CN113509951A - Preparation method and application of visible light catalytic nano material - Google Patents
Preparation method and application of visible light catalytic nano material Download PDFInfo
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a preparation method and application of a visible light catalytic nano material3N4(ii) a Mixing Ni (NO)3)2·6H2Mixing O and melamine, heating to 600-800 ℃ under the protection of nitrogen, calcining for 2-4 h, cooling, soaking the cooled product in an acid solution, and washing with water to obtain CNNi; g to C3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, adding hydrofluoric acid into the suspension under the action of stirring, and reacting the suspension in a high-pressure reaction kettle to form TCNCNNi‑40(ii) a The TCNCNNi-40 is calcined under protective gas atmosphere,and preparing the visible light catalytic nano material. The invention prepares g-C3N4/TiO2The composite photocatalytic material enhances the catalytic activity of the photocatalytic material in a visible light region.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a preparation method and application of a visible light catalytic nano material.
Background
TiO in the current semiconductor photocatalyst2Is the most studied and practical, TiO2Show great potential as ideal and potent photocatalysts in a variety of reactions. TiO22The conduction band side of (A) mainly plays a role of reducing, and the valence band side mainly plays a role of oxidizing. However, due to TiO2Has wider band gap energy and shorter electron-hole pair recombination time, so that the application of the photocatalyst is limited to ultraviolet activation. Although many efforts have been made to solve these problems, the achievement of the results is very limited, and thus, the improvement of the separation efficiency of photogenerated carriers, the reduction of the band gap, and the enhancement of the catalytic activity thereof in the visible region are still TiO2The core problem of photocatalyst research.
Disclosure of Invention
The invention mainly aims to provide a preparation method and application of a visible light catalytic nano material, aiming at enhancing TiO2Catalytic activity of the photocatalyst in the visible light region.
In order to achieve the purpose, the invention provides a preparation method of a visible light catalytic nano material, which comprises the following steps:
calcining melamine at high temperature, grinding and collecting powder to obtain g-C3N4；
Mixing Ni (NO)3)2·6H2Mixing O and melamine, heating to 600-800 ℃ under the protection of nitrogen, calcining for 2-4 h, cooling, soaking the cooled product in an acid solution, and washing with water to obtain CNNi;
g to C3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, adding hydrofluoric acid into the suspension under the action of stirring, and reacting the suspension in a high-pressure reaction kettle to form TCNCNNi-40；
And calcining the TCNCNNi-40 in a protective gas atmosphere to obtain the visible light catalytic nano material.
Optionally, the melamine is calcined at high temperature and then ground to collect powder to obtain g-C3N4The method comprises the following steps:
heating melamine to 400-600 ℃ at a heating rate of 2-10 ℃/min, calcining for 3-5 hours, grinding the calcined product after calcining, and collecting powder to obtain g-C3N4。
Optionally, mixing Ni (NO)3)2·6H2Mixing O and melamine, heating to 600-800 ℃ under the protection of nitrogen, calcining for 3h, cooling, soaking the cooled product in an acid solution, and washing with water to obtain CNNi:
the Ni (NO)3)2·6H2The mass ratio of the O to the melamine is 0.020-2.120 g: 0.035-3.731 g; and/or the presence of a gas in the gas,
in the process of heating to 600-800 ℃, the heating rate is 2-20 ℃/min.
Optionally, mixing Ni (NO)3)2·6H2Mixing O and melamine, heating to 600-800 ℃ under the protection of nitrogen, calcining for 3h, cooling, soaking the cooled product in an acid solution, and washing with water to obtain CNNi:
the acid solution is concentrated hydrochloric acid or concentrated sulfuric acid, and the concentration of the acid solution is 1-10 mol/L; and/or the presence of a gas in the gas,
and the cooling product is soaked in the acid solution for 10-15 hours.
Optionally, mixing g-C3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, adding hydrofluoric acid into the suspension under the action of stirring, and reacting the suspension in a high-pressure reaction kettle to form TCNCNNi-40In the steps of (A):
the g to C3N4The addition ratio of tetrabutyl titanate, CNNi and isopropanol is 1.282-2.850 g: 5.164-6.813 g: 0.010-0.100 g: 50 mL;
the concentration of the hydrofluoric acid is 40 wt%, and the addition volume is 1-4 mL.
