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.     

多孔骨架固定分子催化剂催化CO2加氢制备甲酸研究进展

近年来, 大气中CO₂含量急剧增加, 导致了严重的温室效应. 将CO₂作为C1资源转化为燃料或精细化学品引起了越来越多的关注. 开发高效、 稳定、 可回收利用的催化剂成为CO₂资源化利用的关键. 在众多的CO₂加氢催化剂中, 功能性多孔骨架材料固定型分子催化剂展示出优异的性能, 成为研究的热点之一. 功能性骨架材料, 如多孔有机聚合物(POPs)、 共价有机骨架(COFs)和金属有机骨架(MOFs), 具有比表面积大、 热稳定性高和可调性等特点, 在设计合成催化剂方面发挥着重要作用. 本文介绍了POPs/COFs/MOFs多孔骨架材料固定分子催化剂的开发及在催化CO₂合成甲酸领域的最新进展.     

共价有机框架材料的离子化改性及其催化合成环碳酸酯的性能研究（英文）

共价有机框架(COFs)材料是继金属-有机框架材料之后,在拓扑学基础上发展起来的又一类多孔材料.这类材料是由轻质元素(C, H, O, N, B, Si等)通过可逆共价键连接而成的结晶性有机多孔聚合物,具有比表面积大、骨架密度低、孔道结构规整、可人为设计以及表面易修饰改性等特点,自2005年首次报道以来就引起了人们的广泛关注.经过十多年的发展,COFs材料已经被广泛用于气体吸附/分离、光电、能量存储、非均相催化等研究领域.由于材料的多孔性以及相对稳定的特点,近年来COFs材料作为催化剂或催化剂载体用于多相催化反应已经成为该领域的一个研究热点.但是到目前为止,COFs材料的离子化改性用于异相催化相关研究还相对较少.本文选择二维骨架中含有羟基基团的H₂P-DHPhCOF作为载体,通过两步接枝反应成功地将咪唑型离子液体引入到COF材料的孔道中;采用红外光谱、核磁共振、粉末X射线衍射、热失重分析等方法详细地表征了COF材料在后修饰过程中的变化.研究发现, 1,4-二溴丁烷与N-甲基咪唑基团的引入占据了部分孔道,导致框架材料的孔径和孔容减小.同时,我们还将该改性后的离子型C...     

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,     

构建S型异质结COF/CdS以增强太阳光产氢

高效利用太阳能是解决当前能源危机和环境问题的有效途径.光催化制氢技术具有绿色环保、成本低等优势,且氢气可作为能源载体,其燃烧产物仅为水,因此被认为是实现高效利用太阳能的最佳途径之一.为更好地利用太阳能,研究者们致力于开发具有良好可见光活性的光催化剂.CdS因具有良好的电荷转移能力和在可见光区域强吸收的特性,在光催化制氢...     

基于超分子构筑模块和酰胺插入的螺旋配体的PCN类型金属有机骨架的结构和选择性吸附CO2

首次实现了窗口缩小的小斜方六面体超分子构筑模块(SBB)和酰胺功能化螺旋配体5,5’-(((1,1’-biphenyl)-2,2’-dicarbonyl)bis(azanediyl))diisophthalic acid (H₄L)的链接,形成了一个pcu拓扑的微孔金属有机骨架[Cu₂(L)(H₂O)₂]·DMF·6H₂O(NTUniv-53),其在室温下展示了良好的二氧化碳吸附选择性。由于窗口缩小和酰胺的共同作用,该选择性基本不受温度变化的影响。     

One-dimensional metal–organic frameworks built by coordinating 2,4,6-tris(4-pyridyl)-1,3,5-triazine linker with copper nodes: CO2 adsorption properties

The reaction between 2,4,6-tris(4-pyridyl)-1,3,5-triazine (4-tpt) and copper(II) hexafluoroacetylacetone (Cu(hfa)₂) yields two different 1D metal–organic frameworks (MOFs), [(Cu(hfa)₂)₂(4-tpt)]_n ( 1 ) and [Cu(hfa)₂(4-tpt)]_n ( 2 ). The Cu:4-tpt ratio in the new MOFs is determined by the reaction medium, particularly, the solvent used. The two compounds have been fully characterized, including crystal structure elucidation. [(Cu(hfa)₂)₂(4-tpt)]_n ( 1 ), with a 2:1 Cu:4-tpt ratio, could be precipitated in either 1,1,2-trichloroethane or supercritical CO₂. In ( 1 ), 4-tpt shows a tritopic coordination mode, but only half of the Cu(hfa)₂ subunits act as a node, thus connecting two 4-tpt and giving a 1D network. The other half of Cu(hfa)₂ subunits are connected only to one pyridine and thus protrude along the chains. The later Cu(hfa)₂ fragments show a labile character and can be dissolved in diethyl ether to give the second MOF [Cu(hfa)₂(4-tpt)]_n ( 2 ), with a 1:1 Cu:4-tpt ratio. The compound ( 2 ) has also a 1D structure, with all the incorporated copper atoms acting as nodes. In this case, the packing of the chains defines accessible channels, which are perpendicular to the chain axis. After activation, N₂ adsorption/desorption measurements at 77 K confirm the microporous character of ( 2 ) with an apparent surface area of 190 m² g⁻¹. Besides, at 273 K this material clearly shows a significant adsorption of CO₂ prompted by noncoordinated nitrogen in the triazine linker.     

Preparation and Gas Separation Properties of Metal‐Organic Framework Membranes

Continuous and intergrown metal‐organic framework (MOF) membranes, MIL‐100(In) (MIL represents Materials Institute Lavoisier), were prepared directly on porous anodic alumina oxide (AAO) membranes using an in situ crystallization method. The pore surface of MIL‐100(In) is conferred with polarity due to the presence of the 1, 3,5‐benzenetricarboxylic acid. The thickness of MIL‐100(In) membranes was tuned by varying the reactant concentration of indium chloride and 1, 3,5‐benzenetricarboxylic acid. Single gas permeation measurements on this MOF membrane indicate the large permeances of 0.90 × 10^–6 and 0.81 × 10^–6 mol · m^–2·s^–1·Pa^–1 for CO₂ and CH₄, and relatively high ideal selective factors of 3.75 and 3.38 for CO₂/N₂ and CH₄/N₂, respectively.     

Selective gas adsorption and unique structural topology of a highly stable guest-free zeolite-type MOF material with N-rich chiral open channels

A new multifunctional di-topic tetrazolate-based ligand, 2,3-di-1H-tetrazol-5-ylpyrazine (H(2)dtp) has been designed and synthesized. The solvothermal reaction of this ligand with ZnCl(2) gave a robust guest-free three-dimensional zeolite-like chiral metal-organic framework (MOF) complex, [Zn(dtp)], which crystallized in chiral space group P6(1) and possessed chiral open channels with nitrogen-rich walls and the diameter of approximately 4.1 A. This framework presents a unique uniform etd (8,3) topology, is the first example of its type in MOFs, and exhibits high thermal stability with the decomposition temperature above 380 degrees C and permanent porosity. It is interesting that this material is able to selectively adsorb O(2) and CO(2) over N(2) gas, being a rare example in MOFs. In addition, C(2)H(2) and MeOH adsorption results show that although the framework channel holds nitrogen-rich walls that may provide H-bonding sites, no NH H-bond effect between the guest molecules and microporous surface was observed.     

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...