一个微孔钴基金属有机骨架的合成及其选择性气体吸附

利用硝酸钴与配体5,5''-di(1H-1,2,4-triazol-1-yl)-(1,1''-biphenyl)-2,2''-dicarboxylic acid (H₂DTBDA)进行溶剂热反应,制备了一个结构新颖的金属有机骨架{[Co(DTBDA)]₂·DMF·MeOH}_n (FJI-H37)。FJI-H37不仅具有适合气体分子吸附的0.69 nm的微孔,还具有良好的热稳定性及有机溶剂容忍性。气体吸附测试表明FJI-H37不仅能从C₂H₂/CO₂(体积比50:50)混合气中选择性吸附C₂H₂,还可以从CO₂/N₂(体积比15:85)和CO₂/CH₄(体积比50:50)混合气中选择性捕获CO₂;固定床突破实验进一步证实了其高效的气体分离能力。     

一个微孔钴基金属有机骨架的合成及其选择性气体吸附

利用硝酸钴与配体5,5''-di (1H-1,2,4-triazol-1-yl)-(1,1''-biphenyl)-2,2''-dicarboxylic acid (H₂DTBDA)进行溶剂热反应,制备了一个结构新颖的金属有机骨架{[Co (DTBDA)]₂·DMF·MeOH}_n (FJI-H37)。FJI-H37不仅具有适合气体分子吸附的0.69 nm的微孔,还具有良好的热稳定性及有机溶剂容忍性。气体吸附测试表明FJI-H37不仅能从C₂H₂/CO₂(体积比50∶50)混合气中选择性吸附C₂H₂,还可以从CO₂/N₂(体积比15∶85)和CO₂/CH₄(体积比50∶50)混合气中选择性捕获CO₂;固定床突破实验进一步证实了其高效的气体分离能力。     

一个微孔钴基金属有机骨架的合成及其选择性气体吸附

利用硝酸钴与配体5,5''-di (1H-1,2,4-triazol-1-yl)-(1,1''-biphenyl)-2,2''-dicarboxylic acid (H₂DTBDA)进行溶剂热反应,制备了一个结构新颖的金属有机骨架{[Co (DTBDA)]₂·DMF·MeOH}_n (FJI-H37)。FJI-H37不仅具有适合气体分子吸附的0.69 nm的微孔,还具有良好的热稳定性及有机溶剂容忍性。气体吸附测试表明FJI-H37不仅能从C₂H₂/CO₂(体积比50∶50)混合气中选择性吸附C₂H₂,还可以从CO₂/N₂(体积比15∶85)和CO₂/CH₄(体积比50∶50)混合气中选择性捕获CO₂;固定床突破实验进一步证实了其高效的气体分离能力。     

机器学习筛选用于气体吸附分离和存储的金属有机骨架材料

金属有机框架（Metal-organic framework ,MOF）因其高孔隙率、高比表面积和结构可调性,在气体吸附分离领域广泛应用。随着MOF数量激增,传统分子模拟和实验方法验证MOF性能成本高且速度慢,因此目前MOF筛选工作已转向高通量计算辅助的机器学习（Machine-learning,ML）。机器学习作为一种高效的大数据处理方法,能够在高通量筛选（High-Throughput Computational Screening,HTCS）的基础上对数据进行拟合,从而快速而准确地筛选出气体吸附分离材料,并深入挖掘其结构与性能之间的关系。本文回顾了近年机器学习应用于MOF筛选的研究。本文重点讨论了一些运用机器学习从大量结构中筛选出可用于CH4、H2和CO2等气体吸附分离与储存的MOF材料的工作。同时,我们梳理了当前MOF材料筛选工作中的研究思路和进展,并指出了机器学习在筛选MOF材料工作中面临的一些瓶颈和挑战。最后,对该领域的未来发展前景进行了展望。     

四苯基乙烯基共轭微孔聚合物的制备及其气体吸附

共轭微孔聚合物由于其在气体吸附与分离、非均相催化和光电子等领域的巨大应用前景而广受关注. 本文以四苯基乙烯为基本构筑单元, 通过Sonogashira-Hagihara偶联反应制备了3种共轭微孔聚合物新材料, 研究了结构组成和构建模块对制备聚合物孔性能和气体吸附性能的影响. 氮气吸附测试结果表明, 由1,1,2,2-四炔四苯基乙烯自聚合制备的TPE-CMP1具有较大的比表面积, 为1096 m²·g^-1. 在1.13 bar/273 K条件下, TPE-CMP1的CO₂吸附能力为2.36 mmol·g^-1; 在1.13 bar/77.3 K条件下, TPE-CMP1对H₂的吸附能力为1.35 wt%. 另外, 制备的共轭微孔聚合物展示出较高的CO₂/N₂选择性吸附值. 由于这类多孔聚合物材料具有合成方法简单、优良的物理化学及热稳定性、高的比表面积和CO₂吸附性能, 因此将在气体吸附与分离方面具有潜在的应用前景.     

