阅读说明：本技术 一种硫铟锌/黑磷纳米片光催化活化高铁酸盐降解抗生素的应用 (Application of zinc indium sulfide/black phosphorus nanosheet photocatalytic activation ferrate degradation antibiotic ) 是由 潘宝 赵艳利 秦佳妮 王传义 于 2021-10-09 设计创作，主要内容包括：本发明公开了一种硫铟锌/黑磷纳米片光催化活化高铁酸盐降解抗生素的应用。本发明的技术方案为:在抗生素废水中,加入高铁酸盐和硫铟锌/黑磷纳米片光催化剂,通过pH缓冲剂调节溶液pH值,在光照下反应,间隔一定时间取样检测污染物残留浓度。本发明首次将黑磷纳米片与氧掺杂的硫铟锌复合获得的新型光催化剂与高铁酸盐协同氧化降解环境中抗生素,方法简单易行,使用设备便宜简便、适用于工业化发展,有利于推广从而实现优异的光催化降解污染物性能；应用于环境污染治理,可大幅度提高降解污染物的效率。(The invention discloses an application of sulfur indium zinc/black phosphorus nanosheets in photocatalytic activation of ferrate to degrade antibiotics. The technical scheme of the invention is that ferrate and a sulfur indium zinc/black phosphorus nanosheet photocatalyst are added into antibiotic wastewater, the pH value of the solution is adjusted through a pH buffering agent, the solution reacts under illumination, and sampling is carried out at intervals to detect the residual concentration of pollutants. The invention first compounds the black phosphorus nanosheet and the oxygen-doped sulfur indium zinc to obtain the novel photocatalyst which is cooperated with ferrate to oxidize and degrade antibiotics in the environment, the method is simple and easy to implement, the used equipment is cheap and simple, the method is suitable for industrial development, and the popularization is facilitated, so that the excellent performance of photocatalytic degradation of pollutants is realized; the method is applied to environmental pollution treatment, and can greatly improve the efficiency of degrading pollutants.)

1. The application of the sulfur indium zinc/black phosphorus nanosheet photocatalytic activation ferrate degradation antibiotic is characterized in that ferrate and a sulfur indium zinc/black phosphorus nanosheet photocatalyst are added into antibiotic wastewater, the pH value of a solution is adjusted through a pH buffering agent, the solution reacts under illumination, and sampling is carried out at certain intervals to detect the residual concentration of the pollutant.

2. The application of the zinc indium sulfide/black phosphorus nanosheet photocatalytic activation ferrate degradation antibiotic as claimed in claim 1, wherein the ferrate is potassium ferrate or sodium ferrate.

3. The application of the photocatalytic-activation ferrate degradation antibiotic made of the sulfur-indium-zinc/black-phosphorus nanosheets as claimed in claim 1, wherein in the antibiotic-degradation wastewater system, the amount of ferrate required by each cubic meter of pollutants is 1-1000 g;

the catalyst is a sulfur indium zinc/black phosphorus nanosheet photocatalyst.

4. The application of the zinc indium sulfide/black phosphorus nanosheet photocatalytic activation ferrate degradation antibiotic as claimed in claim 1, wherein the amount of the catalyst required for degrading the pollutant per cubic meter in the antibiotic wastewater system is 10-1000 g.

5. The application of the zinc indium sulfide/black phosphorus nanosheet photocatalytic activated ferrate degradation antibiotic as claimed in claim 1, wherein the zinc indium sulfide/black phosphorus nanosheet photocatalyst generates photo-generated electron energy activated ferrate (Fe) under illumination^VI) To produce Fe as an intermediate valence highly active species^V/Fe^IVThereby improving the efficiency of degrading antibiotics.

6. The application of the zinc indium sulfide/black phosphorus nanosheet photocatalytic activation ferrate degradation antibiotic as claimed in claim 1, wherein the preparation method of the zinc indium sulfide/black phosphorus nanosheet specifically comprises:

mixing the black phosphorus nanosheet dispersion liquid and a sulfur indium zinc sample according to the mass percentage of 0.5% in a sealed container of deionized water, vacuumizing, stirring for 12 hours, centrifugally washing, drying in an oven for 10 hours at 60 ℃, and grinding to obtain the sulfur indium zinc/black phosphorus nanosheet photocatalyst.

