CN111499668A - Anderson-based polyacid type cobalt complex for electrostatic adsorption of gentian violet and application thereof - Google Patents

Anderson-based polyacid type cobalt complex for electrostatic adsorption of gentian violet and application thereof Download PDF

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CN111499668A
CN111499668A CN202010311747.4A CN202010311747A CN111499668A CN 111499668 A CN111499668 A CN 111499668A CN 202010311747 A CN202010311747 A CN 202010311747A CN 111499668 A CN111499668 A CN 111499668A
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gentian violet
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常之晗
王秀丽
田原
徐娜
林宏艳
张语辰
刘倩倩
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Abstract

一种用于静电吸附龙胆紫的基于Anderson型多酸型钴配合物及其应用,该配合物的分子式为:{Co2(3‑bpah)4[CrMo6(OH)6O18]}·4H2O,其中,3‑bpah为N,N’‑双(3‑吡啶甲酰胺)‑1,2环己烷。制备方法是:将Co(NO3)2、N,N’‑双(3‑吡啶甲酰胺)‑1,2环己烷和Na3[CrMo6(OH)6O18]溶解到去离子水中,通过水热法进行合成。通过简单的一步水热法可简单得到,通过静电吸附的方式可高效率降解龙胆紫有机分子,通过配合物中多酸具备的高负电荷结构,可以充分吸引带有正电荷的龙胆紫分子,解决了目前在吸附有机药物方面过分依赖多孔材料的问题。

Figure 202010311747

A kind of cobalt complex based on Anderson type polyacid type for electrostatic adsorption of gentian violet and application thereof, the molecular formula of the complex is: {Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]} 4H 2 O, wherein 3-bpah is N,N'-bis(3-picolinamide)-1,2-cyclohexane. The preparation method is: dissolving Co(NO 3 ) 2 , N,N'-bis(3-picolinamide)-1,2-cyclohexane and Na 3 [CrMo 6 (OH) 6 O 18 ] into deionized water , synthesized by a hydrothermal method. It can be easily obtained by a simple one-step hydrothermal method. The organic molecules of gentian violet can be degraded with high efficiency by electrostatic adsorption. The highly negatively charged structure of the polyacid in the complex can fully attract the positively charged gentian violet. Molecules, solving the current problem of over-reliance on porous materials in the adsorption of organic drugs.

Figure 202010311747

Description

一种用于静电吸附龙胆紫的基于Anderson型多酸型钴配合物 及其应用An Anderson-type polyacid-type cobalt complex for electrostatic adsorption of gentian violet and its application

技术领域technical field

本发明涉及一种用于静电吸附龙胆紫的基于Anderson型多酸型钴配合物及其应用。The invention relates to an Anderson-type polyacid-type cobalt complex for electrostatic adsorption of gentian violet and its application.

背景技术Background technique

龙胆紫因其阳离子能与细菌蛋白质的羧基结合,影响其代谢而产生抑菌作用,它是人们所熟悉的外用药。国外医学家对紫药水(龙胆紫)进行了细致的研究,结果发现它有极强的致癌性。英国药理学家通过动物的反复实验证实,紫药水中的龙胆紫是阳离子碱性染料。这种碱性染料是一种致癌物质,为潜在的致癌剂。因而,如何在使用龙胆紫的过程中能够有效地降解和处理是目前所面临的迫切问题。Gentian violet is a well-known external drug because its cation can combine with the carboxyl group of bacterial protein and affect its metabolism to produce antibacterial effect. Foreign medical scientists have conducted meticulous research on purple syrup (gentian violet), and found that it has strong carcinogenicity. British pharmacologists have confirmed through repeated animal experiments that gentian violet in purple potion is a cationic basic dye. This basic dye is a carcinogen and a potential carcinogen. Therefore, how to effectively degrade and dispose of gentian violet in the process of using gentian violet is an urgent problem currently faced.

