CN107879943A - A kind of iron-based complex and its application - Google Patents
A kind of iron-based complex and its application Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 75
- 229940000489 arsenate Drugs 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 72
- -1 nitrogen-nitrogen dimethyl formaldehyde amide Chemical class 0.000 claims abstract description 69
- 238000001514 detection method Methods 0.000 claims abstract description 30
- BJMBNXMMZRCLFY-UHFFFAOYSA-N [N].[N].CN(C)C=O Chemical compound [N].[N].CN(C)C=O BJMBNXMMZRCLFY-UHFFFAOYSA-N 0.000 claims abstract description 25
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 abstract description 20
- 230000035945 sensitivity Effects 0.000 abstract description 9
- 238000010586 diagram Methods 0.000 description 14
- 229910052785 arsenic Inorganic materials 0.000 description 9
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
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- 238000001179 sorption measurement Methods 0.000 description 7
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- 241000282414 Homo sapiens Species 0.000 description 5
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- 238000000034 method Methods 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
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- 238000002525 ultrasonication Methods 0.000 description 3
- 241000282412 Homo Species 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
本发明公开了一种铁基配合物及其应用，该铁基配合物的制备方法包括：以2‑氨基对苯二甲酸和FeCl3·6H2O为原料，以氮‑氮二甲基甲酰胺为溶剂，并按照每1.3838mmol的2‑氨基对苯二甲酸使用1.3838mmolFeCl3·6H2O和30mL氮‑氮二甲基甲酰胺的比例，将2‑氨基对苯二甲酸和FeCl3·6H2O溶于氮‑氮二甲基甲酰胺中，然后采用水热反应制得铁基配合物。该铁基配合物可以用于检测水体中的砷酸根离子浓度，也可用于去除水体中的砷酸根离子。本发明不仅可以快速检测出水体中的砷酸根离子浓度，检测灵敏度高，而且可以有效去除水体中的砷酸根离子。The invention discloses an iron-based complex and its application. The preparation method of the iron-based complex comprises: using 2-aminoterephthalic acid and FeCl 3 .6H 2 O as raw materials, and using nitrogen-nitrogen dimethyl formaldehyde amide as solvent, and according to the ratio of 1.3838mmol FeCl 3 6H 2 O and 30mL nitrogen-nitrogen dimethylformamide for every 1.3838mmol of 2-aminoterephthalic acid, 2-aminoterephthalic acid and FeCl 3 . 6H 2 O was dissolved in nitrogen-nitrogen dimethylformamide, and then the iron-based complex was prepared by hydrothermal reaction. The iron-based complex can be used to detect the concentration of arsenate ions in the water body, and can also be used to remove the arsenate ions in the water body. The invention not only can quickly detect the arsenate ion concentration in the water body, has high detection sensitivity, but also can effectively remove the arsenate ion in the water body.
Description
技术领域technical field
本发明涉及水体中砷酸根离子检测及去除技术领域，尤其涉及一种铁基配合物及其应用。The invention relates to the technical field of detection and removal of arsenate ions in water bodies, in particular to an iron-based complex and its application.
背景技术Background technique
砷酸根离子是毒性最强和致癌性最强物质之一，广泛存在于大气、水、土壤、有机体等环境中。火山喷发、风华反应、生物体活动、岩石土壤的腐蚀等地质因素都会导致水和土壤中的砷污染，而含砷矿物质的熔炼、含砷杀虫剂和防腐剂的使用、化石燃料的燃烧等人类活动会对环境造成砷污染。如果人类长期接触砷污染的水，会对人体健康产生严重影响，容易诱发皮肤病变、先天畸形、肾病、肝功能损伤、白血病、动脉粥样硬化、癌症等疾病，甚至死亡。出于对砷污染产生的危机和公共水质的关注，世界卫生组织规定“人类引用水源中砷的浓度限值为10μg/L”，因此对水体等环境中砷酸根离子的检测和去除一直是本领域的研究热点。Arsenate ions are one of the most toxic and carcinogenic substances, widely present in the atmosphere, water, soil, organisms and other environments. Geological factors such as volcanic eruptions, blooming reactions, biological activities, and corrosion of rocky soils can all lead to arsenic pollution in water and soil, while the smelting of arsenic-containing minerals, the use of arsenic-containing pesticides and preservatives, and the burning of fossil fuels And other human activities will cause arsenic pollution to the environment. If humans are exposed to arsenic-contaminated water for a long time, it will have a serious impact on human health, and it is easy to induce skin lesions, congenital deformities, kidney disease, liver function damage, leukemia, atherosclerosis, cancer and other diseases, and even death. Out of concern about the crisis caused by arsenic pollution and public water quality, the World Health Organization has stipulated that "the concentration limit of arsenic in human drinking water sources is 10 μg/L", so the detection and removal of arsenate ions in water and other environments has always been the basic research hotspots in the field.
