CN110669037A - 一种锌金属有机框架晶体配合物及其制备和应用 - Google Patents
一种锌金属有机框架晶体配合物及其制备和应用 Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 63
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 58
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 58
- 239000013078 crystal Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000010668 complexation reaction Methods 0.000 title description 2
- 150000002500 ions Chemical class 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013110 organic ligand Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003751 zinc Chemical class 0.000 claims abstract description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
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- 239000003446 ligand Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 5
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- ATWGHWZRHOJITC-UHFFFAOYSA-N [S].C1=CC=NC=C1 Chemical compound [S].C1=CC=NC=C1 ATWGHWZRHOJITC-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
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- 239000002184 metal Substances 0.000 description 11
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 5- (pyridine-3-yl) thiophene-2,5-dicarboxamide sulphur Chemical compound 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
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- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
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- 210000000133 brain stem Anatomy 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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Abstract
本发明提供了一种锌金属有机框架配合物,是将锌盐、含氮有机配体、含氧有机配体在水中混合均匀后移入密闭的高压反应容器中,于130~150℃温度下晶化60~72小时,得到结晶性较好的浅黄色块状晶体;晶体用去离子水洗涤,室温下干燥,即得。该锌金属有机框架配合物的化学式为[Zn(Nptp)(HBTC)]n,分子式为C25H16ZnN4O8S,分子量为597.85。在该锌金属有机框架配合物中加入铅离子之后,配合物由于光诱导电子转移使得荧光强度显著减弱,因此可以有效的识别并检测铅离子,而且这一识别过程具有高灵敏性和选择性,操作过程简便无毒,成本低,收率较高,可重复性好,具有良好的工业应用前景。
Description
技术领域
本发明涉及一种金属有机框架晶体配合物,尤其涉及一种锌金属有机框架晶体配合物及其制备方法;本发明同时还涉及该锌金属有机框架晶体配合物在荧光识别铅离子的应用,属于无机材料领域和金属离子检测领域。
技术背景
