Triazine interlinked covalent organic polymer as an efficient anti-bacterial agent

Herein, we report the synthesis of new covalent organic polymer comprising triazine and o-tolidine by solvothermal method. The formation of polymer was confirmed by Fourier transform infra red spectroscopy (FT-IR), cross polarization–magic angle spinning nuclear magnetic resonance (NMR), transmission electron microscopy, and scanning electron microscopy. Their antibacterial activity toward S. aureus (gram-positive) and P. aeruginosa (gram-negative) was assessed by the optical density measurements and direct contact method. These results have great significance toward the design of new porous polymers for antibacterial applications.     

3D Metal–Organic Frameworks Based on Co(II) and Bithiophendicarboxylate: Synthesis,Crystal Structures,Gas Adsorption,and Magnetic Properties

Three new 3D metal-organic porous frameworks based on Co(II) and 2,2′-bithiophen-5,5′-dicarboxylate (btdc²⁻) [Co₃(btdc)₃(bpy)₂]·4DMF, 1; [Co₃(btdc)₃(pz)(dmf)₂]·4DMF·1.5H₂O, 2; [Co₃(btdc)₃(dmf)₄]∙2DMF∙2H₂O, 3 (bpy = 2,2′-bipyridyl, pz = pyrazine, dmf = N,N-dimethylformamide) were synthesized and structurally characterized. All compounds share the same trinuclear carboxylate building units {Co₃(RCOO)₆}, connected either by btdc^2– ligands (1, 3) or by both btdc^2– and pz bridging ligands (2). The permanent porosity of 1 was confirmed by N₂, O₂, CO, CO₂, CH₄ adsorption measurements at various temperatures (77 K, 273 K, 298 K), resulted in BET surface area 667 m²⋅g⁻¹ and promising gas separation performance with selectivity factors up to 35.7 for CO₂/N₂, 45.4 for CO₂/O₂, 20.8 for CO₂/CO, and 4.8 for CO₂/CH₄. The molar magnetic susceptibilities χ_p(T) were measured for 1 and 2 in the temperature range 1.77–330 K at magnetic fields up to 10 kOe. The room-temperature values of the effective magnetic moments for compounds 1 and 2 are μ_eff (300 K) ≈ 4.93 μ_B. The obtained results confirm the mainly paramagnetic nature of both compounds with some antiferromagnetic interactions at low-temperatures T < 20 K in 2 between the Co(II) cations separated by short pz linkers. Similar conclusions were also derived from the field-depending magnetization data of 1 and 2.     

Tailoring Pore Structure and Morphologies in Covalent Organic Frameworks for Xe/Kr Capture and Separation

As a rising star among porous solid materials, covalent organic frameworks(COFs) with excellent properties including but not limit to facilely controllable structure, high porosity, and multi-chemical functionality represent significant potential for efficient ¹²⁷Xe/⁸⁵Kr capture and separation. In this study, through tuning the length of the organic ligands, two-dimensional(2D) COF mate-rials with identical connection group but different pore properties, denoted as ATFG-COF and TpPa-COF with AA-stacking model and TpBD-COF with AB-stacking model were synthesized and tested for Kr and Xe adsorption for the first time. Adsorption measurements indicate that the narrower pore apertures and higher porosity are conducive for COF materials to capture Xe and Kr. Furthermore, the Henry's constant, isosteric heat of adsorption(Q_st), and ideal adsorbed solution theory(IAST) selectivity of ATFG-COF, the pore size of which is closest to the kinetic diameter of the Xe atom(0.41 nm) among 2D COF materials, were carried out based on the single component sorption isotherms. The results illustrate that the high isosteric heat values of Xe/Kr adsorption on ATFG-COF are 25 and 16 kJ/mol at room temperature, respectively. Henry's law predicts that the selectivity factor of Xe to Kr is 6.07, consistent with the adsorption selectivity(ca. 6) calculated based on the IAST.     