在现有技术中，通常采用连续的荧光法、比色法、电化学技术来检测水体中的砷酸根离子，并采用吸附法、絮凝法、化学氧化法来去除水体中的砷酸根离子，但是这些方法只具备检测或去除的单一功能，而且用于检测砷酸根离子的方法速度慢、检测灵敏度低，用于去除砷的方法对砷酸根离子的去除效果不理想。In the prior art, continuous fluorescence method, colorimetry, and electrochemical techniques are usually used to detect arsenate ions in water, and adsorption, flocculation, and chemical oxidation are used to remove arsenate ions in water, but These methods only have a single function of detection or removal, and the methods for detecting arsenate ions are slow and have low detection sensitivity, and the methods for removing arsenic are not ideal for the removal of arsenate ions.
发明内容Contents of the invention
针对现有技术中的上述不足之处，本发明提供了一种铁基配合物及其应用，不仅可以快速检测出水体中的砷酸根离子浓度，检测灵敏度高，而且可以有效去除水体中的砷酸根。Aiming at the above-mentioned deficiencies in the prior art, the present invention provides an iron-based complex and its application, which can not only quickly detect the concentration of arsenate ions in the water body, has high detection sensitivity, but also can effectively remove the arsenic in the water body Sour root.
本发明的目的是通过以下技术方案实现的：The purpose of the present invention is achieved through the following technical solutions:
一种铁基配合物，其制备方法包括以下步骤：以2-氨基对苯二甲酸和FeCl3·6H2O为原料，以氮-氮二甲基甲酰胺为溶剂，并按照每1.3838mmol的2-氨基对苯二甲酸使用1.3838mmolFeCl3·6H2O和30mL氮-氮二甲基甲酰胺的比例，将2-氨基对苯二甲酸和FeCl3·6H2O溶于氮-氮二甲基甲酰胺中，然后采用水热反应制得铁基配合物。An iron-based complex, the preparation method of which comprises the following steps: taking 2-aminoterephthalic acid and FeCl 3 6H 2 O as raw materials, using nitrogen-nitrogen dimethylformamide as a solvent, and using 1.3838 mmol of 2-aminoterephthalic acid Dissolve 2-aminoterephthalic acid and FeCl 3 6H 2 O in nitrogen-nitrogen dimethylformamide using a ratio of 1.3838 mmol FeCl 3 6H 2 O and 30 mL of nitrogen-nitrogen dimethylformamide base formamide, and then adopt hydrothermal reaction to prepare iron-based complexes.
优选地，所述的采用水热反应制得铁基配合物包括：当2-氨基对苯二甲酸和FeCl3·6H2O溶于氮-氮二甲基甲酰胺后，置于120°的环境中进行20～24小时的水热反应，然后进行固液分离，再对固液分离得到的固体进行清洗，并进行48小时的冷冻干燥，从而制得所述的铁基配合物。Preferably, the preparation of the iron-based complex by the hydrothermal reaction includes: when 2-aminoterephthalic acid and FeCl 3 ·6H 2 O are dissolved in nitrogen-nitrogen dimethylformamide, place in a 120° The hydrothermal reaction is carried out in the environment for 20-24 hours, and then the solid-liquid separation is carried out, and then the solid obtained by the solid-liquid separation is washed and freeze-dried for 48 hours, so as to prepare the iron-based complex.
优选地，所述对固液分离得到的固体进行清洗包括：采用氮-氮二甲基甲酰胺和乙醇分别对固液分离得到的固体进行多次清洗。Preferably, the cleaning of the solid obtained from the solid-liquid separation includes: using nitrogen-nitrogen dimethylformamide and ethanol to respectively clean the solid obtained from the solid-liquid separation for multiple times.
一种上述的铁基配合物的应用，用于检测水体中的砷酸根离子浓度。An application of the above-mentioned iron-based complex is used to detect the concentration of arsenate ions in a water body.
优选地，每5mg的所述铁基配合物对水体中砷酸根离子浓度的检测范围为0.1～50μmol/L。Preferably, the detection range of the concentration of arsenate ions in the water body per 5 mg of the iron-based complex is 0.1-50 μmol/L.
一种上述的铁基配合物的应用，用于去除水体中的砷酸根离子。An application of the above-mentioned iron-based complex for removing arsenate ions in water bodies.
优选地，在去除水体中的砷酸根离子时，所述铁基配合物的用量为0.2g/L，水体的pH值控制在6，处理时间控制在24小时。Preferably, when removing arsenate ions in the water body, the dosage of the iron-based complex is 0.2 g/L, the pH value of the water body is controlled at 6, and the treatment time is controlled at 24 hours.
一种上述铁基配合物的应用，用于检测水体中的砷酸根离子浓度，并去除水体中的砷酸根离子。An application of the above-mentioned iron-based complex is used for detecting the concentration of arsenate ions in a water body and removing the arsenate ions in the water body.
