Impregnated Sulfur in Carbonized Nitrogen-containing Porous Organic Frameworks as Cathode with High Rate Performance and Long Cycle Life for Lithium-sulfur Batteries

The undesirable cycling performance caused by soluble poly sulfides shuttling between anode and cathode has been considered as the main challenge that has hindered its practical applications for lithium-sulfiir(Li-S) batteries. To solve tliis issue effectively, a nitrogen-containing porous carbon, namely JUC-Z2-900,developed from a porous organic framework, namely JUC-Z2, bearing a high surface area(805 m^2/g),small pore size(0.5 mil) and nitrogen doping(2.15%, mass fraction), has been used as a host material for Li-S batteries. The micropores of JUC-Z2-900 can confine the smaller sulfur molecules S2-4, which can essentially alleviate the critical problem of poly sulfide dissolution.Furthermore, nitrogen-containing JUC-Z2-900 can promote chemical adsorption of sulfur. The above two factors can improve the electrochemical performance of Li-S batteries effectively. To compare the eftects of sulfur contents and melt-difiusion strategy in JUC-Z2-900/S composites, a series of JUC-Z2-900/S composites was synthesized and tlieir electrochemical perfbnnances were explored, indicating good rate performance and excellent cycling stability of the composites contributed by both appropriate mass percentage of sulfiir and its confinement in the micropores.     

共价有机骨架的合成及其在气体吸附存储方面的应用

共价有机骨架(COFs)是一种新型的纳米结构材料,由于其独特的性质而受到人们的广泛关注.COFs的结晶.度高,孔径可调,比表面积大,具有良好的抗氧化性能和独特的分子结构,在能源、环境等方面得到了广泛的应用.COFs材料有较高的应用价值,促使人们不断努力研究其基本性质,并调控其结构和功能来提高性能.通过COFs的可设计性...     

A Two-dimensional Covalent Organic Framework for Iodine Adsorption

Radioactive iodine is a notorious pollutant in gas radioactive nuclear waste due to its radiation hazard, volatility, chemical toxicity, and high mobility. Therefore, developing a material with high efficiency-specific iodine capture is significant. Covalent organic framework(COF) has attracted significant attention as a new crystalline porous organic material. Due to its large specific surface and high chemical stability, it is an excellent alternative to adsorbents. Herein, we report a chemically stable two-dimensional COF(termed JUC-609) with specific adsorption of iodine. Adsorption experiments show that JUC-609 has an excellent iodine adsorption capacity as high as 5.9 g/g under 353 K and normal pressure condition, and iodine adsorption after multiple cycles is still maintained. Our study thus promotes the potential application of COFs in the field of environment-related applications.     

Calorimetric Investigation of Adsorption of Organic Compounds by Active Carbons

Enthalpies of wetting of two active carbons and one brown coal coke by several pure liquids (mainly homologous series) were measured at 298.15 K with two quasi-isothermal microcalorimeters. Different measuring cells with cavities of about 0.5 and 15 cm³ were used. The advantage of the larger measuring cell with three independent 15 cm³ cavities is the higher mass of active carbon, leading to a high reproducibility with standard deviations below 1% and a reduced measuring time. Experiments were carried out with n-alkanes, l-alkanols, cycloalkanes and isomers thereof, i.e. 2-propanol, methylcyclohexane, 2,2,4-trimethylpentane (isooctane and 2-ethyl-1-hexanol, and water. Like the polarity, the size and the three-dimensional expansion of the molecules, the energetic and geometric heterogeneity of the adsorbent influences the enthalpy of wetting. This revised version was published online in August 2006 with corrections to the Cover Date.     

