CN104672260B - 由稀土金属有机框架化合物制得的荧光探针材料及其应用 - Google Patents
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Abstract
本申请涉及一类由稀土金属有机框架化合物制得的荧光探针材料及其应用,该荧光材料可以通过荧光强度的变化来定性及定量检测水溶液中钡离子。该荧光探针材料可通过微波加热10分钟快速得到。制备工艺简单,所得产品纯度高,稳定性好,荧光变化可肉眼观察,且选择性很好、抗其它金属离子干扰能力强,是一类理想的可应用于钡离子检测的荧光探针材料。
Description
技术领域
本发明属于荧光检测材料领域,具体涉及一种由稀土金属有机框架化合物制得的荧光探针材料及其应用。
背景技术
钡是碱土金属中最活泼的元素,同时也是人体中存在的一种微量元素。钡及其化合物可广泛用于医疗、陶瓷颜料等行业。然而在常见的钡盐中,除硫酸钡外,其他钡盐均有毒性,有毒性的钡盐一旦被人体吸收会对人体造成巨大的伤害。例如:慢性钡中毒可引起人体上呼吸道及眼结膜的刺激症状,急性钡中毒可导致肌肉毒性、生殖毒性,甚至会致畸致癌致突变。此外,随着国内油田不断的开采,在一些油田和地区也发现了含钡离子的地层水,这些钡离子能和地层水中的硫酸根(SO4 2-)作用生成不溶于水的硫酸盐沉淀,堵塞油层和管线,给油田生产带来严重危害。
随着科学的发展,人们对钡的认识也在不断的深入,其在水溶液中的含量标准和定向检测更是受到了极大的关注,因此对钡离子的快速、准确测定显得尤为重要。目前,测定钡离子的方法有石墨炉原子吸收光谱法、电位滴定法、电感藕合、等离子体-质谱法、荧光探针等。而荧光探针也由于其高的灵敏度而得到广泛的研究与应用。
金属有机框架化合物(MOFs)是近20年来的一个研究热点,该类化合物由金属离子和有机配体组成,由于可选的金属离子以及有机配体较多而表现出结构的多样性,并进而表现出性质及应用方面的多样性,例如在气体的存储与分离、催化、磁性、荧光等方面均有着潜在的应用。更为重要的是,通过金属离子以及有机配体的合理选择与组装可以得到满足不同需要的MOFs材料。
稀土金属有机框架化合物(Ln-MOFs)由于稀土金属离子较好的荧光性质而在荧光探针领域有着重要的应用前景。已有Ln-MOFs用于金属离子检测的相关报导,然而目前主要是集中于Cu2+离子的荧光检测(Liang, Xiao-Qiang et al., Chemical Communications,2014, 50, 6513-6516)、Hg2+(Zhu, Yi-Min et al., Journal of Materials ChemistryA, 2013, 1, 11312-11319)和Fe3+( Yan, Bing et al., Journal of MaterialsChemistry A, 2014, 2, 13691-13697),用于Ba2+离子的检测则尚未有报导。
发明内容
本发明的目的在于针对现有技术的不足,提供一种由稀土金属有机框架化合物制得的荧光探针材料。该荧光探针材料可用于定性及定量检测水溶液中钡离子。
为实现上述发明目的,本发明采用如下技术方案:
一种稀土金属有机框架化合物,其结构式如如式(1)所示:
式(1),
式(1)中,Ln为从La到Tb的三价稀土金属离子中的一种;R1为甲基,R2为氢或甲基,R3任选自C1-C8烷基、C2-C8烯基或C2-C8炔基中的一种;DHBDC为2,5-二羟基对苯二甲酸根,其价态为负二价。
典型地,具有如式(1)所示结构式的化合物有:
[Hmim]Eu(DHBDC)2,在293K下测试得出该化合物晶体属于Pbcn空间群,其晶胞参数为:a = 27.8885(7) Å,b = 11.4437(3) Å,c = 17.7204(5) Å,V = 5655.4(3) Å3,Z =8。该化合物为三维结构,其节点为两个通过配体连接起来的Eu原子,相连的节点通过配体进一步连接成三维骨架结构。孔道中填充有[Hmim]+。该化合物在未经含钡离子的水溶液处理的情况下没有荧光或者荧光较弱。然而该化合物的粉末在浸泡到含钡离子的水溶液中并分离洗涤以后,可以得到具有蓝绿色荧光的粉末,其荧光强度与水溶液中钡离子的浓度呈线性相关。该绿色荧光的激发波长为364 nm,发射波长为483 nm。
[Hmim]Tb(DHBDC)2,在293K下测试得出该化合物晶体属于Pbcn空间群,其晶胞参数为:a = 27.7838(15) Å,b = 11.4340(8) Å,c = 17.7863(8) Å,V = 5650.4(6) Å3,Z =8。该化合物在未经含钡离子的水溶液处理的情况下没有荧光或者荧光较弱。然而该化合物的粉末在浸泡到含钡离子的水溶液中并分离洗涤以后,可以得到具有蓝绿色荧光的粉末,其荧光强度与水溶液中钡离子的浓度呈线性相关。该绿色荧光的激发波长为364 nm,发射波长为483 nm。
以上两种仅为本申请所述化合物的典型代表,本申请所述具有如式(1)所示化学式的化合物不局限于此。
结构式属式(1)的化合物的晶体属正交晶系,空间群为Pbcn。
一种制备如上所述的稀土金属有机框架化合物的方法,包含以下步骤:
a)将咪唑类离子液体、稀土金属盐、和2,5-二羟基对苯二甲酸按摩尔比n:1:2混合;
b)将步骤a)所得的混合物反应完全后,加水洗涤2到3遍,得到稀土金属有机框架化合物粉末。
步骤a)所得的混合物中含结构单元的离子液体所占的比例为n,其中n≥1;所述稀土金属盐任选自含有三价稀土金属离子的化合物。
所述稀土金属盐为Eu(Ac)3•6H2O。
步骤b)混合物反应温度为140~160℃,反应时间为10分钟~5天。
一种如结构式(1)的稀土金属有机框架化合物制得的荧光探针材料,可用于定性及定量检测水溶液中的钡离子。
本申请所提供化合物的制备方法工艺简便、节能环保(均可于微波加热下在10分钟制备得到,反应温度不超过160度)。
本申请的又一目的在于提供一类荧光探针材料,有所述任一具有式(1)化学式的化合物和/或根据上述任一方法制备的化合物。
所述材料可以在加入含钡离子的水溶液以后得到一种绿色荧光的粉末。
应理解,在本申请披露的技术方案范围内,本申请的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合,从而构成新的或优选的技术方案。限于篇幅,在此不再一一累述。
与现有技术相比,本申请具有以下有益效果:
本申请中所提供化合物为具有较好的稳定性,制备过程快速简单,对能源消耗小,易于存储;由该化合物制得的荧光探针材料不但可以定性且可以定量检测水溶液中钡离子及其含量,且该检测效果的可以由肉眼可见的荧光变化来观察,是一类理想的可应用于钡离子检测的荧光探针材料。
附图说明
图1为样品1# [Hmim]Eu(DHBDC)2的晶体结构示意图;
图2为样品1# [Hmim]Eu(DHBDC)2的X-射线粉末衍射图谱,显示该化合物纯度较高,对水及温度均较为稳定;
图3为样品1# 经过含不同浓度钡离子水溶液处理后的粉末的荧光发射图谱,随着钡离子浓度的增加,处理后粉末的荧光强度也随之而增加;
图4为样品1#经过含不同浓度钡离子水溶液处理后的粉末的荧光发射强度与浓度之间线性关系示意图。
具体实施方式
本申请提到的上述特征,或实施例提到的特征可以任意组合。本申请说明书所揭示的所有特征可与任何组合物形式并用,说明书中所揭示的各个特征,可以被任何提供相同、均等或相似目的的替代性特征取代。因此除有特别说明,所揭示的特征仅为均等或相似特征的一般性例子。
下面结合实施例,进一步阐述本申请。应理解,这些实施例仅用于说明本申请而不用于限制本申请的范围。下列实施例中未注明具体条件的实验方法,通常按照常规条件或按照制造厂商所建议的条件。未做特殊说明的情况下,本申请所使用原料,均通过商业途径购买,不经特殊处理直接使用。
