CN112625069A - 一种基于芘四吡唑配体的钴的金属有机框架材料和制备方法及其应用 - Google Patents
一种基于芘四吡唑配体的钴的金属有机框架材料和制备方法及其应用 Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 30
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
一种基于芘四吡唑配体的钴的金属有机框架材料和制备方法及其应用,属于晶态材料的技术领域。化学分子式为Co(H4TPP)(CH3COO)2(H2O)(CH3CN)2,H4TPP为有机配体1,3,6,8‑四(1H‑吡唑‑4‑基)芘。该金属‑有机框架的合成方法为封闭条件下,有机配体1,3,6,8‑四(1H‑吡唑‑4‑基)芘与硝酸钴在N,N‑二甲基甲酰胺和乙酸、乙腈的混合溶液中,经由溶剂热反应得到晶体;此金属‑有机框架材料显示出选择性吸附分离二氧化碳、甲烷和氮气的潜在应用。
Description
技术领域
本发明属于晶态材料的技术领域,技术涉及金属-有机配位聚合物材料,特征是一种钴的金属-有机框架材料、制备方法及其应用研究。
背景技术
金属-有机框架材料(Metal-Organic Frameworks,MOFs),由金属离子及有机配体通过配位键连接而成的三维网络结构,是一类有机-无机杂化多孔材料,具有比表面积大、孔隙率高、孔道结构及性能易调等特征。由于MOFs具有这些独特的优势,已经在分离、传感、催化等多个领域得到迅速发展。
一个稳定的MOFs应该具有较强的配位键以抵抗客体分子的进攻或者金属节点附近具有位阻大及疏水性的功能团。其中,配位键的强度是影响MOFs稳定性的一个非常重要的因素。根据软硬酸碱理论,低价金属离子可以与吡唑配体形成更强的配位键,从而形成更稳定的框架。同时,高稳定MOFs可以在更加严苛的条件下进行应用研究,这将大大拓展MOFs的应用范围。
发明内容
本发明的目的在于提供一种芘四吡唑配体的钴的金属有机框架材料和制备方法及其应用。
本发明的一种基于芘四吡唑配体的钴的金属-有机框架材料,其特征在于,化学分子式为Co(H4TPP)(CH3COO)2(H2O)(CH3CN)2,H4TPP为有机配体1,3,6,8-四(1H-吡唑-4-基)芘。
该金属-有机框架中,Co离子为六配位,周围配位的是4个氮原子和2个氧原子,其中4个氮原子来自四个不同的芘四吡唑配体,2个氧原子分别来自反应体系中的乙酸根离子和水分子;在该金属-有机框架中,Co-O1键的键长是Co-O3键的键长是两种相同的Co-N1键的键长是两种相同的Co-N3键的键长是脱除配位的乙酸根离子和水分子以后,该MOF在沿晶体学a轴方向存在一维的圆形孔道,直径约为在c轴方向存在两种一维孔道,它们的截面尺寸约为
从拓扑学角度看,每个芘四吡唑配体都可以看作是4-连接的节点,与此同时四配位的Co看作是4-连接的顶点,这两种类型的结构单元交替连接形成了一个经典的(4,4)-连接的网络。
所述有机配体为1,3,6,8-四(1H-吡唑-4-基)芘,结构式如下所示:
该配体包含一个芘核和四个吡唑基团;
本发明新型的芘四吡唑配体的合成方法,包括以下两个步骤:
Suzuki反应:将液溴加入到芘和硝基苯溶液于80℃并剧烈搅拌,然后将混合物加热至120℃并保持12小时。反应完成后,与四氢吡喃保护的吡唑硼酸酯,在1,4-二氧六环和水中,加入四(三苯基膦)钯和碳酸钾,密封、抽真空、惰性气体保护,将混合溶液中在100℃下搅拌48h,得到1,3,6,8-四(1-(四氢-2H-吡喃-2-基)-1H-吡唑-4-基)芘。
脱保护:将1,3,6,8-四(1-(四氢-2H-吡喃-2-基)-1H-吡唑-4-基)芘在盐酸乙醇的混合溶液中加热回流脱保护得到1,3,6,8-四(1H-吡唑-4-基)芘。
本发明金属-有机框架材料的合成方法,包括以下步骤:
