CN110358106B - 一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料及其制备方法和应用 - Google Patents
一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料,其如式I所示:Cd2(m‑PIPy)(NDC)3,所述阴离子骨架金属有机框架材料的晶胞参数为a=14.4598,b=17.5129,c=22.1325,α=74.873,β=74.357,γ=87.834;其中,m‑PIPy为1,3‑二([4‑(1‑咪唑基)‑吡啶基]‑亚甲基)苯二溴化物,NDC为1,4‑萘二甲酸。该阴离子骨架金属有机框架材料以m‑PIPy和NDC为配体,构建了一种新的阴离子骨架金属有机框架材料,拓展了金属有机框架材料的种类和应用领域。本发明还公开了该阴离子骨架金属有机框架材料的制备方法和应用。
Description
技术领域
本发明属于金属有机框架材料技术领域,具体涉及一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料及其制备方法和应用。
背景技术
金属有机骨架材料(MOFs)是近十年来发展迅速的一种配位聚合物,其具有三维的孔结构,一般以金属离子为连接点,有机配体位支撑构成空间3D延伸,系沸石和碳纳米管之外的又一类重要的新型多孔材料。作为一种新型多孔材料,金属有机框架材料有着结构丰富、组成多样,优秀的热稳定性和化学稳定性、超高的孔隙率和极大的比表面积等优点,引起了大量研究工作者的关注。金属有机框架材料同时也有着非常好的可修饰性,可以通过实际需要,对有机配体的类型,金属离子的种类及功能基团嫁接等方式,制备出具有特异性的功能金属有机框架材料。合成制备金属有机骨架材料常用的有机配体一般是羧酸含氧类和杂环含氮类配体,如咪唑类和吡啶类杂环上的氮原子为sp2杂化且有孤对电子,它们有着很强的配位能力,并且含氮杂环可形成π-π堆积,能在聚合物框架中形成具有π-π堆积或氢键的化学作用,形成的金属有机框架材料在气体吸附分离、荧光传感、生物医药、化学催化与磁性分子材料等领域具有重要的应用。
硝基芳烃爆炸物,如:三硝基苯酚、三硝基甲苯、二硝基甲苯等化合物,具有制备方法成熟、钝感好、便于携带等特点,被广泛应用于军事生产和工业爆破中。该类化合物不仅爆炸威力大,而且毒性大、难降解、致癌能力强,侵入人体后可引起呕吐、抽搐、神经系统紊乱甚至死亡等,同时他们也可以被恐怖份子利用用于恐怖袭击。因此开发硝基爆炸物的快速痕量检测技术,对防止恐怖袭击、维护公共安全和保障人类健康具有重要意义。目前可以利用荧光传感技术来检测痕量硝基芳烃爆炸物。荧光传感检测法是利用荧光信号如波长、强度等的改变来达到分析检测的目的,它具有响应速度快、灵敏度高、操作简便、抗电磁干扰能力强等优点。金属有机框架材料所具有的多孔性、功能化的特点常被用在荧光传感分析研究领域。
目前所应用的金属有机骨架材料一般都是阳离子骨架结构,关于阴离子骨架结构的金属有机框架材料鲜有报道。
发明内容
本发明的目的在于克服上述技术不足,提出一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料,该阴离子骨架金属有机框架材料拓展了金属有机框架材料的种类;本发明第二方面的目的在于,提出一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料的制备方法;本发明第三方面的目的在于,提出一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料的应用。
为达到上述技术目的,本发明的技术方案提供一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料,所述阴离子骨架金属有机框架材料如式I所示:Cd2(m-PIPy)(NDC)3,所述阴离子骨架金属有机框架材料的晶胞参数为a=14.4598,b=17.5129,c=22.1325,α=74.873,β=74.357,γ=87.834;其中,m-PIPy为1,3-二([4-(1-咪唑基)-吡啶基]-亚甲基)苯二溴化物,NDC为1,4-萘二甲酸。
