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,粉末射X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334m²·g^-1。此外,得到的PAF材料对二氧化碳具有较好的吸附能力。     

常温合成硫掺杂微孔碳及其二氧化碳的吸附性能

常温下以间苯三酚和3-甲醛苯并噻吩作为原料,一步法合成了含硫酚醛树脂。在氩气保护下碳化,成功制备出了硫掺杂多孔碳（S-PC）。并利用扫描电镜（SEM）、X射线光电子能谱（XPS）、X射线衍射（XRD）和氮气吸附-脱附仪对材料进行了形貌、结构和性能的表征。实验结果表明,所得样品具有较高比表面积和大量的微孔,经过调控,可以使制备的硫掺杂多孔碳的BET比表面积达到997 m²·g^-1,并使其微孔孔体积达到0.44 cm³·g^-1。得益于较高的比表面积以及其富含微孔的特性,当材料应用于二氧化碳吸附时,具有较高的CO₂吸附量,在273和298 K时分别高达5.13,3.22 mmol·g^-1,并具有良好的选择性。     

壳聚糖基多孔碳材料的制备及其超级电容性能

以胶态SiO₂纳米粒子为模板,壳聚糖为碳源,ZnCl2为活化剂,制备了具有不同比表面积和孔体积的氮掺杂介孔碳。采用多种表征手段对碳材料的微观形貌、比表面积和孔道结构进行了表征,探究了壳聚糖与SiO₂纳米粒子的比例以及ZnCl2活化剂对碳材料孔体积和比表面积的影响。结果表明,在未使用活化剂时碳材料(CSi-1.75)的孔体积高达4.53 cm³·g^-1,但其比表面积最小(729 m²·g^-1);使用ZnCl₂作为活化剂制备的碳材料(CSi-1.75-Zn)比表面积为1032 m²·g^-1,但其孔体积下降到1.99 cm³·g^-1,且具有最多的吡啶氮和吡咯氮。在以6.0 mol·L^-1 KOH为电解液的三电极体系中,当电流密度为0.5 A·g^-1时,CSi-1.75-Zn的比电容为344 F·g^-1,而CSi-1.75的比电容仅为255 F·g^-1。这表明碳材料的比表面积对超级电容性能影响最大,而孔体积影响较小。电容贡献分析结果表明,相对于CSi-1.75,CSi-1.75-Zn的双电层电容和赝电容都得到了提高,这表明更大的比表面积和更多的吡啶氮和吡咯氮有利于提高碳材料的超级电容性能。     

超高比表面积氮掺杂多孔碳材料的制备及其超级电容性能

以蔗糖为碳源、尿素为氮源、草酸钾为活化剂,通过简单的研磨和高温碳化制备了具有超高比表面积(大于3 000 m²·g^-1)的氮掺杂多孔碳材料。采用多种手段对多孔碳材料的微观形貌、比表面积、孔结构和表面氮物种进行了表征,探究了不同温度下草酸钾和尿素对碳材料的比表面积、氮含量和超级电容性能的影响。结果表明,仅使用草酸钾作为活化剂制备的碳材料KC-800的比表面积为1 114 m²·g^-1,而同时使用草酸钾和尿素制备的样品KNC-800的比表面积高达3 033 m²·g^-1。在以6.0mol·L^-1KOH为电解液的三电极体系中,当电流密度为0.5 A·g^-1时,KNC-800的比电容为405 F·g^-1,而KC-800的比电容仅为248 F·g^-1。这表明草酸钾和尿素的加入显著提高了多孔碳材料的比表面积和超级电容性能。电容贡献分析表明,KNC-800的双电层电容值和赝电容值均高于KC-800。KNC-800在电流密度为0.5 A·g^-1时经过10 000次循环后仍能保持98.3%的初始比电容,表现出优异的循环性能。     