密封条件下,1,3,6,8-四(1H-吡唑-4-基)芘(H4TPP)与硝酸钴(Co(NO3)2·6H2O)在N,N-二甲基甲酰胺(DMF)和乙酸,乙腈的混合溶液中,经由溶剂热反应得到该金属-有机框架的晶体。
进一步优选有机配体1,3,6,8-四(1H-吡唑-4-基)芘(H4TPP)与硝酸钴(Co(NO3)2·6H2O)的摩尔比为1:(1~5),每0.05mmol的硝酸钴对应1mL~8mL的DMF,10μL~120μL的乙酸和乙腈,热反应的温度为80℃~120℃,反应时间为24~48小时。
本发明所合成的有机配体属于新型的芘四吡唑配体。本发明构筑的金属-有机框架具有独特的微孔结构,使得该MOF材料在二氧化碳、甲烷吸附和氮气的选择性吸附分离领域具有潜在应用。
附图说明
图1为该金属-有机框架中的芘四吡唑配体的合成路线图。
图2为该金属-有机框架的次级构筑单元图。
图3为该金属-有机框架材料对二氧化碳、甲烷和氮气的吸附等温线图。
具体实施方式
下面结合实施例对本发明作进一步说明,但本发明并不限于以下实施例。实施例1:
在氮气保护下,将液溴(98.9mmol),芘(24.7mmol)以及硝基苯(200mL)加入到500mL圆底烧瓶中,并剧烈搅拌,将该反应体系在加热到120℃并保持12小时。反应完成后,加入1-THP-4-吡唑硼酸酯(24.7mmol)以及1,4-二氧六环(120mL)和水(30mL),加入磁子搅拌,然后添加K2CO3(60.0mmol)和Pd(PPh3)4(1.0mmol),将该反应体系在100℃下搅拌48h。反应完成后,将反应体系的溶剂旋干,残余物溶解在乙酸乙酯(200mL)中,依次用水(200mL×2)和饱和食盐水(250mL)洗涤,经无水Na2SO4干燥后过滤、浓缩。粗产物通过柱层析法(SiO2,石油醚/乙酸乙酯=20:1~1:1)纯化,浓缩后得到淡黄色固体1,3,6,8-四(1-(四氢-2H-吡喃-2-基)-1H-吡唑-4-基)芘(产率为15%)。
将上一步所得淡黄色固体1,3,6,8-四(1-(四氢-2H-吡喃-2-基)-1H-吡唑-4-基)芘和乙醇(50mL)在盐酸(50mL)溶液中,在回流状态下搅拌12小时,反应结束后,旋蒸去除有机溶剂。剩余的固体分散200mL水中,然后滴加饱和碳酸钠水溶液将pH调整到10。所得悬浮液过滤,固体用水洗涤(100mL×3)后,在60℃真空干燥后,即可得淡黄色固体1,3,6,8-四(1H-吡唑-4-基)芘,产率为90%)。1H NMR(DMSO-d6,400MHz)δ13.09(s,2H)8.42(s,2H)8.20(t,J=1.6Hz,1H)8.15(d,J=1.2Hz,2H),7.91(d,J=1.6Hz,2H)。称量配体H4TPP(0.06mmol)和Co(NO3)2·6H2O(0.12mmoL)放入4mL玻璃小瓶中,加入3mL的DMF溶液和20μL的乙酸和乙腈,然后将该小瓶密封后放入超声仪,在室温下超声5分钟。密封后将小瓶置于110℃烘箱中反应24小时。反应结束后关闭烘箱,待冷却至室温后,将小瓶中得到的固体颗粒过滤收集,然后依次用DMF、H2O和EtOH洗涤(5mL×3),显微镜下观察得到金黄色块状晶体(Co(H4TPP)(CH3COO)2(H2O)(CH3CN)2),(产率:64%,基于H4TPP配体)。
实施例2
称量配体H4TPP(0.05mmol)和Co(NO3)2·6H2O(0.20mmoL)放入4mL玻璃小瓶中,加入3mL的DMF溶液和20μL的乙酸和乙腈,然后将该小瓶密封后放入超声仪,在室温下超声5分钟。密封后将小瓶置于120℃烘箱中反应36小时。反应结束后关闭烘箱,待冷却至室温后,将小瓶中得到的固体颗粒过滤收集,然后依次用DMF、H2O和EtOH洗涤(5mL×3),显微镜下观察得到金黄色块状晶体(Co(H4TPP)(CH3COO)2(H2O)(CH3CN)2),(产率:72%,基于H4TPP配体)。
