CN106748728A - 一种乙烯基功能化Zr‑MOFs材料的制备方法 - Google Patents
一种乙烯基功能化Zr‑MOFs材料的制备方法 Download PDFInfo
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Abstract
本发明涉及了一种乙烯基功能化Zr‑MOFs材料UiO‑66‑CH=CH2的制备方法。其方法步骤为:将锆盐、含乙烯基有机配体、DMF和盐酸,按摩尔比1:0.5~2:500~1000:500~1000在室温下超声振荡5~20min,充分混合,放入反应釜中在70~150℃的烘箱中反应10~20h,冷却至室温离心,将沉淀物用DMF和无水甲醇反复洗涤数次,离心分离,得到含有乙烯基功能化Zr‑MOFs材料UiO‑66‑CH=CH2。本发明合成的含有乙烯基功能化Zr‑MOFs材料UiO‑66‑CH=CH2孔隙率高、孔径均匀和比表面积大,并且热稳定性和化学稳定性良好;其合成方法具有工艺简单、重复性好、产率高、工艺条件温和等优点。
Description
技术领域
本发明属于金属有机框架材料制备领域,具体涉及一种乙烯基功能化Zr-MOFs材料UiO-66-CH=CH2的制备方法。
背景技术
金属有机框架(Metal-organic Framework,MOFs)材料是将有机配体和金属离子通过自组装形成的具有重复网络结构的一种类沸石材料,是近几十年来配位化学领域中发展得比较快的新材料。与传统的无机多孔材料相比,MOFs材料具有更大的空隙率和比表面积,尤其是可调节的孔径以及可变的功能基团。目前,MOFs材料已经应用于氢气存储、药物运载、催化反应、生物传感器、气体吸附与分离等方面。金属有机框架材料的研究涉及有机化学、无机化学、配位化学、材料化学、生命科学以及计算机科学等学科的最新成果,因而近年来MOFs受到越来越多研究团队的关注。
有机配体的选择对MOFs材料的结构及性能有很大的影响。在众多的有机配体中,含羧酸、乙烯基双功能基团的有机配体使合成的MOFs材料的结构富于变化、性能多样,从而可以获得多功能的MOFs材料。
发明内容
本发明的目的在于提供一种乙烯基功能化Zr-MOFs材料UiO-66-CH=CH2的制备方法。
本发明采用如下技术方案:
一种乙烯基功能化Zr-MOFs材料UiO-66-CH=CH2的制备方法,其特征在于方法步骤如下:
(1)将锆盐、含乙烯基有机配体、DMF和盐酸,按摩尔比锆盐:含乙烯基有机配体:DMF:盐酸=1:0.5~2:500~1000:500~1000在室温下超声振荡5~20min,充分混合,放入反应釜中在70~150℃的烘箱中反应10~20h;
(2)冷却至室温后离心,将沉淀物分散于DMF中,反复离心洗涤3~5次,离心分离后,将沉淀物分散于无水甲醇中,反复离心洗涤3~5次;
(3)离心分离后的产物放入干燥箱中于60~120℃恒温干燥,冷却至室温后,得到含有乙烯基功能化Zr-MOFs材料UiO-66-CH=CH2。
上述制备方法中,所述的锆盐为Zr(NO3)4·5H2O、ZrCl4和ZrOCl2·8H2O中的一种或者几种。
所述的含有乙烯基的有机配体为:2-乙烯基对苯二甲酸。
本发明的优点是:合成的含有乙烯基功能化Zr-MOFs材料孔隙率高、孔径均匀和比表面积大,乙烯基对气体分子的亲和作用,可用于气体吸附与分离;乙烯基作为活性官能团易与其他小分子发生加成等化学反应,加之锆基MOF的纳米尺寸,可用于细胞内荧光检测;其合成方法具有工艺简单、重复性好、产率高、工艺条件温和等优点,本发明中将该材料命名为ZJU-207。
附图说明
图1为本发明实施例1合成的UiO-66-CH=CH2的粉末X射线衍射图谱。
图2为本发明实施例1合成的UiO-66-CH=CH2的傅里叶红外光谱。
图3为本发明实施例1合成的UiO-66-CH=CH2的77K氮气吸附-脱附曲线。
具体实施方式
下面将结合实施例进一步阐明本发明的内容,但这些实例并不限制本发明的保护范围,在本发明的技术方案的基础上,本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。
实施例1
(1)在聚四氟乙烯衬底内加入ZrCl4(18.66mg,0.08mmol)、2-乙烯基对苯二甲酸(9.6mg,0.05mmol)、DMF(4mL)和盐酸(1mL),在室温下超声振荡10min,充分混合,放入反应釜中在120℃的烘箱中反应15h;