由上述本发明提供的技术方案可以看出，本发明提供的铁基配合物按照每1.3838mmol的2-氨基对苯二甲酸使用1.3838mmolFeCl3·6H2O和30mL氮-氮二甲基甲酰胺的比例，将2-氨基对苯二甲酸和FeCl3·6H2O溶于氮-氮二甲基甲酰胺中，然后采用水热反应制备而成，从而使该铁基配合物具有检测水体中砷酸根离子浓度和去除水体中砷酸根离子的双重功能，克服了现有技术中检测砷酸根离子和去除砷酸根离子功能单一的问题，而且能够预富集水体中的砷酸根离子，检测速度快、检测灵敏度高、检测范围宽、检测限低，在水体中砷酸根离子浓度达到最大限制值之前给予警报，并能将水体中的砷酸根离子有效去除，这有效降低了砷酸根离子污染对环境和人类造成的危害。As can be seen from the technical scheme provided by the present invention above, the iron-based complex provided by the present invention uses 1.3838mmol FeCl 3 6H 2 O and 30mL nitrogen-nitrogen dimethylformamide for every 1.3838mmol of 2-aminoterephthalic acid The ratio of 2-aminoterephthalic acid and FeCl 3 6H 2 O is dissolved in nitrogen-nitrogen dimethylformamide, and then prepared by hydrothermal reaction, so that the iron-based complex has the ability to detect water The dual function of arsenate ion concentration and removal of arsenate ions in water overcomes the problem of single function of detecting arsenate ions and removing arsenate ions in the prior art, and can pre-enrich arsenate ions in water with fast detection speed , High detection sensitivity, wide detection range, low detection limit, an alarm will be given before the concentration of arsenate ions in the water reaches the maximum limit value, and the arsenate ions in the water can be effectively removed, which effectively reduces the pollution of arsenate ions to the environment and harm to humans.
附图说明Description of drawings
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域的普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他附图。In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the accompanying drawings that need to be used in the description of the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For Those of ordinary skill in the art can also obtain other drawings based on these drawings on the premise of not paying creative efforts.
图1为本发明实施例1提供铁基配合物的扫描电镜示意图和透射电镜示意图。FIG. 1 is a schematic diagram of a scanning electron microscope and a schematic diagram of a transmission electron microscope of an iron-based complex provided in Example 1 of the present invention.
图2为本发明实施例1提供铁基配合物的X射线衍射图谱。Fig. 2 is the X-ray diffraction pattern of the iron-based complex provided by Example 1 of the present invention.
图3为本发明实施例1提供铁基配合物对砷酸根离子浓度为0.1～50μmol/L的水体进行浓度荧光检测而得到的荧光强度示意图。Fig. 3 is a schematic diagram of the fluorescence intensity obtained by performing concentration fluorescence detection of the iron-based complex provided by Example 1 of the present invention on a water body with an arsenate ion concentration of 0.1-50 μmol/L.
图4为本发明实施例1提供铁基配合物在其他阳离子或阴离子存在的水体中对砷酸根离子浓度荧光检测而得到的荧光性能示意图。Fig. 4 is a schematic diagram of the fluorescence performance of the iron-based complex provided in Example 1 of the present invention in the water body in which other cations or anions exist to detect the concentration of arsenate ions by fluorescence.
图5为本发明实施例1提供铁基配合物在不同砷酸根离子浓度水体中对砷酸根离子的去除效果示意图。5 is a schematic diagram of the removal effect of iron-based complexes on arsenate ions in water bodies with different concentrations of arsenate ions provided by Example 1 of the present invention.
图6为本发明实施例1提供铁基配合物在不同时间点对水体中砷酸根离子的去除效果示意图。6 is a schematic diagram of the removal effect of iron-based complexes on arsenate ions in water at different time points provided by Example 1 of the present invention.
具体实施方式Detailed ways
下面结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
下面对本发明所提供的铁基配合物及其应用进行详细描述。本发明实施例中未作详细描述的内容属于本领域专业技术人员公知的现有技术。The iron-based complex provided by the present invention and its application are described in detail below. The content not described in detail in the embodiments of the present invention belongs to the prior art known to those skilled in the art.
一种铁基配合物，其制备方法包括以下步骤：以2-氨基对苯二甲酸和FeCl3·6H2O为原料，以氮-氮二甲基甲酰胺为溶剂，并按照每1.3838mmol的2-氨基对苯二甲酸使用1.3838mmolFeCl3·6H2O和30mL氮-氮二甲基甲酰胺的比例，将2-氨基对苯二甲酸和FeCl3·6H2O溶于氮-氮二甲基甲酰胺中，然后采用水热反应制得铁基配合物。An iron-based complex, the preparation method of which comprises the following steps: taking 2-aminoterephthalic acid and FeCl 3 6H 2 O as raw materials, using nitrogen-nitrogen dimethylformamide as a solvent, and using 1.3838 mmol of 2-aminoterephthalic acid Dissolve 2-aminoterephthalic acid and FeCl 3 6H 2 O in nitrogen-nitrogen dimethylformamide using a ratio of 1.3838 mmol FeCl 3 6H 2 O and 30 mL of nitrogen-nitrogen dimethylformamide base formamide, and then adopt hydrothermal reaction to prepare iron-based complexes.
