CN109174189B - 基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料及其制备方法和应用 - Google Patents
基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种基于PCN‑222‑Co@TpPa‑1的多孔结晶核壳杂化材料及其制备方法和应用。采用的技术方案是：将PCN‑222‑Co，对苯二胺(Pa‑1)，2,4,6‑三甲酰基均苯三酚(Tp)，溶剂为均三甲苯和1,4‑二氧六环，超声处理；将容器密封室温放置3天得到深红色物质；用无水丙酮洗涤、过滤、干燥，得到目标产物。本发明所制备的PCN‑222‑Co@TpPa‑1的多孔结晶核壳杂化材料制备方法简单，并且对deacetalization‑Knoevenagel反应展示出良好的催化性能。
Description
技术领域
本发明涉及的是一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料，具体的说，涉及一种催化deacetalization-Knoevenagel反应的多孔结晶杂化材料的制备及其应用。
背景技术
金属有机骨架材料(MOFs)是由金属离子和有机配体或团簇通过配位键形成的多孔结晶材料。类似地，共价有机骨架材料(COFs)是由有机单元通过共价键构筑而成的多孔结晶聚合物。由于两类材料均有高比表面积、可调孔结构和多功能性，引起研究者的广泛兴趣。最近将MOF和COF杂化制备新型多孔MOF@COF杂化材料成为研究热点，新加坡南洋理工大学张华教授课题组在Advanced Materials期刊上报道了一种制备多孔材料MOF@COF杂化材料的新策略。首次报道了一种新型方法，用于制备MOF@COF核壳结构杂化材料，其在光催化分解污染物领域显示出良好的性能。之后，Dong-Pyo Kim课题组在Advanced Materials期刊上报道了一篇制备金属掺杂的核壳MOFs@COF杂化材料的方法，并且其对串联脱氢和加氢反应具有优异的光催化性。由于MOF和COF两种晶态材料优异的性质，制备新型MOF-COF杂化材料以及该类材料在物质分离、异相催化、电子器件等领域的应用将成为今后研究的热点。
串联反应是一种经济、有效和环境友好型的化学方法，已经吸引了广大化学研究者的兴趣。串联反应常指的是两步或两步以上的反应连续发生，无需分离中间产物而直接得到最终产物的一连串反应，能够有效地减少化学物质的使用和污染物的排放。因此，在有机催化领域，串联反应的发展必然会成为一个新的发展方向。
发明内容
本发明的目的是提供一种新型多孔MOF@COF杂化材料——基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料，并研究其作为Lewis酸和
碱双功能催化剂对deacetalization-Knoevenagel反应的催化性能。
本发明采用的技术方案是：一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料，是以PCN-222(Co)为核，对苯二胺(Pa-1)与2,4,6-三甲酰基均苯三酚(Tp)反应生成的共价有机骨架材料为壳，在室温下合成的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料。
上述的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料，其晶体属于四方晶系，空间群为P6/mmm。
一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料的制备方法，包括如下步骤：将PCN-222(Co)、对苯二胺(Pa-1)、均三甲苯和1,4-二氧六环加入到容器内，于常温下超声溶解后，加入2,4,6-三甲酰基均苯三酚(Tp)，继续超声30～60min后，将容器密封，于室温下静置保持3天后，用丙酮洗涤，过滤，干燥，得目标产物。
优选的，上述的一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料的制备方法，所述的PCN-222(Co)的制备方法包括如下步骤：将ZrCl4、钴卟啉(TCPP-Co)、乙酸、DMF和H2O混合均匀，于393K下加热搅拌10-20分钟，缓慢冷却到室温，离心，乙醇洗涤，得PCN-222(Co)。
优选的，上述的一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料的制备方法，按摩尔比，PCN-222(Co):对苯二胺(Pa-1)＝1:1.0～1.5。
优选的，上述的一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料的制备方法，按摩尔比，对苯二胺(Pa-1):2,4,6-三甲酰基均苯三酚(Tp)＝1:1.0～1.6。
本发明的PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料，结构中含有丰富的不饱和的Zr(Ⅳ)、Co(III)中心和亚氨键，可作为Lewis酸和
碱双功能催化剂催化deacetalization-Knoevenagel反应。方法如下：取苯甲醛二甲缩醛、丙二腈、二甲基亚砜和催化剂于反应管中，在搅拌的条件下通入N2，在60℃的条件下反应20h；所述的催化剂是上述的PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料。反应式如下：
本发明的有益效果是：本发明制备的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料中，含有丰富的不饱和的Zr(Ⅳ)、Co(III)中心，可作为Lewis酸位点，而且希夫碱配体上含有亚氨键，可以作为
碱位点。因此，可以使PCN-222(Co)@TpPa-1作为Lewis酸和
碱双功能催化剂催化deacetalization-Knoevenagel反应，结果表明PCN-222(Co)@TpPa-1展示出很好的催化性能。本发明所制备的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料合成方法简单，具有广阔的应用前景。
附图说明
图1是本发明PCN-222(Co)@TpPa-1多孔结晶核壳杂化材料的PXRD谱图。