金属有机骨架材料在吸附分离研究中的应用进展

作为一种新型的纳米多孔材料,金属有机骨架材料（Metal-Organic Frameworks,MOFs）在近二十余年中得到了飞速的发展.MOFs材料由无机金属离子和有机配体通过自组装形成,具有许多优于传统多孔材料的特性.超高的比表面积、较高的孔隙率、可调的孔道尺寸、良好的热稳定性和化学稳定性使得MOFs材料在多个领域中展现出了广阔的应用前景.随着研究的不断深入,MOFs材料被广泛应用于催化反应、吸附分离、生物医学等领域中,并表现出了优异的效果.本文着力于近年来MOFs材料在吸附分离研究中的进展,重点介绍了这类材料在能源气体贮存、碳捕获、膜分离、液相吸附、色谱的分离净化方面的应用,并对其今后的发展进行了展望.     

富羧酸基团的共轭微孔聚合物:结构单元对孔隙和气体吸附性能的影响

Polar groups in the skeletons of conjugated microporous polymers (CMPs) play an important role in determining their porosity and gas sorption performance. Understanding the effect of the polar group on the properties of CMPs is essential for further advances in this field. To address this fundamental issue, we used benzene, the simplest aromatic system, as a monomer for the construction of two novel CMPs with multi-carboxylic acid groups in their skeletons (CMP-COOH@1 and CMP-COOH@2). We then explored the profound effect the amount of free carboxylic acid in each polymer had on their porosity, isosteric heat, gas adsorption, and gas selectivity. CMP-COOH@1 and CMP-COOH@2 showed Brunauer-Emmett-Teller (BET) surface areas of 835 and 765 m²·g^-1, respectively, displaying high potential for carbon dioxide storage applications. CMP-COOH@1 and CMP-COOH@2 exhibited CO₂ capture capabilities of 2.17 and 2.63 mmol·g^-1 (at 273 K and 1.05 × 10⁵ Pa), respectively, which were higher than those of their counterpart polymers, CMP-1 and CMP-2, which showed CO₂ capture capabilities of 1.66 and 2.28 mmol·g^-1, respectively. Our results revealed that increasing the number of carboxylic acid groups in polymers could improve their adsorption capacity and selectivity.     

聚对苯撑乙炔的合成及光谱性能-共轭主链被间位苯环阻隔

报道了一种阻隔型聚对幕撑乙炔((PPE)的合成与电致发光特性,合成的模型小分子证明,在聚对苯撑乙炔(PPV)主链引入间位幕环,可阻隔PPV的有效共轭长度,改变其发光颜色,研究了电致发光暑件ITO／m-PPE／Al的电致发光特性。     

交联聚苯撑乙炔的的合成及其荧光特性

利用Sonogashira偶联反应,首次合成了溶解性好且为乙烯基封端的聚苯撑乙炔化合物（PPE）,通过。HNMR谱、IR光谱对其结构进行了表征．将其热固化后,通过紫外可见吸收光谱和荧光发射光谱分析,证明了PPE的交联能够在一定程度上消除分子链间的相互作用和π-π堆积效应．     

多孔有机骨架:基于傅氏烷基化反应的合成与气体吸附性质

通过傅氏烷基化反应成功地合成了基于四苯锗烷构筑单元的多孔有机骨架材料PAF-9。用红外光谱,粉末X射线衍射,固体核磁共振,热重分析和低温氮气吸附-脱附表征了PAF-9材料的微结构与孔道性质。表征数据表明PAF-9具有非常高的热稳定性和化学稳定性,同时具有较高的比表面积。该PAF材料的BET比表面积为334 m²·g^-1。此外,得到的PAF材料对二氧化碳具有较好的吸附能力。     

质子交换膜用磺化聚芳醚的合成与性能研究

合成了一种用于质子交换膜的新型磺化聚芳醚. 由于特殊单体结构的设计, 在聚合物主链上引入取代基对主链进行保护, 用氯磺酸直接磺化方法在聚芳醚高分子侧基上引入磺酸功能基, 实现了聚合物磺化结构的可控定位合成, 得到了稳定性较好的磺化聚芳醚. 用溶液浇膜法制备了质子交换膜, 考察了质子交换膜的各种性能. 结果表明, 这种膜具有良好的成膜性, 水解性稳定性和优异热稳定性能, 5%的热失重温度为362.3 ℃. 氧化稳定性在80 ℃的Fenton’s试剂(3%的过氧化氢和2 mg/L的FeSO₄)中进行, 膜在69 min时才开始变碎, 表现出良好的氧化稳定性.     