具体地，本发明所提供的铁基配合物其制备方法可以包括以下实施方案：Specifically, the preparation method of the iron-based complex provided by the present invention may include the following embodiments:
(1)2-氨基对苯二甲酸、FeCl3·6H2O、氮-氮二甲基甲酰胺这三者的使用比例最好为1.3838mmol:1.3838mmol:30mL，这一比例不仅可以使制得的铁基配合物对水体中砷酸根离子浓度的检测灵敏度更高，而且能够有效提升对水体中砷酸根离子的去除效果。(1) The ratio of 2-aminoterephthalic acid, FeCl 3 .6H 2 O, and nitrogen-nitrogen dimethylformamide is preferably 1.3838mmol:1.3838mmol:30mL. This ratio can not only make the The obtained iron-based complex has higher detection sensitivity to the concentration of arsenate ions in water, and can effectively improve the removal effect of arsenate ions in water.
(2)将2-氨基对苯二甲酸和FeCl3·6H2O置于氮-氮二甲基甲酰胺中后，最好超声5min并搅拌2小时，从而可以使2-氨基对苯二甲酸和FeCl3·6H2O充分均匀地分解于氮-氮二甲基甲酰胺中。(2) After placing 2-aminoterephthalic acid and FeCl 3 6H 2 O in nitrogen-nitrogen dimethylformamide, it is best to sonicate for 5 minutes and stir for 2 hours, so that 2-aminoterephthalic acid can be And FeCl 3 ·6H 2 O fully and uniformly decomposed in nitrogen-nitrogen dimethylformamide.
(3)所述的采用水热反应制得铁基配合物包括：当2-氨基对苯二甲酸和FeCl3·6H2O溶于氮-氮二甲基甲酰胺后，置于120°的环境中进行20～24小时的水热反应，待降至室温后进行固液分离，再对固液分离得到的固体进行清洗，并进行48小时的冷冻干燥，从而制得八面体结构的铁基配合物。通过将水热反应的反应温度控制在120°，并将水热反应的反应时间控制在20～24小时，从而可以使制得的铁基配合物对水体中砷酸根离子浓度的检测灵敏度更高，而且能够有效提升对水体中砷酸根离子的去除效果。通过对固液分离得到的固体进行清洗，再进行冷冻干燥，从而可以调整所制得铁基配合物的形貌，使所制得铁基配合物的性能更稳定，重复率更高。在实际应用中，当2-氨基对苯二甲酸和FeCl3·6H2O溶于氮-氮二甲基甲酰胺后，可以将其置入反应釜中，再将该反应釜放入鼓风干燥箱中，并以120°进行20～24小时的水热反应，待降至室温后取出反应釜中的悬浮液进行离心分离，再采用氮-氮二甲基甲酰胺和乙醇分别对固液分离得到的固体进行多次清洗，最后置于冷冻干燥装置中进行48小时的冷冻干燥，从而即可制得八面体结构的铁基配合物。(3) The iron-based complex prepared by the hydrothermal reaction includes: when 2-aminoterephthalic acid and FeCl 3 6H 2 O are dissolved in nitrogen-nitrogen dimethylformamide, place them in a 120° The hydrothermal reaction is carried out in the environment for 20 to 24 hours, and the solid-liquid separation is carried out after cooling down to room temperature. Complexes. By controlling the reaction temperature of the hydrothermal reaction at 120° and controlling the reaction time of the hydrothermal reaction at 20-24 hours, the detection sensitivity of the prepared iron-based complex to the concentration of arsenate ions in the water body can be made higher , and can effectively improve the removal effect of arsenate ions in water. By cleaning the solid obtained from solid-liquid separation and then freeze-drying, the morphology of the obtained iron-based complex can be adjusted, so that the performance of the prepared iron-based complex is more stable and the repetition rate is higher. In practical application, when 2-aminoterephthalic acid and FeCl 3 6H 2 O are dissolved in nitrogen-nitrogen dimethylformamide, they can be placed in a reaction kettle, and then the reaction kettle is put into a blast in a dry box, and conduct a hydrothermal reaction at 120° for 20 to 24 hours. After cooling down to room temperature, take out the suspension in the reactor for centrifugation, and then use nitrogen-nitrogen dimethylformamide and ethanol to separate the solid-liquid The separated solid is washed several times, and finally placed in a freeze-drying device for 48 hours of freeze-drying, so that the iron-based complex with octahedral structure can be prepared.
