CN116536770A - 一种钴(ii)配合物单晶及其制备方法和应用 - Google Patents
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Abstract
本发明属于配位化学和吸附去除水中污染物领域，公开了一种钴配合物单晶及其制备方法和应用。其化学式为：{[Co3L(μ2‑O)(DMF)2(H2O)4]·(DMF)3}n，属于单斜晶系，空间群为C2/c,a=29.732(6)Å,b=17.665(4)Å,c=31.723(6)Å,α=90°,β=96.99(3)°,γ=90°,V=16538(6)Å3。其中，L代表5,11,17,23‑四[(间羧基苯基)偶氮]‑25,26,27,28‑四羟基杯[4]芳烃失去四个H原子。该Co(II)配合物单晶能快速吸附去除水中Pb2+、Cd2+，实现较高的吸附容量，对Pb2+和Cd2+表现出高的选择性。该钴配合物单晶能够在水中稳定存在，具有很好的应用前景。
Description
技术领域
本发明涉及配位化学和吸附去除水中污染物领域，具体涉及一种钴配合物单晶及其制备方法和应用。
背景技术
铅(Pb2+)是分布最广、毒性最大的工业污染物之一，可在人体内长期蓄积，对脑、肝、肾、生殖系统和免疫系统造成严重损害。在工业和经济快速增长的背景下，Pb2+污染已成为一个重要的环境问题，几乎所有国家都在集中精力寻找从水溶液中去除Pb2+的有效策略。目前，重金属离子的捕集方法有化学沉淀法、氧化还原法、电解法、膜渗透法、离子交换法和吸附法等，其中吸附法效率高，操作简单，成本低。
微量镉(Cd2+)在水生介质中也具有高毒性，会对呼吸道产生刺激，长期暴露会造成嗅觉丧失症、牙龈黄斑或渐成黄圈。虽然镉化合物不易被肠道吸收，但可经呼吸被体内吸收，积存于肝或肾脏造成危害，尤以对肾脏损害最为明显。到目前为止，人们已经合成了大量的吸附剂，如氧化铝、沸石分子筛、活性炭材料、纳米材料和螯合聚合物。大多数吸附剂由于缺乏结构和功能的可调性，面临着选择性适中和吸收能力低的挑战。因此，为了实现对水溶液中Pb2+和Cd2+的高效去除，开发一种结构和功能可调的新型吸附剂受到了人们的广泛关注。
金属有机骨架(Metal-organic frameworks,MOFs)是一种由有机配体与金属离子或金属簇节点组成的骨架结构，因其具有高比表面积、化学成分可调、孔结构可调等特点，在吸附领域得到了广泛应用(Inorganic Chemistry,2022,61,4，2017-2030)。可以通过选择具有特定官能团的配体或合成修饰具有特定结构和性能的多孔金属有机框架，使其具有去除重金属离子的特殊化学和物理性质。
因此，通过有目的的将不同官能团(羧酸基、偶氮基等)载入到MOFs的孔道中，从而获得更多的活性吸附位点用于吸附去除Pb2+是本发明人目前的研究方向。发明人前期授权的发明专利2022104393339“一种铜(II)配合物单晶及其合成方法和应用”，将其作为吸附剂应用于吸附去除水中铅离子和碘。但其存在如下不足：1、铜(II)配合物单晶对Pb2+吸附动力学缓慢，在200分钟左右才达到吸附平衡；2、铜(II)配合物单晶容易受干扰离子的影响。为此，本发明人后期又进一步进行了此类化合物的研究开发，实现多种金属离子的选择性吸附。
发明内容
针对目前技术现状，本发明目的在于针对Pb2+和Cd2+，提供一种具有更多活性吸附位点的钴配合物单晶；另一目的在于提供其制备方法和应用。
为实现上述发明目的，所述技术方案如下：
