CN112604659B - 一种手性配体交换型cof@mof/l复合材料及其制备方法 - Google Patents
一种手性配体交换型cof@mof/l复合材料及其制备方法 Download PDFInfo
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- CN112604659B CN112604659B CN202011354636.8A CN202011354636A CN112604659B CN 112604659 B CN112604659 B CN 112604659B CN 202011354636 A CN202011354636 A CN 202011354636A CN 112604659 B CN112604659 B CN 112604659B
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- mof
- acid
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- chiral
- ligand
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- 239000003446 ligand Substances 0.000 title claims abstract description 16
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 25
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- 239000012621 metal-organic framework Substances 0.000 claims description 23
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- 239000011259 mixed solution Substances 0.000 claims description 11
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- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 4
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- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 3
- GAWAYYRQGQZKCR-UWTATZPHSA-N (2r)-2-chloropropanoic acid Chemical compound C[C@@H](Cl)C(O)=O GAWAYYRQGQZKCR-UWTATZPHSA-N 0.000 claims description 2
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- IWYDHOAUDWTVEP-SSDOTTSWSA-N (R)-mandelic acid Chemical compound OC(=O)[C@H](O)C1=CC=CC=C1 IWYDHOAUDWTVEP-SSDOTTSWSA-N 0.000 claims description 2
- IWYDHOAUDWTVEP-ZETCQYMHSA-N (S)-mandelic acid Chemical compound OC(=O)[C@@H](O)C1=CC=CC=C1 IWYDHOAUDWTVEP-ZETCQYMHSA-N 0.000 claims description 2