进一步地，本发明所提供的铁基配合物具有检测水体中砷酸根离子浓度和去除水体中砷酸根离子的双重功能：Further, the iron-based complex provided by the present invention has dual functions of detecting the concentration of arsenate ions in water and removing arsenate ions in water:
(1)用于检测水体中砷酸根离子浓度：在采用荧光光谱法检测水体中砷酸根离子浓度时，将水体的pH值控制在6～8，采用本发明所提供的铁基配合物作为检测剂，能够快速检测出水体中砷酸根离子浓度，而且每5mg的所述铁基配合物对水体中砷酸根离子浓度的检测范围为0.1～50μmol/L，即使在含有Mg2+、Al3+、Bi3+、Ag+、Cu2+、Co2+、Zn2+、Ni2+、Mn2+、Pb2+、Cr3+等阳离子和含有Ac-、SO4 2-、HCO3 -、CO3 2-、NO3 -、Cl-、Br-等阴离子的水体中，所述铁基配合物对水体中砷酸根离子浓度的检测依然能够达到没有干扰离子时的检测速度和检测精度，因此本发明所提供的铁基配合物能够预富集水体中的砷酸根，不仅对水体中砷酸根离子浓度具有较高的检测灵敏度、较宽的检测范围和较低的检测限，而且能够实现良好的快速选择性检测。(1) Used to detect the concentration of arsenate ions in the water body: when the concentration of arsenate ions in the water body is detected by fluorescence spectroscopy, the pH value of the water body is controlled at 6 to 8, and the iron-based complex provided by the present invention is used as the detection method agent, which can quickly detect the concentration of arsenate ions in the water body, and the detection range of the concentration of arsenate ions in the water body per 5 mg of the iron-based complex is 0.1-50 μmol/L, even in the presence of Mg 2+ , Al 3+ , Bi 3+ , Ag + , Cu 2+ , Co 2+ , Zn 2+ , Ni 2+ , Mn 2+ , Pb 2+ , Cr 3+ and other cations and Ac - , SO 4 2- , HCO 3 - , CO 3 2- , NO 3 - , Cl - , Br - and other anions in the water body, the iron-based complex can still achieve the detection speed and detection accuracy when there are no interfering ions in the detection of the arsenate ion concentration in the water body, Therefore, the iron-based complex provided by the present invention can pre-enrich arsenate in water, not only has high detection sensitivity, wide detection range and low detection limit for arsenate ion concentration in water, but also can realize Good fast selective detection.
(2)用于去除水体中砷酸根离子：在去除水体中的砷酸根离子时，采用本发明所提供的铁基配合物作为吸附剂，其用量最好为0.2g/L，而水体的pH值最好控制在6，去除处理时间最好控制在24小时，从而可以实现对水体中砷酸根离子的最大吸附去除，达到有效去除水体中砷酸根离子的目的；根据朗格缪尔吸附模型计算可以得出本发明所提供的铁基配合物对水体中砷酸根离子的最大去除量达到125mg/g，这有效降低了砷污染对环境和人类造成的危害。(2) be used for removing arsenate ion in the water body: when removing the arsenate ion in the water body, adopt the iron-based complex provided by the present invention as the adsorbent, its consumption is preferably 0.2g/L, and the pH of the water body The value is best controlled at 6, and the removal treatment time is best controlled at 24 hours, so that the maximum adsorption and removal of arsenate ions in the water can be achieved, and the purpose of effectively removing arsenate ions in the water can be achieved; according to the calculation of the Langmuir adsorption model It can be concluded that the iron-based complex provided by the invention can remove arsenate ions in a maximum amount of 125mg/g, which effectively reduces the harm caused by arsenic pollution to the environment and human beings.
综上可见，本发明实施例不仅具有制备方法简单、容易操作、传质速率快等优点，而且具有检测水体中砷酸根离子浓度和去除水体中砷酸根的双重功能，克服了现有技术中检测砷酸根离子和去除砷酸根离子功能单一的问题，同时能预富集水体中的砷酸根离子，快速检测出水体中的砷酸根离子浓度，检测灵敏度高、检测范围宽、检测限低，在水体中砷酸根离子浓度达到最大限制值之前给予警报，还能有效去除水体中的砷酸根离子，从而降低了砷酸根离子污染对环境和人类造成的危害。In summary, the embodiment of the present invention not only has the advantages of simple preparation method, easy operation, and fast mass transfer rate, but also has the dual functions of detecting the concentration of arsenate ions in the water body and removing arsenate ions in the water body, which overcomes the detection problem in the prior art. Arsenate ions and the single function of removing arsenate ions, at the same time, it can pre-enrich arsenate ions in water, and quickly detect the concentration of arsenate ions in water, with high detection sensitivity, wide detection range, and low detection limit. It can also effectively remove the arsenate ions in the water, thereby reducing the harm caused by arsenate ion pollution to the environment and human beings.
