CN106518843B - 一种基于含咪唑基烟酰腙类有机配体的Cd(II)金属有机框架及其制备方法与应用 - Google Patents
一种基于含咪唑基烟酰腙类有机配体的Cd(II)金属有机框架及其制备方法与应用 Download PDFInfo
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
本发明公开了一种基于含咪唑基烟酰腙类有机配体的Cd(II)金属有机框架及其制备方法与应用，其结构式为：CdmLnXa，其中，m＝n＝a，且m、n、a均为自然数，X为NO3 ‑、Cl‑、Br‑或I‑，L为有机配体L，有机配体的结构式为将有机配体L和CdX2加入至溶剂中混合均匀，加热反应，反应后获得Cd(II)的金属有机框架，本发明制备的金属有机框架在室温下对气体小分子的吸附能力较好。
Description
技术领域
本发明属于无机-有机纳米材料制备技术领域，具体涉及一种含咪唑基烟酰腙类有机配体、基于这种有机配体和Cd(II)离子的金属有机框架及其制备方法。
背景技术
金属有机框架结构(Metal-organic Framework，MOF)是近年来研究的热点，与传统的有孔材料相比，MOF具有多孔、较大的比表面积以及框架内孔体积等特点。MOFs因其具有高比表面积、高孔隙率、高稳定性等性质，使其成为气体吸附的高效材料。由于MOFs材料具有可调节的孔径，因此设计具有合适孔径的MOFs材料用于CO2特异性吸附分离是减少温室气体的一种途径。
目前具有大的空隙率以及大尺寸隧道的金属-有机框架化合物是该领域的研究热点，这不仅是由于其良好的吸附，分离以及储存性能，也是由于其在催化，后修饰合成等方面的潜在用途。目前的MOF可以分为正电性MOF，中电性MOF以及负电性MOF，其中正电性MOF和负电性MOF均含有平衡离子，因而导致了空隙率的急剧下降。而中电性的MOF具有较高的空间体积，一直以来是气体小分子以及有机小分子的理想吸附及分离材料，虽然目前对很多中电性的MOF进行研究，但是含咪唑基的吡啶酰腙类有机配体并将其用于与Cd(II)无机盐的自组装研究未见报道。
发明内容
本发明的目的在于提供一种吡啶酰腙类有机配体及其制备方法，同时，本发明的另一目的是提供基于这种有机配体和Cd(II)的金属有机框架的制备方法及应用。
为实现上述目的，本发明的技术方案为：
一种制备用于合成Cd(II)的金属有机框架的有机配体L的中间体，其化学命名为5-咪唑基烟酸酰肼，其化学结构式为：
一种制备上述中间体的方法，5-溴烟酸与咪唑进行取代反应得到5-咪唑基烟酸，5-咪唑基烟酸与甲醇进行酯化反应得到5-咪唑基烟酸甲酯，5-咪唑基烟酸甲酯与肼进行肼解反应得到中间体5-咪唑基烟酸酰肼。
5-咪唑基烟酸的化学结构式为：
5-咪唑基烟酸甲酯化学结构式为：
一种用于合成Cd(II)的金属有机框架的有机配体L，其化学命名为4-吡啶甲醛-5-咪唑基烟酰腙，其化学结构式为：
一种上述有机配体L的制备方法，中间体5-咪唑基烟酸酰肼与4-吡啶甲醛进行胺与醛的缩合反应得到有机配体L。
优选的，5-咪唑基烟酸酰肼与4-吡啶甲醛的摩尔比为1:(1.1-1.2)。
优选的，所述缩合反应的溶剂为无水乙醇。
优选的，所述缩合反应中添加甲酸。
进一步优选的，缩合反应体系中甲酸的量为0.23-0.28mol/L。
优选的，所述缩合反应的温度为79-84℃，时间为24-28h。
一种Cd(II)的金属有机框架，其结构式为：CdmLnXa，其中，m＝n＝a，且m、n、a均为自然数，L为上述有机配体L，X为NO3 -、Cl-、Br-或I-。