- WIOZZYWDYUOMAY-UHFFFAOYSA-N 2,5-diaminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=C(N)C=C1C(O)=O WIOZZYWDYUOMAY-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明公开了一种手性配体交换型COF@MOF/L复合材料及其制备方法,先合成MOF晶体材料,再合成COF@MOF材料,最后引入手性配体形成COF@MOF/L复合材料。本发明通过交换MOF中的有机配体,引入具有手性结构的有机配体,可用于催化不对称反应,并且能产生晶格缺陷,提升催化性能;COF包覆MOF形成COF@MOF核壳结构,一方面形成多级孔道结构,在吸附污染物小分子的时候会有层层递进的效果,而且片层中间会形成纳米限域效应,提升催化性能,另一方面由于COF的稳定外壳结构MOF在进行有机配体交换过程中不会造成结构坍塌,维持原有骨架的形状。
Description
技术领域
本发明属于COF@MOF复合材料技术领域,具体涉及一种手性配体交换型COF@MOF/L复合材料及其制备方法。
背景技术
多孔材料是一类具有丰富的微观结构的固体材料,在吸附分离、分析、催化、储能、生物等领域受到广泛的关注其中,由金属离子和有机配体配位自组装而形成的金属有机骨架材料MOFs和有机配体基于动态共价键来聚合构筑的共价有机骨架材料COFs,具有低密度、高孔隙率、高比表面、孔道规则、孔径可调以及拓扑结构多样性和可裁剪性等优点,受到研究者的广泛关注。
美国加州大学体系的Pingyun Feng和Xianhui Bu教授团队开发了一种集成的COF@MOF协同装配策略,通过MOF:[(M3-(OH)1-x(O)x(COO)6]型和COF:[B3O3(py)3]型叠加。采用这种策略,acs构型框架的配位驱动组装与COF框架的缩合反应同时发生,并协同作用于一个C3对称的三聚体硼氧化合物分子(tpb)中。吉林大学的裘式纶教授课题组与法国国家科学研究中心的Valentin Valtchev教授证明了MOF可以生长在共价有机骨架(COF)膜上用于制造COF@MOF复合膜。合成的COF@MOF复合膜对H2/CO2混合气体的分离选择性高于单独的COF和MOF。COF@MOF复合膜在H2/CO2气体对混合分离中,超过了聚合物膜的罗伯逊上界,远高于各自的分离值及COF-300,Zn2(bdc)2(dabco)和ZIF-8膜。南京师范大学兰教授通过将NH2-UiO-66共价结合固定在TpPa-1-COF表面,合成了一种具有高表面积、多孔骨架和高结晶度的新型MOF/COF杂化材料。由此得到的多孔多孔混合材料在可见光照射下表现出的光催化H2演化。中山大学的李教授课题组报导了一种介孔MOFs:NH2-MIL-101(Fe)为核心,生成具有介孔COFs:NUT-COF-1(NTU)为外壳的新多孔核壳材料。通过共价连接工艺,复合材料NH2-MIL-101(Fe)@NTU具有良好的结晶度和分级孔隙度,并探讨了MOFs与COFs在多相催化中的协同作用。新加坡南洋理工大学的张华教授课题组将MOFs与COFs相结合,形成了一种新型的MOF@COF核-壳杂化材料,即:合成了具有高结晶度和分级孔结构的NH2-MIL-68@TPA-COF。NH2-MIL-68@TPA-COF作为一种新型的可见光驱动光催化剂,在降解有机污染物方面具有广阔的应用前景。韩国浦航科技大学博士后Dong-Pyo Kim等人报道了一种新型的光催化多功能平台:一种金属掺杂的核-壳结构的MOFs@COFs(Pd/TiATA@LZU1)。这种MOF@COF使用含NH2基的MOFs可以直接生长在COF外壳,而不需要额外的功能化步骤。可见,COF@MOF复合材料的多孔核壳结构,在节能分离技术、光催化H2、分离、能量转化和其他催化领域具有广阔的应用前景。
