CN112403525A - 一种具有配体分子內异面结构的金属有机框架催化剂的制备方法及其应用 - Google Patents
一种具有配体分子內异面结构的金属有机框架催化剂的制备方法及其应用 Download PDFInfo
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Abstract
本发明属于光催化材料技术领域,一种具有配体分子內异面结构的金属有机框架催化剂的制备方法及其应用,其中制备方法:是以带有二甲基吡唑配位基团的萘二亚酰胺的配体H2NDI与金属铜盐中的Cu1+作为节点,通过溶剂热法制得具有配体分子內异面结构的金属有机框架催化剂,其合成路线如下:H2NDI+Cu1+→Cu‑NDI,本发明制备的具有配体分子內异面结构的金属有机框架催化剂Cu‑NDI,得益于受控的自金属中心至配体的电子转移过程,实现了对缺电子烯烃的溴化苯基化双官能化反应,而均相催化剂在此反应中则没有展现出反应性。
Description
技术领域
本发明涉及一种具有配体分子內异面结构的金属有机框架催化剂的制备方法及其应用,属于光催化材料技术领域。
背景技术
自2012年同年报道一价Cu-菲咯啉双膦配合物光催化环化和在无钯条件下使用光活化的一价铜-炔烃配合物催化进行Sonogashira偶联以来,涉及一价铜和二价铜的配合物作为有效可见光光催化剂的研究激增。铜在光催化氧化还原反应中有诸多优点。其氧化还原性能高度可调节,可实现多种类型反应的实现。可以使用不同的配体调节其性能,包括含N,S,羧酸配体等。其易于结合亲核试剂并转移。铜表现出持久的自由基效应,由可见光诱导的光催化循环产生的有机自由基中间体可被铜中心有效地捕获并得到稳定。使用铜配合物实现的各种双官能团化近年来已成为研究热点,其主要使用金属铜和光敏基团配合物进行底物的催化官能团化,具有可替代贵金属,配体选择性广,易合成,选择性高,反应性高的优点。然而,其也存在局限性,均相介质中进行的光反应,因成分不固定,溶液相中不受控制的碰撞往往会淬灭发色团的激发态并减少金属中心的的活性位点。因此,将光还原性染料和铜离子以均相模式直接结合需要一种替代方式。金属有机框架的可修饰性和长程有序性利于在分子层面实现光中心与过渡金属中心距离、朝向、连接方式的有效和均一的调控。将金属有机框架用于光催化可保证金属中心和光敏剂各司其职,避免不必要的电子传递,例如还原性光敏剂受光激发后将电子传递给高价金属。据文献报道分子内扭曲异面可将配体-金属电子通路断开,染料受光激发后电子不易回传,避免发生内部淬灭,同时金属离子与激发态配体之间的扭曲共轭增强了PET生成底物自由基过程中的光子能量利用效率,与未隔断的情况相比反应效率更高,保证电子按照我们的需求而传递给待活化分子。如果将光敏剂分子与过渡金属中心固定在非均相的金属有机框架中,并利用扭曲异面结构将其隔离开,有望维持金属中心和光敏剂两者各自的功能,并实现二者的耦合,提高反应性能。
发明内容
为了克服现有技术中存在的不足,本发明目的是提供一种具有配体分子內异面结构的金属有机框架催化剂的制备方法及其应用。在所制得的具有配体分子內异面结构的金属有机框架内,相互连接的体系允许催化过程中的一价铜中心将电子传递至激发态的光催化中心,避免了光催化中心的失活,而光催化还原态向二价铜催化中心的电子回传过程受到抑制,从而可以有效地协同光催化和过渡金属铜催化循环过程,提升催化效率;金属有机框架材料的非均相特性有利于催化剂的回收。