Optionally, mixing g-C3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, adding hydrofluoric acid into the suspension under the action of stirring, and reacting the suspension in a high-pressure reaction kettle to form TCNCNNi-40In the steps of (A):
the reaction temperature in the high-pressure reaction kettle is 100-200 ℃, and the reaction time is 6-24 hours.
Optionally, mixing g-C3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, adding hydrofluoric acid into the suspension under the action of stirring, and reacting the suspension in a high-pressure reaction kettle to form TCNCNNi-40The method comprises the following steps:
g to C3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, adding hydrofluoric acid into the suspension under the action of stirring, reacting the suspension in a high-pressure reaction kettle, centrifuging the suspension after reaction for many times, collecting solid matters and drying to obtain TCNCNNi-40；
Wherein the times of the multiple centrifugation are 6-10 times; and/or the drying temperature of the drying is 40-80 ℃, and the drying time is 5-24 h.
Optionally, the step of calcining the TCNCNNi-40 in a protective gas atmosphere to obtain the visible light catalytic nanomaterial comprises:
the protective gas is nitrogen or argon; and/or the presence of a gas in the gas,
the temperature rise rate in the calcination process is 3-10 ℃/min, the calcination temperature is 200-400 ℃, and the calcination time is 2-5 h.
Further, the invention also provides a method for degrading atrazine in water, which comprises the following steps:
adding a visible light catalytic nano material into water, and degrading atrazine in the water under the irradiation of visible light; the visible light catalytic nano material is prepared by the preparation method of the visible light catalytic nano material.
Optionally, the addition amount of the visible light catalytic nano material in water is 0.05-0.20 g/L.
The technical scheme provided by the invention prepares g-C3N4/TiO2The composite photocatalytic material, in which TiO2 is used as a typical semiconductor material, has the advantages of low cost, good chemical property and high stability, and g-C3N4Then with narrower band gap energy (Eg ═ 2.67eV) and more negative conduction band position (-1.1eV), TiO2 can generate heterogeneous charge transfer after coupling with it, which is beneficial to the separation of photo-generated electron-hole and enhances its catalytic activity in the visible region.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of an embodiment of a method for preparing a visible light catalytic nanomaterial provided by the present invention;
FIG. 2 is an SEM image of a visible light catalytic nanomaterial prepared by the present invention;
FIG. 3 is a graph showing the change in concentration of ATZ in examples of the present invention and comparative examples;
fig. 4 is a graph of the stability test result of the visible light catalytic nanomaterial prepared in the embodiment of the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
TiO in the current semiconductor photocatalyst2Is the most studied and practical, TiO2Show great potential as ideal and potent photocatalysts in a variety of reactions. TiO22The conduction band side of (A) mainly plays a role of reducing, and the valence band side mainly plays a role of oxidizing. However, due to TiO2Has wider band gap energy and shorter electron-hole pair recombination time, so that the application of the photocatalyst is limited to ultraviolet activation. Although many efforts have been made to solve these problems, the achievement of the results is very limited, and thus, the improvement of the separation efficiency of photogenerated carriers, the reduction of the band gap, and the enhancement of the catalytic activity thereof in the visible region are still TiO2The core problem of photocatalyst research.
Graphite phase carbon nitride (g-C)3N4) The material is a typical high molecular semiconductor material, has the advantages of low cost, good stability, chemical inertness and the like, has higher catalytic activity on organic dye under visible light, and has been widely reported in the field of photocatalysis. However, during the course of the study, it was found that g-C3N4Photocatalytic materialThere are also some disadvantages, such as short lifetime of photo-generated electrons and holes, low utilization of visible light, etc. Therefore, the advantages of the composite photocatalyst are made up for, and the composite photocatalyst with better comprehensive performance is constructed by combining other semiconductor materials while the advantages of the composite photocatalyst are utilized, so that the composite photocatalyst has good scientific research value. And TiO22Is a typical inorganic semiconductor photocatalytic material, has good photoresponse activity and chemical stability, and is compatible with g-C3N4Having a matched band structure, and thus, is matched with g-C3N4And compounding, so that a composite photocatalytic material with better photocatalytic activity than a single component can be constructed.
