CN111471038A - 一种四方晶系Cd-MOF晶体材料及其合成方法和应用 - Google Patents
一种四方晶系Cd-MOF晶体材料及其合成方法和应用 Download PDFInfo
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- CN111471038A CN111471038A CN202010171061.XA CN202010171061A CN111471038A CN 111471038 A CN111471038 A CN 111471038A CN 202010171061 A CN202010171061 A CN 202010171061A CN 111471038 A CN111471038 A CN 111471038A
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Abstract
本发明公开了一种四方晶系Cd‑MOF晶体材料及其合成方法和应用。所述的四方晶系Cd‑MOF晶体材料分子式为:[Cd(L)]·H2O,其中,L表示二(4‑(2‑吡啶基)‑(5‑1H‑1,2,4‑三氮唑基))甲烷脱去两个氢原子,带两个单位负电荷。该材料的合成方法为:取二(4‑(2‑吡啶基)‑(5‑1H‑1,2,4‑三氮唑基))甲烷和Cd(Ac)2·2H2O置于水和DMF组成的混合溶剂中,在NaN3存在的条件下加热反应,即得。本发明所述Cd‑MOF对Fe3+离子、多种阴离子及苦味酸等其它硝基芳烃均具有进行识别作用。
Description
技术领域
本发明涉及金属有机骨架化合物,具体涉及一种四方晶系Cd-MOF晶体材料及其合成方法和应用。
背景技术
分子识别是离子或中性分子等与外来物种间一种特殊的、专一性的相互作用,是主体对外来分析客体的特异性结合同时会表现出某种功能的过程。在分子识别之上逐渐兴起一类能够通过离子或分子结合而使其自身的磁、电或光学等性质发生改变的化合物即化学传感器。用于识别和检测环境中和生物体内重要分析物的荧光传感器是化学传感器领域一个重要的研究方向。荧光分子经过目的性设计合成引入到目标体系中,能够将识别信息转换成荧光信号传递给外界,从而实现了人与分子间的对话,搭起宏观世界和微观世界联系的桥梁,具有这种功能的分子称之为荧光探针分子。
金属有机骨架化合物(MOFs)具有丰富的拓扑结构,较高的比表面积,而且其结构和性质可根据具体的应用进行调节。近年来,MOF材料的研究迅猛发,这类晶体材料在催化、气体存储、药物缓释等领域也展现了优于其他传统材料的特点。此外,由于的MOF材料独特的光电特性及其它性质,使它们成为开发高性能化学传感器的重要材料。现有技术中,d10过渡金属镉与有机配体配位形成的MOF化合物有很多,如:
公开号为CN109134518A的发明专利,公开了一种金属有机框架物Cd-MOF晶体材料,其化学式为[Cd2(NTA)2(DMF)(H2O)]n,其一个结构单元,是由两个Cd2+,两个配体阴离子NTA2-,两个主体H2O分子和两个主体DMF分子组成;该材料可作为电解水析氧催化剂应用。
公开号为CN 110240706 A的发明专利,公开了一种新型Cd-MOF材料及其制备方法和应用,所述Cd-MOF材料的分子式为C24H19Cd1.5N10O3,摩尔质量M=664.09g/mol,六方晶系,晶胞参数为: α/°=90,β/°=90,γ/°=120,Z=18。该材料对苦味酸有良好的选择性。
公开号为CN 108546551 A的发明专利公开了一种荧光探针,其以Cd2+的金属有机框架材料Cd-MOF为基体,通过“原位还原”方法引入具有特殊蓝光发射的稀土金属离子Eu2+做荧光探针。该发明所述荧光探针对Fe3+离子表现出灵敏的识别性,荧光淬灭率达到99%,可用于水体中Fe3+离子的识别检测。
但上述现有Cd-MOF材料仅能单一的对Fe3+离子或苦味酸进行识别,无法同时对Fe3 +离子、阴离子及苦味酸等其它硝基芳烃进行识别。
发明内容
