CN113171764A - 一种il/mof/cof复合材料及其制备方法、应用 - Google Patents
一种il/mof/cof复合材料及其制备方法、应用 Download PDFInfo
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Abstract
本发明公开了一种用于气体吸附分离的离子液体IL/MOF/COF复合材料的制备及其制备方法,先合成MOF晶体材料,再合成IL/MOF材料,最后COF材料,形成用于气体吸附的IL/MOF/COF复合材料。本发明的IL/MOF/COF复合材料形成了核壳结构,具有较高的稳定性,具有很高的比表面积、孔隙率,大大增加了材料的吸附和分离性能。结构中存在的不饱和配位点及配体官能团等可与气体分子间产生较强的亲和力,使其在气体吸收中具有巨大的应用前景。
Description
技术领域
本发明属于新材料技术领域,具体涉及一种IL/MOF/COF复合材料及其制备方法、应用。
背景技术
离子液体(IL)是一种由阴、阳离子组成的极性溶剂,具有稳定性高和环境友好的特点,而且IL能通过改变阴、阳离子类型或离子所带基团实现功能化设计。金属-有机框架材料(MOF)是近十年来发展迅速的一种配位聚合物,具有三维的孔结构,一般以金属离子为连接点,有机配位体支撑构成空间3D延伸,具有高比表面积、高孔隙率、孔径可调等特点,较其他多孔材料具有更广泛的应用前景,在吸附分离、催化剂、磁性和光学材料、小分子气体存储等领域均展示出较大的应用潜力。共价有机骨架(COF)是一类结晶性的有机多孔材料,基于可逆化学反应将功能单元以共价键的形式连接成高度有序的二维层叠层结构或特定的三维拓扑结构。
近几十年来,随着世界工业发展,人口增加等原因,大气中CO2的浓度不断升高,CO2的捕集及有效利用是亟待解决的资源环境问题。MOF材料在CO2吸收中具有重要作用,由于IL对CO2良好的亲和性,将IL与MOF复合有望提高对CO2的吸收量和选择性。但是,将IL引入MOF中占据了部分空腔体积,使IL/MOF材料对气体吸收量降低。现有技术中有采用IL/MOF复合材料增加了CO2的亲和力的同时降低了CH4和N2的亲和力,从而使其对CO2/CH4、CO2/N2分离选择性分别提高了2倍和3倍以上;但是,由于负载IL前后MOF材料的孔径分布不发生改变,证实了负载的IL会导致MOF孔道阻塞,导致吸附容量小的缺点。
发明内容
为解决上述技术问题,本发明采用的技术方案是:一种IL/MOF/COF复合材料,包括有由内至外依次设置的IL、MOF、COF,所述MOF为NH2-MIL-68晶体,所述COF为TPA-COF材料,所述IL包裹在MOF内部形成核壳结构,TPA-COF材料通过化学键连接MOF。
作为上述技术方案的优选,IL、MOF、COF形成具有高结晶度和分级孔隙率的核壳结构。
IL/MOF/COF复合材料的制备方法,包括以下步骤:
步骤1,合成NH2-MIL-68:取一定量的In(NO3)3·x H2O和2-氨基对苯二甲酸,将其溶解在一定量的DMF中,超声至溶液均一后,移入反应釜中,在100-150℃的鼓风干燥箱中高压反应2-3h,将反应后形成的悬浮液冷却到室温后,再用N,N-二甲基甲酰胺收集,并用无水甲醇洗涤数遍,离心,80℃烘干过夜,最终得到NH2-MIL-68粉末;
步骤2,IL/MOF:将具有亲水特性的IL、1-正丁基-3-甲基咪唑甲基硫酸盐溶解于惰性溶剂中,再将NH2-MIL-68粉末与IL溶液混合,在120℃温度下搅拌22-26小时,获得均匀稳定的混合物,之后将惰性溶剂挥发,获得核壳结构的IL/MOF复合材料;
步骤3,合成IL/MOF/COF:将邻二氯苯/乙醇/乙酸按体积比20:5:1的比例混合形成混合液,将IL/MOF复合材料加入到混合液中在高压釜容器24-48小时内保持在100-200℃,分离出的IL/NH2-MIL-68/TPA-COF杂化材料,洗涤,离心,干燥,得到高度结晶分级孔结构的IL/MOF/COF复合材料。
作为上述技术方案的优选,所述步骤(1)鼓风干燥箱中温度为125℃,搅拌反应2.5小时。
作为上述技术方案的优选,所述步骤(2)中温度为35℃,搅拌6小时。
作为上述技术方案的优选,所述步骤(3)高压釜容器中温度为150℃,搅拌24小时。
