New Microporous Materials for Acetylene Storage and C2H2/CO2 Separation: Insights from Molecular Simulations

Force‐field based grand‐canonical Monte Carlo simulations are used to investigate the acetylene and carbon dioxide uptake capacity, as well as the C₂H₂/CO₂ adsorption selectivity of three novel microporous materials: Magnesium formate, Cu₃(btc)₂, and cucurbit[6]uril. Because no comparable computational studies of acetylene adsorption have been reported so far, the study focuses on systems for which experimental data are available to permit a thorough validation of the simulation results. The results for magnesium formate are in excellent agreement with experiment. The simulation predicts a high selectivity for acetylene over CO₂, which can be understood from a detailed analysis of the structural features that determine the affinity of Mg‐formate towards C₂H₂. For Cu₃(btc)₂, preliminary calculations reveal the necessity to include the interaction of the sorbate molecules with the unsaturated metal sites, which is done by means of a parameter adjustment based on ab‐initio calculations. In spite of the high C₂H₂ storage capacity, the C₂H₂/CO₂ selectivity of this material is very modest. The simulation results for the porous organic crystal cucurbit[6]uril show that the adsorption characteristics that have been observed experimentally, particularly the very high isosteric heat of adsorption, cannot be understood when an ideal structure is assumed. It is postulated that structural imperfections play a key role in determining the C₂H₂ adsorption behavior of this material, and this proposition is supported by additional calculations.     

微孔配位聚合物作为新型储氢材料的研究

微孔配位聚合物性质独特、结构多样,具有广泛的应用前景,它已成为近几年来一个热门的研究领域。本文简要介绍该类化合物作为一种新型的储氢材料,在合成、结构和储氢性能方面的研究进展。     

A Rod‐Packing Microporous Hydrogen‐Bonded Organic Framework for Highly Selective Separation of C2H2/CO2 at Room Temperature

Self‐assembly of a trigonal building subunit with diaminotriazines (DAT) functional groups leads to a unique rod‐packing 3D microporous hydrogen‐bonded organic framework (HOF‐3). This material shows permanent porosity and demonstrates highly selective separation of C₂H₂/CO₂ at ambient temperature and pressure.     

Metal Microporous Aromatic Polymers with Improved Performance for Small Gas Storage

A novel metal‐doping strategy was developed for the construction of iron‐decorated microporous aromatic polymers with high small‐gas‐uptake capacities. Cost‐effective ferrocene‐functionalized microporous aromatic polymers (FMAPs) were constructed by a one‐step Friedel–Crafts reaction of ferrocene and s‐triazine monomers. The introduction of ferrocene endows the microporous polymers with a regular and homogenous dispersion of iron, which avoids the slow reunion that is usually encountered in previously reported metal‐doping procedures, permitting a strong interaction between the porous solid and guest gases. Compared to ferrocene‐free analogues, FMAP‐1, which has a moderate BET surface area, shows good gas‐adsorption capabilities for H₂ (1.75 wt % at 77 K/1.0 bar), CH₄ (5.5 wt % at 298 K/25.0 bar), and CO₂ (16.9 wt % at 273 K/1.0 bar), as well as a remarkably high ideal adsorbed solution theory CO₂/N₂ selectivity (107 v/v at 273 K/(0–1.0) bar), and high isosteric heats of adsorption of H₂ (16.9 kJ mol^?1) and CO₂ (41.6 kJ mol^?1).     

Microporous Polymers as Potential Hydrogen Storage Materials

Microporous organic polymers offer the possibility of storing hydrogen safely at low temperatures and moderate pressures via physisorption. A range of polymers of intrinsic microporosity (PIMs) have been studied. The best PIM to date is based on a triptycene monomer and takes up 2.7% H₂ by mass at 10 bar/77 K. Hypercrosslinked polymers (HCPs) also show promising performance, particularly at pressures >10 bar. The form of the H₂ isotherm is influenced by the micropore distribution, a higher concentration of ultramicropores (pore size <0.7 nm), as found in PIMs, being associated with enhanced low pressure adsorption. The performance of polymers relative to other microporous materials (carbons and metal‐organic frameworks) is compared and promising methods to enhance the hydrogen uptake of microporous polymers are suggested.

