CN114736344A - 一种含有不同孔环境的方格共价有机框架及其制备方法与应用 - Google Patents
一种含有不同孔环境的方格共价有机框架及其制备方法与应用 Download PDFInfo
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Abstract
本发明涉及新材料技术领域,具体涉及一种含有不同孔环境的方格共价有机框架及其制备方法与应用。本发明提供的共价有机框架具有不同孔环境规整排列的方格异孔结构;所述孔环境包括亲水孔和疏水孔。本发明提出的COF是首例同时具有多种孔环境的COF,其是以精心设计的异边醛基单体和氨基单体为原料,在酸催化剂的作用下,通过席夫碱反应得到的多孔功能材料。本发明采用的制备方法具有广泛适用性,且通过改变原料成分、反应条件即可得到类似结构的COF材料。本发明制备得到的不同孔环境的方格COF具有高的比表面积和高的结晶性,同时对可见光有优异的吸收能力,这些特征使其在光催化和光电子传输方面有较高的潜在应用价值。
Description
技术领域
本发明涉及新材料技术领域,具体涉及一种含有不同孔环境的方格共价有机框架及其制备方法与应用。
背景技术
有机多孔材料是一类由C、H、O、N等轻质元素,经过共价键连接而成的具有丰富孔结构的材料。有机多孔材料具有质量轻、孔径可调节、可修饰等特点。迄今为止,有机多孔材料在气体吸附与分离、能量存储、光电材料、异相催化等领域表现出广阔的应用前景。对于有机多孔材料的发展而言,一些创新的结构设计与功能应用还在迅速更新中,探索具有新颖功能与高效性能的有机多孔材料对于开发新的应用十分重要。
共价有机骨架(COF)是一种新兴结晶性的多孔有机聚合物。自Yaghi及其同事于2005年报道了开创性工作以来,COF已成为功能材料设计的强大平台。
迄今为止,COF的结构研究主要集中在框架的拓扑结构和孔道工程上。拓扑结构的类型和孔的修饰在调节COF的性能中起着重要作用;设计具有不同大小和特定对称性的单体可以调控框架的拓扑结构;COF的孔道表面工程则主要通过预修饰或后修饰调节骨架的化学组成,同时实现孔的功能化。
自2014年Zhao和他的同事首次报道了异孔COF以来,一系列异孔COF已经被设计和合成出来。但是,目前异孔COF材料的研究主要关注于孔的形状和大小差异化,对不同孔环境的设计和研究还未涉及。
为此,特提出本发明。
发明内容
针对现有异孔COF材料研究领域存在的问题,本发明提出一种新型结构的异孔COF材料及其制备方法与应用。
第一方面,本发明提供的共价有机框架,为具有不同孔环境、且规整排列的方格异孔结构;所述孔环境包括亲水孔和疏水孔。
本发明通过对现有异孔结构材料的深入研究后发现,目前主要采取的多单体混合策略构建,无法保证结构的不同孔环境的均匀规整排列,因此目前相关材料报道主要集中在孔的形状和大小差异化的研究。
而本发明首次设计并合成了异边单体,并将其引入COF结构中,制备出不同孔环境均匀规整排列的方格异孔材料。所得COF材料不仅具有常规异孔COF材料所具有的较好的化学稳定性和热稳定性,不含金属元素,无毒无害等优点,而且还具有较高的比表面积和结晶性,以及较强的可见光吸收能力,为光电子传输以及不同极性的反应物和产物提供较好的传递扩散微反应环境,因而在光催化降解染料和光催化化学反应以及质子传输等燃料电池等领域具有良好的应用前景。
进一步地,所述亲水孔中亲水基团选自烷氧基、巯基链、氨基链、羧酸酯或磺酸基中的一种。所述疏水孔中疏水基团选自烷基、含氟链或含氟芳基。
本发明在研究中发现,亲水基团与疏水基团之间存在一定的匹配关系,能够更好的提高COF的综合性能,如更高的比表面积、更高的结晶性、更高的稳定性。
