阅读说明：本技术 一种新型纳米复合物及其制备方法和在污水检测上的应用 (Novel nano-composite, preparation method thereof and application thereof in sewage detection ) 是由 朱韵 张东岳 于 2020-05-13 设计创作，主要内容包括：本发明公开了一种新型纳米复合物的制备方法,包括以下步骤：1)将氨基酸和甲基伞形酮按按投料摩尔比为1:1加入水中混合均匀；2)在水热反应釜中进行水热反应,反应温度为100℃～240℃,反应时间为5h～20h；3)反应结束后,所得产物先进行离心,取上清液透析,干燥,得到发射蓝色荧光的纳米颗粒；4)将步骤3)得到的纳米颗粒配成溶液；5)将步4)的溶液与金属离子溶液在Tris-HCl缓冲液体系中混合形成纳米复合物。本发明所制备的含有金属离子的新型纳米复合物可以用于检测污水中磷酸根含量。(The invention discloses a preparation method of a novel nano composite, which comprises the following steps: 1) adding amino acid and methyl umbelliferone into water according to the feeding molar ratio of 1:1, and uniformly mixing; 2) carrying out hydrothermal reaction in a hydrothermal reaction kettle at the reaction temperature of 100-240 ℃ for 5-20 h; 3) after the reaction is finished, centrifuging the obtained product, taking supernatant for dialysis, and drying to obtain blue fluorescent nanoparticles; 4) preparing the nano particles obtained in the step 3) into a solution; 5) mixing the solution obtained in the step 4) with a metal ion solution in a Tris-HCl buffer solution system to form a nano-composite. The novel nano-composite containing metal ions prepared by the invention can be used for detecting the content of phosphate radicals in sewage.)

1. A method for preparing a novel nano-composite, which is characterized by comprising the following steps:

1) adding amino acid and methyl umbelliferone into water according to the feeding molar ratio of 1:1, and uniformly mixing;

2) carrying out hydrothermal reaction in a hydrothermal reaction kettle at the reaction temperature of 100-240 ℃ for 5-20 h;

3) after the reaction is finished, centrifuging the obtained product, taking supernatant for dialysis, and drying to obtain blue fluorescent nanoparticles;

4) preparing the nano particles obtained in the step 3) into a solution;

5) mixing the solution obtained in the step 4) with a metal ion solution in a Tris-HCl buffer solution system to form a nano-composite.

2. The method as claimed in claim 1, wherein the amino acid is one of L-arginine, D-arginine, L-tryptophan or D-tryptophan.

3. The method as claimed in claim 1, wherein the methylumbelliferone is one of 4-methylumbelliferone, 4-methylumbelliferone sodium salt, 3, 4-dimethyl umbelliferone or 3, 4-dimethyl umbelliferone sodium salt.

4. The method as claimed in claim 1, wherein the metal ion solution is FeCl₃、AlCl₃、MgCl₂、ZnCl₂Or AgNO₃An aqueous solution of (a).

5. The method as claimed in claim 1, wherein the amino acid is D-arginine, the methylumbelliferone is 4-methylumbelliferone, and the metal ion solution is FeCl₃And (3) solution.

6. The method for preparing a novel nano-composite according to claim 1, wherein the reaction temperature in the step 2) is 180 ℃ and the reaction time is 12 h.

7. The method of claim 1, wherein the concentration of the nanoparticles in step 4) is 0.25mg/mL, and the concentration of the metal ion solution is 0.2 mM.

8. A novel nanocomposite obtained by the production method according to any one of claims 1 to 7.

9. The use of the novel nanocomposite of claim 8 for wastewater detection.

Technical Field

The invention belongs to the field of environment functional materials, and relates to a novel nano composite, a preparation method thereof and application thereof in sewage detection.

Background

Phosphorus in water is mainly derived from weathering of phosphorus-containing ores, industrial wastewater, domestic sewage and agricultural drainage. A large amount of phosphorus-containing wastewater is discharged from chemical fertilizers, pesticides, food processing, fermentation, detergents, smelting, electroplating and other industries; a large amount of used phosphorus-containing detergent and human body metabolites enter a river channel through an urban drainage system; one part of phosphate fertilizer applied in farmlandThe excrement of livestock and poultry raised in rural areas contains a large amount of phosphorus and can also be washed by rainwater to enter the water body; the phosphorus contained in the bottom mud or the newly generated sediment can be dissolved into water under certain conditions, so that secondary pollution is caused. Phosphorus in aqueous environments can exist in both solutions and suspensions, as well as in sediments. Phosphorus in water exists almost as various forms of phosphate, respectively orthophosphate (PO)₄ ^3-) Condensed phosphate (pyrophosphate P)₂O₇ ^4-Metaphosphate (PO)₃)₃ ^3-And polyphosphates) and organic phosphorus compounds. Phosphorus in the sediment is mainly inorganic orthophosphate which exists in the form of insoluble salt such as calcium, magnesium, aluminum, iron and the like, and the high dissolved oxygen content is beneficial to dissolving out the insoluble salt. The water living things are harmed by over high phosphorus content, when the phosphorus content is more than 0.2mg/L, water eutrophication is realized, the seaweed proliferates in a large amount, and the decomposition process of the decomposed seaweed consumes a large amount of dissolved oxygen in water, so that the water living things such as fishes and the like are anoxic and even die by suffocation. Phosphorus in natural water and uncontaminated ground water is typically < 0.1 mg/L. The Chinese 'surface water environmental quality Standard' (GB3838-2002) stipulates that the total phosphorus content of the I-type water cannot exceed 0.02 mg/L; the total phosphorus content of the water for II class is not more than 0.1mg/L (calculated by P).