目前,已开发出多种方法,如光催化降解、化学降解,Fenton-based氧化,臭氧化等。然而,上述技术存在选择性差、成本高、不可重复使用等问题。而活性碳,金属有机框架等材料具有比表面积高、孔隙率高、环境友好等特点被认为是吸附有机染料的理想候选材料。然而,目前此类吸附材料大多依赖多孔材料,制备要求条件高,同时此类材料难以进行脱附。Currently, various methods have been developed, such as photocatalytic degradation, chemical degradation, Fenton-based oxidation, ozonation, etc. However, the above technologies have problems such as poor selectivity, high cost, and non-reusability. Materials such as activated carbon and metal-organic frameworks are considered as ideal candidates for the adsorption of organic dyes due to their high specific surface area, high porosity, and environmental friendliness. However, most of these adsorbent materials currently rely on porous materials, which require high preparation conditions and are difficult to desorb.

目前的主要问题是:如何在制备出一种可吸附有机药物的材料,进而满足其作为药物吸附材料时对染料吸附活性的不同要求。The main problem at present is: how to prepare a material that can adsorb organic drugs, so as to meet the different requirements for dye adsorption activity when it is used as a drug adsorption material.

发明内容SUMMARY OF THE INVENTION

本发明要解决的技术问题是提供一种用于静电吸附龙胆紫的基于Anderson型多酸型钴配合物及其应用,通过简单的一步水热法可简单得到,通过静电吸附的方式可高效率降解龙胆紫分子,解决了在吸附染料时对多孔材料难以脱附的问题。The technical problem to be solved by the present invention is to provide an Anderson-type polyacid-type cobalt complex for electrostatic adsorption of gentian violet and its application, which can be easily obtained by a simple one-step hydrothermal method, and can be obtained by electrostatic adsorption. The efficient degradation of gentian violet molecules solves the problem of difficult desorption of porous materials when adsorbing dyes.

本发明的技术方案是:The technical scheme of the present invention is:

一种用于静电吸附龙胆紫的基于Anderson型多酸型钴配合物,选用多酸阴离子、有机配体,金属钴离子作为构建单元,采用水热法制备得到,并通过X射线单晶衍射表征其结构。An Anderson-type polyacid-type cobalt complex for electrostatic adsorption of gentian violet is prepared by using a hydrothermal method by selecting polyacid anions, organic ligands, and metal cobalt ions as building blocks, and through X-ray single crystal diffraction characterize its structure.

该配合物的分子式如下:The molecular formula of this complex is as follows:

{Co2(3-bpah)4[CrMo6(OH)6O18]}·4H2O;{Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]}·4H 2 O;

其中,3-bpah为N,N’-双(3-吡啶甲酰胺)-1,2环己烷。Wherein, 3-bpah is N,N'-bis(3-pyridinecarboxamide)-1,2cyclohexane.

一种用于静电吸附龙胆紫的基于Anderson型多酸型钴配合物,制备具体步骤如下:A kind of cobalt complex based on Anderson type polyacid type for electrostatic adsorption of gentian violet, the specific preparation steps are as follows:

将Co(NO3)2、N,N’-双(3-吡啶甲酰胺)-1,2环己烷和Na3[CrMo6(OH)6O18]溶解到去离子水中,所述Co(NO3)2,N,N’-双(3-吡啶甲酰胺)-1,2环己烷和Na3[CrMo6(OH)6O18]摩尔比为1:1:1,并用HCl溶液将pH值调整到4.35后搅拌30分钟,转移到聚四氟乙烯高温反应釜内衬中,倒入高压反应釜在120℃的环境下进行水热反应,在该温度下保持4天,并逐渐降温,得到紫色晶体产物并清洗干燥,得到{Co2(3-bpah)4[CrMo6(OH)6O18]}·4H2O。Co(NO 3 ) 2 , N,N'-bis(3-pyridinecarboxamide)-1,2-cyclohexane and Na 3 [CrMo 6 (OH) 6 O 18 ] were dissolved in deionized water, the Co (NO 3 ) 2 ,N,N'-bis(3-pyridinecarboxamide)-1,2-cyclohexane and Na 3 [CrMo 6 (OH) 6 O 18 ] in a molar ratio of 1:1:1 and HCl The pH value of the solution was adjusted to 4.35 and then stirred for 30 minutes, transferred to the lining of the polytetrafluoroethylene high-temperature reaction kettle, poured into the autoclave to carry out hydrothermal reaction under the environment of 120 ° C, kept at this temperature for 4 days, and The temperature was gradually lowered to obtain purple crystal product, which was washed and dried to obtain {Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]}·4H 2 O.