Based on the concept, the invention provides a preparation method of a visible light catalytic nano material, which is to mix TiO with2And g-C3N4Are complexed and are in g-C3N4/TiO2On the basis of the above-mentioned material, the CNNi nano tube can be further doped, and can be made into TCNCNNi-40-400Fig. 1 shows an embodiment of a method for preparing a visible light catalytic nanomaterial provided by the present invention. Referring to fig. 1, in this embodiment, the preparation method of the visible light catalytic nanomaterial includes the following steps:
step S10, calcining melamine at high temperature, grinding and collecting powder to obtain g-C3N4；
First, in this example, g-C was prepared by high temperature calcination3N4And the method has the advantage of higher product purity. Said high temperature calcination producing g-C3N4Comprises the following steps: heating melamine to 400-600 ℃ at a heating rate of 2-10 ℃/min, calcining for 3-5 hours, grinding the calcined product after calcining, and collecting powder to obtain g-C3N4. The high-temperature calcination may be, for example, putting melamine into a crucible, then calcining the melamine in a muffle furnace or a carbonization furnace, and then grinding the calcined product with a mortar, specifically, in a specific embodiment of the present invention, the following embodiments are provided: putting a certain amount of melamine into an aluminum oxide crucible with a cover, and then putting the crucible into a muffle furnace for 2-10 timesHeating to 400-600 ℃ at a heating rate of 400/min, calcining for 3-5 h at the temperature, transferring the calcined product into an agate mortar after calcining is finished, grinding and collecting powder to obtain the g-C3N4。
Step S20, adding Ni (NO)3)2·6H2Mixing O and melamine, heating to 600-800 ℃ under the protection of nitrogen, calcining for 2-4 h, cooling, soaking the cooled product in an acid solution, and washing with water to obtain CNNi;
then, preparing the CNNi nanotube by adopting a high-temperature calcination mode, which comprises the following steps: a certain amount of Ni (NO)3)2·6H2Uniformly mixing O and melamine, grinding into powder, heating the obtained powder to 600-800 ℃ under the protection of nitrogen, carrying out heat preservation calcination for 2-4 h at the temperature, and naturally cooling to room temperature to obtain a CNNi crude product; and then, soaking the obtained CNNi crude product in an acid solution, slowly pouring the acid solution after the soaking is finished, and washing with water for several times to obtain a product CNNi. Further, in step S20, the Ni (NO)3)2·6H2The mass ratio of the O to the melamine is 0.020-2.120 g: 0.035-3.731 g. Furthermore, in the process of heating to 600-800 ℃ in step S20, the heating rate is preferably set to 2-20 ℃/min, and the appearance and performance of the prepared CNNi product are more stable. In addition, the acid solution is concentrated hydrochloric acid or concentrated sulfuric acid, and the concentration of the acid solution is 1-10 mol/L, preferably 1-10 mol/L. In addition, the soaking time of the cooling product in the acid solution is 10-15 hours.
It should be noted that, in other embodiments of the present invention, step S20 may be performed before step S10, or step S20 and step S10 are performed simultaneously, and it is only necessary to complete the g-C operations before the next operation (i.e., before step S30), respectively3N4And preparing CNNi.
Step S30, mixing g-C3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, adding hydrofluoric acid into the suspension under the action of stirring, and adding the suspension into the solutionReacting in a high-pressure reaction kettle to form TCNCNNi-40；
In the respective preparation to obtain g-C3N4And after CNNi, compounding the CNNi and TiO through hydrothermal reaction, wherein the specific steps comprise: a certain amount of g-C3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare a suspension, ultrasonically dispersing for 15-30 min, then adding hydrofluoric acid into the suspension under the stirring action, mechanically stirring for 10-20 min after the addition is finished, fully dispersing the hydrofluoric acid in the suspension, sealing the suspension in a high-pressure reaction kettle for reacting for a certain time, centrifuging the obtained reaction solution for multiple times after the reaction is finished, collecting solid substances and drying to obtain TCNCNi Ni-40(ii) a Wherein the times of the multiple centrifugation are 6-10 times; and/or the drying temperature of the drying is 40-80 ℃, and the drying time is 5-24 h.