Selective sensing of CrVI and FeIII ions in aqueous solution by an exceptionally stable TbIII-organic framework with an AIE-active ligand

We herein report a new lanthanide metal-organic framework (MOF) that exhibits excellent chemical stability, especially in the aqueous solution over a wide pH range from 1 to 14. In contrast to many reported lanthanide MOFs, this Tb-based MOF emits cyan fluorescence inherited from the integrated AIE-active ligand, rather than Ln³⁺ ions. More remarkably, its fluorescence signal features a highly selective and sensitive “turn-off” response toward CrO₄²⁻, Cr₂O₇²⁻ and Fe³⁺ ions, highlighted with the low detection limits down to 68.18, 69.85 and 138.8 ppm, respectively. Thus, the exceptional structural stability and sensing performance render this material able to be a superior luminescent sensor for heavy metal ions in wastewater.     

Recent developments in the adsorptive removal of heavy metal ions using metal-organic frameworks and graphene-based adsorbents

Clean and potable water is a growing concern around the globe. Among the different water pollutants, heavy metal ions pose a serious health concern to all living beings. The quest for new adsorbents to remove heavy metal ions received a boost with the development in the field of metal-organic framework (MOF). The advancement in synthetic strategies and designing of MOF enabled the researchers to tune the adsorption characteristics and tailor the material specific to a heavy metal ion. Similar to MOF, graphene-based two-dimensional and three-dimensional materials are also promising due to the diverse functionalization possibilities and cost-effectiveness. There had been growing interest in applying MOF and graphene-based materials for the removal of heavy metal ions in the past decade. This review summarizes these developments in detail.     

电子束敏感材料的原子尺度结构研究

分子筛和金属有机骨架(MOF)材料以其独特的孔道和骨架结构在催化、 储能、 干燥及净化和吸附分离等领域有着广泛应用, 对其结构的原子尺度表征对于深入理解其构效关系具有重要意义. 但其大孔道结构和有机骨架使得它们对电子束辐照极为敏感, 在常规透射电镜成像模式下结构会很快被破坏变为非晶, 从而无法获得孔道和骨架的原子排列信息. 最近发展起来的基于积分差分相位衬度扫描透射电子显微(iDPC-STEM)技术在电子敏感材料和轻元素组分成像方面展现出明显优势, 使得对多孔骨架材料及烃池物种的表征成为了可能. 本文综述了本课题组近期利用该技术对分子筛和MOF材料原子尺度结构方面的研究. 将iDPC-STEM技术应用到ZSM-5分子筛催化剂中, 实现了对该分子筛的原子级骨架结构的成像分析. 在MOF体系中, 利用该技术观察到MIL-101骨架内部有机连接体与金属节点的配位方式, 在此基础上解析了MIL-101结构中有机配体的连接和金属节点的苯环结构, 并观察了MOF的原子级表面、 界面和缺陷等局域结构特征. 最后对iDPC-STEM技术在原子尺度成像方面的应用潜力进行了总结与展望.     

二维金属有机框架材料的合成及电催化应用

二维金属有机框架材料(MOFs)由于具备高比表面积、 多孔性以及丰富的活性位点等优异特性而受到广泛关注, 并且在电催化领域展现出巨大的应用潜力. 研究者们已在二维MOFs的可控制备与电催化性能调控方面取得许多突破性进展, 显示出相关研究对开发高性能电催化剂的关键作用. 本文总结了二维MOFs的自上而下和自下而上合成策略以及二维MOFs衍生物的典型合成方法, 概述了二维MOFs在各尺度下的电催化性能调控策略, 并介绍了各种合成方法和调控策略在电催化中的应用. 最后讨论了该领域面临的挑战, 并对未来的发展方向进行了展望.     

二次离子电池高比容量负极碳载体的研究进展

二次离子电池商业化负极石墨的比容量已接近理论比容量. 合金型负极和金属负极因具有高比容量而受到广泛关注, 但其循环性能差和安全性问题限制了实际应用, 据此提出载体设计策略. 碳材料具有来源广泛、 易于调控等特性, 常用作二次离子电池高比容量负极的载体. 本文从碳载体的孔结构、 比表面积、 电子导电率、 离子导电率、 杂原子掺杂和界面修饰的角度出发, 综述了其在硅基、 磷基、 锗基、 锡基负极以及金属锂、 钠等负极中的研究进展, 展望了碳载体的发展前景和方向.     