进一步的,所述Co(NO3)2与去离子水的摩尔比为0.04mol/L。Further, the molar ratio of Co(NO 3 ) 2 to deionized water is 0.04mol/L.

进一步的,所述HCl溶液的浓度为1mol/L。Further, the concentration of the HCl solution is 1 mol/L.

进一步的,所述降温速度为10℃/h。Further, the cooling rate is 10°C/h.

一种基于Anderson型多酸型钴配合物在静电吸附龙胆紫中的应用。An application of Anderson-type polyacid-type cobalt complexes in electrostatic adsorption of gentian violet.

一种基于Anderson型多酸型钴配合物在静电吸附龙胆紫中的应用,具体操作如下:A kind of application based on Anderson type polyacid type cobalt complex in electrostatic adsorption of gentian violet, the specific operation is as follows:

取配合物{Co2(3-bpah)4[CrMo6(OH)6O18]}·4H2O在黑暗环境下将样品浸泡在含有龙胆紫溶液中,搅拌8min-10min。Take the complex {Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]}·4H 2 O and soak the sample in a solution containing gentian violet in a dark environment, and stir for 8min-10min.

本发明的有益效果是:The beneficial effects of the present invention are:

1、本发明配合物{Co2(3-bpah)4[CrMo6(OH)6O18]}·4H2O中金属钴离子呈现为六配位模式,多酸呈现为四配位模式,多酸与中心金属形成了一维链结构,3-bpah呈现为双配位模式,与中心金属配位,进而连接了相邻的一维链结构,形成了二维层;利用多酸基配位配合物结构中多酸具备的高负电荷,实现了对龙胆紫的静电吸附。解决了针对有机染料的吸附中,对多孔材料的依赖的问题,同时也突破了目前有机染料吸附材料在重量、吸附效率等方面的局限性。1. In the complex of the present invention {Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]}·4H 2 O, the metal cobalt ion exhibits a six-coordination mode, and the polyacid exhibits a four-coordination mode, The polyacid forms a one-dimensional chain structure with the central metal, and 3-bpah presents a double coordination mode, which coordinates with the central metal, and then connects the adjacent one-dimensional chain structure to form a two-dimensional layer; The high negative charge of the polyacid in the complex structure realizes the electrostatic adsorption of gentian violet. It solves the problem of dependence on porous materials in the adsorption of organic dyes, and also breaks through the limitations of the current organic dye adsorption materials in terms of weight and adsorption efficiency.

2、本发明中的配位配合物通过简单的一步水热法可简单得到,可以不经任何后处理直接使用,具有质轻、吸附效率高、可高批量制备的特点。2. The coordination complex in the present invention can be easily obtained by a simple one-step hydrothermal method, can be used directly without any post-treatment, and has the characteristics of light weight, high adsorption efficiency and high batch preparation.