图2是本发明PCN-222(Co)@TpPa-1多孔结晶核壳杂化材料的FT-IR谱图。
图3是本发明PCN-222(Co)@TpPa-1多孔结晶核壳杂化材料的SEM与TEM谱图；
其中，a:PCN-222(Co)的SEM谱图；b:TpPa-1的SEM谱图；c:PCN-222(Co)@TpPa-1杂化材料SEM谱图；d:PCN-222(Co)@TpPa-1杂化材料的TEM谱图。
图4是本发明PCN-222(Co)@TpPa-1多孔结晶核壳杂化材料N2 sorptionisotherms谱图。
图5是实施例2反应的产率随时间变化的核磁共振氢谱图。
图6是本发明PCN-222(Co)@TpPa-1多孔结晶核壳杂化材料进行四轮循环催化反应的催化活性。
图7是本发明PCN-222(Co)@TpPa-1多孔结晶核壳杂化材料进行四轮循环催化反应的PXRD图。
具体实施方式
实施例1一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料(一)制备方法如下
1)PCN-222(Co)的制备
于容器中，将1.0g ZrCl4、1.0g钴卟啉(TCPP-Co)、12mL乙酸、200mL DMF和5mL H2O混合均匀，于393K下加热搅拌15分钟，缓慢冷却到室温，离心，乙醇洗涤，得PCN-222(Co)。
2)PCN-222(Co)@TpPa-1的制备
将48mg PCN-222(Co)和48mg对苯二胺(Pa-1)加入到体积为5mL的小瓶中，加入1.5mL均三甲苯和1.5mL 1,4-二氧六环，室温下，超声1小时，使对苯二胺均匀的分布在PCN-222(Co)表面，之后加入72mg 2,4,6-三甲酰基均苯三酚(Tp)，继续超声30～60min。最后将小瓶密封，室温下静置3天，三天后用丙酮洗涤，过滤，干燥，得到目标产物，即基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料，产率为80％。
(二)检测
1、由图1可见，通过X射线粉末衍射(PXRD)证实PCN-222(Co)@TpPa-1杂化材料被成功合成，PCN-222(Co)@TpPa-1杂化材料的衍射峰与PCN-222(Co)和TpPa-1的衍射峰一致。由于TpPa-1峰强度较弱，PCN-222(Co)@TpPa-1杂化材料表现出类似PCN-222(Co)峰型结构。
2、由图2可见，FT-IR光谱显示，PCN-222(Co)@TpPa-1杂化材料的典型特征峰与PCN-222(Co)或TpPa-1的特征峰值类似。如在1604cm-1和1416cm-1特征峰来源于PCN-222(Co)羧基的对称和非对称拉伸振动，1255cm-1和1578cm-1特征峰来源于TpPa-1的C-N与C＝C伸缩振动，其结果表明PCN-222(Co)@TpPa-1杂化材料被成功合成。
3、通过扫描电镜(SEM)和透射电镜(TEM)研究了PCN-222(Co)@TpPa-1复合材料的形貌。扫描电镜显示，PCN-222(Co)为柱形结晶，其表面光滑，TpPa-1为片状形态。当PCN-222(Co)表面长出类似于片状的TpPa-1时，原始的PCN-222(Co)表面变得粗糙。TEM图像分析显示，PCN-222(Co)表面涂有TpPa-1层，厚度约为25nm。
4、由图4可见，采用BET法通过N2吸附-解吸的方法测定了PCN-222(Co)@TpPa-1杂合材料的孔隙特征，结果表明PCN-222(Co)@TpPa-1杂合材料显示微孔性质且比表面积为484m2g-1。
如图1-图3可见，本发明合成的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料，该晶体结构属于四方晶系，空间群为P6/mmm。其是以PCN-222(Co)为核，对苯二胺(Pa-1)与2,4,6-三甲酰基均苯三酚(Tp)反应生成的共价有机骨架为壳，利用室温合成的方法构筑出一种新型的基于PCN-222(Co)@TpPa-的多孔结晶核壳杂化材料。
实施例2
(一)以实施例1制备的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料作为催化剂对deacetalization-Knoevenagel反应进行催化。
方法如下：
1)催化剂的活化处理：取一定量的实施例1制备的PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料，在298K加热条件下抽真空干燥24小时。
2)方法：取50mg的活化后的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料、2.0mmol的苯甲醛二甲缩醛、2.1mmol丙二腈、2mL二甲基亚砜到10mL的反应管中，通入N2，温度为60℃，反应时间为20h。反应式如下：
(二)检测
1、如图5所示，在该反应进行的过程中，该基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料对deacetalization-Knoevenagel反应的催化性能的实验结果用核磁共振氢谱检测，进行不同时间段的监测，随着反应时间的增长，该反应的产率逐渐增加，当反应进行到20h的时候，该反应的转化率已经达到最大为97.3％。
2、Deacetalization-Knoevenagel反应中催化剂的可回收再利用性
催化剂的回收：反应结束后，过滤，将催化剂与反应混合物分离，用甲醇洗涤，再在甲醇中浸泡4小时，滤出，烘干。
循环实验的具体操作：利用回收的催化剂催化deacetalization-Knoevenagel反应，在60℃下反应20h。
如图6和图7所示，循环实验进行到第4轮，催化剂的活性仍然没有下降。说明本发明的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料作为deacetalization-Knoevenagel反应催化剂可循环利用。
Claims (8)
1.一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料，其特征在于，是以PCN-222(Co)为核，对苯二胺Pa-1与2,4,6-三甲酰基均苯三酚Tp反应生成的共价有机骨架材料为壳，构筑的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料。
