CN106188107B - 多功能锌基有机无机杂化材料、其制备方法与应用 - Google Patents
多功能锌基有机无机杂化材料、其制备方法与应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 9
- -1 bipyridyl dioctyl phthalate anion Chemical class 0.000 claims abstract description 6
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
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- 239000011701 zinc Substances 0.000 claims description 6
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- 238000010276 construction Methods 0.000 claims description 5
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
本发明公开了一种多功能锌基有机无机杂化材料、其制备方法与应用。所述多功能锌基有机无机杂化材料具有下述化学式:[Zn2(bpydb)(atz)2](DMA)8,其中bpydb为联吡啶二甲酸阴离子配体,atz为3‑氨基‑1,2,4‑三氮唑阴离子,DMA为N,N‑二甲基乙酰胺,所述多功能锌基有机无机杂化材料结晶于三方晶系(trigonal),空间群为P3121,晶胞参数为 本发明多功能锌基有机无机杂化材料具有较高的BET比表面积与孔隙率,并且具有较好的耐高温性能,其制备工艺简单,原料廉价易得,反应条件温和,易于大批量制备。本发明的多功能锌基有机无机杂化材料在C2H2储存、选择性分离及苦味酸荧光识别方面有良好应用价值,可广泛应用于工业化气体储存与液相中苦味酸污染物的识别。
Description
技术领域
本发明涉及晶态材料的制备,特别涉及一种多功能锌基有机无机杂化材料及其制备方法与应用。
背景技术
作为一类先进的多孔晶态材料,金属有机框架在过去的几十年里表现出了迅速发展,并在能源气体的储存与环境污染物的识别领域表现出了许多潜在的可应用价值。一般而言,金属有机框架是由金属节点与有机配体组成的。相比较于金属节点,有机配体更具有选择性与可设计性。科学家们可以利用有机合成的方法设计出各种含有不同配原子与极性官能团的有机配体来构筑金属有机框架材料,然而该方法通常需要较长的合成路线以及昂贵的合成试剂,对材料的成本控制十分不利。另一方面,采用混合配体策略来构筑金属有机框架材料被证明是一种廉价的向材料中引入活性基团与调控框架结构的优良方法。人们可以选择含有羧基类配体与氮唑类配体一同来构筑混合配体的金属有机框架材料,一般也会得到不错的效果。但是在使用混合配体构筑的金属有机框架中,框架的穿插一直以来是困扰着研究人员的难题。
发明内容
本发明的主要目的在于提供一种多功能锌基有机无机杂化材料、其制备方法与应用,以克服现有技术的不足。
为实现前述发明目的,本发明采用的技术方案包括:
本发明实施例提供了一种多功能锌基有机无机杂化材料,其具有下述化学式:[Zn2(bpydb)(atz)2](DMA)8,其中bpydb为联吡啶二甲酸阴离子配体,atz为3-氨基-1,2,4-三氮唑阴离子,DMA为N,N-二甲基乙酰胺,bpydb的结构简式如下:
所述多功能锌基有机无机杂化材料结晶于三方晶系(trigonal),空间群为P3121,晶胞参数为
