Molecular Mechanisms behind Acetylene Adsorption and Selectivity in Functional Porous Materials

Since its first industrial production in 1890s, acetylene has played a vital role in manufacturing a wide spectrum of materials. Although current methods and infrastructures for various segments of acetylene industries are well-established, with emerging functional porous materials that enabled desired selectivity toward target molecules, it is of timely interest to develop new efficient technologies to promote safer acetylene processes with a higher energy efficiency and lower carbon footprint. In this Minireview, we, from the perspective of materials chemistry, review state-of-the-art examples of advanced porous materials, namely metal–organic frameworks and decorated zeolites, that have been applied to the purification and storage of acetylene. We also discuss the challenges on the roadmap of translational research in the development of new solid sorbent-based separation technologies and highlight areas which require future research efforts.     

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。     

A Triptycene-Based Porous Organic Polymer that Exhibited High Hydrogen and Carbon Dioxide Storage Capacities and Excellent CO2/N2 Selectivity

A novel porous organic polymer (POP) has been constructed through the condensation of triptycene tricatechol and 1,3,5‐benzenetris(4‐phenylboronic acid). This triptycene‐based POP exhibited high H₂ uptake (up to 1.84 wt% at 77 K, 1 bar), large CO₂ adsorption capacity (up to 18.1 wt% at 273K, 1 bar), and excellent CO₂/N₂ adsorption selectivity (up to 120/1). The influence of solvent on the gas adsorption performance of the POP has also been investigated.     

Porous Aerogels and Adsorption of Pollutants from Water and Air: A Review

Aerogels are open, three-dimensional, porous materials characterized by outstanding properties, such as low density, high porosity, and high surface area. They have been used in various fields as adsorbents, catalysts, materials for thermal insulation, or matrices for drug delivery. Aerogels have been successfully used for environmental applications to eliminate toxic and harmful substances—such as metal ions or organic dyes—contained in wastewater, and pollutants—including aromatic or oxygenated volatile organic compounds (VOCs)—contained in the air. This updated review on the use of different aerogels—for instance, graphene oxide-, cellulose-, chitosan-, and silica-based aerogels—provides information on their various applications in removing pollutants, the results obtained, and potential future developments.     

Enhanced Formaldehyde‐Vapor Adsorption Capacity of Polymeric Amine‐Incorporated Aminosilicas

Airborne formaldehyde, which is a highly problematic volatile organic compound (VOC) pollutant, is adsorbed by polymeric amine‐incorporated silicas (aminosilicas), and the factors that affect the adsorption performance are systematically investigated. Three different types of polymeric amines 1) poly(ethyleneimine) branched (PEIBR); 2) poly(ethyleneimine) linear (PEILI); and 3) poly(allylamine) (PAA) are impregnated into two types of porous silicas [SBA‐15 and mesocellular foam (MCF) silicas] with systematic changes of the amine loadings. The adsorption results demonstrate that the adsorption capacity increases along with the amine loading until the polymeric amines completely fill the silica pores. This results in the MCF silica, which has a larger pore volume and hence can accommodate more polymeric amine before completely filling the pore, giving materials that adsorb more formaldehyde, with the largest adsorption capacity, q, of up to 5.7 mmol_HCHO g^?1 among the samples studied herein. Of the three different types of polymers, PAA, comprised of 100 % primary amines, showed the highest amine efficiency μ (mmol_HCHO/mmol_N) for capturing formaldehyde. The chemical structures of the adsorbed formaldehyde are analyzed by ¹³C cross‐polarization magic‐angle spinning (CP‐MAS) NMR, and it is demonstrated that the adsorbed formaldehyde is chemically attached to the aminosilica surface, forming hemiaminal and imine species. Because the chemical adsorption of formaldehyde forms covalent bonds, it is not desorbed from the aminosilicas below 130 °C based on temperature‐programed‐desorption (TPD) analysis. The high formaldehyde‐adsorption capacity and stability of the trapped formaldehyde on the amine surface in this study reveal the potential utility of aminosilicas as formaldehyde abatement materials.     

Organic Fluorescent Molecule with High Solid State Lumines- cent Efficiency and Protonation Stimuli-response

A novel organic fluorophor with high solid state luminescent efficiency based on 1,4-bis（2,2-di（pyridin-2-yl）- vinyl）benzene （BDP2VB） was designed and synthesized. It emits faintly in solution, but becomes a strong emitter in the aggregate state, demonstrating its aggregation induced emission （AIE） property. According to the crystal struc- ture analysis, J-type aggregation was formed in the packing mode of the molecule, which was demonstrated to be beneficial to gain high fluorescent quantum efficiency in solid state. Additionally, the emission color of BDP2VB can change dramatically in solid state as well as in solution by the protonation stimuli.     