一步碳化多孔有机材料制备多孔碳及其性能的研究

开发并利用清洁的、可再生的能源是解决环境污染问题和能源短缺的有效方法.碳化含碳量较高的多孔有机材料制备的多孔碳,具有较高的比表面积,良好的物化稳定性,优良的机械性能等优点,在清洁能源的存储、分离、能量的存储与转化领域有广泛的应用.常见的由多孔有机材料制备多孔碳的方法主要是非活化碳化法和活化碳化法.不同的制备方法得到的多孔碳形貌,孔结构各不形同.多孔碳材料自身的结构性质可以影响其应用.合理的设计并调控多孔碳的“孔”,发挥孔尺寸的“筛分效应”可以有效地对气体进行存储和分离.在锂电等能量转化领域,“限域效应”是影响锂电性能的重要因素.多孔碳材料中较小的孔可以限域活性成分,而较大的孔可以快速传输,两种孔的协同效应可以使锂电性能大大提升.本综述系统地归纳了一步碳化多孔有机材料制备多孔碳的方法及其优势,详细地介绍了其在气体吸附、存储、分离以及电化学等领域的应用.最后,结合多孔碳材料的研究现状,提出由多孔有机材料制备多孔碳材料所面临的挑战,同时也展望了多孔碳材料的应用前景.     

超分子有机框架:具有周期性孔结构的超分子聚合物

本文概述了水相周期性超分子有机框架(supramolecular organic frameworks,SOFs)的研究进展.首先介绍了水相超分子聚合物和多孔材料研究的背景,然后分别描述了二维单层、三维金刚石型和立方型SOF的构建、结构表征及功能.最后就SOF的未来应用前景做出了分析和展望.     

多孔聚苯醚的合成及气体储存

通过厄尔曼缩合反应合成了一种具有dia-c5 拓扑结构的多孔聚苯醚JUC-Z6, 并对其结构进行了表征. 结果表明, 该化合物具有高热稳定性(214℃ 失重5%), 高化学稳定性、 高BET比表面积(192 m²/g)及窄孔径分布(1.36 nm). 低压气体吸附测试结果表明, JUC-Z6在多孔材料中具有较高的吸附焓(氢气4.1 kJ/mol, 二氧化碳33.7 kJ/mol, 甲烷4.1 kJ/mol).     

基于羧甲基纤维素钠制备氮掺杂多孔炭及其电容性能研究

以羧甲基纤维素钠(NaCMC)为碳源, 利用直接炭化工艺(无需进一步活化)制备多孔炭材料; 然后, 以CO(NH₂)₂为氮源, 形成了氮掺杂多孔炭材料. 氮的存在形式包括吡啶N、石墨N和吡咯N. 实验结果表明, 羧甲基纤维素钠与CO(NH₂)₂之间的配比可以有效控制氮存在形式、含量、样品的比表面积及孔的结构等. 样品的电化学性能测试表明, 氮掺杂后多孔炭材料的超电容性能得到了显著提升. 以carbon-N-1:20为例, 其比表面积可达858 m²·g^-1, 远高于未经氮掺杂carbon-blank 的463 m²·g^-1, 其质量比电容则由94.0 F·g^-1提高到了156.7F·g^-1.     

NPE在有序介孔炭上的吸附行为研究

采用有序介孔硅为硬模板制备了具有不同孔径的有序介孔炭(OMCs). 氮气吸附测试表明, 有序介孔炭具有丰富的介孔表面和集中的介孔分布. 以壬基酚聚氧乙烯醚(NPE)为探针分子, 研究了大分子酚类在有序介孔炭上的吸附行为. 吸附研究表明, NPE在有序介孔炭上的吸附满足Langmuir吸附模型. 孔结构分析表明, 大于1.5 nm的孔的表面积是决定NPE吸附量的关键因素, 而有序介孔炭的最可几孔径决定吸附速率的大小. 与吸附量相比, 吸附速率更容易受环境温度的影响. 动力学研究表明, NPE在有序介孔炭上的吸附满足准二级动力学方程.     

