CN106693906A - APTES改性MIL‑101(Cr)材料的制备方法 - Google Patents
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Abstract
本发明公开了APTES改性MIL‑101(Cr)材料的制备方法,该方法一种金属有机骨架化合物MIL‑101(Cr)的制备以及使用APTES(3‑氨丙基‑三乙氧基硅烷)对其进行后修饰处理的方法,该方法包括如下步骤:(1)MIL‑101(Cr)晶体粗产物的合成;(2)MIL‑101(Cr)晶体粗产物的活化;(3)将活化后一定量的MIL‑101(Cr)与溶剂通过超声混合,再加入一定量的APTES,将混合液装入三口瓶并在油浴中搅拌,对混合液其进行离心,并用无水乙醇洗涤剩余固体三次并在真空烘箱中干燥即可得到APTES修饰的产物。该方法具有操作简单易行的优点。
Description
技术领域
本发明涉及一种金属有机骨架化合物的制备方法,特别是涉及一种APTES改性MIL-101(Cr)的制备方法。
背景技术
金属有机骨架化合物(Metal-OrganicFrameworks,MOFs)是由无机金属离子或者金属簇与有机配体通过配位作用自组装形成的具有网络结构的晶体材料。其具有超高的比表面积,高孔隙率、孔径均匀、良好的热稳定性以及结构可调等优点,已经广泛的应用于离子交换、药物传递与缓释、气体的吸附与储存(如H2、CH4)、气体分离等场合。
法国凡尔赛大学G.Ferey教授等人在2005年将一定比例的九水硝酸铬,氢氟酸,对苯二甲酸,去离子水在220℃环境下加热8h,获得绿色的粉末晶体MIL-101(Cr)(MIL-Material Institute Lavoisier),其分子式为Cr3F(H2O)2O[(O2C)-(C6H4)-(CO2)]3·nH2O(n值一般为25),BET(BrunauerEmmerTeller)比表面积和朗格缪尔表面积分别为4100m2/g、5900m2/g,根据Dubinin-Raduskhvich方程得出孔体积为2m3/g。与大多数MOF材料相比,该材料具有更好的水热稳定性,其骨架结构在高温下(275℃)不改变,且在高温活化后含大量不饱和金属活性位点(coordinatively unsaturated metal sites,CUS,也叫路易斯酸位)。
金属有机骨架化合物通常用于气体吸附与分离领域,此外由于可对金属有机骨架化合物进行表面改性引入某些特定基团以提高其某一特定功能。如杨祝红等人通过改变合成配体中2-氨基对苯二甲酸的含量合成了不同氨基含量的NH2-MIL-53(Al),考察了氨基含量对CO2吸附性能的影响。发现表明随着氨基含量的增加,低压下NH2-MIL-53(Al)的CO2吸附性能也随之增加,0.1MPa下其最大吸附容量可达3.3mmol/g。周晶晶等人制备高氨基功能化MOFs材料MIL-101(Cr)-NH2,并考察不同碱度下材料对N2和CO2的吸附性能。结果表明当NaOH和有机配体NH2BDC的摩尔比为4:2时,合成的MIL-101(Cr)-NH2材料BET比表面积最高为2594m2/g,有最好的CO2选择性吸附性能,273.4K时达25.9mmol/g。
发明内容
本发明公开了一种APTES改性MIL-101(Cr)的制备方法,该方法包括如下步骤:
(a)MIL-101(Cr)的合成:将一定量的Cr(NO3)3·9H2O、对苯二甲酸H2BDC加入装有去离子水的三口瓶里并在油浴里搅拌一段时间,随后将混合溶液移入聚四氟乙烯内衬里,并向其中滴入氢氟酸,然后装入高压反应釜反应在220℃高温下反应8h。
(b)MIL-101(Cr)晶体粗产物的活化:对反应釜进行冷却,并将内衬里的混合液移入三口烧瓶,在向其中加入15ml的DMF后在40℃的油浴中搅拌1h。取溶液进行过滤,取滤液依次经过离心、乙醇洗、NH4F溶液洗、去离子水洗,然后取固体进行干燥。
(c)对活化的MIL-101(Cr)进行APTES改性:将活化的MIL-101(Cr)、一定量的APTES与适量溶剂通过超声震荡,然后在油浴里加热搅拌,取混合液进行离心,接着用乙醇洗涤三次,然后真空干燥即可。
步骤(a)中采用水热合成法合成MIL-101(Cr)粉末晶体。
步骤(a)加入的Cr(NO3)3·9H2O、对苯二甲酸H2BDC、氢氟酸的摩尔比为1:1:3。
步骤(b)所选用的乙醇为78℃的热乙醇,去离子水为100℃的热水,NH4F的质量浓度为1mol/L,离心时转速为8000r/min,时长为10min。
步骤(b)的干燥是在150℃的真空干燥烘箱里脱气除水8h。
步骤(c)所选用的溶剂为无水乙醇。
步骤(c)所选用的改性剂为APTES(3-氨丙基-三乙氧基硅烷)。
步骤(c)所加入的MIL-101(Cr)是0.2g,30ml的无水乙醇,0.175ml的APTES。
步骤(c)中加热搅拌时长为12h,温度为85℃,每次离心时转速为8000r/min,时长为10min。