固相微萃取-顶空-气相色谱-质谱法测定美甲贴中6种挥发性有机物的含量

称取美甲贴样品0.0010g置于20mL顶空瓶中,在选定的条件下[孵化温度为36℃,孵化时间为15min,振动器转速为300r·min^-1,固相微萃取(SPME)温度为常温和样品的萃取次数为10次]进行顶空采样和固相微萃取,并将所得挥发性有机物(VOCs,包括所需测定的丙酮、正己烷、乙酸乙酯、乙酸异丙酯、甲苯和乙酸丁酯等6种化合物)引入气相色谱-质谱仪中进行分析。用HP-VOC色谱柱(60m×0.25mm,0.25μm)在40~250℃区间以程序升温模式进行色谱分离,并在电子轰击离子源和选择离子扫描模式等条件下进行质谱测定。采用外标法定量。测得上述6种VOCs的质量在相同的范围(2~250ng)内与其相应的峰面积呈线性关系,其检出限(3.14s)也相同(0.5ng)。以实际样品为基体,在5个浓度水平上加入标准溶液进行回收试验,测得其回收率为80.0%~110%,测定值的相对标准偏差(n=7)为0.030%~5.0%。     

Chemistry of Soft Porous Crystals: Structural Dynamics and Gas Adsorption Properties

In this Minireview, we discuss the fundamental chemistry of soft porous crystals (SPCs) by characterizing their common structural features and the resulting structural softness and transitions. In particular, we focus on the recently emerging properties based on metastable transitions and those arising from local dynamics. By comparing the resulting adsorption properties to those of commonly applied rigid adsorbents, we highlight the potential of SPCs to revolutionize adsorption‐based technologies, considering our current understanding of the thermodynamic and kinetic aspects. We provide brief outlines for the experimental and computational characterization of such phenomena and offer an outlook toward next‐generation SPCs likely to be discovered in the next decade.     

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.     

综合化学实验:多孔沸石咪唑框架的制备、表征与染料吸附性能研究

推荐一个以物理化学知识为主、包含无机化学和结构化学内容的综合化学实验。通过简便的室温沉淀方法制备纳米尺寸的多孔材料沸石咪唑框架ZIF-67。利用粉末X射线衍射仪和扫描电子显微镜对化合物的结构和形貌进行表征。通过紫外-可见分光光度计测试化合物对染料分子的吸附性能,深入研究该化合物的固-液吸附过程。本综合实验充分体现了“合成-表征-分析”的基础科学研究过程和“物质-结构-性能”的科研思维模式,使化学基础知识、基本实验技能和前沿学术研究相结合,可以加深学生对基础知识的理解,提高学生的基本实验技能和综合运用学科知识的能力。     

氧化铜/二氧化硅多孔复合材料的制备及其对亚甲基蓝的吸附性能

采用聚乙二醇（PEG）为模板,通过溶胶凝胶法-水热法制备出CuO/SiO2多孔复合材料,使用FTIR、HRTEM、XRD和BET等技术手段对目标产物进行了表征;研究添加CuO质量及反应温度等反应条件对复合材料的孔结构特征的影响。 用目标产物作为吸附材料,研究了其对有机染料亚甲基蓝的吸附性能,结果表明,CuO/SiO2多孔复合材料对亚甲基蓝具有良好的吸附效果,尤其是含CuO质量分数为15%的样品在用量0.015 g、体系pH=9、搅拌时间为2 h的条件下,对10 mL亚甲基蓝（4 mg/L）的去除率最高可达97.17％。 对吸附的过程和机理进行了初步探讨。     

High CO2‐Capture Ability of a Porous Organic Polymer Bifunctionalized with Carboxy and Triazole Groups

A new porous organic polymer, SNU‐C1 , incorporating two different CO₂‐attracting groups, namely, carboxy and triazole groups, has been synthesized. By activating SNU‐C1 with two different methods, vacuum drying and supercritical‐CO₂ treatment, the guest‐free phases, SNU‐C1‐va and SNU‐C1‐sca , respectively, were obtained. Brunauer–Emmett–Teller (BET) surface areas of SNU‐C1‐va and SNU‐C1‐sca are 595 and 830 m²g^?1, respectively, as estimated by the N₂‐adsorption isotherms at 77 K. At 298 K and 1 atm, SNU‐C1‐va and SNU‐C1‐sca show high CO₂ uptakes, 2.31 mmol g^?1 and 3.14 mmol g^?1, respectively, the high level being due to the presence of abundant polar groups (carboxy and triazole) exposed on the pore surfaces. Five separation parameters for flue gas and landfill gas in vacuum‐swing adsorption were calculated from single‐component gas‐sorption isotherms by using the ideal adsorbed solution theory (IAST). The data reveal excellent CO₂‐separation abilities of SNU‐C1‐va and SNU‐C1‐sca , namely high CO₂‐uptake capacity, high selectivity, and high regenerability. The gas‐cycling experiments for the materials and the water‐treated samples, experiments that involved treating the samples with a CO₂‐N₂ gas mixture (15:85, v/v) followed by a pure N₂ purge, further verified the high regenerability and water stability. The results suggest that these materials have great potential applications in CO₂ separation.     