优选的，金属有机框架的单晶结晶于单斜晶系，属于P 1 21/c 1空间群，每个不对称单元中均有一个Cd金属中心，每个Cd金属中心均处在变形四面体{CdN4OX}的配位环境中，每个Cd为六配位，每个Cd金属中心与四个不同有机配体L上的N配位，每个有机配体L有两个吡啶上的N、一个咪唑上的N和其中一个酰肼上的N参与配位。
一种Cd(II)的金属有机框架的制备方法，将上述有机配体L和CdX2加入至溶剂中混合均匀，加热反应，反应后获得Cd(II)的金属有机框架，即Cd-MOF，其中，X为NO3 -、Cl-、Br-或I-。
优选的，所述溶剂为有机溶剂。
进一步优选的，所述有机溶剂为N,N-二甲基甲酰胺(DMF)。
优选的，有机配体L和CdX2摩尔比为1:(3-4.5)。
优选的，将有机配体L加入溶剂后，形成的溶液中有机配体L的浓度为4.79×10-3-6.84×10-3mol/L。
优选的，所述反应的温度为90-120℃，时间为72-80小时。
一种材料，包含上述金属有机框架。
一种上述金属有机框架或上述材料在吸附二氧化碳中的应用。
本发明的有益效果为：
1.本发明首次制备了能够与Cd(II)形成金属-有机框架的有机配体L(4-吡啶甲醛-5-咪唑基烟酰腙)，及能够制备有机配体L的中间体5-咪唑基烟酸酰肼，Cd(II)与有机配体L形成的金属-有机框架的金属中心仍然与平衡阴离子配位，不仅没有减少隧道的有效体积，并且为我们提供了不同的MOF内环境，为研究其对MOF材料气体吸附性能的影响提供了有利条件。
2.本发明制备的金属有机框架在室温下对气体小分子的吸附能力较好；二氧化碳的吸附量在195K，684mmHg达到101.50cm3g-1at STP(STP：标准状况，温度为273.15K，压力为一个标准大气压，101.325kPa)。
附图说明
图1本发明的构建Cd(II)的金属有机框架的有机配体L的红外图谱；
图2本发明的构建Cd(II)的金属有机框架的有机配体L的核磁图谱；
图3实施例1中Cd(II)的金属有机框架的红外图谱；
图4实施例1中的Cd(II)的金属有机框架的热重曲线；
图5本发明的Cd-MOF的单晶结构图；
图6本发明的Cd-MOF的三维结构图；
图7实施例1、2、3和4中的Cd-MOF的粉末X射线衍射图谱(PXRD)；
图8实施例1的CO2吸附和脱吸附曲线。
具体实施方式
下面结合附图及具体实施例对本发明作进一步说明。
中间体5-咪唑基烟酸的制备：
N2保护下，5-溴烟酸(3.0g,15mmol)、咪唑(1.4g,21mmol)、碳酸铯(14.5g,45mmol)、碘化亚铜(0.6g,3mmol)加入到150mL的三口瓶中，15mLDMF作溶剂，在油浴120℃下加热24h。反应结束后倒入250mL水中，静置，抽滤，用盐酸调节滤液pH至5～6，抽滤，将滤液蒸至1/3析出固体，抽滤，晾干，得白色固体1.6g，产率56％。IR(v,cm-1):3436(w),3126(w),3100(w),2402(w),1693(m),1604(s),1511(m),1437(w),1339(s),1287(m),1121(w),1068(s),858(w),774(m),724(w),691(w),648(w),552(w).1H NMR(300MHz,CDCl3,25℃,TMS,ppm):δ＝9.15(s,1H,–C5H3N),9.01(s,1H,–C5H3N),8.46(s,1H,–C5H3N),8.44(s,1H,–C3H3N2),7.93-7.95(d,J＝6.0Hz,1H,–C3H3N2),7.14-16(d,J＝6.0Hz,1H,–C3H3N2).
