An Extra-Large-Pore Pure Silica Zeolite with 16×8×8-Membered Ring Pore Channels Synthesized using an Aromatic Organic Directing Agent

Extra-large-pore zeolites for processing large molecules have long been sought after by both the academia and industry. However, the synthesis of these materials, particularly extra-large-pore pure silica zeolites, remains a big challenge. Herein we report the synthesis of a new extra-large-pore silica zeolite, designated NUD-6, by using an easily synthesized aromatic organic cation as structure-directing agent. NUD-6 possesses an intersecting 16×8×8-membered ring pore channel system constructed by four-connected (Q⁴) and unusual three-connected (Q³) silicon species. The organic cations in NUD-6 can be removed in nitric acid to yield a porous material with high surface area and pore volume. The synthesis of NUD-6 presents a feasible means to prepare extra-large pore silica zeolites by using assembled aromatic organic cations as structure-directing agents.     

Ruthenium-Catalyzed Direct Asymmetric Reductive Amination of Diaryl and Sterically Hindered Ketones with Ammonium Salts and H2

A Ru-catalyzed direct asymmetric reductive amination of ortho-OH-substituted diaryl and sterically hindered ketones with ammonium salts is reported. This method represents a straightforward route toward the synthesis of synthetically useful chiral primary diarylmethylamines and sterically hindered benzylamines (up to 97 % yield, 93–>99 % ee). Elaborations of the chiral amine products into bioactive compounds and a chiral ligand were demonstrated through manipulation of the removable and convertible -OH group.     

Charge-Tagged DNA Radicals in the Gas Phase Characterized by UV/Vis Photodissociation Action Spectroscopy

Adenosine radicals tagged with a fixed-charge group were generated in the gas phase and structurally characterized by tandem mass spectrometry, deuterium labeling, and UV/Vis action spectroscopy. Experimental results in combination with Born–Oppenheimer molecular dynamics, ab initio, and excited-state calculations led to unambiguous assignment of adenosine radicals as N-7 hydrogen atom adducts. The charge-tagged radicals were found to be electronically equivalent to natural DNA nucleoside radicals.     

化学教育走进雄安——白洋淀环保主题暑期实践活动

在京津冀一体化、雄安新区建设和"绿水青山就是金山银山"生态文明思想的三大政策背景下,由首都师范大学化学(师范)专业师生组成的京冀科育团队于2019年暑假走进雄安新区,以化学教育为核心、以环境保护为主题、以提升学科核心素养为导向,开展了兼具化学专业特色和教师教育特色的暑期实践活动。     

BiPO4/石墨烯光电极的制备及其光电催化性能（英文）

光电催化(PEC)氧化法是一种使用半导体电极材料在光和电的共同作用下处理水中有机污染的有效方法.在PEC工艺中,施加偏压不仅可以利用电催化对有机污染物进行降解,而且在偏压作用下,光生电子-空穴对能够得到有效的分离和传输,从而大大提高了机物污染物的去除速率.尽管PEC技术已经取得了许多重要的突破,但是能量转换效率仍然无法满足实际应用.因此,开发具有优异性能,良好稳定性和低成本的光电极材料是一项具有挑战性的研究工作.本文采用两步电沉积法制备了BiPO4纳米棒/还原氧化石墨烯/FTO复合光电极(BiPO4/r GO/FTO).电镜结果表明,电沉积制得的纳米棒状磷酸铋均匀负载在石墨烯纳米片层表面.采用甲基橙为模型体系,考察了复合光电极的光电催化活性.BiPO4/r GO/FTO复合电极的光电催化降解速率是BiPO4/FTO光电极的2.8倍,显示出优良的光电催化活性.实验进一步研究了工作电压和BiPO4沉积时间对甲基橙光电降解性能的影响.最佳的BiPO4沉积时间为45 min,最佳工作电压为1.2 V.捕获实验和ESR实验表明羟基自由基(·OH)和超氧化物自由基(·O2-)是该电极的主要活性物种.BiPO4/r GO/FTO复合电极经过四次循环实验后其降解甲基橙效率保持不变,显示出高稳定性,采用光电流,交流阻抗及其荧光测试对其光催化机理进行推测.结果表明该复合光电极具有高PEC活性的主要原因是:石墨烯的引入加快了BiPO4的电子空穴的分离,拓宽了石墨烯的可见光吸收范围;同时,石墨烯诱导产生的BiPO4混合相也进一步促进了光生电子空穴的分离,提高了光电降解活性.     

