

海洋柔性立管防弯器结构非线性刚度拓扑优化

防弯器是海洋柔性立管过弯保护的关键附件, 对提高立管的结构安全性具有重要意义. 目前, 防弯器结构设计主要采用尺寸优化方法. 然而, 与拓扑优化方法相比, 该方法能提供的设计空间有限, 其在提高防弯器的力学性能, 以及探索防弯器创新构型方面具有很大不足. 本文在Dirichlet边界条件下, 以最大化弯曲刚度为目标, 对同时考虑材料和几何非线性的防弯器结构拓扑优化方法进行研究. 通过引入Helmholtz-PDE过滤和Heaviside惩罚, 以克服优化中出现的棋盘格现象和灰度单元等数值不稳定性问题. 与此同时, 研究引入了对称算子, 以提高往复性载荷作用下防弯器结构的承载能力和可制造性, 并且采用伴随法对优化问题的灵敏度进行了推导. 此外, 为了提高结构分析和优化的效率, 研究还基于PETSc库建立了并行程序框架. 数值算例中, 在材料体分比相同的情况下, 对防弯器结构分别进行了2D和3D非线性拓扑优化, 并对两种优化结果的承载能力进行了对比. 数值算例结果表明, 相比于防弯器2D拓扑优化结果, 在大部分波浪载荷方向下, 3D拓扑优化所给出的防弯器设计方案具有更为优越的结构性能. 本文所建立的3D非线性拓扑优化技术, 为深水恶劣海况下的高性能防弯器结构设计提供了新的理论模型和实现技术.