CN107433205B - 共价有机框架负载钴催化剂及其制备和应用 - Google Patents
共价有机框架负载钴催化剂及其制备和应用 Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
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- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
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Abstract
本发明公开了一种新型异相催化剂Co(II)@TF‑TA COF的制备:共价有机框架(COFs)材料负载金属钴用于催化二氧化碳和环氧化合物合成环碳酸酯化合物。该材料的结构单元中含有钴‑卟啉复合物,可以用于催化二氧化碳和环氧化合物之间的反应。此外,COFs具有较大的比表面积和开放的孔道结构,可以增强对二氧化碳的吸附能力。因此Co(II)@TF‑TA COF在常温、常压条件下可以同时实现对二氧化碳气体的吸附和催化转化生成环碳酸酯。反应底物种类可扩展、反应产率高、催化剂可循环使用、操作简便、产物附加值高。
Description
技术领域
本发明涉及一种新型异相催化剂Co(II)@TF-TA COF的制备:共价有机框架(COFs)材料负载金属钴用于(二氧化碳吸附与转化)催化二氧化碳和环氧化合物反应合成环碳酸酯化合物。
背景技术
二氧化碳是一种温室气体,寻找简单便捷的方法降低环境中的二氧化碳浓度和含量已经成为人类迫切需要解决的问题。二氧化碳和环氧化合物可以在催化剂的催化作用下反应生成环碳酸酯化合物,而环碳酸酯又是一种高附加值的化学品,可用于非质子极性溶剂、制药、精细化工中间体等领域。迄今为止,人们已经开发出了多种可用于催化该反应的催化剂,包括:有机催化剂(如:席夫碱、季胺盐、季膦盐、离子液体)、金属复合物(如:金属-salen复合物、金属-卟啉复合物)、金属氧化物、功能性聚合物等。遗憾的是,多数催化剂催化该反应的条件都需要较高的温度和压力,这极大地限制了这些催化剂的应用。因此,开发出一种可以在常温、常压条件下就能催化二氧化碳转化的催化剂已经成为迫切需要实现的目标。
共价有机框架(Covalent organic frameworks,COFs)材料也被称为“有机分子筛”,具有孔道结构开放有序、易于进行化学修饰改性、化学/热稳定性好等优点,是一种新型的有机聚合物多孔材料(参考文献1:A.P.A.I.Benin,N.W.Ockwig,M.O′Keeffe,A.J.Matzger and O.M.Yaghi,Science,2005,310,1166.)。近年来,以COFs为催化剂载体负载金属化合物用于制备异相反应催化剂已经成为材料领域研究的新热点。
在这里,我们制备出了一种新型的COFs材料Co(II)@TF-TA COF,该材料的结构单元中含有钴-卟啉复合物,可以用于催化二氧化碳和环氧化合物之间的反应。此外,由于COFs具有较大的比表面积和开放的孔道结构,可以增强其对二氧化碳的吸附能力,因此Co(II)@TF-TA COF在常温、常压条件下就可以同时实现对二氧化碳气体的吸附和催化转化生成环碳酸酯。
发明内容
在这里,我们制备出了一种新型的COFs材料Co(II)@TF-TA COF,该材料的结构单元中含有钴-卟啉复合物,可以用于催化二氧化碳和环氧化合物之间的反应。此外,COFs具有较大的比表面积和开放的孔道结构,可以增强对二氧化碳的吸附能力。因此Co(II)@TF-TA COF在常温、常压条件下可以同时实现对二氧化碳气体的吸附和催化转化生成环碳酸酯。
为实现本发明目的,其采用具体技术方案如式1所示:
Co(II)@TF-TA COF的制备方法如下:首先,负载金属钴的氨基卟啉单体Co(II)@TAPP(参考文献2:Jiang,X.et al.Journal of Catalysis,2014,313,159-167;MakotoYuasa,Kenichi Oyaizu,Aritomo Yamaguchi,and MichiKuwakado,J.Am.Chem.Soc.2004,126,11128-11129.)和醛基芘单体TFPPy(参考文献3:Mohammad Gulam Rabbani,Ali KemalSekizkardes,Oussama M.El-Kadri,Bilal R.Kaafaranic and Hani M.El-Kaderi.,J.Mater.Chem.,2012,22,25409.)的合成都参考文献中的方法进行。得到这两种单体后,利用氨基和醛基之间的席夫碱反应,在真空条件下通过溶剂热反应合成Co(II)@TF-TA COF:在10mL的安瓿瓶中加入Co(II)TAPP(36.6mg,0.05mmol)和TFPPy(30.9mg,0.05mmol)粉末,之后加入混合溶剂1,4-二氧六环/均三甲苯/N,N’-二甲基乙酰胺/3mmol/L醋酸溶液(0.7mL/0.7mL/0.5mL/0.1mL),加料后将安瓿瓶超声处理使粉末在溶剂中充分分散溶解。将安瓿瓶放入液氮中使溶剂冷冻成固体,抽真空条件下(~20Pa)将安瓿瓶管口密封。之后将安瓿瓶放入140℃烘箱中静置反应3-7天。得到的固体粉末用丙酮洗涤抽滤至溶剂无色,于100℃条件下烘干12h得到棕色固体粉末Co(II)@TF-TA COF,产率80-90%。