为了更加清晰地展现出本发明所提供的技术方案及所产生的技术效果，下面以具体实施例对本发明实施例所提供的铁基配合物及其应用进行详细描述。In order to more clearly demonstrate the technical solutions provided by the present invention and the resulting technical effects, the iron-based complexes provided in the embodiments of the present invention and their applications will be described in detail below with specific examples.
实施例1Example 1
一种铁基配合物，其制备方法包括以下步骤：将1.3838mmol的2-氨基对苯二甲酸和1.3838mmol的FeCl3·6H2O置于30mL氮-氮二甲基甲酰胺中，超声5分钟并搅拌2小时，然后将其置入50mL的反应釜中，再将该反应釜放入鼓风干燥箱中，并以120°进行20小时的水热反应，待鼓风干燥箱内温度降至室温后取出反应釜中的悬浮液进行离心分离，再采用氮-氮二甲基甲酰胺和乙醇分别对固液分离得到的固体进行多次清洗，最后置于冷冻干燥装置中进行48小时的冷冻干燥，从而即可制得所述的铁基配合物。An iron-based complex, the preparation method of which comprises the following steps: placing 1.3838 mmol of 2-aminoterephthalic acid and 1.3838 mmol of FeCl 3 6H 2 O in 30 mL of nitrogen-nitrogen dimethylformamide, and ultrasonically for 5 minutes and stirred for 2 hours, then put it into a 50mL reaction kettle, put the reaction kettle into a blast drying oven, and carry out a hydrothermal reaction at 120° for 20 hours, and wait for the temperature in the blast drying oven to drop. After reaching room temperature, take out the suspension in the reaction kettle for centrifugation, then use nitrogen-nitrogen dimethylformamide and ethanol to wash the solid obtained from solid-liquid separation several times, and finally place it in a freeze-drying device for 48 hours. Freeze-drying, so that the iron-based complex can be prepared.
具体地，对本发明实施例1所提供的铁基配合物进行以下形貌和性能检测：Specifically, the following morphology and performance tests were performed on the iron-based complex provided in Example 1 of the present invention:
(1)对本发明实施例1所提供的铁基配合物进行形貌观察，从而可以得到如图1所示的扫描电镜示意图和透射电镜示意图；其中，图1a为本发明实施例1所提供的铁基配合物的扫描电镜示意图，图1b为本发明实施例1所提供的铁基配合物的透射电镜示意图。由图1可以看出：本发明实施例1所提供的铁基配合物为八面体结构，并且形貌规则。(1) Observing the morphology of the iron-based complex provided in Example 1 of the present invention, so that a schematic diagram of a scanning electron microscope and a schematic diagram of a transmission electron microscope can be obtained as shown in Figure 1; wherein, Figure 1a is provided in Example 1 of the present invention A schematic diagram of a scanning electron microscope of an iron-based complex. FIG. 1b is a schematic diagram of a transmission electron microscope of the iron-based complex provided in Example 1 of the present invention. It can be seen from FIG. 1 that the iron-based complex provided by Example 1 of the present invention has an octahedral structure and regular morphology.
(2)采用X射线衍射仪对本发明实施例1所提供的铁基配合物进行检测，从而可以得到如图2所示的X射线衍射图谱。由图2可以看出：本发明实施例1所制得的产物确实是铁基配合物。(2) Using an X-ray diffractometer to detect the iron-based complex provided in Example 1 of the present invention, so that an X-ray diffraction pattern as shown in FIG. 2 can be obtained. It can be seen from Figure 2 that the product obtained in Example 1 of the present invention is indeed an iron-based complex.
(3)配制浓度为0.1μmol/L、0.5μmol/L、1μmol/L、5μmol/L、10μmol/L、20μmol/L、30μmol/L、40μmol/L、50μmol/L的砷酸根溶液各100ml，并调节pH为6，然后分别加入5mg本发明实施例1所提供的铁基配合物，超声5min后搅拌10min，再用荧光光谱仪检测各浓度砷酸根溶液的荧光强度，从而可以得到如图3所示的荧光强度示意图。由图3可以看出：本发明实施例1所提供铁基配合物对砷酸根浓度为0.1～50μmol/L的水体进行砷酸根离子浓度荧光检测，其荧光强度与砷酸根浓度呈现良好的线性关系，随着水体中砷酸根离子浓度的增加，荧光强度呈现线性增强趋势；而由荧光强度和砷酸根离子浓度可以计算出本发明实施例1所提供铁基配合物其检测限为56nmol/L(4.2ppb)，低于世界卫生组织规定浓度(10ppb)。(3) Prepare 100ml of arsenate solutions with concentrations of 0.1μmol/L, 0.5μmol/L, 1μmol/L, 5μmol/L, 10μmol/L, 20μmol/L, 30μmol/L, 40μmol/L, and 50μmol/L, And adjust the pH to 6, then add 5 mg of the iron-based complex provided in Example 1 of the present invention respectively, stir for 10 minutes after ultrasonication for 5 minutes, and then use a fluorescence spectrometer to detect the fluorescence intensity of the arsenate solution at each concentration, thereby obtaining the results shown in Figure 3. The schematic diagram of the fluorescence intensity is shown. It can be seen from Figure 3 that the iron-based complex provided in Example 1 of the present invention performs fluorescence detection of arsenate ion concentration on water bodies with arsenate concentration of 0.1-50 μmol/L, and the fluorescence intensity has a good linear relationship with the arsenate concentration. , with the increase of arsenate ion concentration in the water body, the fluorescence intensity presents a linear enhancement trend; and from the fluorescence intensity and arsenate ion concentration, it can be calculated that the detection limit of the iron-based complex provided in Example 1 of the present invention is 56nmol/L ( 4.2ppb), lower than the World Health Organization concentration (10ppb).