土壤柱液相色谱多级吸附法测定污染物的土壤有机碳吸附常数

建立了利用土壤柱液相色谱多级吸附测定污染物的土壤有机碳吸附常数(KOC)的新方法。用这种方法通过一次实验就可获得多个不同浓度的样品在土壤中的吸附量,从而通过吸附等温线计算出KOC。用该法测定的戊唑醇、保棉磷、敌草隆、莠去津、扑草净、苯酚、萘在欧洲3#标准土壤中的log KOC分别为2.70,2.87,2.47,2.26,3.09,1.51和2.77,与文献值基本一致。     

NPE在有序介孔炭上的吸附行为研究

采用有序介孔硅为硬模板制备了具有不同孔径的有序介孔炭(OMCs). 氮气吸附测试表明, 有序介孔炭具有丰富的介孔表面和集中的介孔分布. 以壬基酚聚氧乙烯醚(NPE)为探针分子, 研究了大分子酚类在有序介孔炭上的吸附行为. 吸附研究表明, NPE在有序介孔炭上的吸附满足Langmuir吸附模型. 孔结构分析表明, 大于1.5 nm的孔的表面积是决定NPE吸附量的关键因素, 而有序介孔炭的最可几孔径决定吸附速率的大小. 与吸附量相比, 吸附速率更容易受环境温度的影响. 动力学研究表明, NPE在有序介孔炭上的吸附满足准二级动力学方程.     

多孔有机聚合物吸附分离水体系中有机污染物研究和应用进展

有机物对水体的污染严重威胁生态环境安全和人类健康。 如何有效控制和消除水体系中的有机污染物是当前全球性热点问题之一,基于多孔材料的高效吸附是处理水体有机污染的有效方法。 多孔有机聚合物(Porous Organic Polymers,POPs)具有比表面积高、物理化学稳定性好、易修饰等特点,作为新型吸附剂在处理水体系有机污染方面具有广阔的应用前景。 本文综述了近10年来新型多孔有机聚合物对水体系中有机溶剂、农药与杀虫剂、有机染料等污染物的吸附分离研究进展。     

双金属同构金属-有机框架材料CAU-21-Al/M的合成、氮气吸附及复合膜性能

通过掺杂金属的方式实现了双金属同构金属-有机框架材料的制备, 采用X射线粉末衍射(PXRD)确定了多种金属在双金属CAU-21材料中的最大掺杂量, 使用扫描电子显微镜(SEM)观察了掺杂金属对材料形貌的影响. 热重分析(TGA)结果表明, CAU-21系列材料均具有较好的热稳定性. 氮气气体吸附测试及以CAU-21-Al/M为填料的混合基质膜对N₂气的渗透实验结果与掺杂金属离子尺寸大小呈相反的关系, 证实了双金属可实现对孔道结构及气体吸附性能的调控.     

Pyrolysis of Porous Organic Polymers under a Chlorine Atmosphere to Produce Heteroatom-Doped Microporous Carbons

Three types of cross-linked porous organic polymers (either oxygen-, nitrogen-, or sulfur-doped) were carbonized under a chlorine atmosphere to obtain chars in the form of microporous heteroatom-doped carbons. The studied organic polymers constitute thermosetting resins obtained via sol-gel polycondensation of resorcinol and five-membered heterocyclic aldehydes (either furan, pyrrole, or thiophene). Carbonization under highly oxidative chlorine (concentrated and diluted Cl₂ atmosphere) was compared with pyrolysis under an inert helium atmosphere. All pyrolyzed samples were additionally annealed under NH₃. The influence of pyrolysis and additional annealing conditions on the carbon materials’ porosity and chemical composition was elucidated.     