为了实现上述发明目的,解决已有技术中所存在的问题,本发明采取的技术方案是:以带有二甲基吡唑配位基团的萘二亚酰胺配体H2NDI与金属铜盐中的 Cu1+作为节点,通过溶剂热法制得具有配体分子內异面结构的金属有机框架催化剂,其合成路线如下:
H2NDI+Cu1+→Cu-NDI;
所述金属铜盐选自氯化亚铜、碘化亚铜、溴化亚铜或三氟甲烷磺酸亚铜甲苯联合体中的一种;
所述配体H2NDI,分子式为C24H18N6O4,具有如下(A)分子结构式,
所述Cu-NDI的制备方法,包括以下步骤:
步骤1、将15~20g乙酰丙酮添加到80~100mL去离子水中,再加入15~18mL 摩尔浓度为12mol/L的浓盐酸,然后在冰浴中搅拌,再将10~14g饱和亚硝酸钠溶液滴入上述溶液中,静置20~23min,打开搅拌,将12~15g摩尔浓度为17mol/L的水合肼加入反应中,形成蓝色沉淀物,继续添加80~100mL乙醇直至蓝色沉淀完全溶解,然后将pH值调至中性,再将12~15g摩尔浓度为17mol/L的水合肼滴加到上述溶液中,保持反应温度80~85℃下5~6小时,直至反应溶液变成金黄色,最后,蒸发溶剂,并将产物用乙醇洗涤3~5次,然后通过过滤收集并在60~65℃下干燥,得到白色粉末;
步骤2、将1,4,5,8-萘四甲酸二酐与步骤1所制得的白色粉末按1:2~3的摩尔比装入干燥的Schlenk烧瓶中,在氮气氛围下加入40~60mL无水N,N-二甲基甲酰胺溶液,在快速搅拌中将反应混合物在115~125℃下加热10~12h,再将烧瓶冷却至室温后的深棕色反应混合物溶液倒入140~160mL乙醚中搅拌,通过过滤分离出黄色固体,将其从体积比为1:2~3:2~4的水、N,N-二甲基甲酰胺及乙醚的溶液中重结晶,最后将产物过滤并在70~75℃下真空干燥,得到浅黄色晶体,即配体H2NDI;
步骤3、将步骤2所制得的H2NDI配体与金属铜盐按照1:2~5的摩尔比溶解于盛有4~6mL N,N-二甲基甲酰胺溶液的玻璃小瓶中,压盖密封,置于高压釜中,经过 4~5h的升温,使温度升至110~120℃并保持24~30h,最后经过8~10h降温至室温,得到黄色棱形晶体,即目标材料具有配体分子內异面结构的金属有机框架催化剂 Cu-NDI。
所述方法制备的具有配体分子內异面结构的金属有机框架催化剂在光催化烯烃溴化芳基化双官能团化反应中的应用。
本发明有益效果是:一种具有配体分子內异面结构的金属有机框架催化剂的制备方法及其应用,其中制备方法:是以带有二甲基吡唑配位基团的萘二亚酰胺配体H2NDI与金属铜盐中的Cu1+作为节点,通过溶剂热法制得具有配体分子內异面结构的金属有机框架催化剂,其合成路线如下:
H2NDI+Cu1+→Cu-NDI;
所述方法制备的具有配体分子內异面结构的金属有机框架催化剂Cu-NDI与现有技术相比,Cu-NDI中的光敏中心与二价铜催化中心得到了更好的隔离,激发态的光敏剂和二价铜催化中心在光激发下都能够得到很好的保持,Cu-NDI具有较好的单相电子导通性质,可以更好的协同光催化循环和铜催化循环,高效地实现了光催化烯烃溴化芳基化双官能团化反应,采用该方法制备的铜基金属有机框架催化剂原料价格低廉,得到的金属有机框架化合物化学性质稳定。
附图说明
图1是实施例1制得的配体H2NDI的核磁共振波谱图。
图2是实施例1制得的配体H2NDI的紫外可见吸收光谱图。
图3是实施例1目标材料Cu-NDI的晶体结构示意图。
图4是实施例1目标材料Cu-NDI的循环伏安曲线图。
图5是实施例1目标材料Cu-NDI的固体紫外吸收光谱图。
图6是实施例5催化产物的核磁共振波谱图。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例1