Further, in step S30, the g-C3N4The addition ratio of tetrabutyl titanate, CNNi and isopropanol is 1.282-2.850 g: 5.164-6.813 g: 0.010-0.100 g: 50 mL; the concentration of the hydrofluoric acid is 40 wt%, and the addition volume is 1-4 mL. Furthermore, the reaction temperature in the high-pressure reaction kettle is 100-200 ℃, and the reaction time is 6-24 hours.
And step S40, calcining the TCNCNNi-40 in a protective gas atmosphere to obtain the visible light catalytic nano material.
The TCNCNNi is obtained in the preparation-40Then, for the TCNCNNi-40Calcining to obtain TCNCNNi-40-400The nanotube composite material is the visible light catalytic nanomaterial. Wherein the protective gas used in step S40 is nitrogen or argon, preferably nitrogen; and/or the heating rate in the calcining process is 3-10 ℃/min, the calcining temperature is 200-400 ℃, and the calcining time is 2-5 h.
The technical scheme provided by the invention prepares g-C3N4/TiO2The composite photocatalytic material, in which TiO2 is taken as a typical semiconductor material, has the advantages of low cost, good chemical property and high stabilityG to C3N4Then the crystal has narrower band gap energy (Eg ═ 2.67eV) and more negative conduction band position (-1.1eV), and heterogeneous charge transfer can occur after TiO2 is coupled with the crystal, so that separation of photo-generated electrons and holes is facilitated, and the catalytic activity of the crystal in a visible light region is enhanced; then, at g-C3N4/TiO2On the basis, the CNNi nanotube is further doped, so that the surface characteristics of a TiO2 crystal structure, a surface functional group, a surface hydroxyl group and the like are changed, the absorption performance of the catalyst on the catalyst is promoted, and the catalytic activity on a small-molecule intermediate product is improved, so that the mineralization is greatly improved; the TCNCNNi finally prepared-40-400The nanotube composite material has good stability and photocatalytic activity as a visible light catalytic nanomaterial, can be suitable for various photocatalytic fields, has easily obtained raw materials and simple preparation method, and is easy to realize industrial production.
Atrazine (ATZ) is a selective triazine herbicide that is widely used in agricultural production. In recent years, ATZ is frequently detected as a novel micro-pollutant in water environment, the concentration of ATZ in rivers in partial areas is as high as 11.4 mug/L, and the maximum content of ATZ in surface water is far more than 3.0 mug/L specified in quality standard of surface water environment (GB 3838-2002). Research shows that ATZ has certain toxic effect on human and organisms, such as carcinogenesis and endocrine dyscrasia of human body. In addition, the ATZ has good water solubility and long half-life period, and is difficult to naturally degrade and remove, so that the ATZ is permanently enriched in a water environment. Therefore, it is necessary to develop a water treatment technology for efficiently removing ATZ from a water body.
The visible light catalytic nano material prepared by the method provided by the invention has good stability and photocatalytic activity, and can be used for removing ATZ in water. Based on the above, the invention provides a method for degrading atrazine in water, which comprises the following steps: adding a visible light catalytic nano material into water, and degrading atrazine in the water under the irradiation of visible light; the visible light catalytic nano material is prepared by the preparation method of the visible light catalytic nano material. The visible light catalytic nano material provided by the invention is used for treating water, ATZ in water can be effectively degraded under visible light irradiation, the operation method is simple, the degradation efficiency is high, and the removal rate can reach 100%.