步骤(c)中在100℃的真空干燥箱中干燥8h。
附图说明
图1为MIL-101(Cr)的制备流程图。
图2 APTES-MIL-101(Cr)的制备流程图。
图3 MIL-101(Cr)和APTES-MIL-101(Cr)的XRD图谱。
图4为MIL-101(Cr)和APTES-MIL-101(Cr)的FTIR图谱。
图5为MIL-101(Cr)和APTES-MIL-101(Cr)的N2吸附脱附等温线图。
图6.1为微孔孔径分布图,可知MIL-101(Cr)含大量的微孔,在经APTES改性后,部分微孔被APTES分子占据。
图6.2为介孔孔径分布图,可知MIL-101(Cr)含孔径为2.30nm的介孔,经APTES改性后,介孔孔径变为2.08nm
图7为MIL-101(Cr)SEM图。
图8为APTES-MIL-101(Cr)SEM图。
具体实施方式
如图1-8所示,本发明涉及到一种金属有机骨架化合物MIL-101(Cr)的制备以及使用APTES(3-氨丙基-三乙氧基硅烷)对其进行后修饰处理的方法,该方法包括如下步骤:
(a)MIL-101(Cr)的合成:将3g的Cr(NO3)3·9H2O、1.23g的对苯二甲酸加入装有36ml的去离子水的三口瓶里并在油浴里搅拌1h,随后将混合溶液移入聚四氟乙烯内衬里,并向其中滴入0.375ml氢氟酸,然后装入高压反应釜反应在220℃高温下反应8h。
(b)MIL-101(Cr)晶体粗产物的活化:对反应釜进行冷却,并将内衬里的混合液移入三口烧瓶,在向其中加入15ml的DMF后在40℃的油浴中搅拌1h。取溶液进行过滤,取滤液依次经过离心、乙醇洗、NH4F溶液洗、去离子水洗,然后取固体进行干燥(78℃的热乙醇,去离子水为100℃的热水,NH4F的质量浓度为1mol/L,离心时转速为8000r/min,时长为10min,在150℃的真空烘箱干燥8h)。
(c)对活化的MIL-101(Cr)进行APTES改性,命名为APTES-MIL-101(Cr):将活化的0.2gMIL-101(Cr)、0.175ml的APTES与30ml的乙醇超声震荡5min,然后在85℃油浴里加热搅拌12h,取混合液进行离心,接着用乙醇洗涤三次(每次离心时转速为8000r/min,时长为10min),然后在100℃真空干燥箱中干燥8h即可。
本发明利用水热合成法合成MIL-101(Cr)以及通过后处理修饰对MIL-101(Cr)进行改性,通过XRD、FTIR、BET、SEM、N2吸附脱附等温线、元素分析等手段对MIL-101(Cr)和APTES-MIL-101(Cr)进行表征,结果如图1-8及表1所示。
表1为MIL-101(Cr)和APTES-MIL-101(Cr)的结构参数表
Claims (10)
1.APTES改性MIL-101(Cr)材料的制备方法,其特征在于:该方法包括如下步骤:
(a)MIL-101(Cr)的合成:将一定量的Cr(NO3)3·9H2O、对苯二甲酸H2BDC加入装有去离子水的三口瓶里并在油浴里搅拌一段时间,随后将混合溶液移入聚四氟乙烯内衬里,并向其中滴入氢氟酸,然后装入高压反应釜反应在220℃高温下反应8h;
(b)MIL-101(Cr)晶体粗产物的活化:对反应釜进行冷却,并将内衬里的混合液移入三口烧瓶,在向其中加入15ml的DMF后在40℃的油浴中搅拌1h;取溶液进行过滤,取滤液依次经过离心、乙醇洗、NH4F溶液洗、去离子水洗,然后取固体进行干燥;
(c)对活化的MIL-101(Cr)进行APTES改性:将活化的MIL-101(Cr)、一定量的APTES与适量溶剂通过超声震荡,然后在油浴里加热搅拌,取混合液进行离心,接着用乙醇洗涤三次,然后真空干燥即可。
2.根据权利要求1所述的APTES改性MIL-101(Cr)材料的制备方法,其特征在于:步骤(a)中采用水热合成法合成MIL-101(Cr)粉末晶体。
3.根据权利要求1所述的APTES改性MIL-101(Cr)材料的制备方法,其特征在于:步骤(a)加入的Cr(NO3)3·9H2O、对苯二甲酸H2BDC、氢氟酸的摩尔比为1:1:3。
4.根据权利要求1所述的APTES改性MIL-101(Cr)材料的制备方法,其特征在于:步骤(b)所选用的乙醇为78℃的热乙醇,去离子水为100℃的热水,NH4F的质量浓度为1mol/L,离心时转速为8000r/min,时长为10min。
5.根据权利要求1所述的APTES改性MIL-101(Cr)材料的制备方法,其特征在于:步骤(b)的干燥是在150℃的真空干燥烘箱里脱气除水8h。
6.根据权利要求1所述的APTES改性MIL-101(Cr)材料的制备方法,其特征在于:步骤(c)所选用的溶剂为无水乙醇。
7.根据权利要求1所述的APTES改性MIL-101(Cr)材料的制备方法,其特征在于:步骤(c)所选用的改性剂为APTES(3-氨丙基-三乙氧基硅烷)。