附图说明Description of drawings

图1为本发明多酸基配合物的配位模式和二维层结构图;Fig. 1 is the coordination mode and two-dimensional layer structure diagram of the polyacid-based complex of the present invention;

图2为本发明多酸基金属有机配合物的红外图;Fig. 2 is the infrared image of the polyacid-based metal-organic complex of the present invention;

图3为本发明多酸基金属有机配合物的X射线粉末衍射图;Fig. 3 is the X-ray powder diffraction pattern of the polyacid-based metal-organic complex of the present invention;

图4为本发明多酸基金属有机配合物的的吸附染料实验流程图;Fig. 4 is the experiment flow chart of the adsorption dye of the polyacid-based metal organic complex of the present invention;

图5为配合物在不同时间吸附龙胆紫不同时间后的紫外-可见吸收光谱图;Fig. 5 is the ultraviolet-visible absorption spectrogram after the complex adsorbs gentian violet for different time at different time;

图6为经过本发明的多酸基金属有机配合物吸附前后的龙胆紫溶液颜色对比图。6 is a color comparison diagram of the gentian violet solution before and after the adsorption of the polyacid-based metal-organic complex of the present invention.

具体实施方式Detailed ways

实施例Example

将1mmol Co(NO3)2,1mmol 3-bpah,1mmol Na3[CrMo6(OH)6O18]先后溶解到25mL去离子水中,并用1mol/L HCl溶液将pH值调整到4.35后搅拌30分钟后转移到聚四氟乙烯高温反应釜内衬中,后倒入高压反应釜在120℃的环境下进行水热反应,在该温度下保持四天,并以10℃/h速度逐渐降温,后得到紫色晶体产物并清洗干燥,得到{Co2(3-bpah)4[CrMo6(OH)6O18]}·4H2O。Dissolve 1 mmol Co(NO 3 ) 2 , 1 mmol 3-bpah and 1 mmol Na 3 [CrMo 6 (OH) 6 O 18 ] into 25 mL of deionized water successively, adjust the pH to 4.35 with 1 mol/L HCl solution, and stir for 30 After minutes, it was transferred to the lining of the polytetrafluoroethylene high-temperature reaction kettle, and then poured into the high-pressure reaction kettle for hydrothermal reaction at 120 °C, kept at this temperature for four days, and gradually cooled at a speed of 10 °C/h, Afterwards, purple crystals were obtained and washed and dried to obtain {Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]}·4H 2 O.

对制备出的{Co2(3-bpah)4[CrMo6(OH)6O18]}·4H2O配位配合物样品进行单晶X射线衍射、红外、X射线粉末衍射结构表征;在Rigaku Ultima IV粉末X射线衍射仪上收集完成粉末衍射数据,操作电流为40mA,电压为40kV。采用铜靶X射线。固定扫描,接收狭缝宽为0.1mm。密度数据收集使用2θ/θ扫描模式,扫描范围5°到50°,扫描速度为5°/s,跨度为0.02°/次。数据拟合使用Cerius2程序,单晶结构粉末衍射谱模拟转化使用Mercury1.4.1X–射线粉末衍射(PXRD)在Ultima IV X–射线粉末衍射仪上测试。通过红外和XRD表征(图2和图3),证明该材料的组成的均一性和高晶度,The prepared samples of {Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]}·4H 2 O coordination complexes were characterized by single crystal X-ray diffraction, infrared and X-ray powder diffraction; Complete powder diffraction data were collected on a Rigaku Ultima IV powder X-ray diffractometer operating at 40 mA and 40 kV. A copper target X-ray was used. Fixed scanning, receiving slit width of 0.1mm. Density data were collected using a 2θ/θ scan mode with a scan range of 5° to 50°, a scan speed of 5°/s, and a span of 0.02°/pass. The data were fitted using the Cerius2 program, and the single-crystal structure powder diffraction spectrum simulations were transformed using Mercury 1.4.1 X-ray powder diffraction (PXRD) tests on an Ultima IV X-ray powder diffractometer. The compositional homogeneity and high crystallinity of the material were demonstrated by infrared and XRD characterizations (Figures 2 and 3),