本发明要解决的技术问题是提供一种结构新颖,对Fe3+离子、多种阴离子及苦味酸等其它硝基芳烃均具有进行识别作用的四方晶系Cd-MOF晶体材料及其合成方法和应用。
本发明所述的四方晶系Cd-MOF晶体材料,其分子式为:[Cd(L)]·H2O,其中,L表示二(4-(2-吡啶基)-(5-1H-1,2,4-三氮唑基))甲烷脱去两个氢原子,带两个单位负电荷;该材料属于四方晶系,I41/a空间群,晶胞参数为: α=90.00°,β=90.00°,γ=90.00°。
本发明还提供上述四方晶系Cd-MOF晶体材料的合成方法,具体为:取二(4-(2-吡啶基)-(5-1H-1,2,4-三氮唑基))甲烷和Cd(Ac)2·2H2O置于混合溶剂中,在NaN3存在的条件下于加热条件下反应,反应物冷却,有晶体析出,收集晶体,即得;其中,所述的混合溶剂为水与N,N-二甲基甲酰胺的组合物。
本发明所述合成方法中,涉及的二(4-(2-吡啶基)-(5-1H-1,2,4-三氮唑基))甲烷为配体,其可参考现有文献(Alexey N.Gusev,Ivan Nemec Versatile coordinationmodes of bis[5-(2-pyridine-2-yl)-1,2,4-triazole-3-yl]alkanes in Cu(II)complexes Dalton Trans.,2014,43,7153–7165.)进行制备,在此不再详述。
本发明所述合成方法中,只有在NaN3存在的条件下才能反应得到目标产物。所述NaN3的用量通常为二(4-(2-吡啶基)-(5-1H-1,2,4-三氮唑基))甲烷物质的量的0.1以上,优选为1-5倍。
本发明所述合成方法中,二(4-(2-吡啶基)-(5-1H-1,2,4-三氮唑基))甲烷和Cd(Ac)2·2H2O的摩尔比为化学计量比,在实际操作过程中,Cd(Ac)2·2H2O的量可相对过量,通常为1:1-5。在混合溶剂的组成中,水与N,N-二甲基甲酰胺的体积比优选为1:1-4,更优选为1:2-3。所述混合溶剂的用量可根据需要确定,通常以能溶解参加反应的原料为宜。具体地,以0.1mmol的二(4-(2-吡啶基)-(5-1H-1,2,4-三氮唑基))甲烷为基准计算,全部原料所用混合溶剂的总用量通常为2-10mL。在具体溶解的步骤中,可将各原料分别用混合溶剂中的某一种组分溶解,然后再混合在一起反应;也可将所有原料混合在一起后再加混合溶剂溶解。
本发明所述合成方法中,反应优选是在≥50℃的条件下进行,进一步优选在100-160℃的条件下进行,更优选是在120-140℃的条件下进行。反应过程中可采用TLC跟踪检测反应是否完全。申请人的试验表明,当反应在≥50℃的条件下进行时,反应时间≥1h即有目标产物生成,随着时间的延长,目标产物的产率随之提高。当反应在120-140℃条件下进行且反应的时间控制在36-72h时,目标产物的产率可达到50-60%。反应得到的晶体优选再用水、乙醇或N,N-二甲基甲酰胺进行洗涤以除去目标产物表面多余的未反应物和反应过程中生成的副产物。
本发明所述合成方法中,用于盛装原料进行反应的反应容器最好是能够承受一定压力及温度的容器,具体可以是水热反应釜、密闭式低压硬质玻璃管或密闭式玻璃瓶。
此外,本申请人发现上述四方晶系Cd-MOF晶体材料能够有效识别某些阴离子、阳离子或硝基芳烃,因此,本发明还包括上述四方晶系Cd-MOF晶体材料在检测阴离子、阳离子或硝基芳烃中的应用。其中,所述的阴离子为选自CrO4 2-、Cr2O7 2-和MnO4 -中的至少一种;所述的阳离子为Fe3+;所述的硝基芳烃为4-硝基苯酚和/或苦味酸。
与现有技术相比,本发明的特点在于:
1、提供了一种结构新颖的四方晶系Cd-MOF晶体材料及其合成方法,采用原位模板方法进行合成四方晶系Cd-MOF,成本更低,且副产物少,更易于产业化;
2、本发明所述的四方晶系Cd-MOF晶体材料具有较好的稳定性、孔隙率和发光性能,且对Fe3+离子、多种阴离子及苦味酸和4-硝基苯酚等均具有进行很好的识别作用,可以用于检测前述各种相关物质。
附图说明