8.根据权利要求1所述的APTES改性MIL-101(Cr)材料的制备方法,其特征在于:步骤(c)所加入的MIL-101(Cr)是0.2g,30ml的无水乙醇,0.175ml的APTES。
9.根据权利要求1所述的APTES改性MIL-101(Cr)材料的制备方法,其特征在于:步骤(c)中加热搅拌时长为12h,温度为85℃,每次离心时转速为8000r/min,时长为10min。
10.根据权利要求1所述的APTES改性MIL-101(Cr)材料的制备方法,其特征在于:步骤(c)中在100℃的真空干燥箱中干燥8h。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108404871A (zh) * | 2018-04-20 | 2018-08-17 | 万玉梅 | 一种高吸附性金属有机骨架材料的制备方法 |
CN110540654A (zh) * | 2019-08-09 | 2019-12-06 | 河南圣玛斯科技有限公司 | 一种金属有机骨架mil-101的氨基功能化修饰方法 |
CN110629094A (zh) * | 2018-06-25 | 2019-12-31 | 中国科学院苏州纳米技术与纳米仿生研究所 | 一种碳氮化合物晶粒细化剂及其制备方法与应用 |
CN113502057A (zh) * | 2021-07-14 | 2021-10-15 | 华中科技大学 | 一种基于有机金属骨架复合材料的热管理涂层的制备方法 |
CN113817172A (zh) * | 2021-08-11 | 2021-12-21 | 梅州绿盛林业科技有限公司 | 用于纯化铁皮石斛多糖类化合物的金属有机骨架材料及纯化方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104014320A (zh) * | 2014-06-19 | 2014-09-03 | 天津科技大学 | 一种富集痕量速灭威的水相金属有机框架分子印迹材料 |
CN104262400A (zh) * | 2014-07-31 | 2015-01-07 | 华南理工大学 | 大孔容的多级孔道mil-101材料及制备方法和应用 |
CN105503958A (zh) * | 2015-08-28 | 2016-04-20 | 浙江理工大学 | 乙二胺修饰的mil-101及其制备方法 |
-
2016
- 2016-12-31 CN CN201611266269.XA patent/CN106693906A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104014320A (zh) * | 2014-06-19 | 2014-09-03 | 天津科技大学 | 一种富集痕量速灭威的水相金属有机框架分子印迹材料 |
CN104262400A (zh) * | 2014-07-31 | 2015-01-07 | 华南理工大学 | 大孔容的多级孔道mil-101材料及制备方法和应用 |
CN105503958A (zh) * | 2015-08-28 | 2016-04-20 | 浙江理工大学 | 乙二胺修饰的mil-101及其制备方法 |
Non-Patent Citations (1)
Title |
---|
YOUNG KYU HWANG 等: "Amine Grafting on Coordinatively Unsaturated Metal Centers of MOFs: Consequences for Catalysis and Metal Encapsulation", 《ANGEW. CHEM.》 * |
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CN108404871A (zh) * | 2018-04-20 | 2018-08-17 | 万玉梅 | 一种高吸附性金属有机骨架材料的制备方法 |
CN110629094A (zh) * | 2018-06-25 | 2019-12-31 | 中国科学院苏州纳米技术与纳米仿生研究所 | 一种碳氮化合物晶粒细化剂及其制备方法与应用 |
CN110540654A (zh) * | 2019-08-09 | 2019-12-06 | 河南圣玛斯科技有限公司 | 一种金属有机骨架mil-101的氨基功能化修饰方法 |
CN113502057A (zh) * | 2021-07-14 | 2021-10-15 | 华中科技大学 | 一种基于有机金属骨架复合材料的热管理涂层的制备方法 |
CN113817172A (zh) * | 2021-08-11 | 2021-12-21 | 梅州绿盛林业科技有限公司 | 用于纯化铁皮石斛多糖类化合物的金属有机骨架材料及纯化方法 |
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