Further, when the visible light catalytic nano material is used for degrading the TAZ in the water body, the addition amount of the visible light catalytic nano material in the water is 0.05-0.20 g/L, and within the addition amount range, the removal rate of the visible light catalytic nano material to the ATZ in the water body reaches 100% after 5min under the condition of irradiation of visible light.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Putting 20g of melamine into an alumina crucible with a cover, then putting the crucible into a muffle furnace, heating to 400 ℃ at a heating rate of 10 ℃/min, calcining for 5h at the temperature, transferring the calcined product into an agate mortar after the calcination is finished, grinding and collecting powder to obtain g-C3N4；
(2) 1.2g of Ni (NO)3)2·6H2Mixing O and 2.04g of melamine uniformly, grinding the mixture into powder, heating the obtained powder to 800 ℃ at a heating rate of 15 ℃/min under the protection of nitrogen, calcining the powder for 3 hours, and naturally cooling the powder to room temperature to obtain a CNNi crude product; then, soaking the obtained CNNi crude product in 200mL of hydrochloric acid solution with the concentration of 5mol/L for 12 hours, slowly pouring out the acid solution, and washing with water for 6 times to obtain a product CNNi;
(3) 2.85g g-C3N45.6g of tetrabutyl titanate, 40mg of CNNi and 50mL of isopropanol are mixed to prepare a suspension, ultrasonic dispersion is carried out for 15min, then 2mL of hydrofluoric acid (with the concentration of 40 wt%) is added into the suspension under the stirring action, mechanical stirring is carried out for 20min after the addition is finished, the suspension is sealed in a high-pressure reaction kettle, reaction is carried out for 24h at 180 ℃, after the reaction is finished, the suspension is centrifuged for 6 times, solid matters are collected and dried for 10h at 80 ℃, and TCNCNNi is obtained-40；
(4) The TCNCNNi obtained-40In the presence of nitrogen gasUnder protection, heating to 400 ℃ at the heating rate of 10 ℃/min, and calcining for 4h to prepare TCNCNNi-40-400The nano particles are the visible light catalytic nano material.
Example 2
(1) Putting 20g of melamine into an alumina crucible with a cover, then putting the crucible into a muffle furnace, heating to 500 ℃ at a heating rate of 2 ℃/min, calcining for 3h at the temperature, transferring the calcined product into an agate mortar after the calcination is finished, grinding and collecting powder to obtain g-C3N4；
(2) 0.02g of Ni (NO)3)2·6H2Mixing O and 0.035g of melamine uniformly, grinding into powder, heating the obtained powder to 600 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, calcining for 2h, and naturally cooling to room temperature to obtain a CNNi crude product; then, soaking the obtained CNNi crude product in 200mL of 1mol/L acid solution for 15h, slowly pouring off the acid solution, and washing with water for 6 times to obtain a product CNNi;
(3) 2.754g g-C3N46.813g of tetrabutyl titanate, 100mg of CNNi and 50mL of isopropanol are mixed to prepare suspension, ultrasonic dispersion is carried out for 30min, 4mL of hydrofluoric acid (with the concentration of 40 wt%) is added into the suspension under the stirring action, mechanical stirring is carried out for 10min after the addition is finished, the suspension is sealed in a high-pressure reaction kettle, reaction is carried out for 6h at 200 ℃, 8 times of centrifugation are carried out on the suspension after the reaction is finished, solid matters are collected and dried for 5h at 60 ℃, and TCNCNNi is obtained-40；
(4) The TCNCNNi obtained-40Heating to 300 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen, and calcining for 2h to prepare TCNCNNi-40-400The nano particles are the visible light catalytic nano material.
Example 3
(1) Putting 20g of melamine into an alumina crucible with a cover, then putting the crucible into a muffle furnace, heating to 600 ℃ at a heating rate of 8 ℃/min, calcining for 4h at the temperature, transferring the calcined product into an agate mortar after the calcination is finished, grinding and collecting powder to obtain g-C3N4；
(2) 2.12g of Ni (NO)3)2·6H2Mixing O and 3.731g of melamine uniformly, grinding the mixture into powder, heating the obtained powder to 700 ℃ at a heating rate of 20 ℃/min under the protection of nitrogen, calcining the powder for 4 hours, and naturally cooling the powder to room temperature to obtain a CNNi crude product; then, soaking the obtained CNNi crude product in 200mL of 10mol/L acid solution for 10h, slowly pouring off the acid solution, and washing with water for 6 times to obtain a product CNNi;
(3) 1.282g g-C3N45.164g of tetrabutyl titanate, 10mg of CNNi and 50mL of isopropanol are mixed to prepare suspension, ultrasonic dispersion is carried out for 20min, 1mL of hydrofluoric acid (with the concentration of 40 wt%) is added into the suspension under the stirring action, mechanical stirring is carried out for 15min after the addition is finished, the suspension is sealed in a high-pressure reaction kettle, reaction is carried out for 15h at 100 ℃, 10 times of centrifugation is carried out on the suspension after the reaction is finished, solid matters are collected and dried for 24h at 40 ℃, and TCNCNNi is obtained-40；
(4) The TCNCNNi obtained-40Heating to 200 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, calcining for 5h to prepare TCNCNNi-40-400The nano particles are the visible light catalytic nano material.
