CN111205195B - 含羰基的共价有机框架KT-Tp COFs材料及制备方法及应用 - Google Patents
含羰基的共价有机框架KT-Tp COFs材料及制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种含羰基的共价有机框架KT‑Tp COFs材料及制备方法及应用,含羰基的共价有机框架KT‑Tp COFs材料具有式(IV)所示结构:
Description
技术领域
本发明属于高分子有机多孔材料领域,特别是涉及一类含羰基共价有机框架材料KT-Tp COFs、制备方法及应用。
背景技术
目前,电化学能量由于能够有效地进行存储和转化,被认为是很有前途的可持续能源之一。具有代表性的电化学能量存储设备包括电池,燃料电池和超级电容器等。期中,超级电容器由于其超快速的充放电,高的能量密度,极好的比容量和超长的使用寿命等优势而受到了广泛的关注。电极材料在超级电容器的性能中起着至关重要的作用。迄今为止,对于碳基电极材料的开发已经取得了很大的进展,但是由于碳基材料缺少氧化还原基团,通常显现出较低的电容量。另一方面,金属氧化物和有机聚合物等具有较高的赝电容,而这些材料仍有着功率密度低和循环性差的缺点。因此,设计合成兼具出色的氧化还原活性和优异的耐用性的新型电极材料对于提高超级电容器的卓越性能至关重要。
共价有机骨架(Covalent organic Frameworks(COFs))是由稳定的共价键构成的新兴多孔和结晶网络聚合物。由于重量轻,孔隙率高,结构明确和易于功能化等特点,COFs材料已被广泛研究用于气体存储和分离,催化,光电,传感和药物输送等多个领域。此外,由于COFs规则的纳米通道有利于电子和质子的转移,并且可将预先设计的具有氧化还原活性的构建基元引入COFs中,故而COFs作为电极材料可以应用于电化学储能领域。典型示例包括将对苯二酚,酰亚胺,三嗪,和吩嗪基元引入到COFs的骨架中,这些骨架表现出一定的储能性质。但是,大多数基于COFs的电极都面临着相对较低的电容或较差的耐用性的挑战。在这种情况下,迫切需要开发出具有丰富氧化还原活性位点的COFs电极,以构建具有卓越性能的能量存储设备。
发明内容
本发明的目的是克服现有技术的不足,提供一种合成含羰基的共价有机框架KT-Tp COFs材料的其中一种中间体2,7-二氨基芘-4,5,9,10-四酮(I-3)。
本发明的第二个目的是提供2,7-二氨基芘-4,5,9,10-四酮(I-3)的制备方法。
本发明的第三个目的是提供一种含羰基的共价有机框架KT-Tp COFs材料。
本发明的第四个目的是提供一种含羰基的共价有机框架KT-Tp COFs材料的制备方法。
本发明的第五个目的是提供一种含羰基的共价有机框架KT-Tp COFs材料的应用。
本发明的技术方案概述如下:
2,7-二氨基芘-4,5,9,10-四酮,具有式(I-2)所示结构:
2,7-二氨基芘-4,5,9,10-四酮的制备方法,包括如下步骤:
1)芘-4,5,9,10-四酮(II)的合成:
芘与高碘酸钾和氯化钌反应,生成芘-4,5,9,10-四酮(II);
2)2,7-二硝基芘-4,5,9,10-四酮(III)的合成:
在加热的条件下,4,5,9,10-四酮(II)在硫酸和硝酸的共同作用下,反应生成2,7-二硝基芘-4,5,9,10-四酮(III);
3)2,7-二氨基芘-4,5,9,10-四酮(I-2)的合成:
2,7-二硝基芘-4,5,9,10-四酮(III)与氢氧化钠和连二亚硫酸钠反应,再与二氯二氰基苯醌反应生成2,7-二氨基芘-4,5,9,10-四酮(I-2);
反应式如下:
一种含羰基的共价有机框架KT-Tp COFs材料,具有式(IV)所示结构:
其中:m=0-2;n=2。
优选地:m=0、n=2或m=2、n=2。
一种含羰基的共价有机框架KT-Tp COFs材料的制备方法,包括如下步骤:
将化合物(I)和化合物(V)分散于1,4-二氧六环或分散于1,4-二氧六环和均三甲苯的混合溶液中得到分散液,加入乙酸水溶液作催化剂,混合均匀,反应得到含羰基的共价有机框架KT-Tp COFs材料(IV);
反应式如下:
其中,m=0-2,n=2。