以及,所述多功能锌基有机无机杂化材料的主要红外吸收峰为:3365br,3165w,1680s,1622s,1615s,1362s,1242m,1081m,822m,819s,763s。
进一步的,所述多功能锌基有机无机杂化材料具有由三氮唑连接金属锌形成的一维螺旋次级构筑单元(SBUs)链,所述单元链中的锌离子存在两种不同的配位构型,在其中的一种配位构型中,由一个五配位的锌离子(Zn2)与其对称操作五配位的Zn原子以及两个三氮唑基团组成双核金属单元,而在另一种配位构型中,由另一个五配位的锌离子(Zn1)与其对称操作五配位的Zn原子沿着晶体c方向延伸形成一维螺旋次级构筑单元链,所述次级构筑单元链通过联吡啶苯甲酸配体在三维方向相互连接组成具有一维双孔型孔道的所述多功能锌基有机无机杂化材料。
本发明实施例还提供了所述多功能锌基有机无机杂化材料的制备方法,其包括:将摩尔比为4:1:5~4:1:10的锌盐、联吡啶苯甲酸配体和3-氨基-1,2,4-三氮唑在溶剂中充分混合,之后在温度为120~130℃条件下固化处理48~72h,获得黄色块状晶体,即为所述的多功能锌基有机无机杂化材料。
其中,所述锌盐包括六水硝酸锌,但不限于此。
其中,所述溶剂包括DMA,但不限于此。
在一些较为具体的实施方案中,所述制备方法包括:将锌盐、联吡啶苯甲酸配体与3-氨基-1,2,4-三氮唑混合均匀得到混合物,再加入到溶剂中,其中所述混合物与溶剂的用量比为310mg:3mL~310mg:6mL,常温搅拌30~40min,充分混合后,再进行固化处理。
在一些较为具体的实施案例中,所述的制备方法包括:将六水硝酸锌、联吡啶苯甲酸与氨基三氮唑混合匀得到混合物,然后加入到DMA中,常温搅拌30min,得到混合液;120℃下烘制72h,然后将固体分离;用DMA将上述固体洗涤3-5次,即可得到黄色块状杂化晶体材料。
本发明实施例还提供了所述多功能锌基有机无机杂化材料于储存C2H2、选择性分离C2H2或识别苦味酸中的应用。
进一步的,本发明实施例还提供了所述多功能锌基有机无机杂化材料于制备C2H2储存材料或苦味酸识别材料中的用途。
进一步的,本发明实施例还提供了C2H2储存材料,其由所述的多功能锌基有机无机杂化材料制成。
本发明实施例还提供了一种C2H2储存材料或C2H2选择性吸附材料的制备方法,其包括:将所述多功能锌基有机无机杂化材料以二氯甲烷浸泡60~72小时,之后在真空环境中于30~40℃加热24~36h。
在一些较为具体的实施案例中,所述C2H2选择性吸附材料的制备方法包括:将所述多功能锌基有机无机杂化材料用二氯甲烷浸泡72小时以交换其孔道中的高沸点DMA分子,取将交换后的所述多功能锌基有机无机杂化材料在30℃下、真空度1m bar下加热24h以除去其孔道中的二氯分子,填装到存放C2H2吸附剂的装置中备用即可。
本发明实施例还提供了一种苦味酸识别材料,其由所述多功能锌基有机无机杂化材料制成。
本发明实施例还提供了一种苦味酸识别方法,其包括:将所述多功能锌基有机无机杂化材料分散到DMA溶剂中,再加入可能含苦味酸的待分析液体,然后进行荧光测试。
进一步的,所述的苦味酸识别方法包括:将所述的多功能锌基有机无机杂化材料充分研磨后,再均匀分散(例如可借助超声分散方式)到DMA溶剂中。
与现有技术相比,本发明的优点包括:
(1)本发明提供的多功能锌基有机无机杂化材料具有较高的BET比表面积与孔隙率,并且具有较好的耐高温性能及热稳定性,并且在客体分子脱除后仍然可以保持原始的框架结构;
(2)本发明提供的多功能锌基有机无机杂化材料的制备工艺合成原料廉价易得,反应条件温和,易于大批量制备;
(3)本发明提供的多功能锌基有机无机杂化材料在273K时对C2H2的吸附量能达到215cm3g-1,而CH4的吸附量只有25cm3g-1,因此在乙炔的储存领域有良好的潜在应用价值;并且对苦味酸表现出了优异的选择性荧光识别作用,可应用于工业化气体储存与液相中苦味酸污染物的识别。