超高比表面积氮掺杂多孔碳材料的制备及其超级电容性能

以蔗糖为碳源,尿素为氮源,草酸钾为活化剂,通过简单的研磨和高温碳化制备了具有超高比表面积(大于3 000 m²·g^-1)的氮掺杂多孔碳材料。采用多种手段对多孔碳材料的微观形貌、比表面积、孔结构和表面氮物种进行了表征,探究了不同温度下草酸钾和尿素对碳材料的比表面积、氮含量和超级电容性能的影响。结果表明,仅使用草酸钾作为活化剂制备的碳材料KC-800 的比表面积为 1 114 m2·g^-1,而同时使用草酸钾和尿素制备的样品 KNC-800 的比表面积高达 3 033 m²·g^-1。在以 6.0mol·L^-1 KOH 为电解液的三电极体系中,当电流密度为 0.5 A·g^-1时,KNC-800 的比电容为 405 F·g^-1,而 KC-800 的比电容仅为248 F·g^-1。这表明草酸钾和尿素的加入显著提高了多孔碳材料的比表面积和超级电容性能。电容贡献分析表明,KNC-800的双电层电容值和赝电容值均高于KC-800。KNC-800在电流密度为0.5 A·g^-1时经过10 000次循环后仍能保持98.3%的初始比电容,表现出优异的循环性能。     

季铵型阳离子纤维素对水中腐殖酸的吸附

以异丙醇为分散剂,碱纤维与3-氯-2-羟丙基三甲基氯化铵反应,醚化接枝制得一种环境功能材料-季铵型阳离子纤维素（QACC）。用红外光谱、X-射线衍射和电镜扫描对材料的结构进行了表征：红外光谱中1644cm^-1处存在明显的季铵基的弯曲振动。经过改性的QACC结晶度下降,比表面积增加。研究了QACC对腐殖酸的吸附性能：pH=8、318K时,QACC对腐殖酸的饱和吸附容量为622mg·g^-1;其表观活化能为6.45kJ·mol^-1;吸附符合Lagergren二级动力学方程,吸附速率随温度升高而加快;吸附等温模型符合Langmuir等温式,为单分子层吸附;吸附腐殖酸的ΔH、ΔS、ΔG分别为：20.3kJ·mol^-1、77.8J·mol^-1·K-1、-4.44kJ·mol^-1,吸附主要为化学吸附。     

同步合成模板法制备热解炭及其电化学电容性能研究

研究制备新型炭材料是提高电化学电容器性能的有效途径。本文以二氧化硅干凝胶为模板,以合成间苯二酚-甲醛(RF)干凝胶为炭前驱体,采用同步合成模板法制得了比表面积达1100m²·g^-1,孔径分布集中,平均孔径为4.5nm的炭材料。循环伏安研究表明,与比表面积为1720m²·g^-1的活性炭相比,本研究制得的炭材料具有更优异的电化学电容性能,2mV·s^-1时比容量达195F·g^-1。     

热处理对二氧化锰电化学行为的影响

以高锰酸钾和醋酸锰为前驱体, 通过液相沉淀法合成得到二氧化锰. 在不同温度热处理条件下研究二氧化锰的结构转变及其作为超级电容器电极材料的电化学行为. 采用X射线衍射(XRD), 扫描电镜(SEM), 氮气物理吸附和热重(TG)等手段表征产物的结构特点; 采用循环伏安和恒流充放电等方法表征其电化学行为. 结果表明: 合成的二氧化锰是具有中孔特征的α-MnO₂, 比表面积为253 m²·g^-1, 颗粒尺寸在50-100 nm之间. 350 °C以下的低温热处理使氧化锰仍能保持α-MnO₂的晶体结构, 比表面积为170 m²·g^-1左右, 单电极比电容值由原来未热解时的267 F·g^-1增加到250 °C热处理后的286 F·g^-1. 高温热处理(>450 °C)导致氧化锰逐渐过渡为α-Mn₂O₃, 且表面积下降约为30 m²·g^-1, 比电容急剧下降. 低温热处理后氧化锰的电化学稳定性明显提高, 在50 mV·s^-1的快速扫描速率下, 电极具有良好的倍率特性.     

无模板剂合成用于超级电容器的二氧化锰/石墨烯复合材料

以尿素、四水合氯化锰和氧化石墨烯为原料,采用水热法并通过热分解制备了一种具有石墨烯包覆结构的石墨烯-二氧化锰复合材料,利用扫描电子显微镜、X射线衍射、比表面积（BET）、拉曼光谱和热失重等技术对其形貌、晶体结构及表面结构进行了表征;在三电极条件下利用循环伏安法、恒流充放电法和交流阻抗法测试了材料的电化学性能,并考察了不同石墨烯含量对材料比电容的影响. 结果表明,在不添加模板剂的条件下制备的复合材料中二氧化锰是具有介孔结构的α-MnO₂,当复合15%（质量分数）的石墨烯后材料的比表面积从109 m²·g^-1提高到168 m²·g^-1. 复合材料具有更好的电化学性能,在0.2 A·g^-1电流密度下复合材料的比电容达到最大值（454 F·g^-1）,远高于纯二氧化锰的值（294 F·g^-1）. 在2 A·g^-1的电流密度下恒流充放电2000 次后复合材料的比电容保持率为92%.     