晶体结构测定:用显微镜选取合适大小的单晶,室温下采用Bruker SMART APEXII衍射仪(石墨单色器,Mo-Ka)收集衍射数据。扫描方式衍射数据使用SADABS程序进行吸收校正。数据还原和结构解析分别使用SAINT和SHELXTL程序完成。最小二乘法确定全部非氢原子坐标,并用理论加氢法得到氢原子位置。采用最小二乘法对晶体结构进行精修。其晶体学衍射点数据收集与结构精修的部分参数如表1所示:Determination of crystal structure: A single crystal of suitable size was selected with a microscope, and the diffraction data were collected by Bruker SMART APEXII diffractometer (graphite monochromator, Mo-Ka) at room temperature. Scan-mode diffraction data were corrected for absorption using the SADABS program. Data restoration and structure analysis were done using the SAINT and SHELXTL programs, respectively. The least squares method determines the coordinates of all non-hydrogen atoms, and the theoretical hydrogenation method is used to obtain the positions of the hydrogen atoms. The crystal structure was refined using the least squares method. Some parameters of its crystallographic diffraction point data collection and structure refinement are shown in Table 1:

表1Table 1

Figure BDA0002458100690000031
Figure BDA0002458100690000031

通过单晶X射线衍射数据,分析可知,该配合物{Co2(3-bpah)4[CrMo6(OH)6O18]}·4H2O中金属离子呈现为六配位模式,多酸呈现为四配位模式,多酸与中心金属形成了一维链结构,3-bpah呈现为双配位模式,与中心金属配位,进而连接了相邻的一维链结构,形成了二维层(图1)。According to the single crystal X-ray diffraction data, the analysis shows that the metal ion in the complex {Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]}·4H 2 O presents a six-coordination mode, and the polyacid It is a four-coordination mode, the polyacid forms a one-dimensional chain structure with the central metal, and 3-bpah presents a double-coordinated mode, which coordinates with the central metal, and then connects the adjacent one-dimensional chain structure to form a two-dimensional chain structure. layer (Figure 1).

配位配合物的吸附性能:将上述步骤所获得的多酸基配位配合物材料取50mg{Co2(3-bpah)4[CrMo6(OH)6O18]}·4H2O样品进行测试,在黑暗环境下将样品浸泡在100mL0.3mmol/L龙胆紫溶液下,每隔1分钟取10m L龙胆紫溶液样品进行紫外吸附测试,将取出的龙胆紫溶液转移至紫外分光光度计进行紫外吸收光谱图测试,扫描波数范围为400-700cm-1。前后总共取8次溶液,吸附反应时间为8分钟。图5为样品的龙胆紫相应紫外吸附峰随时间变化图。紫外峰峰值与龙胆紫溶液的浓度呈正向线性关系。所以可以间接求得吸附前后龙胆紫溶液的浓度值,吸附前的溶液浓度为Co,吸附后浓度为Ct,计算龙胆紫的吸附量的公式为qt(mmol g-1)=(C0-Ct)V/W,V为溶液体积,W为配合物的质量。在本实施例中,Co为0.3mmol/L,Ct为0.048mmol/L,V为100mL,W为50mg,代入至公式,计算可得吸附量为0.504mmol g-1,平均吸附速率为0.063mmol g-1min-1 Adsorption performance of coordination complexes: 50mg {Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]}·4H 2 O samples were taken from the polyacid-based coordination complex materials obtained in the above steps. For the test, soak the sample in 100 mL of 0.3 mmol/L gentian violet solution in a dark environment, take 10 mL of gentian violet solution sample every 1 minute for UV adsorption test, and transfer the taken out gentian violet solution to UV spectrophotometry The UV absorption spectrogram was tested with the meter, and the scanning wavenumber range was 400-700 cm -1 . A total of 8 solutions were taken before and after, and the adsorption reaction time was 8 minutes. Figure 5 is a graph showing the change of the corresponding UV adsorption peaks of gentian violet with time. There was a positive linear relationship between the peak value of UV and the concentration of gentian violet solution. Therefore, the concentration of gentian violet solution before and after adsorption can be obtained indirectly. The concentration of the solution before adsorption is C o , and the concentration after adsorption is C t . The formula for calculating the adsorption capacity of gentian violet is q t (mmol g -1 )= (C 0 -C t )V/W, where V is the volume of the solution and W is the mass of the complex. In this example, C o is 0.3 mmol/L, C t is 0.048 mmol/L, V is 100 mL, and W is 50 mg. Substituting into the formula, the calculated adsorption amount is 0.504 mmol g -1 , and the average adsorption rate is 0.063mmol g -1 min -1