将20g乙酰丙酮添加到100mL去离子水中,再加入18mL摩尔浓度为12mol/L的浓盐酸,然后在冰浴中搅拌。再将14g饱和亚硝酸钠溶液滴入上述溶液中,静置20 min。打开搅拌,将12g摩尔浓度为17mol/L的水合肼加入反应中,形成蓝色沉淀物。继续添加100mL乙醇直至蓝色沉淀完全溶解,然后将pH值调至中性。再将13.5g摩尔浓度为17mol/L的水合肼滴加到上述溶液中,保持反应温度80℃下5h,直至反应溶液变成金黄色。最后,蒸发溶剂,并将产物用乙醇洗涤3次,然后通过过滤收集并在60℃下干燥,得到白色粉末15g,产率67%。
称取上述白色粉末(0.75g,6.8mmol)与1,4,5,8-萘四甲酸二酐(0.86g,3.2 mmol)装入干燥的Schlenk烧瓶中,在氮气氛围下加入50mL无水N,N-二甲基甲酰胺溶液。在快速搅拌中将反应混合物在120℃下加热12h,再将烧瓶冷却至室温后的深棕色反应混合物溶液倒入150mL乙醚中搅拌。通过过滤分离出黄色固体,将其从体积比为5mL:15mL:10mL的水、N,N-二甲基甲酰胺及乙醚的溶液中重结晶。最后将产物过滤并在70℃下真空干燥,得到浅黄色晶体,即配体H2NDI 1.1g,产率75%。核磁共振波谱图,如图1所示,紫外可见吸收光谱图,如图2所示。
称取H2NDI配体(6.0mg,0.011mmol)与碘化亚铜(8.0mg,0.042mmol) 溶解于盛有5mLN,N-二甲基甲酰胺溶液的玻璃小瓶中,压盖密封,置于高压釜中,经过4h的升温,使温度升至120℃并保持24h,最后经过8h降温至室温,得到黄色棱形晶体,即目标材料具有配体分子內异面结构的金属有机框架催化剂Cu-NDI 8.1mg,产率84%,晶体结构示意图,如图3所示。循环伏安曲线图,如图4所示。固体紫外吸收光谱图,如图5所示。
实施例2
称取H2NDI配体(6.0mg,0.011mmol)与氯化亚铜(4.2mg,0.042mmol),溶解于盛有5mL N,N-二甲基甲酰胺溶液的玻璃小瓶中,压盖密封,置于高压釜中,经过4h的升温,使温度升至120℃并保持24h,最后经过8h降温至室温,得到黄色棱形晶体,即目标材料具有配体分子內异面结构的金属有机框架催化剂Cu-NDI 6.2mg,产率64%。
实施例3
称取H2NDI配体(6.0mg,0.011mmol)与溴化亚铜(5.7mg,0.04mmol),溶解于盛有5mL N,N-二甲基甲酰胺溶液的玻璃小瓶中,压盖密封,置于高压釜中,经过4h的升温,使温度升至120℃并保持24h,最后经过8h降温至室温,得到黄色棱形晶体,即目标材料具有配体分子內异面结构的金属有机框架催化剂Cu-NDI 5.5mg,产率57%。
实施例4
称取H2NDI配体(6.0mg,0.011mmol)与三氟甲烷磺酸亚铜甲苯联合体 (15.5mg,0.03mmol)溶解于盛有5mLN,N-二甲基甲酰胺溶液的玻璃小瓶中,压盖密封,置于高压釜中,经过4h的升温,使温度升至110℃并保持30h,最后经过 10h降温至室温,得到黄色棱形晶体,即目标材料具有配体分子內异面结构的金属有机框架催化剂Cu-NDI 5.8mg,产率60%。
实施例5
利用化合物Cu-NDI催化甲基丙烯酸苄基酯与4’-溴苯乙酮进行光催化溴化苯基化双官能团化反应。向光催化管中,依次加入4’-溴苯乙酮(120mg,0.6mmol)、甲基丙烯酸苄基酯(35.2mg,0.2mmol)、3mL的干燥乙腈溶液、2,4,6-三甲基吡啶(48 mg,0.4mmol)及金属有机框架催化剂Cu-NDI(10mg,0.01mmol)并使用氩气置换反应体系气体三次,在波长365nm光源辐照下40℃恒温反应12h;将反应液用乙酸乙酯稀释后并用水洗涤、干燥、浓缩,通过薄层层析分离产物,通过核磁表征双官能团化产物产率为87%。催化产物的核磁共振波谱图,如图6所示。