Hierarchically Porous Carbons Derived from Metal–Organic Framework/Chitosan Composites for High‐Performance Supercapacitors

Hierarchically porous carbon materials with high surface areas are promising candidates for energy storage and conversion. Herein, the facile synthesis of hierarchically porous carbons through the calcination of metal–organic framework (MOF)/chitosan composites is reported. The effects of the chitosan (CS) additive on the pore structure of the resultant carbons are discussed. The corresponding MOF/chitosan precursors could be readily converted into hierarchically porous carbons (NPC‐V, V=1, 2, 4, and 6) with much higher ratios of meso‐/macropore volume to micropore volume (V_meso‐macro/V_micro). The derived carbon NPC‐2 with the high ratio of V_meso‐macro/V_micro=1.47 demonstrates a high specific surface area of 2375 m² g^?1, and a high pore volume of 2.49 cm³ g^?1, as well as a high graphitization degree, in comparison to its counterpart (NPC) without chitosan addition. These excellent features are favorable for rapid ion diffusion/transport, endowing NPC‐2 with enhanced electrochemical behavior as supercapacitor electrodes in a symmetric electrode system, corresponding to a high specific capacitance of 199.9 F g^?1 in the aqueous electrolyte and good rate capability. Good cycling stability is also observed after 10 000 cycles.     

A Three-dimensional Covalent Organic Framework for CO2 Uptake and Dyes Adsorption

Environmental pollution is one of the most severe problems facing today, including water pollution and the greenhouse effect. Therefore, developing materials with high-efficiency dyes adsorption and CO₂ uptake is significant. Covalent organic frameworks(COFs), as a burgeoning class of crystalline porous polymers, present a promising application potential in areas related to pollution regulation due to their exciting surface properties. Herein, we report a 3D COF with a high specific surface area(BET about 2072 m²/g) by utilizing tetrahedral and rectangle building blocks connected through[4+4] imine condensation reactions to synthesize. The obtained COF not only can separate dyes from water effectively but also shows a remarkable CO₂ uptake capacity. This research thus provides a promising material to remove dyes and adsorb CO₂ in environmental remediation.     

Gas sorption properties of microporous metal organic frameworks

A low-temperature gas sorption study has been carried out on four three-dimensional microporous metal organic framework (MMOF) structures and two two-dimensional layered structures. The pore characteristics are analyzed based on the argon adsorption-desorption isotherms at 87 K. The results from hydrogen sorption experiments conducted at 77 and 87 K show that all MMOFs have a relatively high hydrogen uptake, with adsorbed hydrogen densities falling in the range of liquid hydrogen. Isosteric heats of hydrogen adsorption data calculated based on the Clausius-Clapeyron equation are consistent with these observations, indicating strong sorbent-sorbate interactions.     

碳化多孔有机骨架制备氮掺杂多孔碳及其气体吸附研究

通过简单的一步碳化方法, 以含氮的多孔有机骨架JUC-Z2为碳前驱物制备出氮掺杂多孔碳材料. 与原始JUC-Z2材料相比, 制备的多孔碳材料显示出明显提高的气体吸附量和增强的吸附焓. 其中JUC-Z2-900的CO₂吸附量高达113 cm³·g^-1, H₂吸附量也达到246 cm³·g^-1, 超过了大部分报道的多孔材料. 尤其是JUC-Z2-900的CH₄吸附量在273 K, 1 bar下高达60 cm³·g^-1, 据我们所知, 这一值为目前报道材料的最高值. 除此之外, 样品还显示出选择性吸附CO₂的能力, 273 K下, JUC-Z2-900的CO₂/N₂的选择性高达10, CO₂/H₂的选择性也高达66. 另外, 样品具有很高的热稳定性, 有望应用在碳捕获和清洁能源储存等领域.     

Novel Porous Aromatic Framework with Excellent Separation Capability of CO2 in N2 or CH4

A novel porous aromatic framework, PAF-52, was obtained via the polymerization of tetrahedral mono- mer tetrakis（4-cyanodiphenyl） methane（TCDPM） with the aid of a facile ionothermal method. PAF-52 has a surface area of 1159 m2/g（BET）, and shows a considerable high separation ability of CO2 in N2 or CH4 respectively at room temperature, using gas-chromatography experiments as evidence,