CN116689034A - 含有Cu(I)的MOF催化剂及催化制备环状碳酸酯类化合物的应用 - Google Patents
含有Cu(I)的MOF催化剂及催化制备环状碳酸酯类化合物的应用 Download PDFInfo
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
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Abstract
本发明公开了一种含有Cu(I)的MOF催化剂,该催化剂为以均苯三甲酸为模版前体化合物制得的含有Cu(I)活性位点的金属‑有机骨架结构催化剂。本发明同时公开了一种含有上述催化剂的催化体系,同时本发明还公开了一种制备环状碳酸酯类化合物的方法。本发明提供的催化体系具有良好的催化活性,并获得了较高的α‑亚烷基环碳酸酯收率;通过循环测试证明,[CuI]‑Cu‑BTC/[Emim][OAc]体系在反应后易于分离,可重复使用至少5次且催化活性无明显降低。
Description
技术领域
本发明属于化学化工领域,具体涉及一种含有Cu(I)的MOF催化剂及催化制备环状碳酸酯类化合物的应用。
背景技术
化石燃料的过度消耗已经导致了严重的能源危机和环境问题,同时也加速了大气中二氧化碳(CO2)的积累。CO2作为一种绿色、无毒、廉价、可再生的C1资源。然而,CO2具有两个正交的大π键,是一种高度氧化、热力学稳定和动力学惰性分子,这使得将CO2转化为其他高附加价值精细化学产品通常需要强碱、有机溶剂、贵金属等传统催化剂和苛刻的反应条件。因此,实现在温和条件下对CO2的化学转化利用对低碳和可持续发展具有重要意义。
环状碳酸酯是优良的极性有机溶剂和有机中间体,在医疗制药、萃取、电化学、高分子合成等方面有着广泛应用。利用光气、烯烃、二醇等为原料合成环状碳酸酯的方法存在着安全、环保、经济成本等方面的问题。所以,以炔醇和CO2为原料一步合成环状碳酸酯的方法由于其绿色、安全、具有100%原子经济性的优点成为了近年来不可替代的工业化合成环状碳酸酯的方法。利用该方法合成环状碳酸酯的过程中,目前已开发出的常见催化体系有醋酸银/1,8-二氮杂二环十一碳-7-烯(Yamada W,Sugawara Y,Cheng H M,et al.EuropeanJournal of Organic Chemistry,2007,2007(16):2604-2607.),醋酸银/四正丁基溴化胺(Song Q W,He L N.Advanced Synthesis&Catalysis,2016,358(8):1251-1258.)和氯化亚铜/离子液体(Gu Y,Shi F,Deng Y.Journal of Organic Chemistry,2004,69(2):391-394.),银-原甲酸三甲酯框架材料(Zhang G,Yang H,Fei H.ACS catalysis,2018,2018(3):2519-2525.)等,但这些催化体系普遍存在着含有贵金属、反应温度高、循环性能差、不易分离回收等相关问题。因此,开发出绿色环保、反应条件温和、易于分离回收且可循环使用的高效催化剂一直是极具挑战性的研究热点问题。
金属-有机框架材料(MOFs)是金属离子/原子簇和有机配体通过配位作用构成的一类具有稳定的骨架结构、丰富的拓扑结构的新型多孔材料。由于MOFs独特的孔隙率高、比表面积大、孔径有序可调等特点,使其在催化、气体分离固定、电化学等方面具有极高的潜在价值。通过引入开放活性位点、引入活性中心或有机官能团、构筑缺陷位点等方法可以对MOFs进行催化活性调节。目前,合成MOFs的方法主要有扩散法、固态反应法、水热法等,而这些方法在不同程度上具有高温高压、耗时长、合成工艺复杂等缺点,而利用电化学合成法反应条件温和、反应迅速、操作简单和转化率高等优点合成MOFs是一种新型便捷的途径。