图1为本发明实施例1制得的最终产物的结构图,其中,(a)为最终产物的配位环境图(H原子被省略);(b)为最终产物的Cd1的配位多面体图;(c)为最终产物中配体的配位模式图;(d)为最终产物的金属骨架图;(e)为最终产物沿b轴方向的孔道结构图;(f)为最终产物沿a轴方向的三维结构图;
图2为本发明实施例1制得的最终产物的X-射线粉末衍射图;
图3为本发明实施例1制得的最终产物的热稳定性图,其中,(a)为最终产物的热重曲线图;(b)为最终产物的变温粉末图;
图4为本发明实施例1制得的最终产物在相同浓度下对不同金属阳离子和阴离子单独存在以及混合存在下的荧光结果,其中,(a)为实施例1制得的最终产物在相同浓度下对不同金属阳离子的荧光强度柱状图;(b)为实施例1制得的最终产物在相同浓度下对不同阴离子的荧光强度柱状图;(c)为实施例1制得的最终产物对Fe3+以及其与其它离子混合存在下的荧光强度柱状图;(d)为实施例1制得的最终产物对MnO4 -以及其与其它离子混合存在下的荧光强度柱状图;(e)为实施例1制得的最终产物对Cr2O7 2-以及其与其它离子混合存在下的荧光强度柱状图;(f)为实施例1制得的最终产物对CrO4 2-以及其与其它离子混合存在下的荧光强度柱状图;
图5A为本发明实施例1制得的最终产物在不同浓度的Fe3+、Cr2O7 2-、CrO4 2-、MnO4 -存在下的荧光滴定图;其中,(a)为Fe3+,(b)为Cr2O7 2-,(c)为CrO4 2-,(d)为MnO4 -;
图5B为Fe3+、Cr2O7 2-、CrO4 2-、MnO4 -对实施例1制得的最终产物的Stern-Volmer拟合图;其中,(a)为Fe3+,(b)为CrO4 2-,(c)为Cr2O7 2-,(d)为MnO4 -;
图5C为Fe3+、Cr2O7 2-、CrO4 2-、MnO4 -离子浓度与淬火效率的关系,插图显示了传感器的线性响应范围;其中,(a)为Fe3+,(b)为CrO4 2-,(c)为Cr2O7 2-,(d)为MnO4 -;
图6为本发明实施例1制得的最终产物的悬浮液中分别加入相同浓度(120μM)的各种硝基芳烃、富电子芳烃和硝基甲烷,并在一定条件下监测配合物的荧光发射强度变化图,其中,图(a)为实施例1制得的最终产物在相同浓度的不同硝基芳烃存在下的荧光谱图;(b)为实施例1制得的最终产物在相同浓度的富电子芳烃和硝基甲烷存在下的荧光谱图;(c)为实施例1制得的最终产物在不同硝基芳烃存在下的荧光强度柱状图;
图7为本发明实施例1制得的最终产物对4-硝基苯酚(4-NP)和苦味酸(PA)的检测限的研究,其中,(a)和(b)分别为实施例1制得的最终产物在不同浓度4-NP和PA存在下的荧光滴定图;(c)和(d)分别为4-NP和PA对实施例1制得的最终产物的Stern-Volmer拟合图;(e)和(f)分别为4-NP和PA的浓度与淬火效率的关系曲线,插图显示了传感器的线性响应范围。
具体实施方式
下面结合具体实施例对本发明作进一步的详述,以更好地理解本发明的内容,但本发明并不限于以下实施例。
以下各实施例中涉及的二(4-(2-吡啶基)-(5-1H-1,2,4-三氮唑基))甲烷(以下也简称为配体L)按下述方法制备而得:
1)将丙二酸二乙酯与水合肼在乙醇为溶剂的条件下以物质的量为1:2的比例在常温条件下反应2-4h,得到丙二酸二酰肼;
2)将2-氰基吡啶和步骤1)制得的丙二酸二酰肼按2:1的摩尔比在以乙醇为溶剂的条件并加入10g绿豆大小的钠粒,50-100℃回流2-4h,抽滤,加入体积为反应所得固体2倍的乙二醇,在160℃下关环,当溶剂体积剩下1/3时,加入适量蒸馏水,抽滤,烘干,得到二(4-(2-吡啶基)-(5-1H-1,2,4-三氮唑基))甲烷。
实施例1:按下述路线合成[Cd(L)]·H2O(以下也简称为配合物1)
称取配体L(0.1mmol)、Cd(Ac)2·2H2O(0.2mmol)和NaN3(0.1mmol),加入到带有聚四氟乙烯内衬(容积为25mL)的水热反应釜中,然后加入8mL由水和DMF组成的混合溶剂(V水:VDMF=1:3),在室温下用磁力搅拌器搅拌20min,密封后将反应釜置于140℃条件下反应72h,然后以10℃/h梯度降温至室温,观察聚四氟乙烯内衬中有无色块状晶体析出,滤去母液,用DMF洗涤,干燥,得到无色块状晶体,产率为50%。