低成本硫掺杂多孔碳材料的制备及其超级电容性能

以廉价的胶态二氧化硅为模板,蔗糖为碳源,硫酸为预碳化试剂和硫源,通过硬模板法制备了相对廉价的硫掺杂多孔碳(SSC-T,T℃代表碳化温度)材料。采用多种表征方法对多孔碳材料的微观形貌、孔道结构、比表面积和表面硫物种进行了表征,探究了硫酸和碳化温度对多孔碳材料的微观形貌、孔道结构和比表面积的影响。结果表明,碳化温度对碳的孔结构、比表面积和硫元素的含量有显著的影响,其中900℃碳化得到的样品SSC-900具有最大的比表面积、孔体积和比电容,远高于未加入硫酸制备的碳材料SC-900,表明硫酸的加入可以提高碳材料的比表面积、孔体积,进而提高碳材料的比电容。与昂贵的有序介孔碳CMK-3相比,SSC-900具有成本更低、孔径更大和电容性能更好的优点。在以6.0 mol·L^-1 KOH为电解质的三电极体系中,在0.5 A·g^-1的电流密度下,SSC-900的比电容可以达到357 F·g^-1,而SC-900和CMK-3的比电容分别仅为152和266 F·g^-1。电容贡献分析表明,SSC-900的双层电容值和赝电容值均高于SC-900。此外,SSC-900在0.5 A·g^-1的电流密度下循环10 000次后仍能保持98.4%的初始比电容。     

Facile Synthesis of Ultrastable Porous Aromatic Frameworks by Suzuki–Miyaura Coupling Reaction for Adsorption Removal of Organic Dyes

Porous aromatic frameworks (PAFs) with robust structure, high stability, and high surface area have attracted intense interest from scientists in diverse fields. However, there are still very few reports on the adsorption of organic dyes by PAFs. In this work, four new PAFs have been facilely synthesized by the polymerization of a tetrahedral-shaped (four-node) monomer with a series of three-node monomers through Suzuki–Miyaura coupling reactions. All the obtained materials possess hierarchical porous structures and show high thermal and chemical stability. The Brunauer–Emmett–Teller (BET) surface areas of these PAFs were determined to be 857 m² g⁻¹ for PAF-111 , 526 m² g⁻¹ for PAF-112A , 725 m² g⁻¹ for PAF-112B , and 598 m² g⁻¹ for PAF-113 . Rhodamine B was selected as a model organic dye to test the adsorption capacities of the obtained PAF materials. PAF-111 showed a maximum adsorption capacity of 1666 mg g⁻¹ (167 wt %) for Rhodamine B, which is among the highest values reported to date for porous organic materials. It is noteworthy that PAF-111 could be reused in at least ten cycles under the adsorption conditions without any loss of adsorption capacity. Our study has revealed the great potential and advantages of PAFs as ultrastable adsorption materials for the removal of organic dyes.     

Friedel-Crafts Synthesis of New Porous Aromatic Frameworks for Stabilizing Gas Transport Properties of Highly Permeable Glassy Polymers

Porous aromatic frameworks of new generation, PAF-FC, were prepared by the Friedel-Crafts reaction between tetraphenylmethane and dimethoxymethane and were characterized. The material obtained has the structure similar to that of PAF-11 and exhibits high porosity (S_BET = 768 m² g^?1). Introduction of 10 wt % PAF-FC allows stabilization of the gas transport characteristics of poly[1-trimethylsilyl–1-propyne] (PTMSP) in time. For example, after 500-h annealing at 100°C, the CO₂ permeability coefficient of the PTMSP/PAF-FC composite decreased by 15%, whereas the ideal CO₂/N₂ selectivity increased from 5.6 to 6.1. The resultant gas transport characteristics appeared to be comparable to those of the previously studied porous aromatic frameworks PAF-11. It should be noted that synthesis of PAF–11 requires using expensive chemicals in large amounts, whereas PAF-FC synthesis by linking of aromatic fragments of monomeric monomers using the Friedel-Crafts reaction is much simpler and involves the use of considerably less expensive chemicals.