优选地:m=0、n=2或m=2、n=2。
上述含羰基的共价有机框架KT-Tp COFs材料在电容器中的应用。
本发明的优点:
本发明将邻醌结构引入席夫碱COFs骨架中,实验结果表明具有邻醌结构的COFs骨架比只有孤立的羰基的COFs具有更好的储能性能,含羰基的共价有机框架KT-Tp COFs材料在电容器中的应用。
附图说明
图1为化合物I-2的基本表征,其中a为核磁氢谱图,b为傅里叶红外谱图。
图2为化合物IV-1的粉末X-射线衍射图。
图3为化合物IV-2的粉末X-射线衍射图。
图4为化合物IV-3的粉末X-射线衍射图。
图5为化合物IV(1~3)的红外吸收光谱图。
图6为化合物IV(1~3)的扫速为1mV s-1的循环伏安曲线。
图7为化合物IV(1~3)的恒流充放电曲线。
图8为化合物IV(1~3)的稳定性测试曲线。
具体实施方式
2,7-二氨基9,10-菲醌(I-1)的制备:
根据文献Tetrahedron 2012,68,4882-4887中的合成方法制备。
2,7-二氨基-9H-芴-9-酮(I-3)的制备:
根据文献J.Phys.Chem.B 2009,113,15541-15549中的合成方法制备。
下面结合具体实施例对本发明作进一步的说明。
实施例1
2,7-二氨基芘-4,5,9,10-四酮(I-2)的制备方法,包括如下步骤:
1)芘-4,5,9,10-四酮(II)的合成:
芘与高碘酸钾和氯化钌反应,生成芘-4,5,9,10-四酮(II);根据文献J.Org.Chem.2005,70,707-708。
2)2,7-二硝基芘-4,5,9,10-四酮(III)的合成:
称取芘-4,5,9,10-四酮(II,5g,3.8mmol)于250mL两口圆底烧瓶中,加入浓硫酸(50mL),随后在冰浴中缓慢滴加发烟硝酸(50mL)。该装置置于85℃油浴中回流45min,待反应液冷却到室温后,将其倾倒入盛有冰的烧杯中,待冰全部融化后抽滤,滤饼经水洗涤,在室温下真空干燥,得到淡黄色固体2,7-二硝基芘-4,5,9,10-四酮(III)(5.48g,产率82%)。
3)2,7-二氨基芘-4,5,9,10-四酮(I-2)的合成:
将2,7-二硝基芘-4,5,9,10-四酮(III,1g,2.8mmol)置于500mL两口瓶中,依次加入氢氧化钠(8.9g,224mmol),水(150mL)和连二亚硫酸钠(4.4g,25.5mmol),在油浴中加热到50℃,搅拌15min,反应混合物倾倒入饱和氯化铵溶液(500mL)中,过滤,水洗至滤液呈无色,得到黑色粉末,真空室温干燥一夜,得粗产物,再将粗产物(457mg)和二氯二氰基苯醌(1.5g)和甲醇(30mL)混合,在35℃油浴中搅拌15h,反应液用乙酸乙酯(60mL)稀释,抽滤,乙酸乙酯洗涤得到黑色固体(442mg,产率54%)。
图1(a)为化合物I-2的核磁氢谱,化学位移在5.96ppm的峰归属为氨基的氢,而在7.36ppm的峰归属于芳香氢;(b)为化合物1-2的傅里叶红外光谱图,在波数为3373-3369cm-1出现N-H的伸缩振动吸收峰,在1633cm-1处出现C=O伸缩振动吸收峰;证明化合物为2,7-二氨基芘-4,5,9,10-四酮(I-2)。
反应式如下:
实施例2
含羰基的共价有机框架KT-Tp COFs材料((IV-1),简写为2KT-Tp COF)的制备方法,包括如下步骤:
在10mL Schlenk管中,将2,7-二氨基-9,10-菲醌(I-1,17.9mg,0.075mmol)和1,3,5-三甲酰间苯三酚(V,10.5mg,0.05mmol)分散于1,4-二氧六环(0.2mL)和均三甲苯(0.8mL)的混合溶液中;超声处理2min,得到均匀的分散体,然后加入0.1mL质量浓度为36%乙酸水溶液,超声处理2min,冷冻并在氩气下脱气三遍,将Schlenk管在120℃下放置3天,冷却至室温后,过滤收集沉淀物,依次用N,N-二甲基乙酰胺,四氢呋喃和丙酮洗涤,真空干燥,得到黑色粉末(IV-1,26mg,产率91%)。
图2为实施例2制备的2KT-Tp COF粉末XRD衍射图,证明2KT-Tp COF为二维共价有机框架材料具有较好的结晶性和相纯度。