式1.Co(II)@TF-TA COF的制备
如式2所示,以Co(II)@TF-TA COF为异相催化剂,催化二氧化碳和环氧化合物的反应生成环碳酸酯化合物。在常温常压条件下,将环氧化合物(7.5mmol)、助催化剂四丁基碘化铵(0.015mmol)、Co(II)@TF-TA COF(32.6mg,含有0.015mmol的钴元素)混合搅拌反应48h,产物与催化剂通过过滤或抽滤的方式分离,液相即为催化目标产物环碳酸酯化合物,产率90-99%。式中的R为取代基团(R=甲基/氯甲基/丁基/丁氧基/己基)。
式2.以Co(II)@TF-TA COF为异相催化剂,催化二氧化碳和环氧化合物的反应生成环碳酸酯化合物。
具体步骤如下:
第一步:Co(II)@TF-TA COF的合成:在10mL的安瓿瓶中加入Co(II)TAPP(36.6mg,0.05mmol)和TFPPy(30.9mg,0.05mmol)粉末,之后加入混合溶剂1,4-二氧六环/均三甲苯/N,N’-二甲基乙酰胺/3mmol/L醋酸溶液(0.7mL/0.7mL/0.5mL/0.1mL),加料后将安瓿瓶超声处理使粉末在溶剂中充分分散溶解。将安瓿瓶放入液氮中使溶剂冷冻成固体,抽真空条件下(~20Pa)将安瓿瓶管口密封。之后将安瓿瓶放入140℃烘箱中静置反应3-7天。得到的固体粉末用丙酮洗涤抽滤至溶剂无色,于100℃条件下烘干12h得到棕色固体粉末Co(II)@TF-TA COF,产率80-90%。
第二步:以Co(II)@TF-TA COF为异相催化剂,催化二氧化碳和环氧化合物的反应生成环碳酸酯化合物。在常温常压条件下,在二氧化碳存在下,将环氧化合物(7.5mmol)、助催化剂四丁基碘化铵(0.015mmol)、Co(II)@TF-TA COF(32.6mg,含有0.015mmol的钴元素)混合搅拌反应48h,产物与催化剂通过过滤或抽滤的方式分离,液相即为催化目标产物环碳酸酯化合物,对不同底物的催化产率达到90-99%。
本发明所述的新型异相催化剂Co(II)@TF-TA COF的制备:共价有机框架(COFs)材料负载金属钴用于催化二氧化碳和环氧化合物合成环碳酸酯化合物,其有益效果主要体现在以下三个方面:
1)Co(II)@TF-TA COF具有较高的比表面积(1076m2/g)、开放的一维孔道结构(孔道尺寸1.6nm)、较高的金属钴负载量(2-4wt%),因此该材料具有优异的二氧化碳吸收性能,在室温条件下对二氧化碳的吸附量达到169mg.g-1。
2)Co(II)@TF-TA COF中钴-卟啉复合物结构的存在使得该材料在常温常压条件下就可以高效催化二氧化碳与环氧化合物之间的反应生成环碳酸酯化合物,对不同底物的产率达到90-99%。
3)催化剂具有较好的热稳定性(热分解温度达到400℃)和化学稳定性(可耐受强酸、强碱),催化剂循环使用4次以上催化性能没有出现明显下降。
综上,本发明所述的新型异相催化剂Co(II)@TF-TA COF的制备:共价有机框架(COFs)材料负载金属钴用于催化二氧化碳和环氧化合物合成环碳酸酯化合物,催化剂特殊而又精巧的结构设计有利于促进催化反应的顺利进行、反应底物种类可扩展、反应产率高、催化剂可循环使用、操作简便、产物附加值高。
具体实施方式
下面结合具体实施例对本发明进一步描述,但本发明的保护范围并不仅限于此。
实施例1
第一步:Co(II)@TF-TA COF的合成:在10mL的安瓿瓶中加入Co(II)TAPP(36.6mg,0.05mmol)和TFPPy(30.9mg,0.05mmol)粉末,之后加入混合溶剂1,4-二氧六环/均三甲苯/N,N’-二甲基乙酰胺/3mmol/L醋酸溶液(0.7mL/0.7mL/0.5mL/0.1mL),加料后将安瓿瓶超声处理使粉末在溶剂中充分分散溶解。将安瓿瓶放入液氮中使溶剂冷冻成固体,抽真空条件下(~20Pa)将安瓿瓶管口密封。之后将安瓿瓶放入140℃烘箱中静置反应3天。得到的固体粉末用丙酮洗涤抽滤至溶剂无色,于100℃条件下烘干12h得到棕色固体粉末Co(II)@TF-TACOF,产率85%。