发明内容
本发明的目的是用原位模版电化学合成法合成一种含Cu(I)的金属-有机骨架([CuI]-Cu-BTC)的金属-有机框架材料(MOFs)催化剂。
本发明的催化剂用来催化以CO2和丙炔醇类衍生物为原料制备环状碳酸酯类化合物。以离子液体([Emim][OAc])为碱,在[CuI]-Cu-BTC/[Emim][OAc]催化体系下,将丙炔醇类衍生物和CO2于反应釜中进行催化反应,得到相应的产物的环状碳酸酯类化合物。
一种含有Cu(I)的MOF催化剂,该催化剂为以均苯三甲酸为模版前体化合物制得的含有Cu(I)活性位点的金属-有机骨架结构催化剂。
作为优选,所述催化剂为[CuI]-Cu-BTC,是在Cu-BTC表面构筑缺陷位点并引入Cu(I)活性位点的新型Cu-MOF材料。该催化剂的制备方法是以离子液体体系为电解液,通过原位模板电化学合成法简单快速得到的。
作为优选,所述电化学合成法采用含离子液体的混合液为电解液。
作为优选,所述电化学合成法采用铜箔作为电极的阴极和阳极。
作为优选,该催化剂的红外谱图在490cm-1、729cm-1、1373cm-1和1582cm-1处具有特征峰。
作为优选,所述电解液由均苯三甲酸、离子液体与体积比为1.5~4:0.8~1.5:1的DMF/1,4-二氧六环/H2O混合溶液组成,电解液中离子液体的重量比为5~15%,电解液中均苯三甲酸的摩尔浓度为(1~8)mmol/L。作为进一步优选,所述电解液由离子液体与体积比为2:1:1的DMF/1,4-二氧六环/H2O混合溶液组成,电解液中离子液体的重量比为10%。
作为优选,离子液体为[Bmim][BF4]。
本发明提供了一种以CO2及丙炔醇类衍生物为原料制备环状碳酸酯类化合物的催化体系,其特征在于,包括上述任一项技术方案所述的含有Cu(I)的MOF催化剂以及碱性离子液体1-乙基-3-甲基咪唑乙酸酯。
作为优选,含有Cu(I)的MOF催化剂与1-乙基-3-甲基咪唑乙酸酯的质量/摩尔比为:(5~20)mg/1mmol。进一步优选为:(5~15)mg/1mmol。更进一步优选为(8~10)mg/1mmol。
作为优选,离子液体[Emim][OAc]与丙炔醇类衍生物的摩尔比为0.2~1:1。作为进一步优选,离子液体[Emim][OAc]与丙炔醇类衍生物的摩尔比为0.5:1。
本发明提供了一种以CO2及丙炔醇类衍生物为原料制备环状碳酸酯类化合物的催化剂,该催化体系包括碱性离子液体1-乙基-3-甲基咪唑乙酸酯([Emim][OAc])和一种新型铜-有机框架结构材料(Cu-MOF)材料([CuI]-Cu-BTC)。[CuI]-Cu-BTC/[Emim][OAc]在温和条件下对CO2和丙炔醇类衍生物的反应具有良好的催化活性和可重复使用性。
本发明同时提供了一种制备环状碳酸酯类化合物的方法,利用上述任一技术方案所述的催化体系,以CO2及丙炔醇类衍生物为原料,制备得到所述环状碳酸酯类化合物。
作为优选,反应体系中CO2的压力为0.5~5MPa。作为进一步优选,反应体系中CO2的压力为1~5MPa;更进一步优选为1~3MPa;最优选的CO2的压力为1MPa。
作为优选,反应温度为10~50℃。作为进一步优选,反应温度为20~50℃。更进一步优选为20~40℃。作为具体的优选方案,反应温度为30℃。