图6为经过本发明的多酸基金属有机配合物吸附前后的龙胆紫溶液颜色对比图。左为吸附前,右为吸附后,通过肉眼可见配合物材料可对龙胆紫产生明显的吸附效果。6 is a color comparison diagram of the gentian violet solution before and after the adsorption of the polyacid-based metal-organic complex of the present invention. The left is before adsorption, and the right is after adsorption. It can be seen by the naked eye that the complex material can produce obvious adsorption effect on gentian violet.

结果表明,本发明制备的多酸基配合物基吸附材料,凭借多酸的高负电荷性,可通过静电作用高效吸附龙胆紫。解决了目前针对染料吸附技术中对多孔材料的依赖,并且进一步提高了非多孔材料的吸附染料的速率。The results show that the polyacid-based complex-based adsorption material prepared by the present invention can efficiently adsorb gentian violet through electrostatic action by virtue of the high negative charge of the polyacid. The current dependence on porous materials in dye adsorption technology is solved, and the rate of dye adsorption by non-porous materials is further improved.

以上仅为本发明的具体实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The above are only specific embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (7)

1.一种用于静电吸附龙胆紫的基于Anderson型多酸型钴配合物,其特征是:1. based on Anderson type polyacid type cobalt complex for electrostatic adsorption of gentian violet, it is characterized in that: 该配合物的分子式如下:The molecular formula of this complex is as follows: {Co2(3-bpah)4[CrMo6(OH)6O18]}·4H2O;{Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]}·4H 2 O; 其中,3-bpah为N,N’-双(3-吡啶甲酰胺)-1,2环己烷。Wherein, 3-bpah is N,N'-bis(3-pyridinecarboxamide)-1,2cyclohexane. 2.一种如权利要求1所述的用于静电吸附龙胆紫的基于Anderson型多酸型钴配合物,其特征是:2. a kind of based on Anderson type polyacid type cobalt complex for electrostatic adsorption of gentian violet as claimed in claim 1, is characterized in that: 制备具体步骤如下:The specific steps of preparation are as follows: 将Co(NO3)2、N,N’-双(3-吡啶甲酰胺)-1,2环己烷和Na3[CrMo6(OH)6O18]溶解到去离子水中,所述Co(NO3)2,N,N’-双(3-吡啶甲酰胺)-1,2环己烷和Na3[CrMo6(OH)6O18]摩尔比为1:1:1,并用HCl溶液将pH值调整到4.35后搅拌30分钟,转移到聚四氟乙烯高温反应釜内衬中,倒入高压反应釜在120℃的环境下进行水热反应,在该温度下保持4天,并逐渐降温,得到紫色晶体产物并清洗干燥,得到{Co2(3-bpah)4[CrMo6(OH)6O18]}·4H2O。Co(NO 3 ) 2 , N,N'-bis(3-pyridinecarboxamide)-1,2-cyclohexane and Na 3 [CrMo 6 (OH) 6 O 18 ] were dissolved in deionized water, the Co (NO 3 ) 2 ,N,N'-bis(3-pyridinecarboxamide)-1,2-cyclohexane and Na 3 [CrMo 6 (OH) 6 O 18 ] in a molar ratio of 1:1:1 and HCl The pH value of the solution was adjusted to 4.35 and then stirred for 30 minutes, transferred to the lining of the polytetrafluoroethylene high-temperature reaction kettle, poured into the autoclave to carry out hydrothermal reaction under the environment of 120 ° C, kept at this temperature for 4 days, and The temperature was gradually lowered to obtain purple crystal product, which was washed and dried to obtain {Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]}·4H 2 O. 3.根据权利要求3所述的用于静电吸附龙胆紫的基于Anderson型多酸型钴配合物,其特征是:所述Co(NO3)2与去离子水的摩尔比为0.04mol/L。3. based on Anderson type polyacid type cobalt complex for electrostatic adsorption of gentian violet according to claim 3, it is characterized in that: the mol ratio of described Co(NO 3 ) 2 and deionized water is 0.04mol/ L. 4.