附图说明
图1是本发明实施例1所获[Zn2(bpydb)(atz)2](DMA)8的单晶衍射结构图;
图2是本发明实施例1所获[Zn2(bpydb)(atz)2](DMA)8的双孔结构示意图;
图3是本发明实施例1所获[Zn2(bpydb)(atz)2](DMA)8的BET测试图;
图4是本发明实施例1所获[Zn2(bpydb)(atz)2](DMA)8的气体吸附曲线图;
图5是本发明实施例1所获[Zn2(bpydb)(atz)2](DMA)8的荧光测试图。
具体实施方式
鉴于现有技术中的不足,本案发明人经长期研究和大量实践,得以提出本发明的技术方案,为了使本发明的目的、技术方案及优点更加清楚明白,以下结合具体实施例,对本发明进行进一步详细说明,下列实施例中的方法,如无特别说明,均为本领域的常规方法。
实施例1:多功能锌基有机无机杂化材料的制备
将120mg六水硝酸锌、40mg联吡啶苯甲酸与150mg氨基三氮唑配体烧杯内混合均匀得到混合物,然后加入4mLDMA,常温搅拌30min,得到混合液;将上述混合液转入到10mL带有螺旋塞子的小瓶在120℃下烘制48h,降至室温后过滤、分离后得到产物;用DMA将上述固体洗涤3次,即可得到黄色条状杂化材料晶体,基于有机配体计算产率为75%。主要的红外吸收峰为:3365br,3165w,1680s,1622s,1615s,1362s,1242m,1081m,822m,819s,763s。
实施例2:多功能锌基有机无机杂化材料的制备
将120mg六水硝酸锌、40mg联吡啶苯甲酸与80mg氨基三氮唑配体烧杯内混合均匀得到混合物,然后加入4mLDMA,常温搅拌30min,得到混合液;将上述混合液转入到10mL带有螺旋塞子的小瓶在130℃下烘制72h,降至室温后过滤、分离后得到产物;用DMA将上述固体洗涤3次,即可得到黄色条状杂化材料晶体,基于有机配体计算产率为64%。主要的红外吸收峰为:3365br,3165w,1680s,1622s,1615s,1362s,1242m,1081m,822m,819s,763s。
实施例3:多功能锌基有机无机杂化材料的制备
将120mg六水硝酸锌、40mg联吡啶苯甲酸与120mg氨基三氮唑配体烧杯内混合均匀得到混合物,然后加入6mLDMA,常温搅拌30min,得到混合液;将上述混合液转入到10mL带有螺旋塞子的小瓶在125℃下烘制72h,降至室温后过滤、分离后得到产物;用DMA将上述固体洗涤3次,即可得到黄色条状杂化材料晶体,基于有机配体计算产率为72%。主要的红外吸收峰为:3365br,3165w,1680s,1622s,1615s,1362s,1242m,1081m,822m,819s,763s。
取实施例1中所得的多功能锌基有机无机杂化材料进一步表征,其过程及结果如下:
(1)晶体结构测定
在偏光显微镜下,选取合适大小的单晶在室温下进行X-射线单晶衍射实验。采用Supernova型X射线单晶衍射仪,使用经过石墨单色化的Mo-Kα射线酚为入射辐射源,以扫描方式收集衍射点,经过最小二乘法修正得到晶胞参数,从差值fourier电子密度图利用SHELXL-97直接法解得晶体结构,并经lorent和极化效应修正。所有的H原子由差值傅里叶合成并由理想位置计算确定,详细的晶体测定数据见表1,重要的键长和键角数据见表2-表3,晶体结构见图1。
表1多功能锌基有机无机杂化材料
aR1=Σ||Fo|–|Fc||/Σ|Fo|.bwR2=|Σw(|Fo|2–|Fc|2)|/Σ|w(Fo)2|1/2,where w=1/[σ2(Fo 2)+(aP)2+bP].P=(Fo 2+2Fc 2)/3.