为此,本发明中,优选地,所述亲水基团为烷氧基时,所述疏水基团为烷基;所述亲水基团为碳酸酯时,所述疏水基团为含氟链;所述亲水基团为巯基时,所述疏水基团为含氟链;所述亲水基团为氨基时,所述疏水基团为含氟链;所述亲水基团为苯基时,所述疏水基团为含氟苯。
进一步地,所述共价有机框架还含有卟啉基团,起到利于堆积以及功能化作用。
进一步地,所述共价有机框架的平均孔径为1.4nm,比表面积为1200~1800m2 g–1,总孔隙体积分别为0.49cm3 g-1。
作为本发明的具体实施方式,所述共价有机框架的结构包括:
第二方面,本发明还提供上述共价有机骨架的制备方法,包括:以异边醛基单体、氨基单体为反应原料,在酸催化剂的作用下,通过席夫碱反应制得。
本发明首次设计并合成了异边醛基单体,其与氨基单体在酸催化剂的作用下,制备出具有上述不同孔环境、且均匀规整排列的方格异孔材料。同时还可通过调节单体的取代基团、反应条件获得类似结构的不同孔环境的方格异孔COF材料。
进一步地,所述异边醛基单体为具有疏水基团和亲水基团的醛基芳香单体;所述具有疏水基团和亲水基团的醛基芳香单体选自如下化合物中的一种:
进一步地,本发明所述的具有疏水基团和亲水基的醛基芳香单体是通过下述方法获得:
(1)在碱性溶剂中,4-庚基苯酚与1-溴-2-(2-甲氧基乙氧基)乙烷在催化剂作用下室温反应,经后处理,得到粗产物1-庚基-4-(2-(2-甲氧基乙氧基)乙氧基)苯;
其中,所述溶剂可为DMSO、DMF;所述碱可为氢氧化钾、氢氧化钾;所述催化剂可为碘化钠;
所述4-庚基苯酚与1-溴-2-(2-甲氧基乙氧基)乙烷的摩尔比为1:(1.1-1.5);
所述后处理包括:将反应液水洗,萃取,至水层为中性,经干燥、过滤、旋蒸,得到油状粗品;进一步纯化,得到粗产物1-庚基-4-(2-(2-甲氧基乙氧基)乙氧基)苯。
(2)无水无氧、含有催化剂的溶剂中,1-庚基-4-(2-(2-甲氧基乙氧基)乙氧基)苯与液溴于冰/盐浴中反应,经后处理,得到1,4-二溴-2-庚基-5-(2-(2-甲氧基乙氧基)乙氧基)苯;
其中,所述溶剂可为CCl4、CCl3;所述催化剂可为铁粉;
所述1-庚基-4-(2-(2-甲氧基乙氧基)乙氧基)苯与液溴的摩尔比为1:2;
所述反应的温度为-6~-5℃;
反应过程中,所述液溴先溶于溶剂中,再分批滴加至反应体系中,尾气可用饱和Na2SO3水溶液吸收;
反应结束后,用饱和Na2SO3水溶液(100mL)淬灭反应,并剧烈搅拌直至无色;
所述后处理包括:反应混合物用二氯甲烷萃取,合并有机层,用水洗涤,并用MgSO4干燥有机层,过滤,旋干,得到无色透明液体;通过柱色谱法纯化(洗脱剂为石油醚:乙酸乙酯=10:1),得到1,4-二溴-2-庚基-5-(2-(2-甲氧基乙氧基)乙氧基)苯。
(3)无水无氧的条件下,在催化剂及溶剂中,1,4-二溴-2-庚基-5-(2-(2-甲氧基乙氧基)乙氧基)苯与4-甲酰基苯基硼酸回流反应,得到具有疏水基团和亲水基的醛基芳香单体;
其中,所述溶剂可为THF、二氧六环;所述催化剂可为双(三苯基膦)二氯化钯等钯基催化剂;
所述1,4-二溴-2-庚基-5-(2-(2-甲氧基乙氧基)乙氧基)苯与4-甲酰基苯基硼酸的摩尔比为1:3;
所述反应的温度为100-102℃。
进一步地,所述氨基单体选自氨基卟啉、三氨基苯基苯、四-(4-氨基苯乙烯)、2,4,6-三(4-氨基苯基)-1,3,5-三嗪、4,4,4,4,-甲乙烷四基四苯胺;优选为5,10,15,20-四(4-氨基苯基)卟啉。
进一步地,所述氨基单体与具有疏水基团和亲水基的醛基芳香单体的摩尔比为1:2~1:5,优选1:2。