实施例3
含羰基的共价有机框架KT-Tp COFs材料((IV-2),简写为4KT-Tp COF)的制备方法,包括如下步骤:
在10mL Schlenk管中,将2,7-二氨基芘-4,5,9,10-四酮(I-2,21.9mg,0.075mmol)和1,3,5-三甲酰间苯三酚(V,10.5mg,0.05mmol)分散于1,4-二氧六环(10mL)中;超声处理2min,得到均匀的分散体,然后加入0.2mL质量浓度为36%乙酸水溶液,超声处理2min,冷冻并在氩气下脱气三遍,将Schlenk管在120℃下放置3天,冷却至室温后,过滤收集沉淀物,依次用N,N-二甲基乙酰胺,四氢呋喃和丙酮洗涤,真空干燥,得到黑色粉末(IV-2,29mg,产率89%)。
图3为实施例3制备的4KT-Tp COF粉末XRD衍射图,证明4KT-Tp COF为二维共价有机框架材料具有较好的结晶性和相纯度。
实施例4(对照)
一种含羰基的共价有机框架KT-Tp COFs材料((IV-3),简写为1KT-Tp COF)的制备方法,包括如下步骤:
在10mL Schlenk管中,将2,7-二氨基-9H-芴-9-酮(I-3,15.8mg,0.075mmol)和1,3,5-三甲酰间苯三酚(V,10.5mg,0.05mmol)分散到四氢呋喃(0.5mL)和均三甲苯(0.5mL)的混合溶液中,超声处理2min,得到均匀的分散体,然后加入0.1mL质量浓度为36%乙酸水溶液,超声处理2min,冷冻并在氩气下脱气三遍,将Schlenk管在120℃下放置3天,冷却至室温后,过滤收集沉淀物,依次用N,N-二甲基乙酰胺,四氢呋喃和丙酮洗涤,真空干燥,得到酒红色粉末(IV-3,24mg,产率94%)。
反应式如下:
图4为实施例4制备的1KT-Tp COF粉末XRD衍射图,证明1KT-Tp COF为二维共价有机框架材料具有结晶性。
图5为实施例2-实施例4制备的含羰基的共价有机框架KT-Tp COFs材料的红外谱图,在~3300cm-1处的N-H伸缩振动吸收峰的消失以及在~1250cm-1处C-N伸缩振动吸收峰的加强,证明了二维共价有机材料成功合成。
实施例5
KT-Tp COFs电极材料的制备及电化学电容器(三电极体系)测试,包括如下步骤:
电极材料的制备:
分别称取2.0mg的4KT-Tp COF,2KT-Tp COF和1KT-Tp COF粉末,再分别与3.0mg导电炭黑,5.0μL、5wt%聚四氟乙烯水分散液,0.5mL无水乙醇于3mL样品管中,超声30min,形成均匀的悬浮液。再分别用移液管吸取6μL均匀的悬浮液滴涂在抛光好的玻碳电极的表面上,置于空气中干燥1h。
电容器的测试:循环伏安(CV)曲线在0至0.6V(vsAg/AgCl)的电压范围内进行测试。恒电流充放电(GCD)测试是在0.2Ag-1的电流密度下进行的。根据放电曲线计算出4KT-TpCOF,2KT-Tp COF,1KT-Tp COF的质量电容(Cg),计算公式如下。稳定性测试在5A g-1的电流密度下进行了20000次恒电流充放电测试。
图6为实施例5的循环伏安曲线,由图中可以看出4KT-Tp COF有两对可逆的氧化还原峰,而2KT-Tp COF和1KT-Tp COF均只有一对可逆的氧化还原峰。
图7为实施例5的恒电流充放电曲线,根据放电曲线计算电容量,电流密度为0.2Ag-1时,4KT-Tp COF电极的质量电容是583F g-1,2KT-Tp COF电极的质量电容是256F g-1,1KT-Tp COF电极的质量电容是61F g-1。
图8为实施例5的稳定性测试曲线,在在5Ag-1的电流密度下进行20000次恒电流充放电后,KT-Tp COFs电机表现了出色的循环性(>92%的电容保持率)。
Claims (5)
2.根据权利要求1所述的含羰基的共价有机框架KT-Tp COFs材料,其特征是所述m=0、n=2或m=2、n=2。
4.根据权利要求3所述制备方法,其特征是所述m=0、n=2或m=2、n=2。
5.权利要求1或2所述含羰基的共价有机框架KT-Tp COFs材料在电容器中的应用。
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