CN109232226B - 一种微孔金属有机骨架材料及其制备方法与应用 - Google Patents
一种微孔金属有机骨架材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种微孔金属有机骨架材料及其制备方法与应用。所述微孔金属有机骨架材料的分子式为Cu3(C32H14F12O10),属于单斜晶系、P21/c空间群;其比表面积为600~700 m2/g,微孔孔容为0.20~0.30 cm3/g,微孔直径为1.0~2.0 nm。本发明的微孔金属有机骨架材料制备方法简单、无毒安全,比表面积大,展现出优良的气体吸附储存效果;不但具有良好的结晶度,并且由于其配体上的官能团和特殊的铜链结构,使材料具有良好的热稳定性、化学稳定性以及空气和水稳定性,适用范围广;而且该材料可以在吸附气体后进行脱附,并保持良好晶体结构,从而可以做到多次循环利用,具有很好的应用前景。
Description
技术领域
本发明属于杂化材料技术领域。更具体地,涉及一种微孔金属有机骨架材料及其制备方法与应用。
背景技术
氟利昂系列气体由于其具有沸点低,毒性小,化学稳定性好,常常被用于各种制冷剂、发泡剂、喷雾剂、溶剂和聚合物单体原料。由于人们生产生活对于氟利昂的大量使用,也引发或加剧了一些环境问题,比如臭氧空洞和温室效应。研究表明氟利昂是一类重要的温室气体,并且也是形成臭氧空洞的主要元凶之一。因此,开发针对氟利昂的安全高效的吸附储存材料能在一定程度上缓解此类环境问题。
金属有机骨架材料(Metal-Organic Framework,简称MOF)是通过含氧或者氮等的多齿有机配体与金属元素配位自主装而形成的有特殊孔道结构的类沸石骨架材料。其具有高的比表面积,框架结构可设计,孔道尺寸可调节,孔道表面可修饰等特点。基于这些特点,MOF成为了某些领域的例如能源或温室气体的储存和分离,多相催化,荧光检测等的具有巨大前景的材料。
但是,现有常见的金属有机骨架材料常常存在稳定性不佳、晶体合成条件较为苛刻、对特殊气体吸附储存效果不佳等问题。
发明内容
本发明要解决的技术问题是克服上述现有金属有机骨架材料的缺陷和不足,提供一种新型的单斜晶系微孔金属有机骨架材料,具有相应的优良性能,其比表面积大,微孔吸附量大,展现出了优良的R22和R134a等氟利昂的吸附储存效果;不但具有良好的结晶度,并且由于其配体上的官能团和特殊的铜链结构,使材料具有良好的热稳定性,化学稳定性以及空气和水稳定性,适用范围广。
本发明的目的是提供一种微孔金属有机骨架材料。
本发明另一目的是提供所述微孔金属有机骨架材料的制备方法。
本发明再一目的是提供所述微孔金属有机骨架材料的应用。
本发明上述目的通过以下技术方案实现:
一种微孔金属有机骨架材料,其分子式为Cu3(C32H14F12O10),其结构式如下式(I)所示:
该微孔金属有机骨架材料属于单斜晶系,P21/c空间群。
进一步优选地,所述微孔金属有机骨架材料的比表面积为600~700 m2/g。
优选地,所述微孔金属有机骨架材料的微孔孔容为0.20~0.30 cm3/g。
优选地,所述微孔金属有机骨架材料的微孔直径为1.0~2.0 nm。
另外,上述微孔金属有机骨架材料的制备方法,是将原料A、原料B和反应溶剂混合后,超声处理,再烘干、洗涤,得到产物;所述原料A为有机配体2, 2’-双三氟甲基-4,4’-联苯二羧酸,原料B为金属铜盐。
具体优选地,微孔金属有机骨架材料的制备方法包括如下步骤:
S1. 将原料A、原料B和反应溶剂混合后,超声5~10 min,再烘干,得到微孔金属有机骨架材料的粗产品;
S2. 将所得粗产品用N,N-二甲基甲酰胺洗涤6~9次,再用甲醇洗涤6~9次,得到终产品,蓝色块状晶体。
其中,优选地,所述金属铜盐为Cu(NO3)2•2.5H2O。
优选地,原料A和原料B的质量比为1:1~2。
优选地,步骤S1中反应溶剂为N,N-二甲基乙酰胺和水。
更优选地,原料A(mg)、原料B(mg)、N,N-二甲基乙酰胺(mL)和水(mL)的料液比为1:1~2:0.13~0.14:0.075~0.086。