Phosphorus is one of the essential nutrients for the growth of organisms and is involved in the synthesis and transport of amino acids, proteins, carbohydrates, etc. in the organisms. The growth of plants needs a large amount of phosphorus, and phosphate fertilizers become one of three fertilizers in parallel with nitrogenous fertilizers and potash fertilizers in agricultural production. Phosphorus is an important constituent material of bones and teeth, is a basic component of nucleic acid, enzyme and the like, and is also involved in nerve conduction, regulation of cell metabolism and acid-base balance, so that almost all activities in a human body can not be separated from phosphorus. Excessive intake of phosphorus can hinder calcium absorption, lead to osteoporosis, and even lead to accumulation of large amounts of acetylcholinesterase in the nerve center, causing poisoning, and in severe cases, death. Phosphate plays an important role in organisms such as participating in metabolism and supplementing phosphorus elements required by organisms, but the physiological activity of the organisms is influenced by abnormal content of the phosphate, so that the detection of the phosphate is of great significance.

The conventional methods for detecting phosphate radical are commonly used in titration methods, electrochemical analysis methods and the like, and although the methods can realize effective phosphate radical detection, the methods still have certain limitations on detection sensitivity and accuracy under a complex system. In order to overcome the drawbacks of the above methods, in recent years, the realization of sensing based on fluorescent materials has received increasing attention from researchers. Meanwhile, fluorescence sensing has excellent selectivity and sensitivity, and is widely applied to related fields such as ion, small molecule, free radical, temperature and pH detection. Therefore, the design and synthesis of the novel fluorescent-based nano-composite for realizing the detection of the phosphate radical have important application value and prospect.

Disclosure of Invention

In view of the above, the present invention provides a novel nano-composite, a preparation method thereof, and an application thereof in sewage detection.

The invention specifically provides the following technical scheme:

1. a method for preparing a novel nanocomposite, comprising the steps of:

1) adding amino acid and methyl umbelliferone into water according to the feeding molar ratio of 1:1, and uniformly mixing;

2) carrying out hydrothermal reaction in a hydrothermal reaction kettle at the reaction temperature of 100-240 ℃ for 5-20 h;

3) after the reaction is finished, centrifuging the obtained product, taking supernatant for dialysis, and drying to obtain blue fluorescent nanoparticles;

4) preparing the nano particles obtained in the step 3) into a solution;

5) mixing the solution obtained in the step 4) with a metal ion solution in a Tris-HCl buffer solution system to form a nano-composite.

Furthermore, the amino acid is one of L-arginine, D-arginine, L-tryptophan or D-tryptophan.

Further, the methyl umbelliferone is one of 4-methyl umbelliferone, 4-methyl umbelliferone sodium salt, 3, 4-dimethyl umbelliferone or 3, 4-dimethyl umbelliferone sodium salt.

Further, the metal ion solution is FeCl₃、AlCl₃、MgCl₂、ZnCl₂Or AgNO₃An aqueous solution of (a).

Further, the amino acid is D-arginine, the methylumbelliferone is 4-methylumbelliferone, and the metal ion solution is FeCl₃And (3) solution.

Further, the reaction temperature in the step 2) is 180 ℃, and the reaction time is 12 hours.

2. The novel nano-composite prepared by the preparation method is provided.

3. The application of the novel nano-composite in sewage detection is provided.

The invention has the beneficial effects that: according to the invention, the nano-particles emitting blue fluorescence are successfully prepared through hydrothermal reaction, then metal ions can be utilized to form nano-composites with the nano-particles, and meanwhile, in the process of forming the composites, the metal ions can quench the fluorescence of the luminescent nano-particles through an electron transfer process. On the other hand, phosphate and metal ions can form precipitates, so that the metal ions are separated from the surface of the luminescent nano-particles, and the fluorescence of the luminescent nano-particles is recovered. The detection of phosphate can therefore be achieved by this fluorescence recovery phenomenon.

Drawings

In order to make the purpose, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings:

FIG. 1 is a Transmission Electron Micrograph (TEM) of a blue fluorescent emitting nanoparticle;

FIG. 2 is Fe³⁺A fluorescence spectrum of the quenched luminescent nanoparticle;

FIG. 3 is an X-ray photoelectron spectroscopy (XPS) spectrum of the novel nanocomposite;

FIG. 4 is the result of fluorescence spectrum experiment of the novel nano-composite for detecting phosphate radical;

fig. 5 is a linear relationship experimental result of the novel nano-composite for detecting phosphate.

Detailed Description

Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.