7. The use of the zinc indium sulfide/black phosphorus nanosheet photocatalytically-activated ferrate degradation antibiotic of claim 1, wherein the pH buffer is a borate solution or a phosphate solution, and the concentration is 10-1000g/m³。

8. The application of the photocatalytic-activation ferrate degradation antibiotic prepared from the sulfur indium zinc/black phosphorus nanosheets as claimed in claim 1, wherein the pH range of the ferrate degradation antibiotic wastewater system is 4-10, the reaction temperature is 10-30 ℃, and the reaction time is 0-180 min.

9. The use of the indium zinc sulfide/black phosphorus nanosheet photocatalytic activation ferrate degradation antibiotic of claim 1, wherein the antibiotic contaminant is one or more of tetracycline, carbamazepine, diclofenac sodium, sulfamethoxazole, atenolol, trimethoprim, caffeine, and flumequine.

10. The application of the sulfur indium zinc/black phosphorus nanosheet photocatalytic activation ferrate degradation antibiotic according to claim 1, wherein the light source for illumination is one of a xenon lamp, a mercury lamp, an LED lamp and sunlight.

Technical Field

The invention belongs to the technical field of photocatalytic degradation of environmental pollutants, and particularly relates to application of a zinc indium sulfide/black phosphorus nanosheet photocatalytic-activated ferrate in degradation of antibiotics.

Background

Antibiotics are widely used in the prevention and treatment of human and veterinary diseases, as well as in animal feed additives. However, the antibiotics used cannot be completely absorbed by the body, which results in the continuous input and persistent phenomenon of the antibiotics in the environmental system, and seriously threatens the health of human beings and the stability of the ecological environment. The antibiotics have the characteristics of complex components, difficult degradation and the like, and the removal rate of the antibiotics and other pollutants by most of the traditional water treatment technologies still cannot reach the national allowable discharge standard. Therefore, the research and development of an economic, efficient, green and environment-friendly antibiotic advanced treatment technology has important significance.

By means of photocatalytic oxidation technology, pollutant is degraded into non-toxic harmless H₂O and CO₂So as to realize the purification treatment of the pollutants, and is a promising method for degrading antibiotics. Among them, ferrate oxidation technology and photocatalytic oxidation technology are attracting much attention due to the advantages of environmental protection, mild reaction conditions, no secondary pollution and the like. Metal sulfides have attracted much attention because of their appropriate band gaps and strong visible light absorption characteristics. Compound zinc indium sulfide (ZnIn)₂S₄) Has a suitable band gap, good chemical stability and excellent photocatalytic performance, and is thus considered to be one of the most promising photocatalytic materials. However, the efficiency of both technologies for degrading pollutants has not yet reached the standard of practical application.

Disclosure of Invention

In order to overcome the technical problems, the invention aims to provide the application of the sulfur indium zinc/black phosphorus nanosheet photocatalytic activated ferrate degradation antibiotic, the sulfur indium zinc/black phosphorus nanosheet composite photocatalyst and the ferrate are used for oxidizing and degrading the antibiotic in the environment in a synergistic manner, the method is simple and feasible, the used equipment is cheap and simple, the method is suitable for industrial development, and the popularization is facilitated, so that the excellent performance of photocatalytic degradation of pollutants is realized; the method is applied to environmental pollution treatment, and can greatly improve the efficiency of degrading pollutants.

In order to achieve the purpose, the invention adopts the technical scheme that:

the application of the sulfur indium zinc/black phosphorus nanosheet photocatalytic activation ferrate degradation antibiotic is characterized in that ferrate and a sulfur indium zinc/black phosphorus nanosheet photocatalyst are added into antibiotic wastewater, the pH value of a solution is adjusted through a pH buffering agent, the solution reacts under illumination, and sampling is carried out at intervals to detect the residual concentration of pollutants.

The ferrate is one or a mixture of potassium ferrate and sodium ferrate.

