CN114891234A - 一种存储丙炔气体的铜金属-有机框架材料及其制备方法 - Google Patents
一种存储丙炔气体的铜金属-有机框架材料及其制备方法 Download PDFInfo
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Abstract
Description
技术领域
本发明属于配位化学领域,具体涉及铜金属-有机框架材料及其制备方法和应用。
背景技术
丙炔是石油裂解的成分之一,是一种重要的工业气体,同时也是药物合成、香精香料、精细化工等产品的重要原料。作为基本的化工原料,通常是在高压下用钢瓶来存储,然而传统的丙炔存储方式在撞击或受热下易引发爆炸,同时丙炔的易燃性也使丙炔的处理比大多数气体更具挑战性。因此,迫切需要开发安全有效的多孔固体材料来存储丙炔,以满足各种工业需求,不仅从科学和安全角度上具有重要意义,并且也是能源化学与材料研究中的一个重要方面。
金属-有机框架材料(MOFs)作为一种新型的多孔材料,与传统的沸石和活性炭多孔固体材料相比,金属-有机框架材料具有精确可控的孔隙结构、可定制设计的官能团,以及合成的可扩展性等优点。根据不同气体分子差异性,利用孔效应、开放金属位点以及配体功能化等来增加金属-有机框架结构与气体分子的相互作用,来实现在温和条件下对清洁燃料气体的高密度存储。
发明内容
本发明的目的在于提供一种铜金属-有机框架材料及其制备方法,该金属-有机框架材料可作为丙炔气体存储的功能材料。
第一方面,本发明提供一种铜金属-有机框架材料,其化学式为[Cu2(C27F6H9O6)4/3(C10H8N2)],属于立方晶系,空间群为单胞参数为 α=90°,β=90°,γ=90°,Z=6;其中,C27F6H9O6代表脱去三个甲酸基团氢原子的1,3,5-三(3,5-二氟-4-羧基苯基)苯,C10H8N2代表4,4'-联吡啶。
第二方面,本发明提供一种铜金属-有机框架材料的制备方法,其包括以下步骤:
将硝酸铜、1,3,5-三(3,5-二氟-4-羧基苯基)苯、4,4'-联吡啶和有机溶剂置于高压釜中,再加入三氟乙酸,然后在353~373K下反应,得到所述铜金属-有机框架材料。
进一步地,所述硝酸铜、1,3,5-三(3,5-二氟-4-羧基苯基)苯和4,4'-联吡啶的摩尔比例为(4~6):(1~3):(1~3)。优选地,所述硝酸铜、1,3,5-三(3,5-二氟-4-羧基苯基)苯和4,4'-联吡啶的摩尔比例为4:1:1。
进一步地,所述有机溶剂为N,N-二甲基甲酰胺和乙醇溶液,所述硝酸铜、N,N-二甲基甲酰胺和乙醇的摩尔比为1:(300~400):(300~500)。
进一步地,所述三氟乙酸、N,N-二甲基甲酰胺和乙醇的体积比为1:(5~15):(5~15)。
进一步地,所述反应时间为36h。
第三方面,本发明提供一种铜金属-有机框架材料的应用,所述铜金属-有机框架材料能够作为存储丙炔气体的功能材料。
有机配体1,3,5-三(3,5-二氟-4-羧基苯基)苯和4,4'-联吡啶具有高共轭的苯环、强配位能力的氧原子和氮原子,以及双核铜簇的稳定结构可以构筑出具有新颖结构和特殊功能的的金属-有机框架材料。同时孔表面暴露的电负性氟原子是丙炔分子中弱酸性炔基氢和甲基氢原子的有利结合位点,以实现高密度的丙炔存储。
本发明的有益效果:
(1)提供了一种铜金属-有机框架材料,其合成条件温和、易操作、原料来源充足、产率较高,对反应和纯度的要求较低,适合扩大化生产的要求;
(2)该铜金属-有机框架材料表现出高丙炔存储容量,吸附量高达440~480cm3 g-1。
附图说明
图1为本发明的铜金属-有机框架材料的分子结构图。
图2为本发明的铜金属-有机框架材料的三维结构图。
图3为本发明的铜金属-有机框架材料的丙炔的吸附图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅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作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。
本发明的金属-有机框架材料[Cu2(C27F6H9O6)4/3(C10H8N2)]可以采用常规溶剂热法得到,具体反应式为:
4/3C27F6H12O6+C10H8N2+2Cu(NO3)2→Cu2(C27F6H9O6)4/3(C10H8N2)+4HNO3
C27F6H12O6是1,3,5-三(3,5-二氟-4-羧基苯基)苯的分子式,C10H8N2是4,4'-联吡啶的分子式,C27F6H9O6是1,3,5-三(3,5-二氟-4-羧基苯基)苯脱去三个甲酸基团上氢原子的分子式。
下面结合具体实施例和附图对本发明做进一步说明。
实施例1:
将硝酸铜、1,3,5-三(3,5-二氟-4-羧基苯基)苯和4,4'-联吡啶按4:1:1的摩尔比例混合放入盛有1.5毫升N,N-二甲基甲酰胺和1.5毫升4,4'-联吡啶溶剂的体积为20毫升的聚四氟乙烯内衬的高压釜中,再加入0.12毫升的三氟乙酸溶液,其中硝酸铜的量控制在7毫克左右,然后恒温在353~373K下反应36小时,得到蓝色多边形晶体为铜金属-有机框架材料[Cu2(C27F6H9O6)4/3(C10H8N2)],(C27F6H9O6代表脱去三个甲酸基团氢原子的1,3,5-三(3,5-二氟-4-羧基苯基)苯,C10H8N2代表4,4'-联吡啶)。
实施例2:
将硝酸铜、1,3,5-三(3,5-二氟-4-羧基苯基)苯和4,4'-联吡啶按5:1:2的摩尔比例混合放入盛有2毫升N,N-二甲基甲酰胺和2毫升4,4'-联吡啶溶剂的体积为20毫升的聚四氟乙烯内衬的高压釜中,再加入0.15毫升的三氟乙酸溶液,其中硝酸铜的量控制在9毫克左右,然后恒温在353~373K下反应48小时,得到蓝色多边形晶体为铜金属-有机框架材料[Cu2(C27F6H9O6)4/3(C10H8N2)],(C27F6H9O6代表脱去三个甲酸基团氢原子的1,3,5-三(3,5-二氟-4-羧基苯基)苯,C10H8N2代表4,4'-联吡啶)。
实施例3:
将硝酸铜、1,3,5-三(3,5-二氟-4-羧基苯基)苯和4,4'-联吡啶按8:2:3的摩尔比例混合放入盛有3毫升N,N-二甲基甲酰胺和3毫升4,4'-联吡啶溶剂的体积为20毫升的聚四氟乙烯内衬的高压釜中,再加入0.18毫升的三氟乙酸溶液,其中硝酸铜的量控制在12毫克左右,然后恒温在353~373K下反应48小时,得到蓝色多边形晶体为铜金属-有机框架材料[Cu2(C27F6H9O6)4/3(C10H8N2)],(C27F6H9O6代表脱去三个甲酸基团氢原子的1,3,5-三(3,5-二氟-4-羧基苯基)苯,C10H8N2代表4,4'-联吡啶)。
对实施例1得到的蓝色多边形晶体进行测试。单晶X射线衍射仪测试表明该蓝色晶体为目标化合物,即铜金属-有机框架材料。X-射线单晶衍射数据在Agilent SuperNova单晶衍射仪收集。MoKα钼靶(波长为0.71073埃)以ω扫描方式收集衍射数据。通过SHELXL-2018程序利用直接法和全矩阵最小二乘法得到所有非氢坐标,化合物的“晶体学参数”见表1,分子结构图请见图1,三维结构图请见图2。
表1.铜金属-有机框架材料[Cu2(C27F6H9O6)4/3(C10H8N2)]的晶体学参数与结构解析
注:R1=∑||Fo|-|Fc||/∑|Fo|,wR2=[∑w(Fo 2-Fc 2)2/∑w(Fo 2)2]0.5。
上述实施例中的铜金属有机框架材料是蓝色晶体,该晶体的结构中双核铜离子通过4个1,3,5-三(3,5-二氟-4-羧基苯基)苯和2个4,4'-联吡啶配体的桥连形成了三维结构(图2),因此,它是一个三维结构的金属-有机框架材料。
如表1所示,本发明的晶体结构参数为:化学式为[Cu2(C27F6H9O6)4/3(C10H8N2)],(C27F6H9O6代表脱去三个甲酸基团氢原子的1,3,5-三(3,5-二氟-4-羧基苯基)苯,C10H8N2代表4,4'-联吡啶),属于立方晶系,空间群为单胞参数为 α=90°,β=90°,γ=90°,Z=6。铜金属-有机框架材料可有效存储丙炔气体。在273K和一个大气压下,丙炔的吸附量高达477cm3g-1;当温度升高至298K时,在一个大气压下,丙炔的吸附量达443cm3 g-1,说明该铜金属-有机框架材料能实现在温和条件下高密度丙炔存储。
以上实施方式仅用于说明本发明,而并非对本发明的限制,有关技术领域的普通技术人员,在不脱离本发明的精神和范围的情况下,还可以做出各种变化和变型,因此所有等同的技术方案也属于本发明的范畴,本发明的保护范围应由权利要求限定。
Claims (9)
2.一种铜金属-有机框架材料的制备方法,包括以下步骤:
将硝酸铜、1,3,5-三(3,5-二氟-4-羧基苯基)苯、4,4'-联吡啶和有机溶剂置于高压釜中,再加入三氟乙酸,然后在353~373K下反应,得到所述铜金属-有机框架材料。
3.根据权利要求2所述的方法,其特征在于:所述硝酸铜、1,3,5-三(3,5-二氟-4-羧基苯基)苯和4,4'-联吡啶的摩尔比为(4~6):(1~3):(1~3)。
4.根据权利要求3所述的方法,其特征在于:所述硝酸铜、1,3,5-三(3,5-二氟-4-羧基苯基)苯和4,4'-联吡啶的摩尔比为4:1:1。
5.根据权利要求2所述的方法,其特征在于:所述有机溶剂为N,N-二甲基甲酰胺和乙醇溶液,所述硝酸铜、N,N-二甲基甲酰胺和乙醇的摩尔比为1:(300~400):(300~500)。
6.根据权利要求5所述的方法,其特征在于:所述三氟乙酸、N,N-二甲基甲酰胺和乙醇的体积比为1:(5~15):(5~15)。
7.根据权利要求2所述的方法,其特征在于:所述反应时间为36h。
8.根据权利要求1所述的铜金属-有机框架材料在气体存储领域的应用。
9.根据权利要求8所述的应用,其特征在于,所述铜金属-有机框架材料用于丙炔气体的存储。
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