金属有机框架材料由于其新颖的结构,次级构筑单元以及突出的气体储存、分离、催化、电化学、药物传递、和磁性等方面的性能,使得配合物的设计和合成在无机材料领域中引起了高度关注。金属有机框架材料是一种由金属离子/金属团簇与有机配体通过配位键自组装形成的新型无机-有机复合材料,这种兼具无机组分和有机组分的特殊材料也同时具备了很多新的特性和优点,这种特殊材料的出现迅速成为了研究人员关注的焦点。在金属配合物合成过程中,常见的有机配体有含羧酸配体、含氮配体、既含氮又含羧酸的双功能配体,金属离子来源于金属盐,常见的金属盐有硝酸盐、氯化盐、硫酸盐等。因此合理设计和选择金属离子和有机配体对于构筑具备新型拓扑结构和性能优异的功能材料来说是至关重要的。
铅离子作为一种重金属离子,对于生活环境以及人体健康有着非常严重的威胁,长期接触铅离子会对人体的大脑以及神经系统产生危害从而导致人体智力异常。因此,有效识别铅离子是刻不容缓的。
发明内容
本发明的目的是提供一种锌金属有机框架晶体配合物及其制备方法;
本民的另一目的是对上述锌金属有机框架晶体配合物识别铅离子的性能及机理进行研究,以期作为一种新型功能材料来检测铅离子。
一、锌金属有机框架晶体配合物
本发明锌金属有机框架晶体配合物的其化学式为[Zn(Nptp)(HBTC)]n,分子式为C25H16ZnN4O8S,分子量为597.85。
结构式中,Nptp为N2-(pyridin- 2-yl)-N5-(pyridin-3-yl)thiophene-2,5-dicarboxamide含硫吡啶配体,其结构式如下:
HBTC为含氧配体均苯三酸阴离子,其结构式如下:
锌金属有机框架晶体配合物的制备:是将锌盐、含氮有机配体、含氧有机配体在水中混合均匀后移入密闭的高压反应容器中,于130~150℃温度下晶化60~72小时,得到结晶性较好的浅黄色块状晶体;晶体用去离子水洗涤,室温下干燥,即得锌金属有机框架材料。
所述锌盐为六水合硝酸锌,锌盐与含硫吡啶配体的物质的量之比为4:1;锌盐为六水合硝酸锌与含氧有机配体的物质的量之比为4:1。
锌金属有机框架配合物的晶体学数据为:a=9.4926(5) Å,b=9.9609(5)Å,c=13.3936(7)Å,α=82.1140(10)°,β=78.5910(10)°,γ=68.1680(10)°,V=1149.55(10)Å3,空间群为P-1。表明锌金属有机框架配合物属于三斜晶系。
锌金属有机框架配合物的元素分析数据为:理论值:C,50.22;H,2.70;N,9.37(%)。实验值:C,50.65;H,2.57;N, 9.81(%)。
锌金属有机框架配合物的红外吸收峰为(溴化钾压片, cm−1):3330(w),1681(s),1536(s),1383(s),1265(m),1120(m),933(w),801(m),725(m),670(m),635(w),538(w)。
图1为本发明锌金属有机框架材料中金属及配体的配位环境示意图。可见,在锌金属有机框架材料中同时含有含氧配体和含氮配体,含氧配体和含氮配体同时和二价金属锌进行自组装配位。具体为含氮配体与金属中心配位形成一条条一维的Z字型链,含氧配体将这些一维的Z字型链连起来形成二维层状结构(见图2),最终层与层进行π-π堆积作用进一步形成复杂的三维框架结构(见图3)。
对所得的晶体进行单晶衍射分析,单晶数据于APEX CCD Ⅱ型单晶衍射仪上测试得到,通过SHELXS-97 程序进行晶体结构解析,利用全矩阵最小二乘法确定晶胞参数。图4为本发明锌金属有机框架配合物的粉末X-射线衍射谱图和单晶拟合谱图。图4的数据分析表明,在这种锌金属有机框架材料中同时含有含氧配体和含氮配体,含氧配体和含氮配体同时和二价金属锌进行自组装配位,具体为含氮配体与金属中心配位形成一条条一维的Z字型链,含氧配体将这些一维的Z字型链连起来形成二维层状结构,最终层与层进行π-π堆积作用进一步形成复杂的三维堆积结构。
二、锌金属有机框架配合物对金属离子的荧光响应性能
1、金属有机框架配合物晶体的荧光性能
将金属有机框架配合物晶体材料分散于水中配制成浓度为8.36×10-4mol·L -1水溶液中,采用F-7000FL型荧光光谱仪,在室温下测定了锌配合物的荧光性质,激发光波长为259nm,发射峰位于445nm处。观察到锌配合物发射出很强的青蓝色的荧光。
2、金属有机框架配合物对金属离子的荧光响应性能
将金属有机框架配合物晶体材料分散于浓度均为1.0×10-2mol·L -1 的不同金属硝酸盐(Zn2+、Co2+、Cu2+、Mg2+、Ni2+、Pb2+、Cr3+、K+、Ag+)水溶液中,测试金属硝酸盐的荧光强度的变化。图5为本发明锌金属有机框架配合物对不同金属离子的荧光响应示意图。结果发现,只有加入Pb2+后,配合物的荧光强度急剧下降,而加入其它金属离子的时候,锌配合物的荧光强度没有发生明显的变化。可见,锌金属有机框架配合物对铅离子表现出了较好的识别能力,因此,可用于单一选择性荧光识别Pb2+。
为了测试Pb(NO3)2溶液浓度对于锌金属有机框架配合物荧光强度的影响,我们做了以下实验:将锌金属有机框架配合物分散于去离子水中,分别加入不同浓度的Pb(NO3)2溶液(0mol/L、50×10-6mol/L、75×10-6mol/L、100×10-6mol/L、125×10-6mol/L、150*×10- 6mol/L),测试在不同浓度下的荧光强度的变化。图6为锌金属有机框架材料在不同浓度Pb(NO3)2溶液中的荧光光谱图。图6显示,随着铅离子浓度的增加,锌金属有机框架配合物溶液的荧光强度明显减弱。