IL/MOF/COF复合材料的应用,将IL/MOF/COF复合材料用于气体吸附分离,气体为CO2、CH4和N2中的任意一种或者多种。
作为上述技术方案的优选,将吸附过气体的IL/MOF/COF复合材料采用减压脱附方法进行脱附后循环使用。
作为上述技术方案的优选,所述IL/MOF/COF复合材料进行脱附循环使用的次数为9-12次。
本发明的工作原理是:IL/MOF核壳结构的合成后将COF材料在核壳结构的节点处与MOF结合,得到高度结晶的分级孔结构;然后COF包覆IL/MOF形成IL/MOF/COF核壳结构。一方面IL可以稳定MOF晶体,减少了水分子对金属中心的侵蚀,从而改善了MOF材料的稳定性,形成均匀稳定的NH2-MIL-68晶体复合材料。另一方面MOF材料在多种气体存在的混合体系分离中的选择性较差,IL掺杂可大大提高MOF材料的吸附选择性,但IL的引入可能导致IL占据金属位点而使MOF的对气体的吸附减弱,导致IL可能占据一部分孔体积而使吸附容量有所下降。在NH2-MIL-68复合材料中,加入COF材料,得到高度结晶的分级孔结构。进一步了增强材料的稳定性,并且大大增加了材料的吸附和分离性能。结构中存在的不饱和配位点及配体官能团等可与气体分子间产生较强的亲和力。
本发明的有益效果是:本发明的IL/MOF/COF复合材料,具有高度结晶的分级孔结构,比表面积大,孔隙率高,稳定性强,对CO2、CH4和N2的单组分气体或者多组分气体具有很强的吸附性能和分离性能,使其在气体吸收中具有巨大的应用前景。
附图说明
图1是IL/MOF/COF复合材料的制备流程图;
图2是NH2-MIL-68晶体的扫描图;
图3是IL/NH2-MIL-68复合材料的xrd分析图;
图4中高度结晶分级孔的IL/MOF/COF结构图。
具体实施方式
下面将结合附图对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
如图1-2所示,(1)利用水热法合成NH2-MIL-68粉末,图2是UiO-66-NH2晶体的扫描图。水热法具体过程为:取1.156g的In(NO3)3·x H2O和0.234g 2-氨基对苯二甲酸,将其溶解在12.4mL的DMF中,超声至溶液均一后,移入反应釜中,在100-150℃的鼓风干燥箱中高压反应2-3h,将反应后形成的悬浮液冷却到室温后,再用N,N-二甲基甲酰胺收集,并用无水甲醇洗涤数遍,离心,80℃烘干过夜,最终得到NH2-MIL-68粉末。
(2)将NH2-MIL-68粉末与IL溶液混合,在120℃温度下搅拌22-26小时,获得均匀稳定的混合物。具体过程为:将具有亲水特性的IL,1-正丁基-3-甲基咪唑甲基硫酸盐([BMIM][MeSO4])溶解于反应惰性的溶剂中,再将NH2-MIL-68粉末与IL溶液混合,在120℃温度下搅拌22-26小时,获得均匀稳定的混合物,之后将惰性溶剂挥发即可获得核壳结构的IL/MOF复合材料。图3是UiO-66-NH2-离子液体复合材料的SEM扫描图,可以看出其中含有IL内核。
(3)将TAPB-COF材料加入到高压釜容器中,在100-200℃温度下搅拌8-16小时,得到图4中高度结晶分级孔结构的IL/MOF/COF复合材料。具体过程为:将邻二氯苯/乙醇/乙酸按体积比20:5:1的比例混合形成混合液,将IL/MOF复合材料加入到混合液中在高压釜容器24-48小时内保持在100-200℃,分离出的IL/NH2-MIL-68/TPA-COF杂化材料,洗涤,离心,干燥,得到高度结晶分级孔结构的IL/MOF/COF复合材料。
将上述制得的IL/MOF/COF复合材料进行扫描电镜分析,如图4所示,可证明得到了高度结晶分级孔结构的IL/MOF/COF复合材料。
将该IL/MOF/COF复合材料用于气体分离吸附。并进行吸附能力和孔隙率测试,测试结果如下表所示:
比表面积m2/g | 吸附能力 | 孔体积cm3/g | |
IL/MOF/COF | 1012 | 97.6% | 0.65 |
IL/MOF | 3.6 | 62% | 0.02 |
MOF | 712 | 78% | 0.31 |