手性毒害性有机物污染是我国面临的重要环境问题之一,以其难降解、半挥发易迁移、高毒性、结构复杂、同系物及异构体多等特点成为有机污染物中最棘手的问题。目前常用去除方法为微生物降解法,但是由于实际环境中手性污染物来源及转化过程的复杂性,污染物的浓度/组成变化及其代谢产物多样而存在降解效率低、易产生有毒有害副产物等缺点。因此,急需发展一种高效降解手性污染物的方法。
发明内容
本发明旨在通过合成COF@MOF材料后交换MOF的有机配体,引入具有手性结构的有机配体,利用手性-手性相互作用,有效识别手性毒性污染物并选择性催化降解为无毒物质;利用COF@MOF核壳结构形成的多级孔道结构,在吸附手性污染物的时候形成层层递进的效果,同时利用片层中间形成的纳米限域效应,进而提升催化性能;通过COF的稳定外壳结构MOF,在进行有机配体交换过程中不会造成结构坍塌,维持原有骨架的形状。
为实现上述目的,本发明采用的技术方案是:
一种手性配体交换型COF@MOF/L复合材料,其特征在于,包括有COF包覆MOF晶体材料合成的具有核壳结构的COF@MOF材料,其中L代表手性配体,所述COF@MOF材料的MOF进行合成后配体交换,形成具有手性配体的COF@MOF/L复合材料。
一种手性配体交换型COF@MOF/L复合材料的制备方法,包括有以下步骤:
MOF晶体材料的合成:将一定比例的金属离子盐和MOF有机配体溶于有机溶剂中,在一定温度和压力条件下或微波超声条件下反应一段时间,然后洗涤、干燥,获得MOF晶体材料;
COF@MOF材料的合成:MOF晶体材料溶于含有COF有机配体Ⅰ前驱体溶液中,加热搅拌或超声分散一段时间形成混合溶液,然后向混合溶液中加入COF有机配体Ⅱ前驱体溶液和适量调节剂,在一定温度和压力或微波超声条件下反应一段时间,然后洗涤、干燥,获得具有核壳结构的COF@MOF材料;
COF@MOF/L复合材料的合成:将一定量的手性有机配体溶于有机溶剂中,向其中加入COF@MOF材料,将混合溶液置于隔离交换沉降池中,超声微波反应后静置,抽取反应液的上清液,在上清液中注入手性配体溶液,重复5~8次,离心分离产物,并洗涤干燥,得到COF@MOF/L复合材料。
作为上述技术方案的优选,所述金属离子盐为铝、铬、钛、锆、锌、钴、钙、铜、铁、镍、镁或锰的硝酸盐、氯化盐、硫酸盐或醋酸盐中的任一种或多种的混合物。
作为上述技术方案的优选,所述MOF有机配体为对苯二甲酸、均三苯甲酸、2-氨基对苯二甲酸、2-羟基对苯二甲酸、2,5-吡嗪二羧酸、4-[1,2,4]噻唑-4-苯甲酸、2-甲基咪唑、2-溴对苯二甲酸、2,5-二羟基对苯二甲酸、2,2'-联吡啶-5,5'-二羧酸、2,4,6-三(4-羧基苯基)-1,3,5-三嗪、偶氮苯-4,4-二羧酸、2,5-二氨基对苯二甲酸、4-(4-吡啶基)苯甲酸、中的任意一种。
作为上述技术方案的优选,所述COF有机配体Ⅰ为均苯三甲醛、对苯二甲醛、四(4-甲酰基苯)甲烷、四醛基苯基卟啉、3,3',5,5'-四醛基联苯、1,2,4,5-四(4-甲酰基苯基)苯、2,2'-联吡啶-5,5'-二甲醛、2,5-二羟基对苯二甲醛、2,5-二甲氧基苯-1,4-二甲醛、2,6-萘二羧醛、
作为上述技术方案的优选,所述COF有机配体Ⅱ前驱体溶液为苯二胺、蜜勒胺、1,3,5-三氨基苯、联苯二胺、5,15-(氨苯基)-10,20-苯基卟啉、四(4-氨基苯基)甲烷、三(4-氨基苯基)胺、5,5'-二氨基-2,2'-联吡啶、2,4,6-三(4-氨基苯氧基)-1,3,5-三嗪、1,3,5-三(4-氨基苯基)苯、4,4,4,4-甲乙烷四基四苯胺、 中的任意一种。