进一步地,本发明研究发现,由于异边醛基芳香单体中侧链极性的差异,对于制备高结晶性的材料是困难的。为此,本发明对反应溶剂进行了筛选,并确定的优选组合方式。所述混合溶剂选自邻二氯苯/乙醇、1,4-二氧六环/乙醇或三甲苯/乙醇的组合,两种溶剂的体积比为9:1~1:9;优选邻二氯苯/乙醇。
进一步地,所述酸催化剂选自乙酸或对甲苯磺酸;所述酸催化剂以水溶液形式添加,其浓度为5.5-6M;所述酸催化剂的添加量相对溶剂体积为2%~5%。
进一步地,所述反应的条件为:90~120℃反应24~72h。
进一步地,在所述反应过程中,通过三次液氮中冷冻-解冻循环对体系进行脱气,并火焰枪封管。
进一步地,所述反应结束后,对反应产物进行梯度洗涤,并于60-65℃烘干;洗涤溶剂可选择乙醇、四氢呋喃和丙酮等。
作为本发明的具体实施方式之一,所述共价有机框架的制备方法包括如下步骤:具有疏水基团和亲水基团的醛基芳香单体与5,10,15,20-四(4-氨基苯基)卟啉在乙酸催化作用下,于90~120℃反应24~72h,得到含有卟啉基团的方格COF。随后,将其通过离心洗涤、真空烘箱干燥,得到暗紫色的方格COF。
第三方面,本发明还提供上述共价有机框架在光催化降解染料、光催化化学反应和光电子传输领域中的应用。
本发明的技术方案具有但不限于以下有益效果:
1、本发明所述COF具有不同孔环境规整排列的方格异孔结构,因而具有较高的比表面积和结晶性,因而有利于光电子的快速有序传输,同时优异的结晶性为其不同孔环境的排列提供了基础和保障,有利于不同极性的分子传递。
2、本发明所述COF含有卟啉结构,因而具有强的可见光吸收能力,在光催化降解染料和光催化化学反应以及质子传输等燃料电池等方面有较高的潜在应用价值。
3、本发明所述方格COF由共价键相互连接而成,具有较好的化学稳定性和热稳定性。
4、本发明所述方格COF由轻质元素组成,不含金属元素,无毒无害。
5、本发明所述方法通过选择合适的反应单体作为原料,可通过常规反应即可制得具有不同孔环境的方格COF,合成方法简单、条件温和,同时原料廉价易得,更适用于实验室试验或工业制造。
6、本发明还可通过调节单体的取代基团、反应条件以获得类似结构的不同孔环境的方格异孔COF材料。
附图说明
图1为实施例1所得方格COF的结构示意图。
图2为实施例1中所制备的多种孔道环境的方格COF在77K时的氮气吸脱附曲线图及孔径分布图。
图3为实施例1中所制备的多种孔道环境的方格COF的X射线衍射谱图。
图4为实施例1中所制备的多种孔道环境的方格COF的核磁共振碳谱图。
图5为实施例1中所制备的多种孔道环境的方格COF的红外光谱图。
图6为实施例1中所制备的多种孔道环境的方格COF的热重分析图。
图7为实施例1中所制备的多种孔道环境的方格COF的光电流随时间的响应图。
图8为单体1的核磁氢谱图。
图9为单体1的核磁碳谱图。
具体实施方式
以下实施例用于说明本发明,但不用来限制本发明的范围。
以下实施例中,各试剂均可通过市售购买得到。
其中,实施例1中具有疏水基团和亲水基的醛基芳香单体的结构如下:
其具体制备步骤如下:
(1)100mL的圆底烧瓶中加入4-庚基苯酚(8.46g,44mmol,1.0eq.)、KOH(9.88g,176mmol,4.0eq.)和20mL DMSO,并剧烈搅拌30min;随后加入1-溴-2-(2-甲氧基乙氧基)乙烷(7.40mL,55mmol,1.3eq.)和碘化钠(催化量),然后在室温下搅拌10h;
将反应液倒入400mL水中,用二氯甲烷萃取,直至水层变为中性,用MgSO4干燥有机层,过滤,并通过旋转蒸发得到油状的粗品;通过柱色谱法(石油醚和乙酸乙酯作为洗脱剂)纯化粗产物1-庚基-4-(2-(2-甲氧基乙氧基)乙氧基)苯。