中间体5-咪唑基烟酸甲酯的制备：
称取中间体5-咪唑基烟酸(1.0g,5mmol)加入到圆底烧瓶中，量取MeOH 20mL于100mL的单口圆底烧瓶中，吸取2mL的浓硫酸沿着烧瓶壁缓慢的加入圆底烧瓶中。搅拌使其溶解，安装实验装置(以CH3OH为溶剂，在分水器中加入5mL甲苯)，打开加热搅拌，使其回流4-5h，停止加热搅拌，冷至室温，将反应倒入装有100mL装有二次水的烧杯中，搅拌冰水浴，Na2CO3调pH＝7，抽滤，得固体，待固体晾干后硅胶柱层析，得白色固体0.9g，产率88％。IR(KBr pellet,cm-1):3426(w),3129(m),3096(s),3060(m),3015(w),2961(w),1724(s),1597(m),1504(s),1435(m),1378(w),1321(s),1291(s),1200(m),1171(m),1122(m),1070(m),1020(m),951(m),904(w),837(w),768(m),694(w).1H NMR(300MHz,DMSO,25℃,TMS,ppm):9.26(s,1H,–C5H3N),8.85(s,1H,–C5H3N),8.44(s,1H,–C3H3N2),8.20(s,1H,–C5H3N),4.03(s,3H,-CH3),7.93-7.95(d,J＝6.0Hz,1H,–C3H3N2),7.14-16(d,J＝6.0Hz,1H,–C3H3N2).
中间体5-咪唑基烟酸酰肼的制备：
将中间体5-咪唑基烟酸甲酯(2.03g,10mmol)，20mL乙醇于100mL圆底烧瓶，搅拌滴加N2H4·H2O(5.7mL,100mmol)的乙醇溶液(10mL)，加热回流溶液至无色澄清。TLC跟踪反应完全后，停止反应，大量白色固体析出，冷却，抽滤，滤液有白色絮状固体析出，乙醚洗涤三次，得白色絮状固体2.0g，产率98％。IR(KBr pellet,cm-1):3309(w),3224(w),3104(s),3057(s),1659(s),1629(s),1557(s),1502(s),1439(s),1352(m),1324(m),1271(s),1193(w),1159(w),1108(w),1071(m),1014(s),977(m),908(w),848(w),753(w),702(m),.1HNMR(300MHz,DMSO,25℃,TMS,ppm):10.13(t,1H,-NH)，9.35(s,1H,–C5H3N),9.06(s,1H,–C5H3N),8.44(s,1H,–C3H3N2),8.34(s,1H,–C5H3N),7.93-7.95(d,J＝6.0Hz,1H,–C3H3N2),7.14-16(d,J＝6.0Hz,1H,–C3H3N2),4.85(d,2H,-NH2).
有机配体L的制备：
称取5-咪唑基烟酰肼(0.50g，2.5mmol)，4-吡啶甲醛(0.32g，3.0mmol)，无水乙醇10mL，甲酸0.10mL，回流反应24～28h，待反应液冷却后抽滤，以无水乙醇反复洗涤固体，晾干，得到白色固体0.64g，产率90％。IR(KBr pellet,cm-1)，如图1所示：3075(m),3023(m),2938(m),2816(s),1669(s),1599(s),1572(m),1502(s),1465(m),1416(m),1384(s),1322(s),1274(m),1179(m),1111(w),1061(s),997(m),934(w),896(m),814(m)。1HNMR(300MHz,DMSO-d6,298K,TMS,ppm)δ，如图2所示：12.35(1H,s,-C5H3N),9.18(1H,s,-N＝CH-),9.03(1H,s,-C5H3N),8.69(2H,d,-C5H4N),8.55(1H,s,-C5H3N),8.46(2H,d,-C5H4N),8.44(s,1H,–C3H3N2),7.96(1H,s,-C3H3N2),7.72(2H,d,-C3H3N2),7.21(1H,s,-NH)。Elemental anaylsis(％)calcd for C15H12N6O：C 61.64,H 4.14,N 28.75,O 5.47,Found：C 61.40,H 4.02,N25.78,O 5.07。
2、Cd(II)的金属有机框架的合成
实施例1