(2)冷却至室温后离心,将沉淀物分散于DMF中,反复离心洗涤3次,离心分离后,将沉淀物分散于无水甲醇中,反复离心洗涤3次;
(3)离心分离后的产物放入干燥箱中于70℃恒温干燥,冷却至室温后,得到含有乙烯基功能化Zr-MOFs材料UiO-66-CH=CH2。
图1至图3分别为本例合成的Zr-MOFs材料UiO-66-CH=CH2的粉末X射线衍射图谱、傅里叶红外光谱和77K氮气吸附-脱附曲线。
实施例2
(1)在聚四氟乙烯衬底内加入ZrCl4(11.65mg,0.05mmol)、2-乙烯基对苯二甲酸(9.6mg,0.05mmol)、DMF(4mL)和盐酸(0.5mL),在室温下超声振荡15min,充分混合,放入反应釜中在110℃的烘箱中反应12h;
(2)冷却至室温后离心,将沉淀物分散于DMF中,反复离心洗涤4次,离心分离后,将沉淀物分散于无水甲醇中,反复离心洗涤4次;
(3)离心分离后的产物放入干燥箱中于80℃恒温干燥,冷却至室温后,得到含有乙烯基功能化Zr-MOFs材料UiO-66-CH=CH2。
实施例3
(1)在聚四氟乙烯衬底内加入ZrCl4(23.33mg,0.10mmol)、2-乙烯基对苯二甲酸(15.36mg,0.08mmol)、DMF(8mL)和盐酸(1.8mL),在室温下超声振荡20min,充分混合,放入反应釜中在100℃的烘箱中反应24h;
(2)冷却至室温后离心,将沉淀物分散于DMF中,反复离心洗涤5次,离心分离后,将沉淀物分散于无水甲醇中,反复离心洗涤5次;
(3)离心分离后的产物放入干燥箱中于60℃恒温干燥,冷却至室温后,得到含有乙烯基功能化Zr-MOFs材料UiO-66-CH=CH22。
Claims (3)
1.一种乙烯基功能化Zr-MOFs材料UiO-66-CH=CH2的制备方法,其特征在于方法步骤如下:
(1)将锆盐、含乙烯基有机配体、DMF和冰醋酸,按摩尔比1:0.5~2:500~1000:500~1000在室温下超声振荡5~20min,充分混合,放入反应釜中在70~150℃的烘箱中反应10~20h;
(2)冷却至室温后离心,将沉淀物分散于DMF中,反复离心洗涤3~5次,离心分离后,将沉淀物分散于无水甲醇中,反复离心洗涤3~5次;
(3)离心分离后的产物放入干燥箱中于60~120℃恒温干燥,冷却至室温后,得到含有乙烯基功能化Zr-MOFs材料UiO-66-CH=CH2。
2.根据权利要求1所述的乙烯基功能化Zr-MOFs材料UiO-66-CH=CH2的制备方法,其特征在于,所述的锆盐为Zr(NO3)4·5H2O、ZrCl4和ZrOCl2·8H2O中的一种或者几种。
3.根据权利要求1所述的乙烯基功能化Zr-MOFs材料UiO-66-CH=CH2的制备方法,其特征在于,所述的含有乙烯基的有机配体为:2-乙烯基对苯二甲酸。
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CN113336897A (zh) * | 2021-06-01 | 2021-09-03 | 广东工业大学 | 一种孔内限域聚合有机单体的金属-有机框架基材料及其制备方法和应用 |
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CN110828872A (zh) * | 2019-11-20 | 2020-02-21 | 刘艳蕊 | 一种燃料电池用高温质子交换膜及其制备方法 |
CN113336897A (zh) * | 2021-06-01 | 2021-09-03 | 广东工业大学 | 一种孔内限域聚合有机单体的金属-有机框架基材料及其制备方法和应用 |
CN113336897B (zh) * | 2021-06-01 | 2022-05-10 | 广东工业大学 | 一种孔内限域聚合有机单体的金属-有机框架基材料及其制备方法和应用 |
WO2022252533A1 (zh) * | 2021-06-01 | 2022-12-08 | 广东工业大学 | 一种孔内限域聚合有机单体的金属-有机框架基材料及其制备方法和应用 |
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