表2多功能锌基有机无机杂化材料的主要键长*
表3多功能锌基有机无机杂化材料的主要键角[°]*
对称操作码:1-Y+X,-Y,5/3-Z;2-Y+X,-Y,2/3-Z;3-X,-X+Y,4/3-Z;4+Y,-1+X,1-Z;51+Y,+X,1-Z。
(2)气体吸附测试:
气体吸附脱附曲线由麦克3Flex气体测试工作站上测得,将制备好的样品在仪器上首先进行脱气处理,温度条件为30℃,处理时间为12h,脱气后进行气体吸附脱附分析,其过程全自动控制。
图4是[Zn2(bpydb)(atz)2](DMA)8的气体吸附曲线图,分别测试了273与298K下的C2H2、CO2和CH4的吸附曲线,图中表明:该产品在273K时对C2H2的吸附量能达到218cm3g-1,而CH4的吸附量只有20cm3g-1,说明了该杂化材料具有对C2H2具有较高的储存能力。
(3)荧光检测测试
荧光测试结果由安捷伦Cary Eclipse型荧光光谱仪测得,将制备好的样品首先充分研磨,然后加入到DMA溶液中超声30分钟,然后加入到比色皿中待分析测试。
图5是[Zn2(bpydb)(atz)2](DMA)8的荧光检测图,分别测试了加入20ppm不同取代基苯同系物的荧光图,图中表明:只有苦味酸(2,4,6-三硝基苯酚)可以较好的实现荧光淬灭。
采用同样的表征方式对实施例2-3所获产物进行表征,亦可获得与实施例1相似之测试结果。
应当理解,上述实施例仅为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (7)
1.一种多功能锌基有机无机杂化材料,其特征在于它具有下述化学式:[Zn2(bpydb)(atz)2](DMA)8,其中bpydb为4,4’-(4,4’-二吡啶基-2,6-二基)-二苯甲酸阴离子配体,atz为3-氨基-1,2,4-三氮唑阴离子,DMA为N,N-二甲基乙酰胺,bpydb的结构简式如下:
所述多功能锌基有机无机杂化材料结晶于三方晶系,空间群为P3121,晶胞参数为
以及,所述多功能锌基有机无机杂化材料的主要红外吸收峰为:3365br,3165w,1680s,1622s,1615s,1362s,1242m,1081m,822m,819s,763s;
并且,所述多功能锌基有机无机杂化材料具有由三氮唑连接金属锌形成的一维螺旋次级构筑单元链,所述单元链中的锌离子存在两种不同的配位构型,在其中的一种配位构型中,由一个五配位的锌离子与其对称操作五配位的Zn原子以及两个三氮唑基团组成双核金属单元,而在另一种配位构型中,由另一个五配位的锌离子与其对称操作五配位的Zn原子沿着晶体c方向延伸形成一维螺旋次级构筑单元链,所述次级构筑单元链通过4,4’-(4,4’-二吡啶基-2,6-二基)-二苯甲酸配体在三维方向相互连接组成具有一维双孔型孔道的所述多功能锌基有机无机杂化材料。
2.如权利要求1所述的多功能锌基有机无机杂化材料的制备方法,其特征在于包括:将摩尔比为4:1:5~4:1:10的锌盐、4,4’-(4,4’-二吡啶基-2,6-二基)-二苯甲酸配体和3-氨基-1,2,4-三氮唑混合均匀得到混合物,再加入到溶剂中,其中所述混合物与溶剂的用量比为310mg:3mL~310mg:6mL,常温搅拌30~40min,充分混合后,再在温度为120~130℃条件下固化处理48~72h,获得黄色块状晶体,即为所述的多功能锌基有机无机杂化材料,所述锌盐为六水硝酸锌,所述溶剂为DMA。
3.如权利要求1所述的多功能锌基有机无机杂化材料于储存C2H2、选择性分离C2H2或识别苦味酸中的应用。
4.权利要求1所述的多功能锌基有机无机杂化材料于制备C2H2储存材料或苦味酸识别材料中的用途。
5.一种C2H2储存材料或C2H2选择性吸附材料的制备方法,其特征在于包括:将权利要求1所述的多功能锌基有机无机杂化材料以二氯甲烷浸泡60~72小时,之后在真空环境中于30~40℃加热24~36h。
6.一种苦味酸识别方法,其特征在于包括:将权利要求1所述的多功能锌基有机无机杂化材料分散到DMA溶剂中,再加入含苦味酸的待分析液体,然后进行荧光测试。
7.根据权利要求6所述的苦味酸识别方法,其特征在于包括:将所述的多功能锌基有机无机杂化材料充分研磨后,再均匀分散到DMA溶剂中。
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