将有机配体L(3mg，0.01mmol)、CdBr2(8.16mg，0.03mmol)溶于2mL N,N-二甲基甲酰胺(DMF)中，90℃条件下保温72小时，降温至室温，即得到CdBr-MOF，红外谱图如图3所示，TGA谱图如图4所示，PXRD谱图如7所示。实施例1晶体数据见附表1。
实施例2
有机配体L的制备同实施例1；
将有机配体L(3mg，0.01mmol)、CdCl2(5.50mg，0.03mmol)溶于2mL N,N-二甲基甲酰胺(DMF)中，90℃条件下保温72小时，降温至室温，即得到CdCl-MOF，产物的PXRD表征如图7所示。
实施例3
有机配体L的制备同实施例1；
将有机配体L(3mg，0.01mmol)、Cd(NO3)2(7.28mg，0.03mmol)溶于2mLN,N-二甲基甲酰胺(DMF)中，90℃条件下保温72小时，降温至室温，即得到Cd(NO3)-MOF，产物的PX RD表征如图7所示。
实施例4
有机配体L的制备同实施例1；
将有机配体L(3mg，0.01mmol)、CdI2(10.98mg，0.03mmol)溶于2mLN,N-二甲基甲酰胺(DMF)中，90℃条件下保温72小时，降温至室温，即得到CdI-MOF，产物的PXRD表征如图7所示。
表1 CdBr-MOF的晶体学数据
本发明制备的Cd-MOF的单晶，如图5所示，结晶于单斜晶系，属于P 1 21/c 1空间群，每个不对称单元中均有一个Cd金属中心，每个Cd金属中心均处在变形四面体{CdN4OX}X(X＝NO3 -、Cl-、Br-或I-)的配位环境中，每个Cd为六配位，每个Cd金属中心与四个不同配体上的N配位，每个配体有两个吡啶上的N、一个咪唑上的N和其中一个酰腙上的N参与配位。三维结构图如图6所示。
3、图8为实施例1采用BET比表面检测仪检测的二氧化碳吸附曲线为I型的吸附曲线，二氧化碳的吸附量在195K,684mmHg达到101.50cm3g-1at STP。(STP：标准状况，温度为273.15K，压力为一个标准大气压，101.325kPa)
上述虽然结合附图对本发明的具体实施方式进行了描述，但并非对发明保护范围的限制，所属领域技术人员应该明白，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内。
Claims (10)
1.一种制备用于合成Cd(II)的金属有机框架的有机配体L的中间体，其特征是，其化学结构式为：
2.一种制备权利要求1所述的中间体的方法，其特征是，5-溴烟酸与咪唑进行取代反应得到5-咪唑基烟酸，5-咪唑基烟酸与甲醇进行酯化反应得到5-咪唑基烟酸甲酯，5-咪唑基烟酸甲酯与肼进行肼解反应得到中间体5-咪唑基烟酸酰肼。
3.一种用于合成Cd(II)的金属有机框架的有机配体L，其特征是，其化学结构式为：
4.一种权利要求3所述的有机配体L的制备方法，其特征是，权利要求1所述的中间体5-咪唑基烟酸酰肼与4-吡啶甲醛进行胺与醛的缩合反应得到有机配体L。
5.如权利要求4所述的制备方法，其特征是，所述缩合反应中添加甲酸；
或，所述缩合反应的温度为79-84℃，时间为24-28h。
6.一种Cd(II)的金属有机框架，其特征是，其结构式为：CdmLnXa，其中，m＝n＝a，且m、n、a均为自然数，L为权利要求3所述的有机配体L，X为NO3 -、Cl-、Br-或I-。
7.如权利要求6所述的金属有机框架，其特征是，金属有机框架的单晶结晶于单斜晶系，属于P 1 21/c 1空间群，每个不对称单元中均有一个Cd金属中心，每个Cd金属中心均处在变形四面体{CdN4OX}的配位环境中，每个Cd为六配位，每个Cd金属中心与四个不同有机配体L上的N配位，每个有机配体L有两个吡啶上的N、一个咪唑上的N和其中一个酰肼上的N参与配位。
8.一种权利要求6或7所述的Cd(II)的金属有机框架的制备方法，其特征是，将权利要求3所述的有机配体L和CdX2加入至溶剂中混合均匀，加热反应，反应后获得Cd(II)的金属有机框架，即Cd-MOF，其中，X为NO3 -、Cl-、Br-或I-。
9.一种材料，其特征是，包含权利要求6或7所述的金属有机框架。
10.一种权利要求6或7所述的金属有机框架或权利要求9所述的材料在吸附二氧化碳中的应用。
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| CN104718214A (zh) * | 2012-05-31 | 2015-06-17 | 国立科学研究中心 | 具有改性外表面的改善的有机-无机杂化固体 |
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