本发明的技术方案还提供了一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料的制备方法,包括如下步骤:1,3-二([4-(1-咪唑基)-吡啶基]-亚甲基)苯二溴化物、1,4-萘二甲酸与硝酸镉进行溶剂热反应,合成得到阴离子骨架的金属有机框架材料。
本发明的技术方案还提供了一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料对痕量硝基芳烃爆炸物的传感性质以及检测方面的应用。
与现有技术相比,本发明的有益效果包括:。
1、本发明提供的阴离子骨架金属有机框架材料以1,3-二([4-(1-咪唑基)-吡啶基]-亚甲基)苯二溴化物和1,4-萘二甲酸为配体,构建了一种新的阴离子骨架金属有机框架材料,拓展了金属有机框架材料的种类和应用领域;
2、本发明提供的阴离子骨架金属有机框架材料的制备方法,具有合成方法简单,生产成本低,且能够适用于大规模生产的特点,且所合成的阴离子骨架金属有机框架材料具有产品纯度高的优点;
3、本发明提供的阴离子骨架金属有机框架材料具有较大的淬灭常数和较低的检出限,对于实际检测硝基芳烃化合物的荧光传感器材料具有很大的应用前景。
附图说明
图1为金属中心Cd(Ⅱ)与1,4-萘二甲酸阴离子连接形成阴离子骨架3D网状结构示意图,其中平衡配体为m-PIPy阳离子;
图2为Cd(II)和1,4-萘二甲酸以三种连接方式形成3D框架结构示意图;
图3为阳离子配体m-PIPy被包含在孔道内的结构示意图;
图4为阴离子骨架金属有机框架材料的实验和模拟粉末衍射的PXRD谱图;
图5为阴离子骨架金属有机框架材料的不同硝基芳香烃的荧光图谱;
图6为阴离子骨架金属有机框架材料的不同硝基芳香烃的荧光淬灭效率示意图;
图7为阴离子骨架金属有机框架材料的不同浓度硝基芳香烃TNP的荧光图谱;
图8为阴离子骨架金属有机框架材料的不同浓度硝基芳香烃TNP的Stern–Volmer图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明的实施例提供了一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料,该阴离子骨架金属有机框架材料如式I所示:Cd2(m-PIPy)(NDC)3(I),所述阴离子骨架金属有机框架材料的晶胞参数为a=14.4598,b=17.5129,c=22.1325,α=74.873,β=74.357,γ=87.834;其中,m-PIPy为1,3-二([4-(1-咪唑基)-吡啶基]-亚甲基)苯二溴化物,NDC为1,4-萘二甲酸。
本发明中,m-PIPy的结构式如下所示:
本发明的实施例提供的阴离子骨架金属有机框架材料的不对称单元由一个m-PIPy配体、三个1,4-萘二甲酸配体,两个Cd(Ⅱ)离子组成。单晶X-射线衍射分析表明:该化合物属于三斜晶系,Pī空间群,该化合物中的不对称单元由一个m-PIPy配体、三个1,4-萘二甲酸配体,两个Cd(Ⅱ)离子组成一个具有三维孔洞结构带有二个负电荷的阴离子骨架的框架结构。如图2所示,在不同的配位环境中存在四个晶体学上独立的Cd(II)中心(Cd1、Cd2、Cd3和Cd4)。Cd1与三个双齿螯合的羧酸配体的六个氧原子(O3和O4,O7和O8,O9和O10)和一个单齿配位的羧酸氧原子(O20)配位。Cd2与一个双齿螯合的羧酸配体的两个氧原子(O1,O2)和四个单齿配位的羧酸氧原子(O11,O12,O13,O14)配位。Cd3与两个双齿螯合的羧酸配体的四个氧原子(O15和O16,O23和O24)和两个单齿配位的羧酸氧原子(O17,O18)配位。Cd4与三个双齿螯合的羧酸配体的六个氧原子(O5和O6,O19和O20,O21和O22)和一个单齿配位的羧酸氧原子(O10)配位。如图3所示,阳离子配体m-PIPy配体存在于阴离子框架结构的孔洞中,起到电荷平衡的作用,自身并未参与配位,共同形成金属有机框架化合物。如表1和表2所示,表1为本发明阴离子骨架金属有机框架材料的部分键长和键角(°),表2为本发明阴离子骨架金属有机框架材料的晶胞参数表。
Symmetry codes:(i)x-1,y+1,z;(ii)-x,-y,-z+2;(iii)-x,-y+1,-z+2;(iv)-x+1,-y,-z+1;(v)-x+1,-y-1,-z+1;(vi)x+2,y-1,z;(vii)x+1,y-1,z;(viii)x-2,y+1,z.