A、CO2、CH4和N2纯组分吸脱附测试:采用吸附装置,测定材料对CO2、CH4和N2在三种温度(273K,298K和348K)下的纯组分吸附等温线。利用智能重量吸收分析仪中测量298K和20bar下的气体吸附等温线。所有样品在150℃下重复脱气12小时后进行吸附测量。为了评价材料的稳定性和重复使用性,在TGA装置中进行了9个连续的吸附-再生循环,然后在150℃(升温速率为10℃/min条件下,在100ml/min氮气(99.999%)中进行再生。测试结果是:IL/MOF/COF复合材料在进行了9个连续的吸附再生循环后,复合材料仍具有吸附能力。表明IL/MOF/COF复合材料对CO2、CH4或N2纯组分具有多次的吸脱附循环使用能力。
B、CO2、CH4和N2多组分吸脱附测试
采用吸附装置,利用智能重量吸收分析仪测量材料对CO2、CH4和N2混合物在298K和20bar的吸附等温线。所有样品在150℃下重复脱气12小时后进行吸附测量。测试结果是:IL/MOF/COF复合材料对CO2的吸附率高于CH4和N2。表明:IL/MOF/COF复合材料增加了CO2的亲和力的同时降低了CH4和N2的亲和力,从而使其对CO2/CH4、CO2/N2分离选择性分别提高了3倍和4倍以上。
值得一提的是,本发明专利申请涉及的NH2-MIL-68晶体等技术特征应被视为现有技术,NH2-MIL-68晶体的制备原理,这些技术特征的具体结构、工作原理以及可能涉及到的控制方式、空间布置方式采用本领域的常规选择即可,不应被视为本发明专利的发明点所在,本发明专利不做进一步具体展开详述。
以上详细描述了本发明的较佳具体实施例,应当理解,本领域的普通技术人员无需创造性劳动就可以根据本发明的构思做出诸多修改和变化,因此,凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案,皆应在由权利要求书所确定的保护范围内。
Claims (9)
1.一种IL/MOF/COF复合材料,其特征在于,包括有由内至外依次设置的IL、MOF、COF,所述MOF为NH2-MIL-68晶体,所述COF为TPA-COF材料,所述IL包裹在MOF内部形成核壳结构,TPA-COF材料通过化学键连接MOF。
2.如权利要求1所述的IL/MOF/COF复合材料,其特征在于,IL、MOF、COF形成具有高结晶度和分级孔隙率的核壳结构。
3.IL/MOF/COF复合材料的制备方法,其特征在于,包括以下步骤:
步骤1,合成NH2-MIL-68:取一定量的In(NO3)3·x H2O和2-氨基对苯二甲酸,将其溶解在一定量的DMF中,超声至溶液均一后,移入反应釜中,在100-150℃的鼓风干燥箱中高压反应2-3h,将反应后形成的悬浮液冷却到室温后,再用N,N-二甲基甲酰胺收集,并用无水甲醇洗涤数遍,离心,80℃烘干过夜,最终得到NH2-MIL-68粉末;
步骤2,IL/MOF:将具有亲水特性的IL、1-正丁基-3-甲基咪唑甲基硫酸盐溶解于惰性溶剂中,再将NH2-MIL-68粉末与IL溶液混合,在120℃温度下搅拌22-26小时,获得均匀稳定的混合物,之后将惰性溶剂挥发,获得核壳结构的IL/MOF复合材料;
步骤3,合成IL/MOF/COF:将邻二氯苯/乙醇/乙酸按体积比20:5:1的比例混合形成混合液,将IL/MOF复合材料加入到混合液中在高压釜容器24-48小时内保持在100-200℃,分离出的IL/NH2-MIL-68/TPA-COF杂化材料,洗涤,离心,干燥,得到高度结晶分级孔结构的IL/MOF/COF复合材料。
4.如权利要求3所述的IL/MOF/COF复合材料的制备方法,其特征在于,所述步骤(1)鼓风干燥箱中温度为125℃,搅拌反应2.5小时。
5.如权利要求3所述的IL/MOF/COF复合材料的制备方法,其特征在于,所述步骤(2)中温度为35℃,搅拌6小时。
6.如权利要求3所述的IL/MOF/COF复合材料的制备方法,其特征在于,所述步骤(3)高压釜容器中温度为150℃,搅拌24小时。
7.IL/MOF/COF复合材料的应用,其特征在于,将IL/MOF/COF复合材料用于气体吸附分离,气体为CO2、CH4和N2中的任意一种或者多种。
8.如权利要求7所述的IL/MOF/COF复合材料的应用,其特征在于,将吸附过气体的IL/MOF/COF复合材料采用减压脱附方法进行脱附后循环使用。
9.如权利要求8所述的IL/MOF/COF复合材料的应用,其特征在于,所述IL/MOF/COF复合材料进行脱附循环使用的次数为9-12次。
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