实施例6
利用化合物Cu-NDI催化甲基丙烯酸苄基酯与4’-卤苯类衍生物进行光催化溴化苯基化双官能团化反应的底物拓展。向光催化管中,依次加入摩尔量为0.6mmol 的4’-卤苯类衍生物、甲基丙烯酸苄基酯(35.2mg,0.2mmol)、3mL的干燥乙腈溶液、 2,4,6-三甲基吡啶(48mg,0.4mmol)及化合物Cu-NDI(10mg,0.01mmol)并使用氩气置换反应体系气体三次,在波长365nm光源辐照下40℃恒温反应12h;将反应液用乙酸乙酯稀释后并用水洗涤、干燥、浓缩,通过薄层层析分离产物,通过核磁表征双官能团化产物产率。催化反应的底物拓展,如表1所示。
表1
Claims (2)
1.一种具有配体分子內异面结构的金属有机框架催化剂的制备方法,其特征在于:是以带有二甲基吡唑配位基团的萘二亚酰胺的配体H2NDI与金属铜盐中的Cu1+作为节点,通过溶剂热法制得具有配体分子內异面结构的金属有机框架催化剂,其合成路线如下:
H2NDI+Cu1+→Cu-NDI;
所述金属铜盐选自氯化亚铜、碘化亚铜、溴化亚铜或三氟甲烷磺酸亚铜甲苯联合体中的一种;
所述带有二甲基吡唑配位基团的萘二亚酰胺配体H2NDI,分子式为C24H18N6O4,具有如下(A)分子结构式,
所述Cu-NDI的制备方法,包括以下步骤:
步骤1、将15~20g乙酰丙酮添加到80~100mL去离子水中,再加入15~18mL摩尔浓度为12mol/L的浓盐酸,然后在冰浴中搅拌,再将10~14g饱和亚硝酸钠溶液滴入上述溶液中,静置20~23min,打开搅拌,将12~15g摩尔浓度为17mol/L的水合肼加入反应中,形成蓝色沉淀物,继续添加80~100mL乙醇直至蓝色沉淀完全溶解,然后将pH值调至中性,再将12~15g摩尔浓度为17mol/L的水合肼滴加到上述溶液中,保持反应温度80~85℃下5~6小时,直至反应溶液变成金黄色,最后,蒸发溶剂,并将产物用乙醇洗涤3~5次,然后通过过滤收集并在60~65℃下干燥,得到白色粉末;
步骤2、将1,4,5,8-萘四甲酸二酐与步骤1所制得的白色粉末按1:2~3的摩尔比装入干燥的Schlenk烧瓶中,在氮气氛围下加入40~60mL无水N,N-二甲基甲酰胺溶液,在快速搅拌中将反应混合物在115~125℃下加热10~12h,再将烧瓶冷却至室温后的深棕色反应混合物溶液倒入140~160mL乙醚中搅拌,通过过滤分离出黄色固体,将其从体积比为1:2~3:2~4的水、N,N-二甲基甲酰胺及乙醚的溶液中重结晶,最后将产物过滤并在70~75℃下真空干燥,得到浅黄色晶体,即配体H2NDI;
步骤3、将步骤2所制得的H2NDI配体与金属铜盐按照1:2~5的摩尔比溶解于盛有4~6mLN,N-二甲基甲酰胺溶液的玻璃小瓶中,压盖密封,置于高压釜中,经过4~5h的升温,使温度升至110~120℃并保持24~30h,最后经过8~10h降温至室温,得到黄色棱形晶体,即目标材料具有配体分子內异面结构的金属有机框架催化剂Cu-NDI。
2.根据权利要求1所述方法制备的具有配体分子內异面结构的金属有机框架催化剂在光催化烯烃溴化芳基化双官能团化反应中的应用。
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