(4)配制17份浓度为6.6μmol/L的砷酸根溶液，并分别加入33μmol/L的硝酸盐(硝酸盐的阳离子为Mg2+、Al3+、Bi3+、Ag+、Cu2+、Co2+、Zn2+、Ni2+、Pb2+、Cr3+)和33μmol/L的钠盐(钠盐的阴离子为Ac-、SO4 2-、HCO3 -、CO3 2-、NO3 -、Cl、Br-)，使每份混合后溶液均为100ml，并调节pH为6，然后分别加入5mg本发明实施例1所提供的铁基配合物，超声5min后搅拌10min，再用荧光光谱仪分别检测每份混合后溶液的荧光强度，从而可以得到如图4所示的荧光性能示意图。由图4可以看出：在其他阳离子或阴离子存在的水体中，本发明实施例1所提供铁基配合物对水体中砷酸根离子能够较好的实现选择性检测。(4) Prepare 17 parts of arsenate solution with a concentration of 6.6 μmol/L, and add 33 μmol/L of nitrate (the cations of nitrate are Mg 2+ , Al 3+ , Bi 3+ , Ag + , Cu 2+ , Co 2+ , Zn 2+ , Ni 2+ , Pb 2+ , Cr 3+ ) and 33 μmol/L sodium salt (the anions of sodium salt are Ac - , SO 4 2- , HCO 3 - , CO 3 2- , NO 3 − , Cl, Br − ), so that each part of the mixed solution was 100 ml, and the pH was adjusted to 6, and then 5 mg of the iron-based complex provided in Example 1 of the present invention were added respectively, and stirred for 10 min after ultrasonication for 5 min. Then use a fluorescence spectrometer to detect the fluorescence intensity of each mixed solution separately, so that a schematic diagram of the fluorescence performance as shown in FIG. 4 can be obtained. It can be seen from FIG. 4 that in water bodies where other cations or anions exist, the iron-based complex provided in Example 1 of the present invention can better achieve selective detection of arsenate ions in water bodies.
(5)配制浓度为1ppm、5ppm、10ppm、20ppm、30ppm、40ppm、50ppm、80ppm、100ppm、130ppm、150ppm、180ppm、200ppm、250ppm的砷酸根溶液各25ml，并调节pH为6，然后分别加入5mg本发明实施例1所提供的铁基配合物，超声5min后，在25℃下持续搅拌24小时，随后从每份混合液中移取部分液体离心并通过0.22μm滤膜，收集好滤液并做好标记，最后采用电感耦合等离子体质谱仪分别检测每份标记好滤液的砷酸根离子浓度，从而可以得到如图5所示的不同砷酸根离子浓度水体中对砷酸根离子的去除效果示意图。由图5可以看出：本发明实施例1所提供铁基配合物对水体中砷酸根离子的吸附量随着砷酸根离子初始浓度的增加而增加，但当砷酸根离子初始浓度达到100ppm后，吸附量增加平缓，最大吸附量为125mg/g。(5) Prepare 25ml each of arsenate solutions with a concentration of 1ppm, 5ppm, 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 80ppm, 100ppm, 130ppm, 150ppm, 180ppm, 200ppm, and 250ppm, adjust the pH to 6, and then add 5mg For the iron-based complex provided in Example 1 of the present invention, after ultrasonication for 5 minutes, it was continuously stirred at 25°C for 24 hours, and then part of the liquid was taken from each mixture, centrifuged and passed through a 0.22 μm filter membrane, and the filtrate was collected and made Finally, use an inductively coupled plasma mass spectrometer to detect the concentration of arsenate ions in each marked filtrate, so that the schematic diagram of the removal effect of arsenate ions in water with different concentrations of arsenate ions can be obtained as shown in Figure 5. It can be seen from Figure 5 that the adsorption capacity of the iron-based complex provided in Example 1 of the present invention to arsenate ions in water increases with the increase of the initial concentration of arsenate ions, but when the initial concentration of arsenate ions reaches 100ppm, The adsorption capacity increased slowly, and the maximum adsorption capacity was 125mg/g.