根据权利要求3所述的用于静电吸附龙胆紫的基于Anderson型多酸型钴配合物,其特征是:所述HCl溶液的浓度为1mol/L。4. based on Anderson type polyacid type cobalt complex for electrostatic adsorption of gentian violet according to claim 3, it is characterized in that: the concentration of described HCl solution is 1mol/L. 5.根据权利要求3所述的用于静电吸附龙胆紫的基于Anderson型多酸型钴配合物,其特征是:所述降温速度为10℃/h。5 . The Anderson-type polyacid-type cobalt complex for electrostatic adsorption of gentian violet according to claim 3 , wherein the cooling rate is 10° C./h. 6 . 6.一种如权利要求1所述的基于Anderson型多酸型钴配合物在静电吸附龙胆紫中的应用。6. a kind of application based on Anderson type polyacid type cobalt complex in electrostatic adsorption gentian violet as claimed in claim 1. 7.根据权利要去6所述的基于Anderson型多酸型钴配合物在静电吸附龙胆紫中的应用,其特征是:7. according to the application in electrostatic adsorption gentian violet based on Anderson type polyacid type cobalt complex described in 6, it is characterized in that: 具体操作如下:The specific operations are as follows: 取配合物{Co2(3-bpah)4[CrMo6(OH)6O18]}·4H2O在黑暗环境下将样品浸泡在含有龙胆紫溶液中,搅拌8min-10min。Take the complex {Co 2 (3-bpah) 4 [CrMo 6 (OH) 6 O 18 ]}·4H 2 O and soak the sample in a solution containing gentian violet in a dark environment, and stir for 8min-10min.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103709182A (en) * 2013-12-06 2014-04-09 渤海大学 Transition metal compounds based on semi-rigid, synthetic method and applications
CN103724365A (en) * 2013-12-18 2014-04-16 渤海大学 Transition metal complex based on semirigid bipyridine bisamide organic ligand and terephthalic acid as well as synthetic method and application of transition metal complex
CN103992338A (en) * 2014-03-22 2014-08-20 渤海大学 Copper complex based on dipyridine piperazine ligand and Anderson type polyacid, and synthetic method and application thereof
CN106277159A (en) * 2016-08-09 2017-01-04 渤海大学 A kind of methylene blue and the processing method of Congo red organic pollution

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103709182A (en) * 2013-12-06 2014-04-09 渤海大学 Transition metal compounds based on semi-rigid, synthetic method and applications
CN103724365A (en) * 2013-12-18 2014-04-16 渤海大学 Transition metal complex based on semirigid bipyridine bisamide organic ligand and terephthalic acid as well as synthetic method and application of transition metal complex
CN103992338A (en) * 2014-03-22 2014-08-20 渤海大学 Copper complex based on dipyridine piperazine ligand and Anderson type polyacid, and synthetic method and application thereof
CN106277159A (en) * 2016-08-09 2017-01-04 渤海大学 A kind of methylene blue and the processing method of Congo red organic pollution

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIU-LI WANG等: "Metal(II)–Organic Coordination Polymers Modulated by Two Isomeric Semirigid Bis-Pyridyl-Bis-Amide Ligands: Structures, Fluorescent Sensing Behavior, and Selective Photocatalysis", 《CHEMPLUSCHEM》 *

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