对本实施例所得产物进行表征:
(1)红外光谱分析
主要红外光谱数据(KBr,cm-1):3456(w),1610(s),1571(w),1524(w),1481(s),1443(m),1420(m),1370(w),1285(w),1153(w),1101(w),1049(w),1024(w),1004(w),932(w),800(w),755(s),723(s),637(m),473(w),415(w)。
(2)元素分析
C60H56Zn6N32O8Cl4的元素分析:理论值(%):C,38.18;H,2.99;N,23.75。实验值:C,37.45;H,3.86;N,22.19。
(3)IR和单晶X-ray分析
对本实施例1所得最终产物进行IR和单晶X-ray分析,所得晶体学和结构修正数据如下述表1所示,部分键长键角数据分别如下述表2所示,晶体结构如图1所示,其中(a)为最终产物的配位环境图(H原子被省略);(b)为最终产物的Cd1的配位多面体图;(c)为最终产物中配体的配位模式图;(d)为最终产物的金属骨架图;(e)为最终产物沿b轴方向的孔道结构图;(f)为最终产物沿a轴方向的三维结构图。对所得晶体进行结构表征和解析,确定其晶胞和空间结构,该晶体属于四方晶系,空间群为I41/a。配合物晶胞参数为: α=β=γ=90°。
因此,确定本实施例所得晶体为目标产物配合物1,即[Cd(L)]·H2O,其中,L表示二(4-(2-吡啶基)-(5-1H-1,2,4-三氮唑基))甲烷脱去两个氢原子,带两个单位负电荷。在配合物1的不对称单元中,中心金属离子与配体中的六个氮原子配位形成一个扭曲的CdN6的八面体构型。
表1配合物1的晶体学结构数据
表2配合物1的部分键长键角数据
(4)X-射线粉末衍射分析
对配合物1进行X-射线粉末衍射分析,所得粉末衍射曲线图如图2所示。粉末衍射曲线表明本发明所述方法制得的Cd-MOF晶体材料为纯相,产物单一。
(5)热稳定性分析
图3为配合物1的热重分析图和变温粉末衍射曲线图。运用热重分析了在温度范围30℃-1000℃、升温速率5℃/min,以及在氮气气氛保护的环境下配合物的热稳定性。如图3(a)所示,配合物的热分解分为2个失重过程,最终分解成相应的氧化物。第一阶段(90-120℃),配合物失去了约4.25%的重量,这个可归因于一个游离水分子的失去(理论值:4.16%);第二阶段(450℃-1000℃)一直连续失重,配合物最终分解为CdO,其残余量为29.67%(理论值:4.16%)。为了更进一步确定配合物的热稳定性,研究了加热后样品的粉末衍射曲线图,将其在不同温度下真空加热6小时,得到相应的粉末衍射曲线图。如图3(a,b)所示,溶剂客体分子在加热条件下可从配合物的主体框架中逸出,并且去溶剂化样品的曲线与理论曲线仍然相重合,此结果表明溶剂的逸出,不影响配合物的基本骨架。由图3(b)可知,配合物在400℃之前骨架一直稳定,当温度达到450℃左右,配合物的框架开始坍塌,说明配合物具有较高的热稳定性。
对比例1
重复实施例1,不同的是,将混合溶剂中的DMF用甲醇、乙腈、二氯甲烷、氯仿或DMSO等进行替代。结果没有晶体或其它形状(如粉末)产物生成。
对比例2
重复实施例1,不同的是,将混合溶剂改为仅用水或仅用DMF。结果没有晶体或其它形状(如粉末)产物生成。
对比例3
重复实施例1,不同的是,不同的是,用Cd(NO3)2·4H2O、CdSO4·H2O或CdCl2代替Cd(Ac)2·2H2O,希望得到目前产物,但均未得到晶体,说明用其它镉盐无法达到形成Cd-MOF和结晶的热力学条件。
实施例2:配合物1的合成
重复实施例1,不同的是,将水和DMF的体积比改为1:1。
结果得到无色块状晶体。产率37%。
对本实施例所得产物进行红外分析、元素分析、单晶X-ray分析,确定所得的无色块状晶体为配合物1。
实施例3:配合物1的合成