实验表明,[CuI]-Cu-BTC与丙炔醇类衍生物的质量摩尔比为4.45mg:1mmol,离子液体([Emim][OAc])催化剂与丙炔醇类衍生物的用量摩尔比在0.5:1时催化效果最佳。反应时,在反应釜中加入丙炔醇类衍生物和[CuI]-Cu-BTC、[Emim][OAc]催化剂,反应釜抽真空后,将CO2通入所述反应釜中,并使反应釜中的反应压力维持在1MPa。
反应时,反应釜内的催化反应温度为30℃。反应时间为2~28h,优选范围为2~12h,更优选12h。
所述丙炔醇类衍生物和环状碳酸酯类化合物的结构分别如下:
其中R1和R2分别独立的选自C1-C5的烷基、苯环;或者R1和R2与其相连的碳原子构成3~8元环烷结构。
作为优选,反应体系中,所述丙炔醇类衍生物选自下述各式中的至少一种:
作为优选,该催化体系催化反应的时间为2~12h。
作为具体的实施方案,丙炔醇类衍生物用量为2mmol时,[CuI]-Cu-BTC的用量为0.0089g,离子液体[Emim][OAc]与丙炔醇类衍生物的摩尔比为0.5:1。
在[CuI]-Cu-BTC/[Emim][OAc]体系中,离子液体[Emim][OAc]中的路易斯碱性阴离子[OAc]-活化了丙炔醇类衍生物的羟基,[CuI]-Cu-BTC活化了丙炔醇类衍生物的C≡C,进而共同促进了反应的进行。
本发明的优点和有益效果:
(1)本工作采用原位模板电化学合成法,以离子液体体系为电解液,在Cu-BTC表面构筑缺陷位点并引入Cu(I)活性位点,简单迅速地合成了一种新型含Cu(I)的金属-有机骨架[CuI]-Cu-BTC;
(2)反应条件温和,具有高目标收益率,反应体系无外加有机溶剂,反应后易于分离,具有良好的可重用性,更为绿色环保。
总之,本发明的MOF催化剂采用原位模板电合成方法,以离子液体体系为电解液,在Cu-BTC表面构筑缺陷位点并引入Cu(I)活性位点,简单快速地合成了一种新型MOF材料([CuI]-Cu-BTC);以离子液体([Emim][OAc])为碱,[CuI]-Cu-BTC/[Emim][OAc]体系在不添加任何有机强碱且温和的条件下对CO2和丙炔醇类衍生物的反应具有良好的催化活性,并获得了较高的α-亚烷基环碳酸酯收率;通过循环测试证明,[CuI]-Cu-BTC/[Emim][OAc]体系在反应后易于分离,可重复使用至少5次且催化活性无明显降低。
附图说明
图1是[CuI]-Cu-BTC的红外谱图。
图2是[CuI]-Cu-BTC的XRD谱图。
图3是[CuI]-Cu-BTC的SEM图像。
图4是[CuI]-Cu-BTC的XPS谱图。
图5是[CuI]-Cu-BTC的BET谱图。
图6是以[CuI]-Cu-BTC/[Emim][OAc]作为催化体系时反应产物产率随CO2压力变化图。
图7是以[CuI]-Cu-BTC/[Emim][OAc]作为催化体系时反应产物产率随时间变化图。
图8是[CuI]-Cu-BTC/[Emim][OAc]催化体系循环使用图。
图9是CO2和丙炔醇类衍生物合成环状碳酸酯类化合物的反应流程图。
具体实施方式
下面结合附图和具体实施例对本发明做进一步说明。
下述实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂,如无特殊说明,均可从商业途径获得。
实施例1:制备催化剂[CuI]-Cu-BTC
在40mL体积比为2:1:1的DMF/1,4-二氧六环/H2O混合溶液中加入0.15mmol均苯三甲酸(BTC)和占40mL体积溶剂的重量比为10%的IL([Bmim][BF4]),30℃下搅拌均匀。以该溶液作为电解液,铜箔作为电极的阴极和阳极,在10V的外加电压下进行电解,并迅速形成蓝色沉淀。电解过程结束后将沉淀离心收集,用DMF(3mL×5)和丙酮(3mL×5)洗涤。在60℃干燥12h后,得到[CuI]-Cu-BTC催化剂。
