BO3－3／Mo－MCM－41的制备及其对2－甲氧基萘乙酰化反应的催化性能

 制备了Mo－MCM－41中孔分子筛，并将BO3－3引入到分子筛中制得BO3－3／Mo－MCM－41催化剂．采用XRD，FT－IR，ESR，BET和NH3－TPD对分子筛催化剂的结构及酸强度进行了表征．结果表明，Mo－MCM－41和BO3－3／Mo－MCM－41具有中孔分子筛的特征，有良好的长程有序 性和结晶度；但Mo并未进入分子筛骨架内部而是在分子筛表面以MoO2的形式存在；BO3－3附着于Mo－MCM－41分子筛上形成强酸中心．将BO3－3／Mo－MCM－41用于催化2－甲氧基萘乙酰化反应，考察了催化剂用量、Si／Mo比及BO3－3的引入方式对该反应性能的影响，发现BO3－3／Mo－MCM－41对2－甲氧基萘乙酰化反应具有良好的催化性能．     

Anode-Free Lithium Metal Batteries Based on an Ultrathin and Respirable Interphase Layer

Anode-free lithium (Li) metal batteries are desirable candidates in pursuit of high-energy-density batteries. However, their poor cycling performances originated from the unsatisfactory reversibility of Li plating/stripping remains a grand challenge. Here we show a facile and scalable approach to produce high-performing anode-free Li metal batteries using a bioinspired and ultrathin (250 nm) interphase layer comprised of triethylamine germanate. The derived tertiary amine and Li_xGe alloy showed enhanced adsorption energy that significantly promoted Li-ion adsorption, nucleation and deposition, contributing to a reversible expansion/shrinkage process upon Li plating/stripping. Impressive Li plating/stripping Coulombic efficiencies (CEs) of ≈99.3 % were achieved for 250 cycles in Li/Cu cells. In addition, the anode-free LiFePO₄ full batteries demonstrated maximal energy and power densities of 527 Wh kg⁻¹ and 1554 W kg⁻¹, respectively, and remarkable cycling stability (over 250 cycles with an average CE of 99.4 %) at a practical areal capacity of ≈3 mAh cm⁻², the highest among state-of-the-art anode-free LiFePO₄ batteries. Our ultrathin and respirable interphase layer presents a promising way to fully unlock large-scale production of anode-free batteries.     

Unlocking Reversible Silicon Redox for High-Performing Chlorine Batteries

Chlorine (Cl)-based batteries such as Li/Cl₂ batteries are recognized as promising candidates for energy storage with low cost and high performance. However, the current use of Li metal anodes in Cl-based batteries has raised serious concerns regarding safety, cost, and production complexity. More importantly, the well-documented parasitic reactions between Li metal and Cl-based electrolytes require a large excess of Li metal, which inevitably sacrifices the electrochemical performance of the full cell. Therefore, it is crucial but challenging to establish new anode chemistry, particularly with electrochemical reversibility, for Cl-based batteries. Here we show, for the first time, reversible Si redox in Cl-based batteries through efficient electrolyte dilution and anode/electrolyte interface passivation using 1,2-dichloroethane and cyclized polyacrylonitrile as key mediators. Our Si anode chemistry enables significantly increased cycling stability and shelf lives compared with conventional Li metal anodes. It also avoids the use of a large excess of anode materials, thus enabling the first rechargeable Cl₂ full battery with remarkable energy and power densities of 809 Wh kg⁻¹ and 4,277 W kg⁻¹, respectively. The Si anode chemistry affords fast kinetics with remarkable rate capability and low-temperature electrochemical performance, indicating its great potential in practical applications.     

Understanding the Role of Fluorine Groups in Passivating Defects for Perovskite Solar Cells

Introducing fluorine (F) groups into a passivator plays an important role in enhancing the defect passivation effect for the perovskite film, which is usually attributed to the direct interaction of F and defect states. However, the interaction between electronegative F and electron-rich passivation groups in the same molecule, which may influence the passivation effect, is ignored. We herein report that such interactions can vary the electron cloud distribution around the passivation groups and thus changing their coordination with defect sites. By comparing two fluorinated molecules, heptafluorobutylamine (HFBM) and heptafluorobutyric acid (HFBA), we find that the F/−NH₂ interaction in HFBM is stronger than the F/−COOH one in HFBA, inducing weaker passivation ability of HFBM than HFBA. Accordingly, HFBA-based perovskite solar cells (PSCs) provide an efficiency of 24.70 % with excellent long-term stability. Moreover, the efficiency of a large-area perovskite module (14.0 cm²) based on HFBA reaches 21.13 %. Our work offers an insight into understanding an unaware role of the F group in impacting the passivation effect for the perovskite film.     