表2本发明阴离子骨架金属有机框架材料的晶胞参数表
本发明的阴离子骨架金属有机框架材料以1,3-二([4-(1-咪唑基)-吡啶基]-亚甲基)苯二溴化物(m-PIPy)为配体,构筑阴离子骨架金属有机框架材料,其中1,3-二([4-(1-咪唑基)-吡啶基]-亚甲基)苯二溴化物的制备方法为:4-PIM和间二溴苄在甲醇中反应,得到反应产物;将反应产物与K2CO3溶液反应,得到1,3-二([4-(1-咪唑基)-吡啶基]-亚甲基)苯二溴化物。
在制备m-PIPy的过程中,4-PIM和间二溴苄在加热条件下进行,加热温度为70~80℃,反应时间为15~20h;更优选地,加热温度为78℃,反应时间为18h。
得到反应产物之后,旋干甲醇,向反应产物中加入K2CO3溶液,有大量固体产生,经过抽滤,乙醇重结晶,干燥,得黄色固体粉末m-PIPy。
本发明的实施例还提供了一种对硝基芳烃爆炸物传感的阴离子骨架金属有机框架材料的制备方法,包括如下步骤:1,3-二([4-(1-咪唑基)-吡啶基]-亚甲基)苯二溴化物(m-PIPy)、1,4-萘二甲酸(NDC)与硝酸镉在溶剂中反应,合成得到阴离子骨架的金属有机框架材料。
在制备上述阴离子骨架的金属有机框架材料的过程中,本申请以1,3-二([4-(1-咪唑基)-吡啶基]-亚甲基)苯二溴化物(m-PIPy)为配体,合成了阴离子骨架的金属有机框架材料。
本发明的实施例中,溶剂为本领域技术人员熟知的无机溶剂和/或有机溶剂,对此本申请没有特别的限制,示例的,溶剂为甲醇和水;反应为溶剂热反应,在本发明的实施例中,反应温度为140~180℃,反应时间为3~5天,采用逐步升温的方式从常温升至反应温度,升温速率为2℃/min;在本发明的一些优选实施方式中,反应温度为170℃,反应时间为3天。
溶剂热反应在碱性环境下进行,有利于形成阴离子骨架的金属有机框架材料,碱为本领域技术人员熟知的碱,示例的,碱为氢氧化钠。
反应之后,得到的材料的孔道中可能含有未反应的有机配体和溶剂,还需要进行后续处理,该阴离子骨架的金属有机框架材料的制备方法具体为:
将1,3-二([4-(1-咪唑基)-吡啶基]-亚甲基)苯二溴化物(m-PIPy)、1,4-萘二甲酸(NDC)与硝酸镉在氢氧化钠、甲醇和水中反应,得到黄色透明块状晶体;将黄色块状晶体用乙醇和水洗涤,经过真空干燥,得到阴离子骨架的金属有机框架材料。
本发明的实施例还提供了该阴离子骨架的金属有机框架材料对痕量硝基芳烃爆炸物的传感性质以及检测方面的应用。
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。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明中的实验方法,如无特殊说明,均为常规方法。本发明中所用的实验材料如无特殊说明,均为市场购买得到。
实施例1:
配体m-PIPy的合成,合成路线如下:
在50mL圆底烧瓶中加入4-PIM(10mmol,1.45g),间二溴苄(5mmol,1.32g),甲醇(10mL),78℃搅拌18h。停止反应,冷却至室温。旋干甲醇,向反应液加入K2CO3溶液(K2CO3:H2O=1.3g:20g),有大量固体产生,抽滤,乙醇重结晶,干燥,得黄色固体粉末3.26g,产率59%。
Yield:59%,m.p.:155-180℃;ESI-MS:[M–2Br-]2+m/z=197.35,(Calcd:197.23)
IR(νmax,KBr,cm-1):3405m,1632vs,1529m,1479m,1435m,1392s,1280w,1171m,1061m,1032m,953w,859w,755w,712w.
1H NMR(300MHz,DMSO-d6),δ=8.74(d,J=6.8Hz,4H),8.24(d,J=6.8Hz,4H),7.52(m,4H),7.50(s,4H),5.64(s,4H)
13C NMR(75MHz,DMSO-d6),δ(ppm)=150.7,149.3,148.8,142.5,136.9,136.6,130.4,128.8,128.1,118.5,60.5.
实施例2:
Cd2(m-PIPy)(NDC)3的合成:向20mL聚四氟乙烯瓶中加入Cd(NO3)2·4H2O(0.2mmol,45.7mg),1,4-萘二甲酸(0.2mmol,43.5mg),m-PIPy(0.1mmol,39.2mg),NaOH(0.4mmol,16mg),甲醇(3mL),H2O(5mL)后,密封置于反应釜中,用烘箱以2℃/min的速率将反应釜内混合液的温度升至170℃,并保温3天(4320min)后,再以3℃/h的速率降温至室温,得到黄色透明块状晶体;将黄色透明块状晶体过滤,用乙醇和水洗涤后,真空干燥,得到Cd2(m-PIPy)(NDC)3,收率为51%。IR(νmax,KBr,cm-1):3432m,2924m,1635s,1563s,1510s,1479s,1406s,1358s,1261m,1165m,1114m,1030w,938w,832m,788m,711m.