TCNCNNi prepared for the examples of the invention-40-400The nanoparticles were subjected to SEM testing and SEM images are shown in figure 2. As can be seen from FIG. 2, the visible light catalytic nanomaterial prepared by the embodiment of the invention is in the form of uniformly distributed nanoparticles.
Application example 1
(1) Adding 50mL of ATZ aqueous solution into a quartz reactor, wherein the pH value of the ATZ aqueous solution is regulated and controlled by 0.1M HCl or NAOH, the initial ATZ concentration is 10mg/L, and the pH value of the ATZ aqueous solution is 7.0;
(2) the TCNCNNi prepared in example 1 is added to the aqueous ATZ solution prepared-40-400Nanoparticles and PS (polystyrene), TCNCNNi-40-400The dosage of the nano particles is 0.10g/L, and the dosage of the PS is 0.5 mM;
(3) the reactor was first placed in the dark for an adsorption test for 20min to achieve ATZ and TCNCNNi-40-400Nano meterThe particles were brought into sufficient contact with each other to establish adsorption equilibrium, and then a 400W xenon lamp with a filter (400nm) was horizontally placed outside the reactor (in order to maintain a constant reaction temperature, a cooling water circulation system was provided around the reactor, and the solution in the reactor was subjected to a test by slow magnetic stirring) as a visible light source, and the average light intensity of the surface of the reaction solution in the reactor was 200mW/cm as measured by a photon densitometer2I.e. two standard solar intensities (AM 3G).
The concentration change of ATZ in the aqueous solution was detected and analyzed by high performance liquid chromatography. The detection results are shown in fig. 3 and 4, which indicate that the removal rate of ATZ reaches 100% after 5min of illumination.
Application example 2
The procedure was the same as in application example 1, except that TCNCNNi was used-40-400The amount of nanoparticles added was replaced with 0.05 g/L.
The detection result shows that after 5min of illumination, the removal rate of ATZ reaches 100%.
Application example 3
The procedure was the same as in application example 1, except that TCNCNNi was used-40-400The amount of nanoparticles added was replaced with 0.20 g/L.
The detection result shows that after 5min of illumination, the removal rate of ATZ reaches 100%.
Application example 4
The procedure is as in application example 1, except that TCNCNNi prepared in example 2 is added to the aqueous ATZ solution-40-400And (3) nanoparticles. The detection result shows that after 5min of illumination, the removal rate of ATZ reaches 100%.
Application example 5
Procedure as in application example 1, except that TCNCNNi prepared in example 3 was added to the aqueous ATZ solution-40-400And (3) nanoparticles.
The detection result shows that after 5min of illumination, the removal rate of ATZ reaches 100%.
Comparative example 1
The procedure is as in application example 1, except that no TCNCNNi is added to the aqueous ATZ solution-40-400And (3) carrying out pure light treatment on the nano particles, namely the ATZ aqueous solution.
The concentration change of ATZ in the aqueous solution was detected and analyzed by high performance liquid chromatography. The detection result is shown in fig. 3, which indicates that ATZ is stable in water, and the concentration of ATZ does not change much after pure illumination for 5 min.
Comparative example 2
The procedure was the same as in application example 1, except that TCNCNNi was used-40-400Replacement of nanoparticles into ordinary nano-TiO2。
The concentration change of ATZ in the aqueous solution was detected and analyzed by high performance liquid chromatography. The detection results are shown in FIG. 3, which shows that the removal rate of ATZ is less than 10% after 5min of illumination.
Application example 6
(1) ATZ was added again to the ATZ aqueous solution after completion of the treatment in application example 1 to make the concentration of ATZ 10mg/L, and the pH of the ATZ aqueous solution was adjusted to 7.0 by 0.1M HCl or NAOH, and the TCNCNNi prepared in example 1 was added to the ATZ aqueous solution-40-400Nanoparticles and PS (polystyrene), TCNCNNi-40-400The dosage of the nano particles is 0.10g/L, and the dosage of the PS is 0.5 mM;
(2) the reactor was first placed in the dark for an adsorption test for 20min to achieve ATZ and TCNCNNi-40-400The nanoparticles are fully contacted to establish adsorption equilibrium, then a 400W xenon lamp with a filter (400nm) is horizontally placed outside the reactor to be used as a visible light source, and the average light intensity of the surface of the reaction solution in the reactor is measured by a photon densitometer to be 200mW/cm2I.e. two standard solar intensities (AM 3G).