2.根据权利要求1所述的一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料，其特征在于，所述的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料，其晶体属于四方晶系，空间群为P6/mmm。
3.一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料的制备方法，其特征在于，包括如下步骤：将PCN-222(Co)、对苯二胺Pa-1、均三甲苯和1,4-二氧六环加入到容器内，于常温下超声溶解后，加入2,4,6-三甲酰基均苯三酚Tp，继续超声30～60min后，将容器密封，于室温下静置保持3天后，用丙酮洗涤，过滤，干燥，得目标产物。
4.根据权利要求3所述的一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料的制备方法，其特征在于，所述的PCN-222(Co)的制备方法包括如下步骤：将ZrCl4、钴卟啉TCPP-Co、乙酸、DMF和H2O混合均匀，于393 K下加热搅拌10-20分钟，缓慢冷却到室温，离心，乙醇洗涤，得PCN-222(Co)。
5.根据权利要求3所述的一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料的制备方法，其特征在于，按摩尔比，PCN-222(Co):对苯二胺Pa-1＝1 : 1.0～1.5。
6.根据权利要求3所述的一种基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料的制备方法，其特征在于，按摩尔比，对苯二胺Pa-1: 2,4,6-三甲酰基均苯三酚Tp＝1 : 1.0～1.6。
7.权利要求1或2所述的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料作为催化剂在催化deacetalization-Knoevenagel反应中的应用。
8.根据权利要求7所述的应用，其特征在于，方法如下：取苯甲醛二甲缩醛、丙二腈、二甲基亚砜和催化剂于反应管中，在搅拌的条件下通入N2，在60 ℃的条件下反应20 h；所述的催化剂是权利要求1或2所述的基于PCN-222(Co)@TpPa-1的多孔结晶核壳杂化材料。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574886A (zh) * | 2009-06-19 | 2012-07-11 | 加利福尼亚大学董事会 | 有机金属骨架和其制造方法 |
| KR20160005218A (ko) * | 2014-07-04 | 2016-01-14 | 인천대학교 산학협력단 | 금속 유기 골격체를 이용한 저온 일산화탄소 산화반응 촉매 |
| CN107349961A (zh) * | 2017-06-27 | 2017-11-17 | 哈尔滨理工大学 | 一种NH2‑UIO‑66@TpPa‑1复合材料的制备及光解水制氢 |
| CN107720720A (zh) * | 2016-08-10 | 2018-02-23 | 中国科学院大连化学物理研究所 | 基于共价有机框架材料的多孔碳的制备方法及多孔碳材料 |
| CN108273555A (zh) * | 2018-01-12 | 2018-07-13 | 辽宁大学 | 一种基于UiO-66@SNW-1的多孔结晶核壳杂化材料及其制备方法和应用 |
| CN108452771A (zh) * | 2018-02-14 | 2018-08-28 | 中山大学 | MOF衍生的碳基光子晶体-含卟啉的COFs复合材料及其制备方法和应用 |
-
2018
- 2018-09-07 CN CN201811044684.XA patent/CN109174189B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574886A (zh) * | 2009-06-19 | 2012-07-11 | 加利福尼亚大学董事会 | 有机金属骨架和其制造方法 |
| KR20160005218A (ko) * | 2014-07-04 | 2016-01-14 | 인천대학교 산학협력단 | 금속 유기 골격체를 이용한 저온 일산화탄소 산화반응 촉매 |
| CN107720720A (zh) * | 2016-08-10 | 2018-02-23 | 中国科学院大连化学物理研究所 | 基于共价有机框架材料的多孔碳的制备方法及多孔碳材料 |
| CN107349961A (zh) * | 2017-06-27 | 2017-11-17 | 哈尔滨理工大学 | 一种NH2‑UIO‑66@TpPa‑1复合材料的制备及光解水制氢 |
| CN108273555A (zh) * | 2018-01-12 | 2018-07-13 | 辽宁大学 | 一种基于UiO-66@SNW-1的多孔结晶核壳杂化材料及其制备方法和应用 |
| CN108452771A (zh) * | 2018-02-14 | 2018-08-28 | 中山大学 | MOF衍生的碳基光子晶体-含卟啉的COFs复合材料及其制备方法和应用 |
Non-Patent Citations (2)
| Title |
|---|
| Hybridization of MOFs and COFs: A New Strategy for Construction of MOF@COF Core–Shell Hybrid Materials;Yongwu Peng et al.;《Advanced Materials》;20171114;第1-5页 * |
| Rational Design of MOF/COF Hybrid Materials for Photocatalytic H2 Evolution in the Presence of Sacrificial Electron Donors;Feng-Ming Zhang et al.;《Angewandte Chemie International Edition》;20180807;第12106-12110页 * |
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