CN111215149A - 一种MOF@POP-n复合催化剂及其制备方法和应用 - Google Patents
一种MOF@POP-n复合催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种的MOF@POP‑n复合催化剂及其制备方法和应用,属于化学催化材料技术领域。制备方法包括如下步骤:将二溴苄溶于甲苯中得到溶液A,将1‑乙烯基咪唑溶解在甲苯中得溶液B,将溶液A和溶液B均匀混合,在100‑120℃下,N2氛围下加热12‑24h,冷却后过滤,洗涤得到前驱体;将前驱体与二乙烯基苯及MOF加入到含有偶氮二异丁腈的的N,N‑二甲基甲酰胺溶液中,超声15‑45min,在120‑160℃氮气氛围下加热24‑48h,冷却至室温分离得到目标产物。MOF@POP‑n复合催化剂催化环氧丙烷与二氧化碳生成环状碳酸酯产率最高可达98%,重复利用6次时其转化率仍可达90%以上。
Description
技术领域
本发明涉及一种简单高效的MOF@POP-n复合催化剂及其制备方法和应用,属于化学催化材料技术领域。
背景技术
环状碳酸酯作为一种重要的有机溶剂其广泛地应用在碳酸酯聚合物的生产、非质子的极性溶剂、药物和精细化工的中间体和石油添加剂等方面,是重要的化工原料。目前环状碳酸酯的制备方法主要如下:光气法、烯烃直接氧化碳酰化、由CO2环加成环氧化物。光气法中使用到剧毒的光气,目前已经基本淘汰;通过烯烃直接氧化碳酰化可以从烯烃一步制备环状碳酸酯,然而却需要加入贵金属氧化催化剂,增加了成本。
金属-有机骨架(MOFs)材料由于金属节点和配体的几何形状和连通性的丰富性,其结构和拓扑结构可以针对特定功能进行设计和定制。高的比表面积和孔体积,容易调整的孔径,对CO2对高的捕集和吸收,可以作为捕集固定CO2转化为环状碳酸酯的催化剂。POPs是一类多孔材料,它是通过牢固的共价键将纯有机单体(通常是芳族或共轭)连接在一起而形成的。POPs的多种合成可能性允许在分子水平上精确控制其纳米孔结构和表面化学,旨在通过热力学效应提高CO2的吸附能力和对其他气体的选择性。因此选择将MOF和POP通过合理调控结合在一起形成MOF@POP材料进而催化环状碳酸酯的转化。
发明内容
为解决现有催化过程中存在的贵金属催化剂价格昂贵、催化剂易中毒、易造成二次污染等问题,本发明的目的是提供一种MOF@POP-n复合催化剂及其制备方法与应用,通过先制备POP前驱体产物,再制备出MOF壳体材料,然后在利用POP与MOF之间的相互作用,将POP负载到MOF表面,形成一种高效的MOF@POP-n复合催化剂。
本发明采用的技术方案为:一种MOF@POP-n复合催化剂,制备方法包括如下步骤:
1)将二溴苄溶于甲苯中得到溶液A,将1-乙烯基咪唑溶解在甲苯中得溶液B,将溶液A和溶液B均匀混合,在N2氛围下加热进行反应,冷却后过滤,洗涤得到前驱体;
2)将前驱体与二乙烯基苯及MOF壳体材料加入到含有偶氮二异丁腈的N,N-二甲基甲酰胺溶液中,超声15-45min,在120-160℃氮气氛围下加热24-48h,冷却至室温分离得到MOF@POP-n复合催化剂。
优选地,上述的一种MOF@POP-n复合催化剂,步骤1)中,所述二溴苄可以为邻二溴苄、间二溴苄、对二溴苄中任意一种。
优选地,上述的一种MOF@POP-n复合催化剂,步骤1)中,按摩尔比,二溴苄:1-乙烯基咪唑=1:2-2.5。
优选地,上述的一种MOF@POP-n复合催化剂,步骤1)中,所述的反应为在100-120℃下反应12-24h。