作为上述技术方案的优选,所述手性有机配体为S-扁桃酸、R-扁桃酸、D-(+)-对甲基二苯甲酰酒石酸(一水物)、L-(-)-对甲基二苯甲酰酒石酸(一水物)、D-(+)-二苯甲酰酒石酸(一水物)、D-酒石酸二异丙酯L-(-)-二苯甲酰酒石酸(一水物)、L-(-)-二苯甲酰酒石酸(无水物)、右旋樟脑磺酸、左旋樟脑磺酸、R-2-氯丙酸、S-2-氯丙酸、L-乳酸、组氨酸、谷氨酸、酪氨酸、半胱氨酸、联二萘酚(BINOL)、1,1'-联萘-2,2'-双二苯膦(BINAP)或
作为上述技术方案的优选,所述调节剂为甲酸、乙酸、苯甲酸、乙二酸、氢氟酸、氢氰酸或三氟乙酸。
作为上述技术方案的优选,所述有机溶剂为无水甲醇、无水乙醇、丙酮、正己烷、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、二氯甲烷、三氯甲烷、四氯甲烷、石油醚、四氢呋喃、吡啶、吡咯、乙腈、甲苯、1,4-二氧六环中的任意一种或多种的混合物。
本发明的有益效果是:本发明通过合成COF@MOF后交换MOF中的有机配体,引入具有手性结构的有机配体,可用于催化不对称反应,并且能产生晶格缺陷,提升催化性能;COF包覆MOF形成COF@MOF核壳结构,一方面形成多级孔道结构,在吸附污染物小分子的时候会有层层递进的效果,而且片层中间会形成纳米限域效应,提升催化性能,另一方面由于COF的稳定外壳结构MOF在进行有机配体交换过程中不会造成结构坍塌,维持原有骨架的形状;MOF结构包含氨基酸或异变糖酸等手性功能有机配体后,可以利用手性-手性相互作用,有效识别cis-氟氯菊脂、cis-氯菊脂等手性毒性污染物并选择性催化降解为无毒物质。
附图说明
图1是本发明的反应原理图;
图2是实施例1、2、3和对比例的苯乙烯降解过程性能对比图。
具体实施方式
下面将对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
在本发明的描述中,需要说明的是,术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为方位或位置关系,仅是为了便于描述本发明和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此不能理解为对本发明的限制。此外,术语“第一”、“第二”、“第三”仅用于描述目的,而不能理解为指示或暗示相对重要性。
实施例1
合成COF01@MIL-101/L1
1)MIL-101的合成
将硝酸铬水合物(800mg),对苯二甲酸(332mg)和氢氧化钠(200mg)分散在去离子水(15ml)中并搅拌5分钟,然后反应溶液转移到50ml聚四氟乙烯衬里的不锈钢高压釜中,并在150℃烘箱中反应12h。然后让高压釜冷却至室温,离心收集绿色沉淀物,室温下用DMF洗涤绿色沉淀物除去大部分未反应的对苯二甲酸,然后用乙醇在100℃的高压釜中进一步洗涤24小时除去未反应的对苯二甲酸。之后在80℃下干燥得到MIL-101样品。
2)COF01@MIL-101的合成
将80mg的MIL-101溶于加入了2,2'-联吡啶-5,5'-二甲醛(0.04mmol)的DMF(5ml)溶液中,并在65℃下搅拌2h,然后在搅拌过程中加入蜜勒胺(0.05mmol)和22μL乙酸,继续搅拌1h。然后在120℃下加热搅拌24h,离心分离产物,用DMF和去离子水和甲醇分别洗涤3次,在85℃真空烘箱中干燥5h,获得COF01@MIL-101产物。
3)COF01@MIL-101/L1的合成:
配制10mM的D-组氨酸的DMF溶液,取8mL,向其中加入2)所制备的COF01@MIL-101(100mg),将混合溶液置于隔离交换沉降池中,超声微波反应1h后静置30min,然后抽取反应液上清液2mL,注入新鲜的2mL 10mM的D-组氨酸溶液,重复超声微波-静置-抽取5~8次,离心分离产物,并用DMF和甲醇洗涤,冷冻干燥24h,获得COF01@MIL-101/L1样品。
实施例2
合成COF02@ZIF-8/L2复合材料
1)ZIF-8的合成