超薄骨架有序介孔CdS/NiS的制备及光催化产氢性能

采用有序介孔氧化硅为硬模板, 通过纳米浇筑法制备了由螺旋骨架构建的有序介孔硫化镉(CdS)光 催化材料. 该光催化材料具有约5 nm厚的超薄骨架和大的比表面积(238 m²/g), 能有效缩短光催化反应中 光生电荷迁移到表面进行反应的距离并同时提供更多的反应活性位点, 从而增强光催化性能. 通过原位化学沉积法将不同量的助催化剂硫化镍(NiS)沉积到有序介孔CdS表面, 得到了一系列超薄骨架有序介孔CdS/NiS复合光催化材料. 可见光照射下的光催化产氢活性测试结果表明, 负载适量NiS的有序介孔CdS具有显著增强的光催化产氢活性(3.84 mmol?h^-1?g^-1), 约为负载相同量NiS的普通商业化CdS材料(0.22 mmol?h^-1?g^-1)的17.5倍.     

MIL-53(Al)衍生的Rh单原子催化剂在间氯硝基苯选择性加氢制间氯苯胺反应中的应用

卤代苯胺是化学工业中重要的中间体,主要用于制造药物、聚合物、染料等含氮化学品,用多相金属催化剂催化卤代硝基芳烃加氢制备卤代苯胺是一种高效,绿色和可持续发展的生产工艺.该过程需要选择性加氢硝基基团,同时避免卤素基团的脱卤副反应发生.然而,化学选择性加氢存在巨大的挑战,难点在于催化剂的精准设计,一方面要求具备对硝基基团合适的加氢能力,另一方面要阻止对卤素基团的脱卤副反应发生.基于此,研制高效多相金属催化剂用于卤代硝基芳烃选择性加氢制备卤代苯胺反应引起了高度关注.近年来,单原子金属催化剂受到越来越多的关注,并在卤代硝基芳烃选择性加氢制备卤代苯胺反应中显现出极大的潜力.本文通过在金属有机骨架材料MIL-53(Al)自组装的过程中将金属Rh原位嫁接其骨架结构中,继而通过限域热解的方法制备了Rh@Al2O3@C单原子催化剂,其在间氯硝基苯(m-CNB)加氢制间氯苯胺(m-CAN)反应中显现了高效催化选择性.球差校正高角度环形暗场模式的透射电镜,CO作为探针分子的红外光谱和X射线光电子能谱等结果发现,Rh是以单原子的形式均匀的分布在Al2O3上并被无定型碳包覆,且Rh化学价态呈正价.而27Al固体核磁共振与密度泛函理论计算的结果则进一步确定Al2O3@C载体中存在的五配位的Al物种(AlV)是锚定Rh单原子的主要位点,AlV的不饱和的配位结构可以有效地稳定Rh单原子,对形成Rh位点的单原子分散至关重要.在间氯硝基苯选择性加氢制间氯苯胺反应中,与等体积浸渍法制备的Rh/C和Rh/γ-Al2O3纳米催化剂相比,Rh@Al2O3@C单原子催化剂表现出优异催化性能:其在313 K,氢气压力为20 bar的温和条件下转换频率(TOF)高达2317 molm-CNB·molRh-1·h-1,优于已报道的多相金属催化剂,是目前的最高值.此外,该催化剂展现出极佳的稳定性能,经过五次循环后,该催化剂对m-CAN的选择性仍旧保持在98％左右.Rh@Al2O3@C单原子催化剂的优异催化性能源自于金属单原子结构的形成对于金属位点电子结构的有效调节,进而调控催化剂加氢性能并实现对加氢脱卤副反应的抑制;与此同时,Rh@Al2O3@C催化剂增进了酸位点的可及性,从而促进了其串联步骤中包含的脱水反应的发生,进而有效提高催化剂的反应活性.