重复实施例1,不同的是,将水和DMF的体积比改为1:4,反应改在100℃下进行(反应至完全约72h)。
结果得到无色块状晶体。产率28%。
对本实施例所得产物进行红外分析、元素分析、单晶X-ray分析,确定所得的无色块状晶体为配合物1。
实施例4:配合物1的合成
重复实施例1,不同的是,将水和DMF的体积比改为1:2,反应改在50℃下进行(反应至完全约80h)。
结果得到无色块状晶体。产率20%。
对本实施例所得产物进行红外分析、元素分析、单晶X-ray分析,确定所得的无色块状晶体为配合物1。
实验例1:配合物1对阴、阳离子的荧光传感性质研究
(1)配合物1作为发光传感器应用范围的研究
固态荧光实验表明,配合物1具有较强的发射荧光,在367nm处有一个强发射峰(激发波长为304nm)。
将配合物1的悬浮液对浓度为10-2M的各种金属阳离子硝酸盐水溶液(Na+、K+、Li+、Ni2+、Mg2+、Co2+、Mn2+、Al3+、Cr3+、Cu2+、Zn2+、Cd2+、Ag+、Sn2+、Fe2+、Fe3+)和各种阴离子水溶液(SCN-、F-、Cl-、ClO-、Br-、BrO3-、I-、IO3-、Ac-、CO3 2-、S2O3 2-、S2O8 2-、CrO4 2-、Cr2O7 2-、MnO4 -)的检测,结果如图4(a)和图4(b)所示,Fe3+、CrO4 2-、Cr2O7 2-、MnO4 -在280μM的浓度下,对配合物1的淬灭效率分别为98.4%,77.8%,90.2%,96.6%,也说明这四种离子对配合物1具有明显的淬灭效果,但在相同的条件下,其它金属阳离子和阴离子的淬灭效率要低得多。
(2)配合物1对Fe3+、CrO4 2-、Cr2O7 2-、MnO4 -的识别
混合离子中选择性地检测出Fe3+、CrO4 2-、Cr2O7 2-、MnO4 -在实际中得到广泛应用。图4(c)-(f)为分别为含有Fe3+、CrO4 2-、Cr2O7 2-、MnO4 -的配合物1水溶液中加入相同浓度的不同离子后的相对荧光强度。结果表明,与只加入Fe3+、CrO4 2-、Cr2O7 2-、MnO4 -差异不大,表明了配合物1可以实现对Fe3+、CrO4 2-、Cr2O7 2-、MnO4 -的选择性检测。
(3)配合物1识别Fe3+、CrO4 2-、Cr2O7 2-、MnO4 -的灵敏性及检测限
采用摩尔浓度分别为0-120μM的Fe3+、CrO4 2-、Cr2O7 2-、MnO4 -水溶液与配合物1的水的悬浮液等体积混合。灵敏度检测结果如图5A至图5C所示。
从图5A可看出,随着Fe3+、CrO4 2-、Cr2O7 2-、MnO4 -浓度的升高,配合物1的荧光发射强度逐渐减弱。通过Stern-Volmer(S-V)方程分析:I0/I=Ksv[A]+1,其中I0是加入分析物之前配合物1的初始荧光强度,I是加入分析物之后配合物1的荧光强度,[A]是分析物的摩尔浓度(单位:mol/L),Ksv是猝灭常数(单位:M-1)。图5B显示了Fe3+、CrO4 2-、Cr2O7 2-、MnO4 -离子对配合物1的S-V拟合图,并将四种离子的S-V方程总结于表3中。如图5B所示,在低浓度下曲线趋于一条直线,计算所得淬灭常数分别为:1.09×104M-1、7.16×103M-1、1.21×104M-1、2.80×104M-1,但是在高浓度下Stern-Volmer(S-V)曲线偏离这一条直线,这可能是由于自吸附和能量转移过程,如图5C所示,猝灭效率(I0-I)/I0与四种离子的浓度在一定范围内具有良好的线性相关性。相关性可由方程式表示:(I0-I)/I0=CKsv+1,其中I0和I分别是不存在和存在四种离子时配合物1的荧光强度,C为四种离子的浓度,将猝灭效率与离子浓度的关系式总结于表4中。通过使用以下公式确定LOD值:LOD=3σ/S,其中σ表示没有分析物的初始强度配合物1的标准偏差,S表示上述线性曲线的斜率。结果为:配合物1对Fe3+、CrO4 2-、Cr2O7 2-、MnO4 -四种离子检测限的值分别为87μM、73μM、73μM、5μM。