The concentration change of ATZ in the aqueous solution was detected and analyzed by high performance liquid chromatography. The results are shown in FIG. 4, which indicates that the removal rate of ATZ after the treatment is about 96%.
Application example 6
(1) Adding ATZ into the ATZ aqueous solution (namely the ATZ aqueous solution with 100% degradation) treated in the application example 1 again to ensure that the concentration of the ATZ reaches 10mg/L, and regulating the pH value of the ATZ aqueous solution to be 7.0 by 0.1M HCl or NAOH;
(2) the procedure was the same as in application example 1;
(3) the procedure was the same as in application example 1.
The concentration change of ATZ in the aqueous solution was detected and analyzed by high performance liquid chromatography. The results are shown in FIG. 4, which indicates that the removal rate of ATZ after the treatment is about 97%.
Application example 7
(1) Adding ATZ again into the ATZ aqueous solution (namely the ATZ aqueous solution with 97% degradation) treated in the application example 6 to ensure that the concentration of the ATZ reaches 10mg/L, and regulating the pH value of the ATZ aqueous solution to be 7.0 by 0.1M HCl or NAOH;
(2) the procedure was the same as in application example 1;
(3) the procedure was the same as in application example 1.
The concentration change of ATZ in the aqueous solution was detected and analyzed by high performance liquid chromatography. The results are shown in FIG. 4, which indicates that the removal rate of ATZ after the treatment is about 95%.
Application example 8
(1) Adding ATZ again into the ATZ aqueous solution (namely the ATZ aqueous solution with 95% degradation) treated in the application example 6 to ensure that the concentration of the ATZ reaches 10mg/L, and regulating the pH value of the ATZ aqueous solution to be 7.0 by 0.1M HCl or NAOH;
(2) the procedure was the same as in application example 1;
(3) the procedure was the same as in application example 1.
The concentration change of ATZ in the aqueous solution was detected and analyzed by high performance liquid chromatography. The results are shown in FIG. 4, which indicates that the removal rate of ATZ after treatment is about 93%.
Application example 9
(1) Adding ATZ into the ATZ aqueous solution (namely the ATZ aqueous solution with 93 percent degradation) treated in the application example 6 again to ensure that the concentration of the ATZ reaches 10mg/L, and regulating the pH value of the ATZ aqueous solution to be 7.0 by 0.1M HCl or NAOH;
(2) the procedure was the same as in application example 1;
(3) the procedure was the same as in application example 1.
The concentration change of ATZ in the aqueous solution was detected and analyzed by high performance liquid chromatography. The detection results are shown in fig. 4 (in fig. 4, run1, run2, run3, run4, and run5 correspond to application example 1, application example 6, application example 7, application example 8, and application example 9, respectively), indicating that the removal rate of ATZ after treatment is about 91%.
As can be seen from the comparison of the above application examples 1 to 5 with the comparative examples 1 to 2 (i.e., FIG. 3), the ATZ molecule is relatively stable in water, the concentration thereof does not change much after 5min of pure light irradiation, and ordinary TiO2The removal rate of the nano-particles to ATZ after 5min is only less than 10%, while the TCNCNNi prepared by the embodiment of the invention-40-400The degradation efficiency of the photocatalytic nano material to ATZ is as high as 100%.
As can be seen from the comparison of application example 1 with application examples 6 to 9 described above (i.e., FIG. 4), TCNCNNi prepared in the examples of the present invention-40-400The photocatalytic nano material has good stability, and still keeps high removal rate on ATZ in a water body under the condition of multiple use.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A preparation method of a visible light catalytic nano material is characterized by comprising the following steps:
calcining melamine at high temperature, grinding and collecting powder to obtain g-C3N4；
Mixing Ni (NO)3)2·6H2Mixing O and melamine, heating to 600-800 ℃ under the protection of nitrogen, calcining for 2-4 h, cooling, soaking the cooled product in an acid solution, and washing with water to obtain CNNi;
g to C3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, and adding hydrofluoride into the suspension under the action of stirringAcid, and then reacting the suspension in a high pressure reaction kettle to form TCNCNNi-40；
And calcining the TCNCNNi-40 in a protective gas atmosphere to obtain the visible light catalytic nano material.