优选地,所述烘干的条件为置于75~85 ℃下48~72 h。
另外,上述微孔金属有机骨架材料在气体吸附和/或气体储存中的应用,以及在氟利昂(如氟利昂R22或R134a)的吸附和/或储存中的应用,均应在本发明的保护范围之内。
本发明具有以下有益效果:
1. 本发明制备的的金属有机骨架材料可用于氟利昂R22和R134a等的吸附储存,可以实现常温常压对于氟利昂R22和R134a的高效吸附;而且可以在吸附气体后进行脱附,并保持良好晶体结构,从而可以做到多次循环利用。
2. 本发明金属有机骨架材料的制备方法简单,无毒安全。通过使用Cu(Ⅱ)金属离子和有机配体2,2’-双三氟甲基-4,4’-联苯二羧酸,基于“一锅法”在75~85 ℃烘箱中合成得到,由于有机配体特意引入的三氟甲基,联苯的刚性结构,以及较为特殊的铜链结构,使之具有较大的比表面积,足够大的孔道,一定的柔性以及与氟利昂较强的相互作用。
3. 本发明的金属有机骨架材料具有良好的热稳定性,化学稳定性,并且在空气和水的环境能长期保持良好的晶体结构,适用范围广。
附图说明
图1为本发明微孔金属有机骨架材料晶体样品图。
图2为本发明微孔金属有机骨架材料结构示意图。
图3为本发明实施例1~4中制备的微孔金属有机骨架材料粉末XRD图谱。
图4为本发明实施例4中制备的微孔金属有机骨架材料的红外图谱。
图5为实施例4所制备的微孔金属有机骨架材料在77 K、0~100 KPa条件下的氮气吸附等温线。
图6为实施例4所制备的微孔金属有机骨架材料在298 K、0~100 KPa条件下的R22和R134a吸附等温线。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明,以下实施例所用试剂和材料均为市购。
以下实施例中制备微孔金属有机骨架材料的原料为:
有机配体:2,2’-双三氟甲基-4,4’-联苯二羧酸;
金属铜盐:Cu(NO3)2•2.5H2O;
反应溶剂:N,N-二甲基乙酰胺、水。
实施例1
顺序将15mg 2,2’-双三氟甲基-4,4’-联苯二羧酸、15mg Cu(NO3)2•2.5H2O加入至10 mL玻璃瓶中,再加入1.90mL N,N-二甲基乙酰胺和1.13mL水,超声5 min,放入75 ℃烘箱,静置72 h,降至室温,得到微孔金属有机骨架材料的粗产品;粗产品用N,N-二甲基甲酰胺洗涤6次,再用甲醇洗涤6次,得到终产品,蓝色块状晶体,即为微孔金属有机骨架材料。
上述制备的微孔金属有机骨架材料晶体空间群为P21/c,晶胞参数为10.4982,29.3526,33.7985,90.0,90.0,95.212。
将晶体进行XRD粉末衍射表征,得到衍射图谱如图3中实施例1样品所示,与实施例4单晶数据模拟一致。材料在77 K,0~100 KPa条件下,N2的吸附量为154 cm3/g;在298 K,0~100 KPa下,R22和R134a的吸附量分别为32 cm3/g和27 cm3/g,其性能与实施例4样品大致相同。
实施例2
顺序称取15 mg 2,2’-双三氟甲基-4,4’-联苯二羧酸,30 mg Cu(NO3)2•2.5H2O,2.06 mL N,N-二甲基乙酰胺和1.28 mL水,超声10 min,放入85 ℃烘箱,静置48h,降至室温,得到微孔金属有机骨架材料的粗产品;粗产品用N,N-二甲基甲酰胺洗涤9次,再用甲醇洗涤9次,得到终产品,蓝色块状晶体,即为微孔金属有机骨架材料。
上述制备的微孔金属有机骨架材料晶体空间群为P21/c,晶胞参数为10.5001,29.2489,33.8134,90.0,90.0,95.310。
将晶体进行XRD粉末衍射表征,得到衍射图谱如图3中实施例2样品所示,与实施例4单晶数据模拟一致。材料在77 K,0~100 KPa条件下,N2的吸附量为149 cm3/g;在298 K,0~100 KPa下,R22和R134a的吸附量分别为30 cm3/g和26 cm3/g,其性能与实施例4样品大致相同。