该催化剂的红外谱图如图1所示,在1373cm-1和729cm-1处对应的苯环C=C拉伸和C-H弯曲特征峰与1582cm-1处C=O的拉伸振动特征峰共同表明了[CuI]-Cu-BTC中BTC配体的存在,490cm-1处特征峰对应的Cu-O证明了Cu-BTC的形成;
该催化剂的XRD谱图如图2所示,[CuI]-Cu-BTC的布拉格峰和Cu-BTC的峰对应良好,表明[CuI]-Cu-BTC和Cu-BTC有着相似的晶体结构;
该催化剂的SEM图像如图3所示,图中显示[CuI]-Cu-BTC平均尺寸为400nm,形貌不规则;
该催化剂的XPS谱图如图4所示,图4a是[CuI]-Cu-BTC的全光谱,谱图中只出现了代表Cu、O、C元素的特征峰,而N和B元素特征峰并没有出现,说明电解液中的IL([Bmim][BF4])没有进入MOF材料的缺陷中,图4b为Cu元素的区域高分辨率XPS光谱,在935.11eV和932.89eV处出现的Cu 2p3/2峰,表明[CuI]-Cu-BTC表面同时含有Cu+和Cu2+;
该催化剂的BET谱图如图5所示,图中数据表示[CuI]-Cu-BTC中存在少量中孔(Vmeso=0.41cm3g-1),总比表面积为129.44mg2-1,上述结果均表明,Cu(I)活性位点成功结合到Cu-BTC表面,该[CuI]-Cu-BTC是含有Cu+的MOF材料。
实施例2:制备4,4-二甲基-5-亚甲基-1,3-二氧戊环-2-酮,反应流程图见图6。
将2mmol的2-甲基-3-丁炔-2-醇、特定量(0.0089g)的催化剂([CuI]-Cu-BTC)、1mmol碱性离子液体(1-乙基-3-甲基咪唑乙酸盐,[Emim][OAc])加入到容积为22mL的具有聚四氟乙烯内衬的不锈钢高压反应釜中,将反应釜密封,抽真空后,充入1MPa的CO2气体,将反应釜放入恒定温度的油浴锅中,搅拌,进行合成反应。反应后,离心,分离出固体[CuI]-Cu-BTC,以乙酸乙酯为萃取剂,从含离子液体的反应混合液中萃取出产物,用氘代试剂为溶剂,以三聚甲醛为内标经核磁共振氢谱法可计算4,4-二甲基-5-亚甲基-1,3-二氧戊环-2-酮的产率。产物纯品通过柱色谱分离,以乙酸乙酯/石油醚(1:25)为洗脱液。
实施例3:考察CO2压力对反应产率的影响
参考实施例2,进一步考察CO2压力对反应产率的影响规律,以[CuI]-Cu-BTC/[Emim][OAc]体系为催化剂,进行如下实验::反应条件为:2-甲基-3-丁炔-2-醇(2mmol),催化剂[CuI]-Cu-BTC(0.0089g),[Emim][OAc](1mmol),反应时间为12h,反应温度为30℃,相应测试数据如图6,由图6可知:CO2压力为1Mpa,产物产率达到91%,进一步增加CO2压力,产物产率不再有明显变化。
实施例4:考察反应时间对反应产率的影响
参考实施例2,进一步考察反应时间对反应产率的影响,进行如下实验,反应条件为:2-甲基-3-丁炔-2-醇(2mmol),[CuI]-Cu-BTC(0.0089g),催化剂[Emim][OAc](1mmol),CO2压力为1Mpa,反应温度为30℃,相应测试数据如图7所示:反应进行到12h,产物产率达到91%,进一步延长反应时间,产物产率不再有明显变化。