In the system for degrading the antibiotic wastewater, the amount of ferrate required by each cubic meter of pollutants is 1-1000 g.

The catalyst is a sulfur indium zinc/black phosphorus nanosheet photocatalyst.

In the system for degrading the antibiotic wastewater, the dosage of the catalyst required by each cubic meter of pollutants is 10-1000 g.

The sulfur indium zinc/black phosphorus nanosheet catalyst generates photoproduction electron energy to activate ferrate (Fe) under illumination^VI) To produce Fe as an intermediate valence highly active species^V/Fe^IVThereby improving the efficiency of degrading antibiotics.

The preparation method of the sulfur indium zinc/black phosphorus nanosheet specifically comprises the following steps:

mixing the black phosphorus nanosheet dispersion liquid and a sulfur indium zinc sample according to the mass percentage of 0.5% in a sealed container of deionized water, vacuumizing, stirring for 12 hours, centrifugally washing, drying in an oven for 10 hours at 60 ℃, and grinding to obtain the sulfur indium zinc/black phosphorus nanosheet photocatalyst.

The pH buffer is borate solution or phosphate solution with the concentration of 10-1000g/m³。

The pH range of the ferrate-degrading antibiotic wastewater system is 4-10, the reaction temperature is 10-30 ℃, and the reaction time is 0-180 min.

The antibiotic wastewater is one or more of tetracycline, carbamazepine, diclofenac, sulfamethoxazole, sulfadimethoxine, atenolol, trimethoprim, caffeine and flumequine.

The light source of illumination is one of xenon lamp, mercury lamp, LED lamp, sunlight.

The invention has the beneficial effects that:

(1) the invention firstly uses the sulphur indium zinc/black phosphorus nano-sheet photocatalysis-ferrate synergistic coupling technology to degrade antibiotic pollutants, and uses photoproduction electrons generated by a photocatalyst to activate ferrate (Fe)^VI) Generating the highly active species Fe^V/Fe^IVThereby greatly improving the degradation efficiency of pollutants;

(2) the sulfur indium zinc/black phosphorus nanosheet material has universality, is suitable for sulfur indium zinc/black phosphorus nanosheets synthesized by different precursors and different methods, and is beneficial to large-scale popularization;

(3) the coupling technology of the invention is simple and easy to implement, does not need complex and expensive equipment, is environment-friendly, has no secondary pollution, has mild reaction conditions, and is beneficial to popularization and application in pollution treatment technology.

Drawings

FIG. 1 is an activity diagram of the photocatalytic synergy of zinc indium sulfide/black phosphorus nanosheets and ferrate for degrading Trimethoprim (TMP).

FIG. 2 is an activity diagram of zinc indium sulfide/black phosphorus nanosheets photocatalytic synergistic degradation of Carbamazepine (CBZ) by ferrate.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings.

An application of zinc indium sulfide/black phosphorus nanosheets in photocatalytic activation of ferrate to degrade antibiotics is disclosed, wherein the specific embodiment is as follows:

adding ferrate and a sulfur indium zinc/black phosphorus nanosheet photocatalyst into antibiotic wastewater, adjusting the pH value of the solution through a pH buffering agent, reacting under illumination, and sampling at certain intervals to detect the residual concentration of pollutants.

The ferrate is one or a mixture of potassium ferrate and sodium ferrate.

The catalyst is a sulfur indium zinc/black phosphorus nanosheet photocatalyst.

In the system for degrading the antibiotic wastewater, the amount of ferrate required by each cubic meter of pollutants is 1-1000 g.

In the system for degrading the antibiotic wastewater, the dosage of the catalyst required by each cubic meter of pollutants is 10-1000 g.

The sulfur indium zinc/black phosphorus nanosheet catalyst generates photoproduction electron energy to activate ferrate (Fe) under illumination^VI) To produce Fe as an intermediate valence highly active species^V/Fe^IVThereby improving the efficiency of degrading antibiotics.