如无特别说明,实施例中对样品的测试条件如下:
X–射线粉末衍射物相分析(XRD)在Rigaku公司的MiniFlex2型X射线衍射仪上进行,Cu靶,K α 辐射源(λ= 0. 154184 nm)。
激发和发射光谱在Perkin Elmer公司的LS55型荧光分光光度仪上进行。
X–射线单晶衍射在Agilent公司的Xcalibur E型单晶衍射仪上进行,Mo靶,K α 辐射源(λ= 0.07107 nm),测试温度295 K。并通过Shelx 2013进行结构解析。
实施例1:样品1#的制备
将[Hmim]Cl、Eu(Ac)3•6H2O和2,5-二羟基对苯二甲酸按照3:1:2的比例混合,微波加热到160度,10分钟后取出,冷却并于室温下使用无水乙醇和水洗涤两次,干燥即可得到相应粉末样品。
实施例2:样品1#的制备
将[Hmim]Cl、Eu(Ac)3•6H2O和2,5-二羟基对苯二甲酸按照10:1:2的比例混合,加入反应釜中并置于烘箱中加热到160度,5天后取出,冷却并于室温下使用无水乙醇和水洗涤三次,干燥即可得到相应粉末样品。
实施例3:样品2#的制备
将[Hmim]Cl、Tb(Ac)3•6H2O和2,5-二羟基对苯二甲酸按照1:1:2的比例混合,加入反应釜中并置于烘箱中加热到160度,5天后取出,冷却并于室温下使用无水乙醇和水洗涤两次,干燥即可得到相应粉末样品。
样品的结构表征
采用X-射线单晶衍射对样品进行表征,并通过Shelx 2013对样品结构进行解析。结果显示,样品1#~样品2#均具有化学式(1)中所示通式,下面以样品1#为典型代表详细说明。
其中,样品1#的晶体结构由x-射线单晶衍射得到,如图1所示。样品1#晶体属于Pbcn空间群,其晶胞参数为:a = 27.8885(7) Å,b = 11.4437(3) Å,c = 17.7204(5) Å,V= 5655.4(3) Å3,Z = 8。图1中大的纯黑色的球表示Eu原子,与之相连的灰黑色的球表示O原子,六元环上灰白色的球表示C原子,五元环上的白色小球表示N原子。样品1#的粉末XRD衍射图谱如图2所示,根据其晶体结构模拟得到的理论XRD衍射图谱,如图2下方模拟谱图所示,图2上方的样品峰为实际测得的衍射图,两图相比,峰位置一致,表明所得样品为纯相。
样品2#的晶体结构由X-射线单晶衍射得到,样品2#晶体属于Pbcn空间群,其晶胞参数为:a = 27.7838(15) Å,b = 11.4340(8) Å,c = 17.7863(8) Å,V = 5650.4(6) Å3,Z= 8。
应用实施例1
将100 mg样品1#置于10 mL含钡离子浓度分别为0.00098、0.01、0.039和0.1 mol/L的水溶液中,搅拌一段时间后分离出下层粉末,并用水洗涤两到三次。
样品1#经钡离子的水溶液处理后的粉末的的发射光谱如图3所示。可以看出,样品1#在紫外光的激发下在483 nm处有强烈的发射,并且其发射峰的强度随着所使用钡离子水溶液浓度的变化而改变,呈线性关系。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (2)
1.一种稀土金属有机框架化合物的应用,其特征在于:用于定性及定量检测水溶液中的钡离子;所述的化合物结构式如式(1)所示:
式(1),
式(1)中,Ln为Eu3+;R1为甲基,R2为氢或甲基,R3任选自C1-C8烷基、C2-C8烯基或C2-C8炔基中的一种;DHBDC为2,5-二羟基对苯二甲酸根,其价态为负二价。
2.根据权利要求1所述的稀土金属有机框架化合物的应用,其特征在于:结构式属式(1)的化合物的晶体属正交晶系,空间群为Pbcn。
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