实施例3
顺序称取15 mg 2,2’-双三氟甲基-4,4’-联苯二羧酸,18 mg Cu(NO3)2•2.5H2O,2.00 mL N,N-二甲基乙酰胺和1.20 mL水,超声5 min,放入80 ℃烘箱,静置48 h,降至室温,得到微孔金属有机骨架材料的粗产品;粗产品用N,N-二甲基甲酰胺洗涤7次,再用甲醇洗涤7次,得到终产品,蓝色块状晶体,即为微孔金属有机骨架材料。
上述制备的微孔金属有机骨架材料晶体的晶胞参数为其晶体空间群为P21/c,晶胞参数为10.4532,29.4582,33.9548,90.0,90.0,95.785。
将晶体进行XRD粉末衍射表征,得到衍射图谱如图3中实施例3样品所示,与实施例4单晶数据模拟一致。材料在77 K,0~100 KPa条件下,N2的吸附量为162 cm3/g;在298 K,0~100 KPa下,R22和R134a的吸附量分别为34 cm3/g和29 cm3/g,其性能与实施例4样品大致相同。
实施例4
顺序称取90 mg 2,2’-双三氟甲基-4,4’-联苯二羧酸,108 mg Cu(NO3)2•2.5H2O,12.00 mL N,N-二甲基乙酰胺和7.20 mL水,超声10 min,放入80 ℃烘箱,静置72 h,降至室温,得到微孔金属有机骨架材料的粗产品;粗产品用N,N-二甲基甲酰胺洗涤89次,再用甲醇洗涤8次,得到终产品,蓝色块状晶体,即为微孔金属有机骨架材料。
本实施例4合成了以二价铜离子为中心,含三氟甲基官能团的微孔金属有机骨架材料,该上述制备的微孔金属有机骨架材料晶体的空间群是P21/c,晶胞参数为10.5076,29.4609,33.8086,90.0,90.0,95.482。
制备的微孔金属有机骨架材料晶体样品图如图1所示,结构示意图如图2所示,红外图谱如图4所示。
将晶体进行XRD粉末衍射表征,得到衍射图谱如图3中实施例4样品所示,与单晶数据模拟一致。
77 K、0~100 KPa条件下所制备的微孔金属有机骨架材料的氮气吸附等温线如图5所示,其吸附量为158 cm3/g,比表面积为663 m2/g,微孔孔容为0.28 cm3/g,微孔直径约为1.4 nm。298 K、0~100 KPa条件下所制备的微孔金属有机骨架材料的R22和R134a吸附等温线如图6所示,吸附量分别为35 cm3/g和29 cm3/g,表明材料能在常温常压下对R22和R134a进行高效吸附。故其可作为有一定应用前景的氟利昂的工业吸附储存材料。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (9)
2.根据权利要求1所述微孔金属有机骨架材料,其特征在于,其比表面积为600~700m2/g。
3.根据权利要求1所述微孔金属有机骨架材料,其特征在于,其微孔孔容为0.20~0.30cm3/g。
4.根据权利要求1所述微孔金属有机骨架材料,其特征在于,其微孔直径为1.0~2.0nm。
5.权利要求1~4任一所述微孔金属有机骨架材料的制备方法,其特征在于,将原料A、原料B和反应溶剂混合后,超声处理,再烘干、洗涤,得到产物;所述原料A为2,2’-双三氟甲基-4,4’-联苯二羧酸,原料B为金属铜盐。
6.根据权利要求5所述的制备方法,其特征在于,包括如下步骤:
S1.将原料A、原料B和反应溶剂混合后,超声5~10min,再烘干,得到微孔金属有机骨架材料的粗产品;
S2.将所得粗产品用N,N-二甲基甲酰胺洗涤6~9次,再用甲醇洗涤6~9次,得到终产品。
7.根据权利要求5所述的制备方法,其特征在于,所述金属铜盐为Cu(NO3)2·2.5H2O。
8.根据权利要求5或6所述的制备方法,其特征在于,原料A和原料B的质量比为1:1~2。
9.权利要求1~4任一所述微孔金属有机骨架材料在气体吸附中的应用,其特征在于,所述气体为N2、氟利昂R22或氟利昂R134a。
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