表3四种离子对配合物1的Stern-Volmer(S-V)方程
表4四种离子对配合物1的猝灭效率和浓度的方程
实验例2:配合物1对硝基芳烃的荧光传感性质的研究
(1)配合物1作为发光传感器的应用范围的研究
将苦味酸(PA),4-硝基苯酚(4-NP),2,4-二硝基甲苯(2,4-DNT),2,6-二硝基甲苯(2,6-DNT),1,2-二硝基苯(1,2-DNB),1,3-二硝基苯(1,3-DNB),3-硝基甲苯(3-NT),4-硝基甲苯(4-NT),硝基苯(NB)等缺电子芳烃及苯、甲苯等富电子芳烃,硝基甲烷作为缺电子芳烃一起进行研究。
向分散良好的配合物1的悬浮液中分别加入相同浓度(120μM)的各种硝基芳烃、富电子芳烃和硝基甲烷,并在环境条件下监测配合物1的荧光发射强度变化。如图6(a)和图6(b)所示,在所有分析物中,配合物1只对4-NP和PA显示出明显猝灭,我们计算出4-NP和PA对配合物1显示出较高的猝灭效率(~95%和97%),对于其它分析化合物观察不到明显的猝灭效应。如图6(c)所示,所选分析物的猝灭效率排序为:PA>4-NP>NB>3-NT>1,3-DNB>1,2-DNB>2,6-DNT>2,4-DNT>4-NT。这些结果表明配合物1对4-NP和PA的选择性高于其它分析化合物。
(2)配合物1识别4-NP和PA的灵敏性及检测限
用不同浓度的4-NP和PA进行荧光滴定测试。如图7(a)和图7(b)所示,随着4-NP和PA浓度的不断增加,配合物1的荧光强度呈现梯度下降,表明4-NP和PA可以有效地猝灭配合物1的荧光。通过Stern-Volmer(S-V)方程分析荧光猝灭数据:I0/I=Ksv[A]+1,其中I0是加入分析物之前配合物1(2)的初始荧光强度,I是加入分析物之后配合物1的荧光强度,[A]是分析物的摩尔浓度(单位:mol/L),Ksv是猝灭常数(单位:M-1)。在图7(c)和图7(d)中,分别显示了4-NP和PA对配合物1的S-V拟合图,申请人将4-NP和PA的S-V方程总结于表5中。在一定浓度范围内,4-NP和PA的S-V图趋于线性。S-V曲线在浓度较高时,线性关系存在显著偏差,这种偏差表明存在静态和动态淬灭过程。4-NP和PA的Ksv值由相应S-V图的部分线性确定,发现该值为4.80×104M-1和4.83×104M-1。
进一步评估配合物1检测4-NP和PA的能力。计算配合物1对4-NP和PA的检测限。如图7(e)和图7(f)所示,猝灭效率(I0-I)/I0与4-NP和PA浓度在一定范围内具有良好的线性相关性,相关性可由方程式表示:(I0-I)/I0=Ksv C+1,其中I0和I分别是不存在和存在4-NP和PA时配合物1的荧光强度,C为4-NP和PA的浓度,猝灭效率与4-NP和PA浓度的关系式已总结于表6中。通过使用以下公式确定LOD值:LOD=3σ/S,其中σ表示没有分析物的初始强度配合物1的标准偏差,S表示上述线性曲线的斜率。配合物1对4-NP和PA检测限的值分别为15μM、13μM。
表5 PA与4-NP对配合物1的Stern-Volmer(S-V)方程
表6 PA与4-NP对配合物1的猝灭效率和浓度的方程
Claims (9)
2.权利要求1所述的四方晶系Cd-MOF晶体材料的合成方法,其特征在于:取二(4-(2-吡啶基)-(5-1H-1,2,4-三氮唑基))甲烷和Cd(Ac)2·2H2O置于混合溶剂中,在NaN3存在的条件下于加热条件下反应,反应物冷却,有晶体析出,收集晶体,即得;其中,所述的混合溶剂为水与N,N-二甲基甲酰胺的组合物。
3.根据权利要求2所述的合成方法,其特征在于:所述混合溶剂的组成中,水与N,N-二甲基甲酰胺的体积比为1:1-4。
4.根据权利要求2所述的合成方法,其特征在于:反应在≥50℃的条件下进行。
5.根据权利要求2所述的合成方法,其特征在于:反应在100-160℃的条件下进行。
6.权利要求1所述的四方晶系Cd-MOF晶体材料在检测阴离子、阳离子或硝基芳烃中的应用。
7.根据权利要求6所述的应用,其特征在于:所述的阴离子为选自CrO4 2-、Cr2O7 2-和MnO4 -中的至少一种。