聚芳亚胺的合成、结构与性能

以不同的二碘化合物和芳香二胺为单体,通过两种不同的方法经缩聚反应得到了系列高分子量、低分布的聚芳亚胺。其结构由FT-IR, 1H NMR1和元素分析表征。由DSC和TG测定结果可知,该系聚合物具有较高的玻璃化转变温度(Tg＞150℃)和良好的热稳定性(TD＞400℃)。另外,该系聚合物还表现出良好的溶解性能。     

New Poly(arylene ethynylene)s Consisting of Electron‐Deficient Aryleneimide Units

Summary: A new class of poly(arylene ethynylene)s (PAEs) containing an electron‐deficient N‐alkylphthalimide unit was prepared by means of a Sonogashira reaction. Complete solubility of the PAEs was observed by utilizing a 2,6‐diisopropylphenyl side chain. The chemical structure of the novel soluble polymer 3c was confirmed by NMR spectra, whereas the insoluble polymers were characterized by elemental analysis and IR spectra. Fluorescence measurements of 3c indicate a rigid structure and high symmetry in the excited state.

     

Poly(arylene ether)s,poly(arylene thioether)s,and poly(arylene sulfone)s derived from a dihydroxy(imidoarylene) monomer

Novel poly(arylene ether)s, poly(arylene thioether)s, and poly(arylene sulfone)s were synthesized from the dihydroxy(imidoarylene) monomer 1 . The syntheses of poly(arylene ether)s were carried out in DMAc in the presence of anhydrous K₂CO₃ by a nucleophilic substitution reaction between the bisphenol and activated difluoro compounds. Poly(arylene thioether)s were synthesized according to the recently discovered one-pot polymerization reaction between a bis(N,N′-dimethyl-S-carbamate) and activated difluoro compounds in the presence of a mixture of Cs₂CO₃ and CaCO₃. The bis(N,N′-dimethyl-S-carbamate) 3 was synthesized by the thermal rearrangement reaction of bis(N,N′-dimethylthiocarbamate) 2 , which was synthesized from 1 by a phase-transfer catalyzed reaction. The poly(arylene thioether)s were further oxidized to form poly(arylene sulfone)s, which would be very difficult, if not impossible, to synthesize by other methods. All of the polymers described have extremely high T_gs and thermal stability as determined from DSC and TGA analysis. Poly(arylene sulfone)s have the highest T_gs and they are in the range of 298–361°C. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1201–1208, 1998     

基于三蝶烯的微孔聚二胺磷腈

近年来有机多孔聚合物材料由于其在气体吸附分离、气体存储及非均相催化等多个领域具有优良性质而受到国内外科学家们广泛的关注. 三蝶烯是一类具有D_3h刚性对称骨架结构的化合物, 同时它特有的结构特点及其丰富的反应性能使其成为一类构筑有机多孔材料的优良建筑块. 基于六氨基三蝶烯盐酸盐和六氯环三磷腈, 通过N-P型一步聚合法制备了两种聚二胺磷腈多孔材料TrpPOP-1和TrpPOP-2. 材料的结构通过固体核磁共振碳谱、磷谱和红外光谱等进行了表征. 氮气吸脱附等温线表明两种聚合物均具有永久的微孔性质, TrpPOP-1和TrpPOP-2的BET比表面积分别为790和640 m²·g^-1, 主要孔径分别在0.63和0.59 nm左右. 孔径分布较窄的多孔聚合物能与小分子气体有更好的相互作用, 因此, 我们对这两种材料的小分子气体(氢气、二氧化碳和甲醛)吸附性能进行了研究. TrpPOP-1的氢气吸附量在77 K和1.0 bar条件下为1.30 wt%, 二氧化碳吸附量在273 K和1.0 bar条件下为16.2 wt%. 材料TrpPOP-2对甲醛的吸附量在298 K为5.5 mg·g^-1.     

新型含磷和氟聚芳醚的制备、表征及性能

通过分子设计, 成功合成了一种含有三苯基膦结构的二氟单体--4,4’-二氟二苯苯磷氧(BFPPO). 在碱催化条件下, BFPPO与2-双-(4-羟苯基)六氟丙烷(六氟双酚A)缩聚得到一种新型含三苯基膦结构的聚芳醚材料(6F-PAEPO). 使用FTIR,1H NMR, 31P NMR, 和16F NMR等表征手段确定了聚合物的结构, 聚合物表现出良好的热稳定性、有机可溶性、机械性能和光透过性能, 其中聚合物的玻璃化转变温度高达211℃, 空气气氛和氮气气氛下5%热失重温度分别为512℃和523℃, 聚合物薄膜的最大光透过率超过80%. 尤其, 聚合物由于主链中三苯基磷氧结构的存在, 表现出了优异的阻燃性能, 有限氧指数(LOI)达到39.9%.     