A Robust Porous Metal–Organic Framework with a New Topology That Demonstrates Pronounced Porosity and High‐Efficiency Sorption/Selectivity Properties of Small Molecules

A robust porous metal–organic framework (MOF), [Co₃(ndc)(HCOO)₃(μ₃‐OH)(H₂O)]_n ( 1 ) (H₂ndc=5‐(4‐pyridyl)‐isophthalic acid), was synthesized with pronounced porosity. MOF 1 contained two different types of nanotubular channels, which exhibited a new topology with the Schlafli symbol of {4².6⁵.8³}{4².6}. MOF 1 showed high‐efficiency for the selective sorption of small molecules, including the energy‐correlated gases of H₂, CH₄, and CO₂, and environment‐correlated steams of alcohols, acetone, and pyridine. Gas‐sorption experiments indicated that MOF 1 exhibited not only a high CO₂‐uptake (25.1 wt % at 273 K/1 bar) but also the impressive selective sorption of CO₂ over N₂ and CH₄. High H₂‐uptake (2.04 wt % at 77 K/1 bar) was also observed. Moreover, systematic studies on the sorption of steams of organic molecules displayed excellent capacity for the sorption of the homologous series of alcohols (C₁–C₅), acetone, pyridine, as well as water.     

高灵敏宽温区吸附热测定装置的建立

 描述了一个适于气／固体系的宽温区、高灵敏的微分吸附热测定装置．在该装置中，吸附放热由Setaram公司热流式微量热量计测定，吸附量由MKS公司电容式压力传感器测定．此外，设计、制作了可在高真空和宽温区内进行吸附热测定的试样池以及对高活泼金属催化剂进行预处理的试样处理池．用标准物质对热量计进行了标定．为验证该装置对吸附热测定的可靠性，测定了H2在Pt／SiO2和γ－Mo2N上的吸附热，所得结果与文献值一致．数据的误差分析结果表明，吸附热测定的相对误差在4％以内．     

多孔壳聚糖膜的制备及对水中游离余氯的吸附性能

多孔壳聚糖膜的制备及对水中游离余氯的吸附性能;多孔壳聚糖膜;游离余氯;吸附动力学     

A POSS‐Phosphazene Based Porous Material for Adsorption of Metal Ions from Water

The development of adsorptive materials continues to be an important area of research for removal of heavy metal ions from waste water. The adsorption capacity can be modulated by both physical and chemical modification of the adsorbent. Herein, we combine the unique properties of polyhedral oligomeric silsesquioxane (POSS) and organocyclophosphazene as the building units to synthesize a hybrid porous material, abbreviated as PN‐POSS. The synthetic method follows a Heck reaction between hexa(4‐bromophenoxy)cyclotriphosphazene and octavinylsilsesquioxane (OVS). The Brunauer–Emmett–Teller (BET) analysis shows that the material possesses micro‐ and mesopores of 1.5 and 3.8 nm size and a surface area on the order of 500 m² g^?1. These attributes in combination with the donor ability of the phosphazene units qualify the material for high adsorption of Pb²⁺, Hg²⁺ and Cu²⁺ ions with maximal adsorption capacities on the order of 1326, 1927 and 2654 mg g^?1, respectively. The adsorbent exhibits a good regeneration performance and can be effectively used for water treatment.     

一种新型酰胺功能化的共价有机框架用于选择性染料吸附

共价有机框架(covalent organic framework, COF)是一种由轻质元素(C、H、O和N)以共价键的形式连接组成的结晶多孔聚合物,由于其具有规则的孔道、可修饰的骨架以及良好的稳定性而被广泛应用于不同的领域.尤其是将含氮的功能基团连接到COF的骨架中,可以为其吸附特定的染料提供丰富的活性位点.基于此,本工作成功制备了一种酰胺功能化的二维共价有机框架材料(JUC-578),通过一系列的表征证明了该材料具有高的结晶度、均一规整的形貌以及开放的一维介孔孔道.更重要的是,发现JUC-578可以选择性地吸附阳离子染料,并且可以多次循环利用.这主要归因于骨架中的氮作为电子给体与缺电子的染料之间的静电作用以及其他弱相互作用(氢键、偶联作用等).与此同时,JUC-578高的结晶度和有序的孔道也是实现可逆吸附染料非常重要的因素.