(2)250mL圆底烧瓶中加入1-庚基-4-(2-(2-甲氧基乙氧基)乙氧基)苯(3.80g11.2mmol,1.0eq.),在保证无水无氧的条件下,再向烧瓶中加入40mL CCl4;在冰/盐浴中将反应体系降温到–6℃后加入催化量的铁粉,将1.10mL液溴(22.4mmol,2.0eq.)溶于20mLCCl4中,并用滴液漏斗缓慢滴加到反应体系中,尾气用饱和Na2SO3水溶液吸收;6h后,再次滴加20mL溴的CCl4溶液,将反应在冰/盐浴中搅拌过夜;用饱和Na2SO3水溶液(100mL)淬灭反应,并剧烈搅拌直至无色;
反应混合物用二氯甲烷萃取,合并有机层,用水洗涤,并用MgSO4干燥有机层,过滤,旋干,得到无色透明液体;粗产物通过柱色谱法纯化(洗脱剂为石油醚:乙酸乙酯=10:1),得到1,4-二溴-2-庚基-5-(2-(2-甲氧基乙氧基)乙氧基)苯(产率50.4%)。
(3)250mL圆底烧瓶中加入1,4-二溴-2-庚基-5-(2-(2-甲氧基乙氧基)乙氧基)苯(1.06g,2.35mmol,1.0eq.),保证无水无氧的条件下加入4-甲酰基苯基硼酸(1.06g,7.05mmol,3.0eq.)和70mL THF;在氮气氛围下依次加入碳酸钾水溶液(25.0mL 2.0mol L–1)和200mg双(三苯基膦)二氯化钯(II);将反应搅拌并在100℃回流12h;
冷却至室温后,通过旋转蒸发将THF蒸发,用二氯甲烷萃取;合并有机层,并用水洗涤直至水层变为中性并用MgSO4干燥,过滤,并通过旋转蒸发;通过柱色谱法(洗脱剂为石油醚:乙酸乙酯=5:1和石油醚:乙酸乙酯=1:1)纯化油状粗产物,得到2'-庚基-5'-(2-(2-甲氧基乙氧基)乙氧基)-[1,4'-三苯基]-4,4”-二甲醛:(产率81.3%)。
通过表征确定此单体为前述的单体1,具体核磁表征结果如图8和图9。
采用上述相同的制备方法,调整反应原料,获得实施例2-5中的具有疏水基团和亲水基的醛基芳香单体。
其中,实施例2中具有疏水基团和亲水基的醛基芳香单体的结构如下:
实施例3中具有疏水基团和亲水基的醛基芳香单体的结构如下:
实施例4中具有疏水基团和亲水基的醛基芳香单体的结构如下:
实施例5中具有疏水基团和亲水基的醛基芳香单体的结构如下:
实施例1
本实施例提供一种方格COF,其结构如下:
本实施例提供上述方格COF的制备方法,步骤如下:
10mL的斯可莱管中加入5,10,15,20-四(4-氨基苯基)卟啉(27.0mg 0.04mmol)和单体1(0.08mmol),加入邻二氯苯/乙醇(0.1mL/0.9mL)和6M醋酸水溶液(200μL)。然后将Pyrex管在超声仪中超声20min。通过三次液氮中冷冻-解冻循环对体系进行脱气,火焰枪封管,120℃加热72h。离心收集沉淀,用无水THF和丙酮洗涤,60℃真空干燥12h,得到固体产物。
本实施例所得COF的结构示意图及表征结果如图1-7。
实施例2
本实施例提供一种方格COF,其结构如下:
本实施例提供上述方格COF的制备方法,步骤如下:
10mL的斯可莱管中加入5,10,15,20-四(4-氨基苯基)卟啉(27.0mg 0.04mmol)和单体2(0.08mmol),加入邻二氯苯/乙醇(0.3mL/0.7mL)和6M醋酸水溶液(200μL)。然后将Pyrex管在超声仪中超声20min。通过三次液氮中冷冻-解冻循环对体系进行脱气,火焰枪封管,120℃加热72h。离心收集沉淀,用无水THF和丙酮洗涤,60℃真空干燥12h,得到固体产物。
实施例3
本实施例提供一种方格COF,其结构如下:
本实施例提供上述方格COF的制备方法,步骤如下:
10mL的斯可莱管中加入5,10,15,20-四(4-氨基苯基)卟啉(27.0mg 0.04mmol)和单体3(0.08mmol),加入邻二氯苯/乙醇(0.5mL/0.5mL)和6M醋酸水溶液(200μL)。然后将Pyrex管在超声仪中超声20min。通过三次液氮中冷冻-解冻循环对体系进行脱气,火焰枪封管,120℃加热72h。离心收集沉淀,用无水THF和丙酮洗涤,60℃真空干燥12h,得到固体产物。
实施例4
本实施例提供一种方格COF,其结构如下:
本实施例提供上述方格COF的制备方法,步骤如下:
10mL的斯可莱管中加入5,10,15,20-四(4-氨基苯基)卟啉(27.0mg 0.04mmol)和单体4(0.08mmol),加入邻二氯苯/乙醇(0.1mL/0.9mL)和6M醋酸水溶液(200μL)。然后将Pyrex管在超声仪中超声20min。通过三次液氮中冷冻-解冻循环对体系进行脱气,火焰枪封管,120℃加热72h。离心收集沉淀,用无水THF和丙酮洗涤,60℃真空干燥12h,得到固体产物。
实施例5
本实施例提供一种方格COF,其结构如下:
本实施例提供上述方格COF的制备方法,步骤如下:
10mL的斯可莱管中加入5,10,15,20-四(4-氨基苯基)卟啉(27.0mg 0.04mmol)和单体5(0.08mmol),加入邻二氯苯/乙醇(0.1mL/0.9mL)和6M醋酸水溶液(200μL)。然后将Pyrex管在超声仪中超声20min。通过三次液氮中冷冻-解冻循环对体系进行脱气,火焰枪封管,120℃加热72h。离心收集沉淀,用无水THF和丙酮洗涤,60℃真空干燥12h,得到固体产物。
效果验证:
1、实施例2-5所得COF材料的结构及表征结果与实施例1相似。
2、性能测试
将实施例1-5所得COF材料进行测试,结果如表1:
表1
虽然,上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
Claims (10)
1.一种共价有机框架,其特征在于,其具有不同孔环境的方格异孔结构;所述孔环境包括亲水孔和疏水孔。
2.根据权利要求1所述的共价有机框架,其特征在于,所述亲水孔中亲水基团选自烷氧基、巯基链、氨基链、羧酸酯或磺酸基;
所述疏水孔中疏水基团选自烷基、含氟链或含氟芳基。
3.根据权利要求2所述的共价有机框架,其特征在于,所述亲水基团为烷氧基时,所述疏水基团为烷基;
所述亲水基团为碳酸酯时,所述疏水基团为含氟链;
所述亲水基团为巯基时,所述疏水基团为含氟链;
所述亲水基团为氨基时,所述疏水基团为含氟链;
所述亲水基团为苯基时,所述疏水基团为含氟苯。
4.根据权利要求3所述的共价有机框架,其特征在于,所述共价有机框架还含有卟啉基团。
5.权利要求1-4任一项所述共价有机框架的制备方法,其特征在于,包括:以异边醛基单体、氨基单体为反应原料,在酸催化剂的作用下,通过席夫碱反应制得。
7.根据权利要求6所述的制备方法,其特征在于,所述氨基单体与具有疏水基团和亲水基的醛基芳香单体的摩尔比为1:2~1:5,优选1:2。
8.根据权利要求7所述的制备方法,其特征在于,所述反应使用的混合溶剂选自邻二氯苯/乙醇、1,4-二氧六环/乙醇或三甲苯/乙醇的组合,两种溶剂的体积比为9:1~1:9;
优选邻二氯苯/乙醇。
9.根据权利要求8所述的制备方法,其特征在于,包括如下步骤:具有疏水基团和亲水基团的醛基芳香单体与5,10,15,20-四(4-氨基苯基)卟啉在乙酸催化作用下,于90~120℃反应24~72h;反应结束后,离心洗涤、真空烘箱干燥,得到暗紫色的方格COF。
10.权利要求1-4任一项所述共价有机框架在光催化降解染料、光催化化学反应和光电子传输领域中的应用。
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