8.根据权利要求6所述的应用,其特征在于:所述的阳离子为Fe3+。
9.根据权利要求6所述的应用,其特征在于:所述的硝基芳烃为4-硝基苯酚和/或苦味酸。
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CN115073763A (zh) * | 2022-08-04 | 2022-09-20 | 信阳师范学院 | 混合配体构筑的镉(ii)配位聚合物、制备方法及其应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104610313A (zh) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | 具有潜在荧光材料的氧醚双三唑镉配合物及其制备方法 |
CN107715913A (zh) * | 2017-08-30 | 2018-02-23 | 哈尔滨理工大学 | 一种多酸基金属有机框架晶体材料及其制备方法 |
CN110240706A (zh) * | 2019-06-06 | 2019-09-17 | 南京邮电大学 | 一种新型Cd-MOF材料及其制备方法和应用 |
CN110628040A (zh) * | 2019-10-16 | 2019-12-31 | 安阳师范学院 | 基于5-(4-[1,2,4]三唑-1-苯基)-1H-四唑的Cd(Ⅱ)MOF材料 |
CN114682304A (zh) * | 2022-04-13 | 2022-07-01 | 江苏理工学院 | 具有可见光催化降解性能的CuCd-MOF/GO-x复合材料及其制备和应用 |
-
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- 2020-03-12 CN CN202010171061.XA patent/CN111471038B/zh not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104610313A (zh) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | 具有潜在荧光材料的氧醚双三唑镉配合物及其制备方法 |
CN107715913A (zh) * | 2017-08-30 | 2018-02-23 | 哈尔滨理工大学 | 一种多酸基金属有机框架晶体材料及其制备方法 |
CN110240706A (zh) * | 2019-06-06 | 2019-09-17 | 南京邮电大学 | 一种新型Cd-MOF材料及其制备方法和应用 |
CN110628040A (zh) * | 2019-10-16 | 2019-12-31 | 安阳师范学院 | 基于5-(4-[1,2,4]三唑-1-苯基)-1H-四唑的Cd(Ⅱ)MOF材料 |
CN114682304A (zh) * | 2022-04-13 | 2022-07-01 | 江苏理工学院 | 具有可见光催化降解性能的CuCd-MOF/GO-x复合材料及其制备和应用 |
Non-Patent Citations (1)
Title |
---|
曹燕等: "一个基于三氮唑配体Cd-MOFs的离子型探针研究", 《中国化学会2019年中西部地区无机化学化工学术研讨会》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115073763A (zh) * | 2022-08-04 | 2022-09-20 | 信阳师范学院 | 混合配体构筑的镉(ii)配位聚合物、制备方法及其应用 |
CN115073763B (zh) * | 2022-08-04 | 2023-10-20 | 信阳师范学院 | 混合配体构筑的镉(ii)配位聚合物、制备方法及其应用 |
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