优选地,上述的一种MOF@POP-n复合催化剂,步骤2)中,按摩尔比,二乙烯基苯:前驱体为1:1~1:5。
优选地,上述的一种MOF@POP-n复合催化剂,步骤2)中,所述的MOF壳体材料为MOF-74-Zn或MOF-74-Co,制备方法包括如下步骤:
MOF-74-Co的制备:将2,5-二羟基对苯二甲酸和Co(NO3)2·6H2O超声处理溶解于N,N-二甲基甲酰胺-乙醇-水的混合物,转移到衬有特氟龙的不锈钢高压釜中,并将高压釜置于100℃的烘箱中24小时,过滤离心获得MOF-74-Co;
MOF-74-Zn的制备:在搅拌状态下将2,5-二羟基对苯二甲酸和硝酸锌溶解在DMF中,加入去离子水,转移到衬有特氟龙的高压釜中,盖紧瓶盖,放在120℃的烤箱中放置24h,倾析出热的母液后,用DMF彻底洗涤,并将产物浸入无水甲醇中24小时得MOF-74-Zn。
优选地,上述的一种MOF@POP-n复合催化剂,步骤2)中,所述的反应温度为120-160℃,反应时间为24-48h。
上述的一种MOF@POP-n复合催化剂在催化环丙烷与二氧化碳转化成环状碳酸酯中的应用。
优选地,上述的应用,环氧丙烷与MOF@POP-n复合催化剂加入高压反应釜,在1MPa、CO2氛围、80℃下反应12h。
优选地,上述的应用,按摩尔比,环氧丙烷:MOF@POP-n复合催化剂=1:2-2.5。
本发明的有益效果是:
(1)本工艺制备方法简单,原料相对廉价;
(2)采用MOF材料作为载体,其催化活性提高,且不易浸出;
(3)易于回收,可有效减少二次污染,提高其可重复利用性。
附图说明
图1是实施例1制备的MOF-74-Co的FT-IR图。
图2是实施例2制备的MOF@POP-n-1复合催化剂的XRD图。
图3是实施例3制备的MOF@POP-n-2复合催化剂的XRD图。
图4是实施例3制备的MOF@POP-n-3复合催化剂的吸附曲线图。
图5是实施例3制备的MOF@POP-n-3复合催化剂的循环实验收率图。
具体实施方式
实施例1 MOF壳体材料的制备
MOF-74-Co的制备:将0.144g 2,5-二羟基对苯二甲酸和0.713g Co(NO3)2·H2O超声处理溶解于60mL1/1/1(v/v/v)N,N-二甲基甲酰胺-乙醇-水的混合物。然后将透明溶液转移到衬有特氟龙的不锈钢高压釜中,并将高压釜置于100℃的烘箱中24小时,过滤离心获得MOF-74-Co,并对其进行FT-IR测试(图1),其在3850cm-1有羟基的特征峰,证实制备成功。
MOF-74-Zn的制备:在搅拌状态下将2,5-二羟基对苯二甲酸(0.5g,2.6mmol)和硝酸锌(2.0g,7.6mmol)溶解在100ml DMF中。试剂溶解后,加入5ml去离子水。将该溶液转移到衬有特氟龙的高压釜中,盖紧瓶盖,放在120℃的烤箱中放置24h。倾析出热的母液后,将所得物质用DMF彻底洗涤,并将产物浸入无水甲醇中24小时得MOF-74-Zn。
实施例2 MOF@POP-n复合催化剂
1、MOF@POP-n复合催化剂的制备
将6.59g对二溴苄放入20ml甲苯得溶液A,将4.94g1-乙烯基咪唑溶解在20ml甲苯中得溶液B,将溶液A与溶液B混合,并在室温搅拌30min,使搅拌均匀,将上述溶液在120℃下、N2氛围下加热24h,冷却至室温,过滤分离产物,并用甲苯50ml,乙醚50ml洗涤,至滤液无色。后得到前驱体;将1.06g前驱体与487mg二乙烯基苯及400mg MOF-74-Co加入到含有30mg的偶氮二异丁腈的100ml的N,N-二甲基甲酰胺溶液中超声30min,在150℃氮气氛围下加热24h,冷却至室温过滤并用N,N-二甲基甲酰胺、乙醇、乙酸乙酯、乙腈、四氢呋喃洗涤数次,在60-80℃真空干燥12h,得到MOF@POP-n-1,并对其进行XRD测试,如图2所示,可以看出其布拉格衍射峰与MOF-74衍射峰一致,确认制备成功。