上述实施例所得的产品的测试结果相同,具体见下述:
(1)晶体结构的确定:
选取大小合适的高质量单晶样品,在293K下,利用Supernova高分辨单晶衍射仪收集数据。数据收集使用经石墨单色器单色化的Cu-Kα靶射线。数据的吸收校正使用SCALE3 ABSPACK软件完成。晶体结构使用SHELXTL-97程序通过直接法解析得到。先用差值函数法和最小二乘法确定全部非氢原子坐标,并用理论加氢法得到氢原子位置,然后用SHELXTL-97对晶体结构进行精修。结构图见图2至图3。晶体学数据见表1。
表1金属有机框架材料的晶体学数据
图1的芘四吡唑配体合成路线图表明:将液溴加入到芘和硝基苯溶液于80℃并剧烈搅拌,然后将混合物加热至120℃并保持12小时。完成后,与四氢吡喃保护的吡唑硼酸酯,在1,4-二氧六环和水中,加入四(三苯基膦)钯和碳酸钾,密封、抽真空、惰性气体保护,将混合溶液中在100℃下搅拌48h,得到1,3,6,8-四(1-(四氢-2H-吡喃-2-基)-1H-吡唑-4-基)芘。然后将1,3,6,8-四(1-(四氢-2H-吡喃-2-基)-1H-吡唑-4-基)芘在乙醇盐酸的混合溶液中加热回流脱保护得到1,3,6,8-四(1H-吡唑-4-基)芘。
图2为本发明材料的结构图:(a)为钴的配位环境图,(b)为金属-有机框架沿a轴方向的结构图,(c)为沿b轴方向的结构图,(d)为沿c轴方向的结构图。
(2)二氧化碳、甲烷和氮气吸附
图3为本发明材料对二氧化碳、甲烷和氮气的吸附等温线,可以看出该材料能吸附二氧化碳及甲烷,对二氧化碳有较高的吸附量和选择性。
Claims (9)
1.一种基于芘四吡唑配体的钴的金属-有机框架材料,其特征在于,化学分子式为Co(H4TPP)(CH3COO)2(H2O)(CH3CN)2,H4TPP为有机配体1,3,6,8-四(1H-吡唑-4-基)芘。
4.按照权利要求1所述的一种基于芘四吡唑配体的钴的金属-有机框架材料,其特征在于,从拓扑学角度来讲,每个芘四吡唑配体都可以看作是4-连接的连接体,四配位的Co离子看作是4-连接的节点,这两种类型的结构单元交替连接形成了一个(4,4)-连接的网络。
6.按照权利要求5所述的一种基于芘四吡唑配体的钴的金属-有机框架材料,其特征在于,芘四吡唑配体的合成方法,包括以下两个步骤:
Suzuki反应:将液溴加入到芘和硝基苯溶液于80℃并剧烈搅拌,然后将混合物加热至120℃并保持12小时。完成后,与四氢吡喃保护的吡唑硼酸酯,在1,4-二氧六环和水中,加入四(三苯基膦)钯和碳酸钾,密封、抽真空、惰性气体保护,将混合溶液中在100℃下搅拌48h,得到1,3,6,8-四(1-(四氢-2H-吡喃-2-基)-1H-吡唑-4-基)芘。
脱保护:将1,3,6,8-四(1-(四氢-2H-吡喃-2-基)-1H-吡唑-4-基)芘在盐酸乙醇溶液中加热回流脱保护得到1,3,6,8-四(1H-吡唑-4-基)芘。
7.权利要求1-6任一项所述的基于芘四吡唑配体的钴的金属-有机框架材料的制备方法,其特征在于,包括以下步骤:
密封条件下,将1,3,6,8-四(1H-吡唑-4-基)芘(H4TPP)与硝酸钴(Co(NO3)·6H2O)溶于N,N-二甲基甲酰胺(DMF)溶液中,加入微量乙腈和乙酸,通过溶剂热反应得到该金属-有机框架的晶体。
8.按照权利要求7所述的方法,其特征在于,有机配体1,3,6,8-四(1H-吡唑-4-基)芘(H4TPP)与硝酸钴(Co(NO3)2·6H2O)的摩尔比为1:(1~5),每0.05mmol的硝酸钴对应1mL~8mL的DMF,10μL~120μL的乙酸和乙腈,溶剂热反应的温度为80℃~120℃,反应时间为24~48小时。
9.权利要求1-6任一项所述的基于芘四吡唑配体的钴的金属-有机框架材料的应用,在二氧化碳、甲烷、以及氮气等气体的选择性吸附分离方面的应用。
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