(6)配制12份浓度为5ppm的砷酸根溶液各20ml，并调节pH为6，然后分别加入5mg本发明实施例1所提供的铁基配合物，室温下搅拌，分别在搅拌1min、2min、5min、10min、15min、20min、30min、60min、120min、180min、240min、300min时从混合液中移取部分液体离心并通过0.22μm滤膜，收集好滤液并做好标记，最后采用电感耦合等离子体质谱仪分别检测每份标记好滤液的砷酸根离子浓度，从而可以得到如图6所示的不同时间点对水体中砷酸根离子的去除效果示意图。由图6可以看出：砷酸根离子浓度在前5min下降速度非常快，这表明本发明实施例1所提供铁基配合物去除速度较快、去除性能较好；与此同时，本发明实施例1所提供铁基配合物对砷酸根离子的吸附在3h内完全去除，这表明本发明实施例1所提供铁基配合物对水体中的砷酸根离子具有较高的去除效率。(6) Prepare 12 parts of arsenate solution with a concentration of 5ppm, 20ml each, and adjust the pH to 6, then add 5mg of the iron-based complex provided in Example 1 of the present invention, stir at room temperature, and stir for 1min, 2min, respectively. At 5min, 10min, 15min, 20min, 30min, 60min, 120min, 180min, 240min, and 300min, part of the liquid was taken from the mixture, centrifuged and passed through a 0.22μm filter membrane, the filtrate was collected and marked, and finally the inductively coupled plasma was used The mass spectrometer separately detects the concentration of arsenate ions in each marked filtrate, so that a schematic diagram of the removal effect of arsenate ions in the water body at different time points can be obtained as shown in FIG. 6 . It can be seen from Figure 6 that the concentration of arsenate ions decreases very quickly in the first 5 minutes, which shows that the iron-based complex provided in Example 1 of the present invention has a faster removal rate and better removal performance; The adsorption of arsenate ions by the iron-based complex provided by 1 is completely removed within 3 hours, which indicates that the iron-based complex provided by Example 1 of the present invention has a high removal efficiency for arsenate ions in water.
综上可见，本发明实施例不仅可以快速检测出水体中的砷酸根离子浓度，检测灵敏度高，而且可以有效去除水体中的砷酸根离子。In summary, the embodiment of the present invention can not only quickly detect the concentration of arsenate ions in the water body with high detection sensitivity, but also can effectively remove the arsenate ions in the water body.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求书的保护范围为准。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person familiar with the technical field can easily conceive of changes or changes within the technical scope disclosed in the present invention. Replacement should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148752A (en) * | 2015-09-29 | 2015-12-16 | 北京林业大学 | Polyamide reverse-osmosis composite membrane containing MIL type metal-organic framework material and preparation method thereof |
| CN105435652A (en) * | 2015-11-24 | 2016-03-30 | 山东师范大学 | MOF (metal-organic framework) and polyurethane crosslinked membrane as well as preparation method and application thereof |
| CN106731892A (en) * | 2016-12-29 | 2017-05-31 | 中国科学院长春应用化学研究所 | A kind of amido modified MOF films removed to heavy metal ion high definition in blood and preparation method thereof |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148752A (en) * | 2015-09-29 | 2015-12-16 | 北京林业大学 | Polyamide reverse-osmosis composite membrane containing MIL type metal-organic framework material and preparation method thereof |
| CN105435652A (en) * | 2015-11-24 | 2016-03-30 | 山东师范大学 | MOF (metal-organic framework) and polyurethane crosslinked membrane as well as preparation method and application thereof |
| CN106731892A (en) * | 2016-12-29 | 2017-05-31 | 中国科学院长春应用化学研究所 | A kind of amido modified MOF films removed to heavy metal ion high definition in blood and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| SEBASTIAN BAUER 等: "High-Throughput Assisted Rationalization of the Formation of Metal Organic Frameworks in the Iron(III) minoterephthalate Solvothermal System", 《INORGANIC CHEMISTRY》 * |
| SUZY SURBLE 等: "A new isoreticular class of metal-organic-frameworks with the MIL-88 topology", 《CHEM.COMMUN.》 * |
| YUAN-YUAN CAO 等: "High sensitive luminescence metal-organic framework sensor for hydrogen sulfide in aqueous solution: A trial of novel turn-on mechanism", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437365A (en) * | 2022-02-16 | 2022-05-06 | 中国农业科学院植物保护研究所 | A kind of pesticide nano-drug-loading particle skeleton material and its preparation method and application |
| CN114437365B (en) * | 2022-02-16 | 2022-12-27 | 中国农业科学院植物保护研究所 | Pesticide nano drug-loaded particle framework material and preparation method and application thereof |
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