2、MOF@POP-n复合催化剂在催化合成环状碳酸酯中的应用
将1.2ml环氧丙烷与60mg MOF@POP-n-1复合材料催化剂加入高压反应釜,在1MPaCO2氛围80℃下反应12h,反应结束后通过GC检测环状碳酸酯产率。在12h时碳酸丙烯酯的收率可达到98%,重复利用第6次时其转化率仍可达到96%。
MOF@POP-n复合材料催化环氧丙烷与二氧化碳合成环状碳酸酯的合成路线如下:
实施例3 MOF@POP-n复合催化剂
1、MOF@POP-n复合催化剂的制备
将6.59g邻二溴苄放入20ml甲苯中得溶液A,将4.94g1-乙烯基咪唑溶解在20ml甲苯中得溶液B,将溶液A与溶液B混合,并在室温搅拌30min,使搅拌均匀,将上述溶液在120℃下N2氛围下加热24h,冷却至室温,过滤分离产物,并用甲苯50ml,乙醚50ml洗涤,至滤液无色。后得到前驱体;将1.06g前驱体与487mg二乙烯苯及400mg MOF-74-Zn加入到含有30mg的偶氮二异丁腈的100ml的N,N-二甲基甲酰胺溶液中超声30min,在150℃氮气氛围下加热24h,冷却至室温过滤并用N,N-二甲基甲酰胺、乙醇、乙酸乙酯、乙腈、四氢呋喃洗涤数次,在60-80℃真空干燥12h,得到MOF@POP-n-2复合材料催化剂。随后对其进行XRD测试,如图3所示,可以看出其布拉格衍射峰与MOF-74衍射峰一致,表明复合材料制备成功,N2吸附测试,如图4所示。可以看出其含有丰富的微孔结构和少量的介孔结构,BET比表面积可以达到623.1645m2/g.
2、MOF@POP-n复合催化剂在催化合成环状碳酸酯中的应用
将1.2ml环氧丙烷与60mg MOF@POP-n-2复合材料催化剂加入高压反应釜,在1MPaCO2氛围80℃下反应12h,反应结束后通过GC检测环状碳酸酯产率。在12h时碳酸丙烯酯的收率可达到97%,重复利用第6次时其转化率仍可达到96%,如图5所示。
实施例4 MOF@POP-n复合催化剂
1、MOF@POP-n复合催化剂的制备
将6.59g对二溴苄放入20ml甲苯得溶液A,将4.94g1-乙烯基咪唑溶解在20ml甲苯中得溶液B,将溶液A与溶液B混合,并在室温搅拌30min,使搅拌均匀,将上述溶液在120℃下N2氛围下加热24h,冷却至室温,过滤分离产物,并用甲苯50ml,乙醚50ml洗涤,至滤液无色。后得到前驱体;将1.06g前驱体与487mg二乙烯苯及600mg MOF-74-Co加入到含有30mg的偶氮二异丁腈的100ml的N,N-二甲基甲酰胺溶液中超声30min,在150℃氮气氛围下加热24h,冷却至室温过滤并用N,N-二甲基甲酰胺、乙醇、乙酸乙酯、乙腈、四氢呋喃洗涤数次,在60-80℃真空干燥12h,得到MOF@POP-n-3复合材料催化剂。
2、MOF@POP-n复合催化剂在催化合成环状碳酸酯中的应用
将1.2ml环氧丙烷与60mg MOF@POP-n-3复合材料催化剂加入高压反应釜,在1MPaCO2氛围80℃下反应12h,反应结束后通过GC检测环状碳酸酯产率。在12h时碳酸丙烯酯的收率可达到98%,重复利用第6次时其转化率仍可达到94%。
实施例5 MOF@POP-n复合催化剂
1、MOF@POP-n复合催化剂的制备