     

Alkylation of phenol with olefins in the presence of catalysts based on mesoporous aromatic frameworks

Mesoporous polyaromatic frameworks (PAFs) based on tetraphenylmethane were obtained and modified with sulfonic acid groups. The compounds were characterized by solid-state ¹³C NMR and IR spectroscopy, low-temperature nitrogen adsorption-desorption, and transmission electron microscopy. The acidities of the PAF-1-SO₃H and PAF-2-SO₃H samples determined by titration were 3.99 mmol g^–1 and 0.91 mmol g^–1, respectively. The catalytic activity of PAF-SO₃H for alkylation of phenol with linear terminal olefins was investigated. The reaction products were isomeric monoalkylphenols (C-alkylates), and alkyl phenyl ethers (O-alkylates).     

Thermal behavior of aminotrimethoxysilanphosphonate functionalized onto styrene-divinylbenzene copolymer

Abstract

The chlorometylated styrene–divinylbenzene copolymer with different percent of divinylbenzene (code: S-6.7 DVB, S-12DVB, and S-15DVB) was functionalized with 3-hydroxybenzaldehyde for obtaining intermediated polymers. The aminotrimethoxysilanphosphonate groups were grafted by one-pot reactions in tetrahydrofuran using three components: polymers grafted with aldehyde groups (code: CHO-6.7, CHO-12, and CHO-15), 3-aminopropyltrimethoxysilane, diethylphosphite. The aminotrimethoxysilanphosphonate groups functionalized onto styrene-(6.7, 12, and 15%) divinylbenzene copolymer (code: PAF-6.7, PAF-12, and PAF-15) and evolution of the reaction were evidenced by FT-IR spectroscopy and porous structure by N₂ adsorption-desorption, SEM microscopy. The thermal behavior of aldehydes and materials: PAF-6.7, PAF-12, and PAF-15 are different than initial polymer supports.     

Construction of a Stable Crystalline Polyimide Porous Organic Framework for C2H2/C2H4 and CO2/N2 Separation

Utilization of porous materials for gas capture and separation is a hot research topic. Removal of acetylene (C₂H₂) from ethylene (C₂H₄) is important in the oil refining and petrochemical industries, since C₂H₂ impurities deactivate the catalysts and terminate the polymerization of C₂H₄. Carbon dioxide (CO₂) emission from power plants contributes to global climate change and threatens the survival of life on this planet. Herein, 2D crystalline polyimide porous organic framework PAF-120, which was constructed by imidization of linear naphthalene-1,4,5,8-tetracarboxylic dianhydride and triangular 1,3,5-tris(4-aminophenyl)benzene, showed significant thermal and chemical stability. Low-pressure gas adsorption isotherms revealed that PAF-120 exhibits good selective adsorption of C₂H₂ over C₂H₄ and CO₂ over N₂. At 298 K and 1 bar, its C₂H₂ and CO₂ selectivities were predicted to be 4.1 and 68.7, respectively. More importantly, PAF-120 exhibits the highest selectivity for C₂H₂/C₂H₄ separation among porous organic frameworks. Thus PAF-120 could be a suitable candidate for selective separation of C₂H₂ over C₂H₄ and CO₂ over N₂.     

Highly efficient Lewis acid catalytic activity of the tritylium ion at the node of a tensile organic framework

Tritylium salts have been used as Lewis acid catalysts in organic synthesis for a long time. In this work, we found that the Lewis acid catalytic activity of tritylium ions at the node of a tensile framework is significantly improved compared to that of the free tritylium salts. The tritylium-based framework, PAF-201 (PAF, porous aromatic framework), was prepared by acidification of a semi-rigid triphenylcarbinol-based parent framework, PAF-200. When PAF-200 was alternately exposed to HCl and NH₃ gas, a fast allochroic cycle was observed due to repeated formation of tritylium species. Interestingly, the pseudo-first-order reaction rate of a Povarov model reaction catalyzed by PAF-201 as a Lewis acid was ∼3.7 times and ∼4.7 times as those of tritylium tetrafluoroborate and tri(4-biphenyl)carbonium tetrafluoroborate, respectively. Theoretical calculations revealed that the tritylium ion at the node of PAF-201 has a quasi-planar structure. The transformation of triphenylcarbinol in PAF-200 to tritylium in PAF-201 can make the framework taut, and the rebounding force toward the tetrahedral structure is stored. This is favorable for tritylium to activate the imine substrate along with a deformation of the quasi-plane to tetrahedron. PAF-201 could be easily recycled at least three times without evident loss of catalytic activity. This work presents the catalytic activity of the tritylium ion under stress.