六水合硝酸锌(0.717g)和2-甲基咪唑(0.108g)溶于50mlDMF中,超声分散,然后反应溶液转移到100ml聚四氟乙烯衬里的不锈钢高压釜中,并在140℃烘箱中反应24h。冷却到室温,离心得到淡黄色晶粒,用甲醇和DMF分别洗涤3次,在70℃烘箱中干燥。
2)COF02@ZIF-8的合成
将65mg的ZIF-8溶于四醛基苯基卟啉(0.03mmol)的1,4-二氧六环(5ml)溶液中,并搅拌30min,然后在搅拌过程中加入对苯二胺(0.03mmol)和25μL甲酸,继续搅拌1.5h。然后在110℃下加热搅拌20h,离心分离产物,用1,4-二氧六环和甲醇分别洗涤3次,在60℃真空烘箱中干燥8h,获得COF02@ZIF-8产物。
3)COF02@ZIF-8/L2的合成:
配制8mM的L-半胱氨酸的DMF溶液,取5mL,向其中加入2)所制备的COF02@ZIF-8(60mg),将混合溶液置于隔离交换沉降池中,超声微波反应1.5h后静置45min,然后抽取反应液上清液1mL,注入新鲜的1mL 8mM的L-半胱氨酸溶液,重复超声微波-静置-抽取5~8次,离心分离产物,并用DMF和甲醇洗涤,冷冻干燥24h,获得COF02@ZIF-8/L2样品。
实施例3
合成COF03@PCN-160/L3复合材料
1)PCN-160的合成
将ZrCl4(200mg)和2,5-吡嗪二羧酸(100mg)溶于DMF(20mL)中,超声分散5min,滴入三氟乙酸(1.0mL),分散均匀。将混合物置于高温高压反应釜中,在120℃的烘箱中反应72h,冷却至室温后,将固体样品离心分离,并用DMF、甲醇、丙酮洗涤三次,在55℃烘箱中干燥12h,获得PCN-160样品。
2)COF03@PCN-160的合成
将90mg的PCN-160溶于对苯二甲醛(0.02mmol)的1,4-二氧六环(5ml)溶液中,并搅拌2h,然后在搅拌过程中加入1,3,5-三氨基苯(0.02mmol)和15μL乙酸,继续搅拌45min。在100℃高温高压反应釜中反应24h,自然冷却到室温,离心分离产物,用DMF和甲醇分别洗涤3次,在80℃真空烘箱中干燥12h,获得COF03@PCN-160产物。
3)COF03@PCN-160/L3的合成:
配制12mM的1,1'-联萘-2,2'-双二苯膦(BINAP)的DMF溶液,取10mL,向其中加入2)所制备的COF03@PCN-160(100mg),将混合溶液置于隔离交换沉降池中,超声微波反应3h后静置30min,然后抽取反应液上清液2mL,注入新鲜的2mL 12mM的1,1'-联萘-2,2'-双二苯膦(BINAP)溶液,重复超声微波-静置-抽取5~8次,离心分离产物,并用DMF、二氯甲烷、乙醇分别洗涤三次,冷冻干燥24h,获得COF03@PCN-160/L3样品。
本发明的反应原理如图1所示。将实施例1制得的COF01@MIL-101/L1样品、实施例2制得的COF02@ZIF-8/L2样品、实施例3制得的COF03@PCN-160/L3样品进行性能测试,并与分子筛进行数据对比,对比结果如下表所示:
实施例1、2、3应用于氟氯氰菊脂降解降解实验,实验结果如图2所示。可见,利用本发明的制备方法制得的手性配体交换型COF@MOF/L复合材料,比表面积、孔容、平均孔径等性能优异,在氟氯氰菊脂降解应用中降解效果明显,在90min内,三种材料的降解率均达到99%以上。
值得一提的是,本发明专利申请涉及的高温高压反应釜、隔离交换沉降池等技术特征应被视为现有技术,这些技术特征的具体结构、工作原理以及可能涉及到的控制方式、空间布置方式采用本领域的常规选择即可,不应被视为本发明专利的发明点所在,本发明专利不做进一步具体展开详述。
以上详细描述了本发明的较佳具体实施例,应当理解,本领域的普通技术人员无需创造性劳动就可以根据本发明的构思做出诸多修改和变化,因此,凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案,皆应在由权利要求书所确定的保护范围内。