实施例3:
为了表征所合成阴离子骨架的金属有机框架材料的相纯度,对其进行了PXRD表征,得到图4。
如图4所示,利用CIF文件进行了粉末数据的模拟,并将样品所测得的实验数据与其进行对比,可以看出化合物2的粉末衍射数据与由它的单晶晶体结构模拟计算得到的数据保持一致,具有很高的吻合度,这说明了这些聚合物粉末结构与晶体结构保持一致且不含其它杂质。
实施例4:
Cd2(m-PIPy)(NDC)3对不同硝基芳香烃的荧光传感:采用不用的硝基芳烃:2,4,6-苦味酸(TNP),对硝基苯胺(4-NA),对硝基苯酚(4-NP),对硝基甲苯(4-NT),2,4-二硝基甲苯(2,4-DNT),2,4-二硝基氯苯(2,4-DNC),2-硝基苯酚(2-NP),2,4-二硝基苯胺(2,4-DNA)。取5mg Cd2(m-PIPy)(NDC)3分别加入5mL含不同硝基芳烃的DMSO溶液(c=10-4mol/L)中,超声20min后成悬浊液,静置1h后取上层清液进行荧光测试,激发波长λex=360nm。其荧光光谱图如图5,从图可以看出所有八种硝基芳烃化合物都能减弱化合物2的荧光强度,淬灭荧光的程度有所不同,硝基芳烃的荧光淬灭效率为:TNP>2,4-DNA>2,4-DNT>4-NT>4-NP>2,4-DNC>4-NA>2-NP。八种硝基芳烃化合物的荧光淬灭效率如图6所示。
实施例5:
Cd2(m-PIPy)(NDC)3对硝基芳烃化合物TNP的检出限:取5mg Cd2(m-PIPy)(NDC)3加入到5mL不同浓度TNP的DMSO溶液(c=0ppm,10ppm,20ppm,35ppm,50ppm,100ppm)中,超声20min后成悬浊液,静置1h后取上层清液进行荧光测试,激发波长λex=360nm,其图谱如图7所示。由图7可以看出,随着TNP浓度的增加,荧光强度逐渐降低。定量荧光淬灭效率可以借助于Stern-Volmer(SV)方程来解释:(I0/I)=1+KSV[Q],可以观察到当这些硝基芳烃化合物的浓度处于低浓度时,TNP的Stern–Volmer曲线几乎是线性的,如图8所示。Cd2(m-PIPy)(NDC)3相应的Ksv值为KSV=8.98×104M-1,较高的KSV值说明硝基芳烃在MOFs材料的荧光发射中具有较高的淬灭率,用3δ/KSV可计算出Cd2(m-PIPy)(NDC)3对TNP的检出限为3.38ppm。
与其他的基于MOFs材料的荧光传感器相比,本发明Cd2(m-PIPy)(NDC)3具有较大的淬灭常数(KSV)和较低的检出限,对于用于实际检测硝基芳烃化合物的荧光传感器材料具有很大的应用前景。
以上所述本发明的具体实施方式,并不构成对本发明保护范围的限定。任何根据本发明的技术构思所做出的各种其他相应的改变与变形,均应包含在本发明权利要求的保护范围内。
Claims (9)
2.一种如权利要求1所述的阴离子骨架金属有机框架材料的制备方法,其特征在于,包括如下步骤:1,3-二([4-(1-咪唑基)-吡啶基]-亚甲基)苯二溴化物、1,4-萘二甲酸与硝酸镉进行溶剂热反应,合成得到阴离子骨架的金属有机框架材料。
4.根据权利要求3所述的阴离子骨架金属有机框架材料的制备方法,其特征在于,所述4-PIM和所述间二溴苄在加热条件下进行,加热温度为70~80℃,反应时间为15~20h。
5.根据权利要求2所述的阴离子骨架金属有机框架材料的制备方法,其特征在于,所述溶剂热反应的反应温度为140~180℃,反应时间为3~5天。
6.根据权利要求2所述的阴离子骨架金属有机框架材料的制备方法,其特征在于,所述溶剂热反应采用逐步升温的方式将混合液从常温升至反应温度,升温速率为2℃/min。
7.根据权利要求2所述的阴离子骨架金属有机框架材料的制备方法,其特征在于,所述溶剂为甲醇和水。
8.根据权利要求2所述的阴离子骨架金属有机框架材料的制备方法,其特征在于,所述溶剂热反应后还包括将反应产物用乙醇和水洗涤,经过真空干燥,得到阴离子骨架的金属有机框架材料。
9.一种如权利要求1所述的阴离子骨架金属有机框架材料对痕量硝基芳烃爆炸物的传感性质以及检测方面的应用。
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《Multifunctional luminescent Cd (II)-based metal-organic framework material for highly selective and sensitive sensing 2,4,6-trinitrophenol (TNP) and Fe3+ cation》;Jinsong Hu et al.;《MICROPOROUS AND MESOPOROUS MATERIALS》;20180615;第272卷;第177-183页 * |
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