In this work, a tensile tritylium-based organic framework, PAF-201 was prepared. The Lewis acid catalytic ability of PAF-201 was significantly higher than that of tritylium tetrafluoroborate. This work presented the catalytic activity of the tritylium ion under stress.     

铁脂质体/水分配系数测定及影响因素考察

基于PAF-301分子模型通过Li 掺杂或B取代等模式设计了几种新型多孔芳香骨架(PAFs)材料, 采用量子力学和分子力学方法对新材料的储氢性能进行研究. 由量子力学计算得到了不同分子片段与H₂之间的结合能, 并结合DDEC方法计算了各分子片段的原子电荷分布. 利用巨正则蒙特卡洛(GCMC)模拟方法计算了77和298 K下H₂在不同PAFs材料中的吸附平衡性质. 结果表明, H₂直接与苯环的结合能较低, 但掺杂Li 原子能够提高H₂与六元环的结合能, 同时Li 原子体现出较高的正电性质, B原子取代苯环中的两个C原子后, 使得原有C原子电负性增强; 77 K下PAF-301Li 具有最高的储氢性能, 而PAF-C₄B₂H₄-Li₂-Si 和PAF-C₄B₂H₄-Li₂-Ge体现出较好的常温储氢性能, 各种材料的常温储氢性能远低于其低温储氢性能. 通过77 K下H₂在PAFs材料中的等位能面分布和吸附平衡质心密度分布对H₂在PAFs 材料中的优先吸附位置进行分析, 发现在PAF-301 和PAF-301Li 骨架中, 由于中心能量较低的等位能区域范围较宽, H₂在其中存在四个明显的吸附高密度分布区域, 而其它三种PAFs晶胞中心能量较低的等位能区域范围较窄, 使得H₂在其中只存在两个明显的吸附高密度分布区域.     

Hydrogen sorption and electrochemical properties of intermetallic compounds La<Subscript>2</Subscript>MgNi<Subscript>9</Subscript> and La<Subscript>1.9</Subscript>Mg<Subscript>1.1</Subscript>Ni<Subscript>9</Subscript>

Intermetallic compounds La_3–xMg_xNi₉ (x = 1.0, 1.1) were synthesized and their hydrogen sorption and electrochemical properties were studied. The maximum hydrogen storage capacities for La₂MgNi₉ and La_1.9Mg_1.1Ni₉ were shown to be 1.6±0.1 and 1.5±0.1 wt.%, respectively, and the unit cell volume increased by 24% and 16%, respectively, upon the hydrogenation of the alloys. The maximum specific capacity of the electrodes with the La_1.9Mg_1.1Ni₉ and La₂MgNi₉ alloys is 390 mA h g^–1 at a discharge current density of 60 mA g^–1, which is 24% higher as compared to the similar data for the LaNi₅ alloy (315 mA h g^–1). The electrodes demonstrate high specific capacity and performance at high current densities, as well as good cyclic stability.     

Cyclophane-Type Chlorin Dimers from Dynamic Covalent Chemistry of 2,18-Porphyrinyl Dicyanomethyl Diradicals

2,18-Bis(dicyanomethyl)-substituted Ni^II porphyrin 8 and Zn^II porphyrin 11 were prepared and subjected to oxidation with PbO₂ in CH₂Cl₂ at 298 K to give cyclophane-type chlorin dimers ( 9 )₂ and ( 12 )₂ as a consequence of double recombination of biradicals 9 and 12 , respectively. Dimer ( 9 )₂ takes a syn-conformation of two distorted Ni^II chlorins but ( 12 )₂ takes an anti-conformation of relatively planar Zn^II chlorins. At 298 K, dimer ( 9 )₂ is stable and its ¹H NMR spectrum is sharp but becomes broad at high temperature, while the ¹H NMR spectrum of ( 12 )₂ is considerably broad even at 298 K but becomes sharper at low temperature. These results indicate that the chlorin dimers dissociate to radical species, but the activation barrier of the dissociation of ( 12 )₂ is much less than that of ( 9 )₂. The involvement of diradicals in dynamic covalent chemistry has been suggested by thermal scrambling of hetero dimer ( 16 )₂ to give homo dimers ( 9 )₂ and ( 15 )₂.