所述钴配合物单晶，其化学式为：{[Co3L(μ2-O)(DMF)2(H2O)4]·(DMF)3}n，n为正整数，属于单斜晶系，空间群为C2/c, α＝90°,β＝96.99(3)°,γ＝90°,/>其中，L代表5,11,17,23-四[(间羧基苯基)偶氮]-25,26,27,28-四羟基杯[4]芳烃失去四个H原子；DMF代表N,N'-二甲基甲酰胺。
本发明所述钴配合物单晶的制备方法：
将六水合氯化钴(0.05mmol)与H4L(0.01mmol)溶于N,N'-二甲基甲酰胺和蒸馏水中，封入反应瓶中，室温下超声，在恒温的烘箱中放置，然后降至室温，得到红色块状晶体，即为Co(II)配合物单晶。
该配合物可以作为吸附剂应用于吸附去除水中Pb2+和Cd2+。
本发明优点在于：该Co(II)配合物单晶的三维框架结构的孔道内修饰有羧酸基和偶氮基等官能团，有利于与Pb2+作用，进而快速吸附去除水中Pb2+，实现较高的吸附容量，吸附容量可达到493.89mg/g。另外，该化合物在常温下能够较快地吸附去除铅离子，比如铅离子起始浓度为10ppm，Co(II)配合物单晶能够在8分钟以内，吸附去除99.44％的Pb2+，达到吸附平衡。且对Cd2+也具有较好的吸附去除效果：吸附容量达到215.78mg/g；Cd2+起始浓度为10ppm的水溶液中，在180分钟内吸附去除83.15％的Cd2+，达到吸附平衡。此外，在添加水体中常见的一些共存离子(K+、Na+、Ca2+、Mg2+和Sr2+)情况下，此Co(II)配合物单晶对Pb2+和Cd2+表现出高的选择性。
本发明合成工艺简单，收率较高。本发明制备的钴配合物单晶能够在水中稳定存在，具有很好的应用前景。
附图说明
图1为本发明钴配合物晶体中钴的配位环境图。
图2为本发明钴配合物的单晶结构图。
图3为本发明钴配合物衍射图谱，其中1为单晶模拟粉末衍射图谱，2为本发明钴配合物的粉末衍射图谱。
图4为本发明钴配合物在pH不同的水中对Pb2+的吸附等温线图。
图5为本发明钴配合物吸附水中Pb2+(10ppm)的动力学图。
图6为本发明钴配合物在10ppmPb2+添加不同干扰离子动力学曲线图。
图7为本发明钴配合物对Cd2+的吸附等温线图。
图8为本发明钴配合物吸附水中Cd+(10ppm)的动力学图。
图9为本发明钴配合物选择性吸附图。
具体实施方式
下面通过实例对本发明做进一步的说明：
实施例1：合成Co(II)单晶吸附剂
将CoCl2·6H2O(0.05mmol,11.89mg)、H4L(0.01mmol,10.44mg)和混合溶剂(DMF:水＝4.5mL:4.5mL)加入10mL玻璃瓶中。超声处理10分钟后，将瓶子密封，在100℃的烘箱中保存24小时。然后，冷却到室温，得到了红色的块状Co-MOF晶体。所得产物用DMF/水溶液(1:1,V/V)洗涤，室温干燥。收率:8.6mg(45.5％，基于H4L)。单晶模拟粉末衍射图谱与实际钴配合物的粉末衍射图谱相一致，证明材料被成功合成，见图3。
实施例2：本发明钴配合物吸附Pb2+试验
将实施例1制得的红色块状晶体在120℃下活化12小时，研磨1小时后的粉末作为吸附剂。在80mL浓度为0-250ppm的pH不同的Pb2+水溶液(0、10、30、40、60、100、250ppm)中分别加入10mg上述吸附剂在室温下搅拌8小时，达到吸附平衡后，用原子吸收光谱仪器对其进行浓度检测。试验显示：本发明钴配合物单晶的吸附容量在pH为7的时候吸附量最优，达到493.89mg/g，见图4。
在80mL浓度为10ppm的Pb2+的水溶液中加入10mg上述吸附剂，在室温下搅拌30分钟。在不同的时间(0、0.5、1.5、3、5、8、15、20、30分钟)下取样，用原子吸收光谱仪器对其进行浓度检测。试验显示在8分钟内99.44％的铅离子被吸附去除(图5)，这种对Pb2+的良好去除性能可以归因于在吸附剂框架中存在大量可接近的羧酸氧吸附位点，证明本发明新型钴配合物单晶具有较快的吸附速度。