2. The method for preparing the visible light catalytic nano material as claimed in claim 1, wherein the melamine is calcined at high temperature and then ground to collect powder to obtain g-C3N4The method comprises the following steps:
heating melamine to 400-600 ℃ at a heating rate of 2-10 ℃/min, calcining for 3-5 hours, grinding the calcined product after calcining, and collecting powder to obtain g-C3N4。
3. The method of preparing visible light catalytic nanomaterial of claim 1, wherein Ni (NO) is added3)2·6H2Mixing O and melamine, heating to 600-800 ℃ under the protection of nitrogen, calcining for 3h, cooling, soaking the cooled product in an acid solution, and washing with water to obtain CNNi:
the Ni (NO)3)2·6H2The mass ratio of the O to the melamine is 0.020-2.120 g: 0.035-3.731 g; and/or the presence of a gas in the gas,
in the process of heating to 600-800 ℃, the heating rate is 2-20 ℃/min.
4. The method of preparing visible light catalytic nanomaterial of claim 1, wherein Ni (NO) is added3)2·6H2Mixing O and melamine, heating to 600-800 ℃ under the protection of nitrogen, calcining for 3h, cooling, soaking the cooled product in an acid solution, and washing with water to obtain CNNi:
the acid solution is concentrated hydrochloric acid or concentrated sulfuric acid, and the concentration of the acid solution is 1-10 mol/L; and/or the presence of a gas in the gas,
and the cooling product is soaked in the acid solution for 10-15 hours.
5. The method for preparing the visible light catalytic nano material of claim 1, wherein g-C is3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, adding hydrofluoric acid into the suspension under the action of stirring, and reacting the suspension in a high-pressure reaction kettle to form TCNCNNi-40In the steps of (A):
the g to C3N4The addition ratio of tetrabutyl titanate, CNNi and isopropanol is 1.282-2.850 g: 5.164-6.813 g: 0.010-0.100 g: 50 mL;
the concentration of the hydrofluoric acid is 40 wt%, and the addition volume is 1-4 mL.
6. The method for preparing the visible light catalytic nano material of claim 1, wherein g-C is3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, adding hydrofluoric acid into the suspension under the action of stirring, and reacting the suspension in a high-pressure reaction kettle to form TCNCNNi-40In the steps of (A):
the reaction temperature in the high-pressure reaction kettle is 100-200 ℃, and the reaction time is 6-24 hours.
7. The method for preparing the visible light catalytic nano material of claim 1, wherein g-C is3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, adding hydrofluoric acid into the suspension under the action of stirring, and reacting the suspension in a high-pressure reaction kettle to form TCNCNNi-40The method comprises the following steps:
g to C3N4Mixing tetrabutyl titanate, CNNi and isopropanol to prepare suspension, adding hydrofluoric acid into the suspension under the action of stirring, reacting the suspension in a high-pressure reaction kettle, centrifuging the suspension after reaction for many times, collecting solid matters and drying to obtain TCNCNNi-40；
Wherein the times of the multiple centrifugation are 6-10 times; and/or the drying temperature of the drying is 40-80 ℃, and the drying time is 5-24 h.
8. The method for preparing the visible light catalytic nano material as claimed in claim 1, wherein the step of calcining the TCNCNNi-40 in a protective gas atmosphere to prepare the visible light catalytic nano material comprises:
the protective gas is nitrogen or argon; and/or the presence of a gas in the gas,
the temperature rise rate in the calcination process is 3-10 ℃/min, the calcination temperature is 200-400 ℃, and the calcination time is 2-5 h.
9. A method for degrading atrazine in water is characterized by comprising the following steps:
adding a visible light catalytic nano material into water, and degrading atrazine in the water under the irradiation of visible light; wherein the visible light catalytic nano material is prepared by the preparation method of the visible light catalytic nano material as claimed in any one of claims 1 to 8.
10. The method for preparing atrazine in wastewater according to claim 9, wherein the amount of the visible light catalytic nano material added in the water is 0.05-0.20 g/L.
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