     

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.     

二氧化钛柱撑层状氧化锰微孔材料的合成及表征

Na型层状锰氧化物于0.1 mol/L HCl 溶液中离子交换制得前驱体H型层状锰氧化物. H型层状锰氧化物在十二胺乙醇溶液中反应得到层间距为2.62 nm的中间产物——十二胺插入的层状锰氧化物, 该中间产物在异丙醇钛和乙醇的混合溶液中溶剂热处理得到层间距为1.24 nm的钛酸柱撑层状锰氧化物. 在300 ℃条件下经2 h焙烧得到二氧化钛铸型氧化锰微孔材料. 应用XRD, DSC-TGA, SEM, TEM, IR, 氮气吸附实验及元素分析进行了不同阶段所得试样的分析表征. 结果表明十二胺分子在锰氧层间的最大插入量为2.2 mmol/g, 异丙醇钛分子的置换插入生成了组成为Mn_7.00Ti_1.74O_23.3(C₁₂H₂₅NH₂)_0.52•1.93H₂O的铸型层状锰氧化物. 300 ℃焙烧处理所得二氧化钛铸型氧化锰微孔材料的比表面积为140 m²/g.     

Reverse‐Selective Microporous Membrane for Gas Separation

Sort the bigs from the smalls : Reverse‐selective membranes, through which bigger molecules selectively permeate, are attractive for developing chemical processes. A new adsorption‐based reverse‐selective membrane that utilizes a Na cation occluded in a zeolitic framework is presented. The membrane developed enables the selective permeation and separation of bigger polar molecules, such as methanol and water, from hydrogen above 473 K.

     

Microporous Metal–Organic Frameworks for Gas Separation

Microporous metal–organic frameworks (MOFs) are comparatively new porous materials. Because the pores within such MOFs can be readily tuned through the interplay of both metal‐containing clusters and organic linkers to induce their size‐selective sieving effects, while the pore surfaces can be straightforwardly functionalized to enforce their different interactions with gas molecules, MOF materials are very promising for gas separation. Furthermore, the high porosities of such materials can enable microporous MOFs with optimized gas separation selectivity and capacity to be targeted. This Focus Review highlights recent significant advances in microporous MOFs for gas separation.     

微孔材料理论模拟的进展与展望

微孔材料是指孔径小于2 nm的多孔材料, 被广泛应用于非均相催化、吸附、分离、储气等先进工艺中. 按照组成结构分类, 由于这些材料在元素组成及结构特征上的多样性, 因此原则上能够合成的此类材料数目巨大. 仅通过实验手段无法有效地对这些具有潜在应用价值的材料进行研究. 随着计算机资源与数值计算方法的迅速发展, 理论计算方法研究微孔材料不仅可以提供分子水平上对材料特性的认知, 而且可以从微观尺度上揭示实验机理, 有利于建立结构与性能的对应关系, 从而推动新型微孔材料的设计与开发. 综述了近年来针对各种类型微孔材料的理论研究方法及最新的理论研究成果. 指出了理论方法在微孔材料研究进程中存在的主要问题、发展前景及今后的研究方向.     

Nitrogen and Hydrogen Adsorption by an Organic Microporous Crystal

Quick on the uptake : Following its identification during a targeted search, the intriguing crystal structure of 3,3′,4,4′‐tetra(trimethylsilylethynyl)biphenyl was investigated. Simple removal of the included solvent provides an organic crystal with an open microporous structure that has a striking similarity to that of zeolite A (see picture). Reversible adsorption of nitrogen and hydrogen gases at 77 K confirms that the microporosity is permanent.