当在溶液中分别添加10倍Ca2+、Ba2+、Ni2+、Mg2+、Sr2+、K+、Na+时，可以发现吸附剂材料对Pb2+的吸附略有影响(Ca2+、Ba2+和Ni2+三种离子对Pb2+吸附速率略有减少，Mg2+和Sr2+两种离子对Pb2+吸附速率略有增加，K+、Na+两种离子对Pb2+吸附速率变化不大)，但是几乎都在二十分钟之前达到平衡，可见吸附剂材料对Pb2+吸附性能优异。
实施例3：本发明钴配合物吸附Cd2+试验
在80mL浓度为0-200ppm的不同Cd2+水溶液(0、10、20、30、50、100、200ppm)中分别加入10mg上述吸附剂在室温下搅拌8小时，达到吸附平衡后，用原子吸收光谱仪器对其进行浓度检测。试验显示：本发明钴配合物单晶的吸附容量达到215.78mg/g，见图7。
在80mL浓度为10ppm的Cd2+的水溶液中加入10mg上述吸附剂，在室温下搅拌540分钟。在不同的时间(0、3、5、10、30、60、180、300、540分钟)下取样，用原子吸收光谱仪器对其进行浓度检测。试验显示在60分钟内对Cd2+的吸附量可以达到64.14mg/g(图8)，这种对Cd2+的良好去除性能可以归因于在吸附剂框架中存在大量可接近的羧酸氧吸附位点，证明本发明新型钴配合物单晶具有较快的吸附速度。
实施例4：本发明钴配合物选择性吸附试验
在80mL溶液中添加浓度均为10ppm不同金属离子(K+、Na+、Ca2+、Mg2+、Sr2+、Pb2+和Cd2 +)，向此溶液中加入10mg上述吸附剂，在室温下搅拌12h后取样，用原子吸收光谱仪器分别检测不同离子的浓度。试验显示(图9)对Pb2+和Cd2+的去除效果依旧可以达到99.53％和87.34％，对其他离子的去除不足3％，证明本发明新型钴配合物单晶对Pb2+和Cd2+有高的选择性。
经过进一步的研究开发，结果如下：
1、此钴(II)配合物单晶Pb2+吸附仅需要十分钟之内就可以达到吸附平衡，吸附速率极快；
2、在添加不同干扰离子(Ca2+、Ba2+、Ni2+、Mg2+、Sr2+、K+、Na+)的情况下，钴(II)配合物单晶对Pb2+的吸附速率也没有很大干扰，十五分钟之内就可达到吸附平衡，吸附速率快；
3、此钴(II)配合物单晶对Cd2+有一定的去除优势，其最大吸附量为215.78mg/g。
4、此钴(II)配合物单晶对Pb2+和Cd2+有优异的选择吸附效果。
在显微镜下选取合适大小的本发明单晶在室温下进行X–射线衍射实验。在BrukerSmart Apex-II CCD衍射仪上，用经石墨单色器单色化的Mo–Kα射线 以/>方式收集衍射数据。用Bruker SAINT程序进行数据还原。部分结构的衍射数据用SADABS程序进行吸收校正。晶体结构由直接法结合差值Fourier合成解出。全部非氢原子坐标及各向异性参数进行全矩阵最小二乘法修正，C–H原子位置按理论模式计算确定。配合物中金属钴的配位环境见图1；配合物的晶体结构见图2；详细的晶体测定数据见表1。
表1本发明配合物的主要晶体学数据
Claims (2)
1.一种钴配合物单晶，其特征在于，其化学式为：{[Co3L(μ2-O)(DMF)2(H2O)4]·(DMF)3}n，n为正整数，属于单斜晶系，空间群为C2/c,β＝96.99(3)°,γ＝90°,/>其中，L代表5,11,17,23-四[(间羧基苯基)偶氮]-25,26,27,28-四羟基杯[4]芳烃失去四个H原子；DMF代表N,N'-二甲基甲酰胺。
2.如权利要求1所述的钴配合物单晶的应用，其特征在于，将其用于去除水中Pb2+和Cd2 +。
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