Claims (4)
1.一种手性配体交换型COF@MOF/L复合材料的制备方法,其特征在于,包括有以下步骤:
MOF晶体材料的合成:将一定比例的金属离子盐和MOF有机配体溶于有机溶剂中,在一定温度和压力条件下或微波超声条件下反应一段时间,然后洗涤、干燥,获得MOF晶体材料;
COF@MOF材料的合成:MOF晶体材料溶于含有COF有机配体Ⅰ前驱体溶液中,加热搅拌或超声分散一段时间形成混合溶液,然后向混合溶液中加入COF有机配体Ⅱ前驱体溶液和适量调节剂,在一定温度和压力或微波超声条件下反应一段时间,然后洗涤、干燥,获得具有核壳结构的COF@MOF材料;
COF@MOF/L复合材料的合成:将一定量的手性有机配体溶于有机溶剂中,向其中加入COF@MOF材料,将混合溶液置于隔离交换沉降池中,超声微波反应后静置,抽取反应液的上清液,在上清液中注入手性配体溶液,重复5~8次,离心分离产物,并洗涤干燥,得到COF@MOF/L复合材料;
所述金属离子盐为铝、铬、钛、锆、锌、钴、钙、铜、铁、镍、镁或锰的硝酸盐、氯化盐、硫酸盐或醋酸盐中的任一种或多种的混合物;
所述MOF有机配体为对苯二甲酸、均三苯甲酸、2-氨基对苯二甲酸、2-羟基对苯二甲酸、2,5-吡嗪二羧酸、4-[1,2,4]噻唑-4-苯甲酸、2-甲基咪唑、2-溴对苯二甲酸、2,5-二羟基对苯二甲酸、2,2'-联吡啶-5,5'-二羧酸、2,4,6-三(4-羧基苯基)-1,3,5-三嗪、偶氮苯-4,4-二羧酸、2,5-二氨基对苯二甲酸、4-(4-吡啶基)苯甲酸、中的任意一种;
所述COF有机配体Ⅰ为均苯三甲醛、对苯二甲醛、四(4-甲酰基苯)甲烷、四醛基苯基卟啉、3,3',5,5'-四醛基联苯、1,2,4,5-四(4-甲酰基苯基)苯、2,2'-联吡啶-5,5'-二甲醛、2,5-二羟基对苯二甲醛、2,5-二甲氧基苯-1,4-二甲醛、2,6-萘二羧醛、中的任意一种;
所述COF有机配体Ⅱ前驱体溶液为苯二胺、蜜勒胺、1,3,5-三氨基苯、联苯二胺、5,15-(氨苯基)-10,20-苯基卟啉、四(4-氨基苯基)甲烷、三(4-氨基苯基)胺、5,5'-二氨基-2,2'-联吡啶、2,4,6-三(4-氨基苯氧基)-1,3,5-三嗪、1,3,5-三(4-氨基苯基)苯、4,4,4,4-甲乙烷四基四苯胺、中的任意一种;
所述手性有机配体为S-扁桃酸、R-扁桃酸、D-(+)-对甲基二苯甲酰酒石酸、L-(-)-对甲基二苯甲酰酒石酸、D-(+)-二苯甲酰酒石酸、D-酒石酸二异丙酯L-(-)-二苯甲酰酒石酸、L-(-)-二苯甲酰酒石酸、右旋樟脑磺酸、左旋樟脑磺酸、R-2-氯丙酸、S-2-氯丙酸、L-乳酸、组氨酸、谷氨酸、酪氨酸、半胱氨酸、联二萘酚、1,1'-联萘-2,2'-双二苯膦或
2.如权利要求1所述的手性配体交换型COF@MOF/L复合材料的制备方法,其特征在于,所述调节剂为甲酸、乙酸、苯甲酸、乙二酸、氢氟酸、氢氰酸或三氟乙酸。
3.如权利要求1所述的手性配体交换型COF@MOF/L复合材料的制备方法,其特征在于,所述有机溶剂为无水甲醇、无水乙醇、丙酮、正己烷、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、二氯甲烷、三氯甲烷、四氯甲烷、石油醚、四氢呋喃、吡啶、吡咯、乙腈、甲苯、1,4-二氧六环中的任意一种或多种的混合物。
4.如权利要求1-3中任意一项制备方法制成的手性配体交换型COF@MOF/L复合材料,其特征在于,包括有COF包覆MOF晶体材料合成的具有核壳结构的COF@MOF材料,其中L代表手性配体,所述COF@MOF材料的MOF进行合成后配体交换,形成具有手性配体的COF@MOF/L复合材料。
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