     

共轭微孔聚合物膜的制备策略及其分离应用

降低工业分离过程的能耗为缓解全球能源紧缺问题提供了有效途径. 相比传统工业分离技术, 膜分离技术能耗低、经济效益高, 开发高效的膜材料是提升膜分离性能的重要手段. 共轭微孔聚合物(CMP)膜具有刚性永久超微孔道、高孔隙率、孔结构及化学环境可调控、交联骨架稳定性好等优势, 在分离领域具有良好的应用前景. 概述了近年来CMP膜的制备方法并简要对比了其优缺点, 阐述了CMP膜在气体分离、有机溶剂纳滤、离子筛分和手性分离等领域的分离机理和研究进展, 为开发新型具有良好分离性能的CMP膜材料提供研究思路.     

Microporous Polymers from a Carbazole‐Based Triptycene Monomer: Synthesis and Their Applications for Gas Uptake

Two kinds of novel organic microporous polymers TCP s ( TCP‐A and TCP‐B ) were prepared by two cost‐effective synthetic strategies from the monomer of tricarbazolyltriptycene ( TCT ). Their structure and properties were characterized by FT‐IR, solid ¹³C NMR, powder XRD, SEM, TEM, and gas absorption measurements. TCP‐B displayed a high surface area (1469 m² g^?1) and excellent H₂ storage (1.70 wt % at 1 bar/77 K) and CO₂ uptake abilities (16.1 wt % at 1 bar/273 K), which makes it a promising material for potential application in gas storage.     

Conductive Microporous Covalent Triazine‐Based Framework for High‐Performance Electrochemical Capacitive Energy Storage

Nitrogen‐enriched porous nanocarbon, graphene, and conductive polymers attract increasing attention for application in supercapacitors. However, electrode materials with a large specific surface area (SSA) and a high nitrogen doping concentration, which is needed for excellent supercapacitors, has not been achieved thus far. Herein, we developed a class of tetracyanoquinodimethane‐derived conductive microporous covalent triazine‐based frameworks (TCNQ‐CTFs) with both high nitrogen content (>8 %) and large SSA (>3600 m² g^?1). These CTFs exhibited excellent specific capacitances with the highest value exceeding 380 F g^?1, considerable energy density of 42.8 Wh kg^?1, and remarkable cycling stability without any capacitance degradation after 10 000 cycles. This class of CTFs should hold a great potential as high‐performance electrode material for electrochemical energy‐storage systems.     

微孔PI气体分离膜的研究进展

自具微孔材料(PIMs)由于自身刚性分子链的扭曲折叠等会产生高比表面积的微孔结构,相应的膜材料具有优异的气体分离性能。将刚性扭曲的结构单元引入到聚酰亚胺(PI)主链中就得到自具微孔PI。微孔型PI是近年来发展的一种新型PI,其微孔结构使得PI膜的气体分离性能得到很大提升,其中气体渗透系数的提升尤为显著,且保持了传统PI良好的热稳定性、化学稳定性及高力学强度等性质。本文重点介绍了微孔PI以及基于微孔PI复合膜的最新研究进展,并对其未来发展趋势进行了展望。     

Decametallic CoII‐Cluster‐Based Microporous Magnetic Framework with a Semirigid Multicoordinating Ligand

We have synthesized a microporous magnetic framework that contained supertetrahedral decametallic cobalt clusters as nodes and 4‐(tris(hydroxymethyl)methyl)pyridine ligands as linkers in a NaCl‐like network. This complex shows canted antiferromagnetism with spin‐glass behavior. After the removal of the guest molecules, the spin‐canting and spin‐glass behaviors are maintained. The permanent porosity was evaluated by N₂‐adsorption measurements. This complex mainly shows a hydrophobic nature, as validated by MeOH‐ and water‐adsorption measurements, which is consistent with the grand canonical Monte Carlo (GCMC) theoretical simulation.