将6.59g间二溴苄放入20ml甲苯得溶液A,将4.94g1-乙烯基咪唑溶解在20ml甲苯中得溶液B,将溶液A与溶液B混合,并在室温搅拌30min,使搅拌均匀,将上述溶液在120℃下N2氛围下加热24h,冷却至室温,过滤分离产物,并用甲苯50ml,乙醚50ml洗涤,至滤液无色。后得到前驱体;将1.06g前驱体与487mg二乙烯苯及600mg MOF-74-Zn加入到含有30mg的偶氮二异丁腈的100ml的N,N-二甲基甲酰胺溶液中超声30min,在150℃氮气氛围下加热24h,冷却至室温过滤并用N,N-二甲基甲酰胺、乙醇、乙酸乙酯、乙腈、四氢呋喃洗涤数次,在60-80℃真空干燥12h,得到MOF@POP-n-4复合材料催化剂。
2、MOF@POP-n复合催化剂在催化合成环状碳酸酯中的应用
将1.2ml环氧丙烷与60mg MOF@POP-n-4复合材料催化剂加入高压反应釜,在1MPaCO2氛围80℃下反应12h,反应结束后通过GC检测环状碳酸酯产率。在12h时碳酸丙烯酯的收率可达到97%,重复利用第6次时其转化率仍可达到95%。
Claims (10)
1.一种MOF@POP-n复合催化剂,其特征在于,制备方法包括如下步骤:
1)将二溴苄溶于甲苯中得到溶液A,将1-乙烯基咪唑溶解在甲苯中得溶液B,将溶液A和溶液B均匀混合,在N2氛围下加热进行反应,冷却后过滤,洗涤得到前驱体;
2)将前驱体与二乙烯基苯及MOF壳体材料加入到含有偶氮二异丁腈的N,N-二甲基甲酰胺溶液中,超声15-45min,在氮气氛围下加热进行反应,冷却至室温分离得到MOF@POP-n复合催化剂。
2.根据权利要求1所述的一种MOF@POP-n复合催化剂,其特征在于,步骤1)中,所述二溴苄可以为邻二溴苄、间二溴苄、对二溴苄中任意一种。
3.根据权利要求1所述的一种MOF@POP-n复合催化剂,其特征在于,步骤1)中,按摩尔比,二溴苄:1-乙烯基咪唑=1:2-2.5。
4.根据权利要求1所述的一种MOF@POP-n复合催化剂,其特征在于,步骤1)中,所述的反应为在100-120℃下反应12-24h。
5.根据权利要求1所述的一种MOF@POP-n复合催化剂,其特征在于,步骤2)中,按摩尔比,二乙烯基苯:前驱体为1:1~1:5。
6.根据权利要求1所述的一种MOF@POP-n复合催化剂,其特征在于,步骤2)中,所述的MOF壳体材料为MOF-74-Zn或MOF-74-Co,制备方法包括如下步骤:
MOF-74-Co的制备:将2,5-二羟基对苯二甲酸和Co(NO3)2·6H2O超声处理溶解于N,N-二甲基甲酰胺-乙醇-水的混合物,转移到衬有特氟龙的不锈钢高压釜中,并将高压釜置于100℃的烘箱中24小时,过滤离心获得MOF-74-Co;
MOF-74-Zn的制备:在搅拌状态下将2,5-二羟基对苯二甲酸和硝酸锌溶解在DMF中,加入去离子水,转移到衬有特氟龙的高压釜中,盖紧瓶盖,放在120℃的烤箱中放置24h,倾析出热的母液后,用DMF彻底洗涤,并将产物浸入无水甲醇中24小时得MOF-74-Zn。
7.根据权利要求1所述的一种MOF@POP-n复合催化剂,其特征在于,步骤2)中,所述的反应温度为120-160℃,反应时间为24-48h。
8.权利要求1所述的一种MOF@POP-n复合催化剂在催化环丙烷与二氧化碳转化成环状碳酸酯中的应用。
9.根据权利要求8所述的应用,其特征在于,环氧丙烷与MOF@POP-n复合催化剂加入高压反应釜,在1MPa、CO2氛围、80℃下反应12h。
10.根据权利要求9所述的应用,其特征在于,按摩尔比,环氧丙烷:MOF@POP-n复合催化剂=1:2-2.5。
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