图7为本发明锌金属有机框配合物的溶液中I0-I/I对Pb2+浓度所作的Stern-Volmer曲线。由图7可以看出,在低浓度下,I0-I/I与Pb2+浓度呈很好的线性关系,因此该配合物可以有效的识别并检测铅离子。即在5×10-5~1.25×10-4mol/L的浓度范围内,I0-I/I与Pb2+浓度呈如下线性关系:
式中,Ksv为斜率,[Q]为相应金属离子的浓度。随着铅离子浓度从0μL逐渐增加到800μL,发现对应的发射峰的位置没有发生移动,而发射峰的强度随着铅离子浓度的逐渐增大而减弱。
3、锌金属有机框架配合物识别铅离子的机理
已知具有d10金属中心和π-共轭有机配体的骨架可具有光致发光的性质,而MOF的发光通常来自构建组分,即共轭有机配体和/或金属中心。具有芳香族部分或延伸的π系统的有机连接体由于其刚性的分子骨架通常用于构建多孔MOF。这些接头中的π电子对发光有很大贡献,因此发光可归类为基于接头的发光或配体-配体电荷转移(LLCT)、配体到金属电荷转移(LMCT)和金属到配体电荷转移(MLCT)。竞争性的能量吸收是荧光猝灭的可能原因。分析锌配合物的结构可知,在配合物中含氧配体中仅有两个羧基进行配位,而含氧配体中另外一个未配位的羧基就可以充当潜在的活性位点,在识别过程中,暴露出来的活性位点与金属离子发生电荷转移,使铅离子与配合物之间产生弱的相互作用,最后导致能量的转移和荧光猝灭。
综上所述,本发明以锌盐为金属源,采用含硫吡啶配体作为主配体,均苯三酸阴离子作为辅配体,在水溶液中自组装构筑了具有高度荧光响应的锌金属有机框架配合物,在该锌金属有机框架配合物中加入铅离子之后,配合物由于光诱导电子转移使得荧光强度显著减弱,因此可以有效的识别并检测铅离子,而且这一识别过程具有高灵敏性和选择性,操作过程简便无毒,成本低,收率较高,可重复性好,具有良好的工业应用前景。
附图说明
图1为本发明锌金属有机框架材料中金属及配体的配位环境示意图。
图2为本发明锌金属有机框架材料的二维层状结构图。
图3为本发明锌金属有机框架材料的三维堆积结构图。
图4为本发明锌金属有机框架材料的粉末X-射线衍射谱图和单晶拟合谱图。
图5为本发明锌金属有机框架配合物对不同金属离子的荧光响应示意图。
图6为本发明锌金属有机框架配合物在不同浓度Pb(NO3)2溶液中的荧光光谱图。
图7为本发明锌金属有机框配合物的溶液中I0-I/I对Pb2+浓度所作的Stern-Volmer曲线。
具体实施方式
下面通过具体实施例对本发明锌金属有机框架配合物的合成及识别Pb2+的具体应用做进一步说明。
实施例1、锌金属有机框架配合物的制备
称取0.12g(0.4mmol)六水合硝酸锌,0.033g(0.1mmol)含硫吡啶有机配体,0.021g(0.1mmol)均苯三甲酸,在8mL水中混合均匀;将混合物移入具有聚四氟乙烯的反应釜的密闭不锈钢高压反应容器中(容积25mL),于150℃温度下反应3天。反应结束后自然冷却到室温,所得的晶体用去离子水反复洗涤5次,并在室温下干燥,得到结晶性较好的浅黄色块状晶体。产率约为52%(基于主配体Nptp)。
锌配合物的晶体学数据见表1:
实施例2、锌金属有机框架配合物识别检测Pb2+
分别称取2mg的锌金属有机框架配合物晶体,充分研磨后将其分散在5mL去离子水中,超声30min制备成悬浊液;将1.0×10−2 mol·L−1等体积的Zn(NO3)2、Co(NO3)2、Cu(NO3)2、Mg(NO3)2、Ni(NO3)2、Pb(NO3)2、Cr(NO3)3、KNO3、AgNO3溶液加入配合物的悬浮液中测试它们的发光性能。若配合物的荧光强度急剧下降,则说明加入的是Pb2+;若配合物的荧光强度变化不大,则说明加入的是其他金属离子。
Claims (5)
2.如权利要求1所述锌金属有机框架配合物的制备方法,是将锌盐、含氮有机配体、含氧有机配体在水中混合均匀后移入密闭的高压反应容器中,于130~150℃温度下晶化60~72小时,得到结晶性较好的浅黄色块状晶体;晶体用去离子水洗涤,室温下干燥,即得锌金属有机框架材料。
3.如权利要求2所述锌金属有机框架配合物的制备方法,其特征在于:所述锌盐为六水合硝酸锌,锌盐与含硫吡啶配体的物质的量之比为4:1;锌盐为六水合硝酸锌与含氧有机配体的物质的量之比为4:1。
4.如权利要求1所述锌金属有机框架配合物在荧光识别铅离子的应用。
5.如权利要求4所述锌金属有机框架配合物在荧光识别铅离子的应用,其特征在于:在锌金属有机框架配合物的水分散液中,加入Zn2+、Co2+、Cu2+、Mg2+、Ni2+、Pb2+、Cr3+、K+、Ag+溶液,只有加入Pb2+后锌金属有机框架配合物的荧光强度急剧下降,而其它金属离子的加入,锌金属有机框架配合物的荧光强度不发生变化。
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