实施例5:为了进一步研究[CuI]-Cu-BTC/[Emim][OAc]的催化普适性,考察了[CuI]-Cu-BTC/[Emim][OAc]对丙炔醇类衍生物的催化性能,按图8所示反应流程图进行反应,反应条件如下:反应底物(2mmol),CO2压力为1MPa,[CuI]-Cu-BTC(0.0089g),[Emim][OAc](1mmol),反应温度为30℃,反应时间为12~28h。测试结果如下表所示。从表中可知:在温和条件下,[CuI]-Cu-BTC/[Emim][OAc]可以高效催化丙炔醇类衍生物和CO2反应生成环状碳酸酯类化合物。
表1[CuI]-Cu-BTC/[Emim][OAc]催化不同丙炔醇类衍生物与CO2反应
实施例6:为考察催化剂的可重复使用性,进行如下实验,以2-甲基-3-丁炔-2-醇为底物,在进行一次催化反应结束后,通过离心分离方法回收[CuI]-Cu-BTC,用乙酸乙酯(3×2mL)从混合物中提取产物,然后将分离出的IL[Emim][OAc]在70℃下真空干燥12h。回收的[CuI]-Cu-BTC和[Emim][OAc]在相同实验条件下重复使用并测试,相应测试数据如图9所示。从图9可知:[CuI]-Cu-BTC/[Emim][OAc]体系在重复使用5次后催化性能没有明显下降,说明该双组分催化体系具有良好的反应后分离性和可重复使用性。
以上显示和描述了本发明的实施实例,或者附图的技术方案,均体现了本发明以CO2为原料,[CuI]-Cu-BTC/[Emim][OAc]为高效催化体系合成环状碳酸酯类化合物的新方法。
Claims (10)
1.一种含有Cu(I)的MOF催化剂,其特征在于,该催化剂为以均苯三甲酸为模版前体化合物制得的含有Cu(I)活性位点的金属-有机骨架结构催化剂。
2.根据权利要求1所述的含有Cu(I)的MOF催化剂,其特征在于,所述催化剂通过原位模板电化学合成法制得,所述电化学合成法采用含离子液体的混合液为电解液。
3.根据权利要求2所述的含有Cu(I)的MOF催化剂,其特征在于,所述电解液由均苯三甲酸、离子液体与体积比为1.5~4:0.8~1.5:1的DMF/1,4-二氧六环/H2O混合溶液组成,电解液中离子液体的重量百分比为5~15%,电解液中均苯三甲酸的摩尔浓度为(1~8)mmol/L。
4.根据权利要求2或3所述的含有Cu(I)的MOF催化剂,其特征在于,所述离子液体为[Bmim][BF4]。
5.一种以CO2及丙炔醇类衍生物为原料制备环状碳酸酯类化合物的催化体系,其特征在于,包括权利要求1~4任一项所述的含有Cu(I)的MOF催化剂以及碱性离子液体1-乙基-3-甲基咪唑乙酸酯。
6.根据权利要求5所述的催化体系,其特征在于,含有Cu(I)的MOF催化剂与1-乙基-3-甲基咪唑乙酸酯的质量/摩尔比为:(5~20)mg/1mmol。
7.一种制备环状碳酸酯类化合物的方法,其特征在于,利用权利要求5或6所述的催化体系,以CO2及丙炔醇类衍生物为原料,制备得到所述环状碳酸酯类化合物。
8.根据权利要求7所述的制备环状碳酸酯类化合物的方法,其特征在于,反应体系中CO2的压力为0.5~5MPa;反应温度为10~50℃。
9.根据权利要求7所述的制备环状碳酸酯类化合物的方法,其特征在于,反应体系中,1-乙基-3-甲基咪唑乙酸酯与丙炔醇类衍生物的摩尔比为(0.2~1):1;所述丙炔醇类衍生物和环状碳酸酯类化合物的结构分别如下:
其中R1和R2分别独立的选自C1-C5的烷基、苯环;或者R1和R2与其相连的碳原子构成3~8元环烷结构。
10.根据权利要求7所述的制备环状碳酸酯类化合物的方法,其特征在于,反应体系中,所述丙炔醇类衍生物选自下述各式中的至少一种:
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