Hyperbranched poly(arylene ethynylene)s with triphenylamine core for polymer light‐emitting diodes

A series of light‐emitting hyperbranched poly(arylene ethynylene)s (HB‐PAEs) were prepared by the Sonogashira coupling from bisethynyl of carbazole, fluorene, or dialkoxybenzenes (A₂ type) and tris(4‐iodophenyl)amine (B₃ type). For comparison, two linear polymers (L‐PAEs) of the HB analogs were also synthesized. The polymers were characterized by Fourier transform infrared, NMR, and GPC. The HB polymers showed excellent solubility in chloroform, THF, and chlorobenzene when compared with their linear analogs. The number‐average molecular weight (M_n) of the polymers determined from GPC was found to be in the range of 18,600–34,200. The polymers were thermally stable up to 298–330 °C with only 5% weight loss. The absorption maxima of the polymers were between 354 and 411 nm with optical band gap in the range of 2.5–2.9 eV. The HB polymers were found to be highly fluorescent with photoluminescence quantum yields around 33–42%. The highest occupied molecular orbital energy levels of the polymers calculated from onset oxidation potentials were found to be in the range from ?5.83 to ?6.20 eV. Electroluminescence (EL) properties of three HB‐PAEs and one L‐PAE were investigated with device configuration ITO/PEDOT:PSS/Polymer/LiF/Al. The EL maxima of HB‐PAEs were found to be in the range of 507–558 nm with turn‐on voltages around 7.5–10 V and maximum brightness values of 316–490 cd/m². At the same time, linear analog of one HB‐PAE was found to show a maximum brightness of 300 cd/m² at a turn‐on voltage of 8.2 V. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Gas transport properties of novel poly(arylene ether ketone)s containing dibenzoylbiphenyl and benzonaphthone moieties

In this work we present the results from studies on novel poly(arylene ether ketone)s, including gas permeability, wide-angle x-ray diffraction (WAXD), and dynamic mechanical analysis (DMA). Poly(arylene ether ketone)s containing 2,2′- and 3,3′-dibenzoylbiphenyl (DBBP) moieties were characterized to study the effect of biphenyl substitution on gas transport properties. Gas permeabilities of naphthalene-containing poly(arylene ether ketone)s were also measured. Higher permeabilities were observed for polymers prepared with 6F-BPA, compared to 9,9-bis(4-hydroxyphenyl)fluorene (HPF). The naphthalene-containing polymers exhibited higher permeabilities than the DBBP polymers, except for a polymer having the 2,2′-DBBP and tetramethylbiphenyl moieties. Based on our work, and results reported in the literature, the 3,3′-DBBP polymers showed the lowest permeabilities for DBBP-containing poly-(arylene ether ketone)s. The low permeabilities are due to more efficiently packed chains brought on by greater flexibility of the backbone, compared to the other polymers studied. DMA studies confirmed the higher barriers to rotation which are believed to be responsible for 2,2′-DBBP polymers having similar selectivities compared to 3,3′-DBBP polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 425–431, 1998     

Novel Photosensitive Fluorinated Poly(arylene ether) Having Zero Birefringence

Summary: A novel photosensitive fluorinated poly(arylene ether) containing chalcone units was synthesized from decafluorinated chalcone and fluorinated bisphenol at low temperature. Upon UV irradiation, the refractive indices of the polymer film were decreased because of the reduction of electronic polarizability in the chalocone moiety. The decrease was more significant in the in‐plane direction than in the out‐of‐plane direction, and consequently, zero birefringence (at 632.8 nm) was obtained after 90 s of exposure.

The changes in the refractive indices and the birefringence of chalcone‐containing fluorinated poly(arylene ether) films synthesized and measured at 632.8 nm with respect to UV irradiation time.     

Poly(phenylene ethynylene)s with alkoxyphenyl substituents

Two new poly(phenylene ethynylene)s with alkoxyphenyl substituents were synthesized and characterized. The polymers were amorphous, dissolved readily in common organic solvents, and showed glass‐transition temperatures at 162–175 °C. They showed blue photoluminescence both in solution and in the solid state due to the steric interaction between the substituents and the main chain that caused an interruption of the conjugation length. The quantum yields in a tetrahydrofuran solution were up to 0.63. Excimer emission was the dominant product of the photoexcitation of thin films of the polymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1449–1455, 2002