Ultrahigh-Rate Na/Cl2 Batteries Through Improved Electron and Ion Transport by Heteroatom-Doped Bicontinuous-Structured Carbon

Rechargeable sodium/chlorine (Na/Cl₂) batteries are emerging candidates for sustainable energy storage owing to their superior energy densities and the high abundance of Na and Cl elements. However, their practical applications have been plagued by the poor rate performance (e.g., a maximum discharge current density of 150 mA g⁻¹), as the widely used carbon nanosphere cathodes show both sluggish electron-ion transport and reaction kinetics. Here, by mimicking the sufficient mass and energy transport in a sponge, we report a bicontinuous-structured carbon cubosome with heteroatomic doping, which allows efficient Na⁺ and electron transport and promotes Cl₂ adsorption and conversion, thus unlocking ultrahigh-rate Na/Cl₂ batteries, e.g., a maximum discharge current density of 16,000 mA g⁻¹ that is more than two orders of magnitude higher than previous reports. The optimized solid–liquid–gas (carbon–electrolyte–Cl₂) triple interfaces further contribute to a maximum reversible capacity and cycle life of 2,000 mAh g⁻¹ and 250 cycles, respectively. This study establishes a universal approach for improving the sluggish kinetics of conversion-type battery reactions, and provides a new paradigm to resolve the long-standing dilemma between high energy and power densities in energy storage devices.     

Brnsted-Lewis有机-无机杂多酸催化模拟催化裂化汽油的烷基化脱硫反应

合成了一系列Brnsted-Lewis双酸性有机-无机杂多酸,并将其应用于催化模拟催化裂化(FCC)汽油的烷基化脱硫反应中.筛选出脱硫效果最佳的催化剂为Sm_(0.33)[MIM-PS]HPW_(12)O_(40),考察了该催化剂用量、反应温度及反应时间等因素对模拟油中噻吩类硫化物转化率的影响.获得的最佳反应条件为剂/油质量比1∶50、反应温度125℃及反应时间1 h.在最佳反应条件下,3种硫化物噻吩(T)、2-甲基噻吩(2-MT)和3-甲基噻吩(3-MT)均几乎完全转化,即脱硫率都接近100%.催化剂Sm_(0.33)[MIM-PS]HPW_(12)O_(40)具有良好的循环使用性能,循环使用12次,其催化活性基本保持不变.     

Molecular Dynamics Simulations Study of the Interactions between Human Dipeptidyl-Peptidase III and Two Substrates

Human dipeptidyl-peptidase III (hDPP III) is capable of specifically cleaving dipeptides from the N-terminal of small peptides with biological activity such as angiotensin II (Ang II, DRVYIHPF), and participates in blood pressure regulation, pain modulation, and the development of cancers in human biological activities. In this study, 500 ns molecular dynamics simulations were performed on free-hDPP III (PDB code: 5E33), hDPP III-Ang II (PDB code: 5E2Q), and hDPP III-IVYPW (PDB code: 5E3C) to explore how these two peptides affect the catalytic efficiency of enzymes in terms of the binding mode and the conformational changes. Our results indicate that in the case of the hDPP III-Ang II complex, subsite S1 became small and hydrophobic, which might be propitious for the nucleophile to attack the substrate. The structures of the most stable conformations of the three systems revealed that Arg421-Lys423 could form an α-helix with the presence of Ang II, but only part of the α-helix was produced in hDPP III-IVYPW. As the hinge structure in hDPP III, the conformational changes that took place in the Arg421-Lys423 residue could lead to the changes in the shape and space of the catalytic subsites, which might allow water to function as a nucleophile to attack the substrate. Our results may provide new clues to enable the design of new inhibitors for hDPP III in the future.     

电感耦合等离子体发射光谱法(ICP-OES)测定直接法氧化锌中铝、铜、铅、铁、镉、锰

建立了电感耦合等离子体发射光谱法测定直接法氧化锌中铝、铜、铅、铁、镉、锰元素含量的分析方法。确定了溶样方法和分析谱线,对方法精密度和准确度进行了考察,结果表明,各元素的相对标准偏差在2.5%~6.5%,加标回收率在92%~105%,测定结果与其它经典分析方法测定结果一致。所建立的方法准确、快速,适用于直接法氧化锌中多元素同时测定。     

连续相位变化毫米波衍射天线

基于菲涅尔原理及卡塞格伦天线设计方法,设计了一种口面直径为200 mm的卡赛格伦菲涅耳相位修正平面天线。天线采用连续相位修正方式,由一组同心菲涅耳相位修正圆环组成,与传统卡赛格伦抛物面天线相比,该天线具有平面化结构,大大减小了天线自身重量,天线辐射性能较离散相位衍射天线有大幅度提高。在95 GHz频率下,采用物理光学法进行仿真计算,并采用近场扫描系统进行了天线性能测试,天线3 dB波束宽度分别为0.95及1.05,天线实测增益为44.1 dB,天线口面效率为65%。     

New ladder‐type conjugated polymer with broad absorption,high thermal stability,and low band gap

New ladder‐type π‐conjugated polymer poly{6‐alkyl‐pyrrolo[3,2‐b:4,5‐b′]bis‐[1,4]benzothiazine} ( PPBBTZ ) was synthesized through a simple method. PPBBTZ showed good solubility in organic solvents (such as chloroform, tetrahydrofuran, chlorobenzene, o‐dichlorobenzene) and high thermal stability (decomposition temperatures up to 323 °C and 299 °C in nitrogen and air, respectively). The highest occupied molecular orbital and lowest unoccupied molecular orbital energy level estimated from electrochemistry result and absorption spectrum were ?5.46 and ?3.81 eV, respectively, with a band gap of 1.65 eV. More interestingly, PPBBTZ displayed broad absorption from ultraviolet to visible light regions (200–750 nm). These properties suggested PPBBTZ was a good candidate in opto‐electronics. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012