第二步:以Co(II)@TF-TA COF为异相催化剂,催化二氧化碳和环氧氯丙烷的反应生成环碳酸酯化合物。在常温常压条件下,在二氧化碳(压力为常压)存在下,将环氧氯丙烷(7.5mmol)、助催化剂四丁基碘化铵(0.015mmol)、Co(II)@TF-TA COF(32.6mg,含有0.015mmol的钴元素)混合搅拌反应48h,产物与催化剂通过过滤或抽滤的方式分离,液相即为催化目标产物环碳酸酯化合物,产率94%。
实施例2-5
以实施例1获得的Co(II)@TF-TA COF为异相催化剂,催化二氧化碳和环氧氯丙烷的反应生成环碳酸酯化合物,循环使用4次催化性能没有出现明显下降,按照表1所述,其它制备、反应、测试条件,同实施例1。
表1
实施例6-8
在实施例1得到的Co(II)@TF-TA COF的催化作用下,催化二氧化碳和环氧氯丙烷的反应生成环碳酸酯化合物,不同的助催化剂对该反应都表现出了高产率,按照表2所述,其它制备、反应、测试条件,同实施例1。
表2
实施例9-12
在实施例1得到的Co(II)@TF-TA COF的催化作用下,催化二氧化碳和环氧化合物的反应生成环碳酸酯化合物,不同环氧底物对该反应都表现出了高产率,按照表3所述,其它制备、反应、测试条件,同实施例1。
表3
本发明所述的新型异相催化剂Co(II)@TF-TA COF的制备:共价有机框架(COFs)材料负载金属钴用于催化二氧化碳和环氧化合物合成环碳酸酯化合物,该材料的结构单元中含有钴-卟啉复合物,可以用于催化二氧化碳和环氧化合物之间的反应。此外,COFs具有较大的比表面积和开放的孔道结构,可以增强对二氧化碳的吸附能力,室温下吸附量达到169mg g-1。因此Co(II)@TF-TA COF在常温、常压条件下可以同时实现对二氧化碳气体的吸附和催化转化生成环碳酸酯。反应底物种类可扩展、反应产率高、催化剂可循环使用、操作简便、产物附加值高。
Claims (9)
1.共价有机框架材料负载钴催化剂,其特征在于:
以负载金属钴的氨基卟啉单体Co(II)@TAPP和醛基芘单体TFPPy为原料,利用氨基和醛基之间的席夫碱反应,在真空条件下通过溶剂热反应合成Co(II)@TF-TA COF催化剂;产物中Co元素的负载量为2-4 wt%;其中,Co(II)@TAPP和TFPPy的投料摩尔比为0.5-1:0.5-1,溶剂为混合溶剂,混合溶剂为1,4-二氧六环、均三甲苯、N,N’-二甲基乙酰胺、3 mmol/L醋酸溶液,溶剂1,4-二氧六环、均三甲苯、N,N’-二甲基乙酰胺、3 mmol/L醋酸溶液的体积比例为0.5-0.7 mL / 0.5-0.7 mL / 0.5-0.7 mL / 0-0.1 mL;合成负载金属钴的共价有机框架材料的化学反应式如下:
。
2.一种权利要求1所述催化剂的制备方法,其特征在于:
以负载金属钴的氨基卟啉单体Co(II)@TAPP和醛基芘单体TFPPy为原料,利用氨基和醛基之间的席夫碱反应,在真空条件下通过溶剂热反应合成Co(II)@TF-TA COF催化剂;产物中Co元素的负载量为2-4 wt%。
3.按照权利要求2所述的制备方法,其特征在于:
反应温度120-140oC,反应时间3-7天。
4.按照权利要求2所述的制备方法,其特征在于:真空为20-200 Pa。
5.一种权利要求1所述催化剂的应用,其特征在于:以所述Co(II)@TF-TA COF为异相催化剂,催化二氧化碳和环氧化合物的反应生成环碳酸酯化合物。
6.按照权利要求5所述的应用,其特征在于:
在二氧化碳存在下,将环氧化合物、助催化剂、Co(II)@TF-TA COF混合搅拌反应,产物与催化剂通过过滤或抽滤的方式分离,液相即为催化目标产物环碳酸酯化合物;
所述的助催化剂为四丁基碘化铵、四丁基溴化铵和/或四丁基氯化铵;
环氧化合物、助催化剂、 Co(II)@TF-TA COF的用量质量比为500-1000:0.5-2:1;
反应温度范围为25-100 oC或压力范围为0.1-3.0 MPa;反应时间12-72h。
7.按照权利要求6所述的应用,其特征在于:将7.5 mmol环氧化合物 、0.015 mmol助催化剂四丁基碘化铵、含有0.015 mmol的钴元素的Co(II)@TF-TA COF 32.6 mg, 混合搅拌反应48h,对不同底物的催化产率达到90-99%。
8.按照权利要求5、6或7所述催化剂的应用,其特征在于: 二氧化碳的压力为0.1-3.0MPa,其中不含有或还可存在的气体为空气、氧气、氮气中的一种或二种以上。
9.按照权利要求5、6或7所述催化剂的应用,其特征在于:对二氧化碳和不同环氧化合物都表现出了>90%高产率;催化剂循环使用4次以上催化性能没有出现明显下降,所有的反应和操作过程简单方便,原料的价格相对较低,产物环碳酸酯具有较高的附加值。
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