The sulfur indium zinc/black phosphorus nanosheet is prepared by the following method: and mixing the black phosphorus nanosheet dispersion liquid and a sulfur indium zinc sample in a sealed container of deionized water, vacuumizing, stirring for 12h, centrifugally washing, drying for 10h, and grinding to obtain the sulfur indium zinc/black phosphorus nanosheets.

The buffer solvent is borate solution or phosphate solution with the concentration of 10-1000g/m³。

The pH range of the ferrate-degrading antibiotic wastewater system is 4-10, the reaction temperature is 10-30 ℃, and the reaction time is 0-180 min.

The antibiotic wastewater is one or more of tetracycline, carbamazepine, diclofenac, sulfamethoxazole, sulfadimethoxine, atenolol, trimethoprim, caffeine and flumequine.

The illumination light source is one of a xenon lamp, a mercury lamp, an LED lamp and sunlight.

Example 1

The black phosphorus nanosheet is prepared by dissolving 1g of black phosphorus blocky crystal in 100mL of N-methylpyrrolidone (NMP) reagent and performing ultrasonic dispersion for 10h to obtain a dispersion liquid of the black phosphorus nanosheet in NMP; synthesizing sulfur indium zinc by a hydrothermal method; and mixing the sulfur indium zinc and black phosphorus nanosheet dispersion liquid in a sealed container of deionized water according to the mass percent of 0.5%, vacuumizing, stirring for 12h, centrifugally washing, and drying for 10h to obtain the sulfur indium zinc/black phosphorus nanosheet.

Example 2

The prepared zinc indium sulfide/black phosphorus nanosheet is used for degrading trimethoprim antibiotic in cooperation with ferrate, the reaction is carried out in a 50mL glass reactor, the temperature is controlled at the constant temperature (25 +/-1 ℃) of a laboratory, and 20mM hydroxylamine (NH) is prepared firstly₂OH) solution, 10mM sodium borate buffer solution, 100mM ferrate solution and 20. mu.M trimethoprim solution by using the sodium borate buffer solution. Weighing 1mg of sulfur indium zinc/black phosphorus nanosheet, weighing 10mL of ferrate solution, adding 10mL of trimethoprim solution into a reactor, continuously stirring, reacting under visible light, filtering 1mL of reaction solution at intervals of 1min through a filter membrane into a liquid chromatography sample feeding bottle added with 10 mu L of hydroxylamine solution, and detecting and analyzing the obtained sample by high performance liquid chromatography.

Example 3

The prepared zinc indium sulfide/black phosphorus nanosheet is used for degrading carbamazepine antibiotic in cooperation with ferrate, the reaction is carried out in a 50mL glass reactor, the temperature is controlled at the constant temperature (25 +/-1 ℃) of a laboratory, and 20mM hydroxylamine (NH) is prepared₂OH) solution, 10mM sodium borate buffer solution, 100mM ferrate solution and 20. mu.M trimethoprim solution by using the sodium borate buffer solution. Weighing 1mg of sulfur indium zinc/black phosphorus nanosheet, weighing 10mL of ferrate solution, adding 10mL of carbamazepine solution into a reactor, continuously stirring, reacting under visible light, filtering 1mL of reaction solution at intervals of 1min through a filter membrane into a liquid chromatography sample feeding bottle added with 10 mu L of hydroxylamine solution, and detecting and analyzing the obtained sample by using high performance liquid chromatography.

Fig. 1 is an activity diagram of the photocatalytic co-degradation of Trimethoprim (TMP) by the sulphur indium zinc/black phosphorus nanoplatelets and the ferrate in example 2, the reaction time is 3min, the degradation efficiency of TMP reaches 99.9%, which is 3.3 times and 9.0 times of the photocatalytic degradation efficiency of the blank ferrate and the sulphur indium zinc/black phosphorus nanoplatelets, respectively.

Fig. 2 is an activity diagram of the photocatalytic co-degradation of Carbamazepine (CBZ) by zinc indium/black phosphorus nanoplates in example 3 with ferrate, and the degradation efficiency of TMP reaches 78.5% after 3min of reaction, which is 1.2 and 1.52 times higher than the photocatalytic degradation efficiency of blank ferrate and zinc indium/black phosphorus nanoplates, respectively.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.