UTSA-280的氨改性以及C2H4/C2H6分离性能研究

炼厂干气中回收乙烯是扩宽C₂H₄来源的有效途径,但C₂H₄和C₂H₆物理性质和分子尺寸非常接近,分离困难.金属有机骨架材料（MOFs）近年来在低碳烃分离领域展现出广阔的前景.本工作采用氨吸附改性调节UTSA-280的结构,通过一维直孔道大小的调节实现C₂H₄/C₂H₆的高效分离.改性后的UTSA-280具有独特的超微孔结构能提升C₂H₄的吸附,而完全不吸附稍大的C₂H₆,实现理想的C₂H₄/C₂H₆吸附选择性（>1000）.结果表明,改性后的UTSA-280的C₂H₄吸附量可提高至2.83 mmol/g,与未改性的材料相比增加29%,并且能阻挡C₂H₆的吸附,最终达到>1200的C₂H₄/C₂H₆选择性.蒙特卡罗分子模拟（GCMC）计算C₂H₄/C₂H₆混合气体（1：1）的吸附得出,改性后UTSA-280孔内的C₂H₄吸附相比于C₂H₆具有更多的吸附分布.通过C₂H₄/C₂H₆混合气体穿透实验测试,改性后的UTSA-280材料能展现出48 min以上的分离时间,相比于未改性的材料,分离性能提升近1倍.     

Recent advances in metal-organic frameworks for lithium metal anode protection

The lithium metal battery has been considered as a promising candidate for next generation batteries.However,safety concerns caused by uncontrollable lithium dendrite growth on lithium anode are severely hampering the commercial application.Metal-organic frameworks(MOFs)become one of the most attractive materials due to the high porosity,structural designability and tunability.With unique open channels and pores as well as functional components in MOFs,the transportation and deposition of lithium ions can be regulated,which leads to enhanced electrochemical prope rties.Various strategies for lithium metal protection are proposed in recent wo rks on applications of MOFs in lithium metal batteries.In this review,we highlight latest key approaches in this field and discuss the prospects for MOFs in advanced Li anodes.     

Covalent Adaptable Networks with Tunable Exchange Rates Based on Reversible Thiol–yne Cross‐Linking

The design of covalent adaptable networks (CANs) relies on the ability to trigger the rearrangement of bonds within a polymer network. Simple activated alkynes are now used as versatile reversible cross‐linkers for thiols. The click‐like thiol–yne cross‐linking reaction readily enables network synthesis from polythiols through a double Michael addition with a reversible and tunable second addition step. The resulting thioacetal cross‐linking moieties are robust but dynamic linkages. A series of different activated alkynes have been synthesized and systematically probed for their ability to produce dynamic thioacetal linkages, both in kinetic studies of small molecule models, as well as in stress relaxation and creep measurements on thiol–yne‐based CANs. The results are further rationalized by DFT calculations, showing that the bond exchange rates can be significantly influenced by the choice of the activated alkyne cross‐linker.     

Tiara[5]arenes: Synthesis,Solid‐State Conformational Studies,Host–Guest Properties,and Application as Nonporous Adaptive Crystals

Tiara[5]arenes (T[5]s), a new class of five‐fold symmetric oligophenolic macrocycles that are not accessible from the addition of formaldehyde to phenol, were synthesized for the first time. These pillar[5]arene‐derived structures display both unique conformational freedom, differing from that of pillararenes, with a rich blend of solid‐state conformations and excellent host–guest interactions in solution. Finally we show how this novel macrocyclic scaffold can be functionalized in a variety of ways and used as functional crystalline materials to distinguish uniquely between benzene and cyclohexane.     

Chitosan‐modified graphene oxide as a modifier for improving the structure and performance of forward osmosis membranes

Chitosan (CS) with good hydrophilicity and charged property was used to modify graphene oxide (GO), the obtained GO‐CS was used as a novel modifier to fabricate thin film composite forward osmosis (FO) membranes. The results revealed that the amino groups on CS reacted with carboxyl groups on GO, and the lamellar structure of the GO nanosheets was peeled off by CS, resulting in the reducing of their thicknesses. The GO‐CS improved the hydrophilicity of polyethersulfone (PES) substrate, and their contact angles decreased to 64° with the addition of GO‐CS in the substrate. GO‐CS also increased the porosity of the substrate and surface roughness of FO membrane, thereby optimizing the water flux and reverse salt flux of FO membrane. The average water flux of the FO membrane reached the optimal flux of 21.34 L/(m² h) when GO‐CS addition was 0.5 wt%, and further addition of GO‐CS to the substrate would decrease the water flux of FO membrane, and the reverse salt flux also decreased to the lowest value of 2.26 g/(m² h). However, the salt rejection of the membrane increased from 91.4% to 95.1% when GO‐CS addition increased from 0.5 to 1.0 wt% under FO mode using 1 mol/L sodium chloride (NaCl) solution as draw solution (DS). In addition, high osmotic pressure favored water permeation, and at the same concentration of DS, magnesium chloride (MgCl₂) exhibited better properties than NaCl. These results all suggested that GO‐CS was a good modifier to fabricate FO membrane, and MgCl₂ was a good DS candidate.