CN113559908A - Ternary composite photocatalytic material, preparation method thereof and method for degrading PPCPs in water - Google Patents
Ternary composite photocatalytic material, preparation method thereof and method for degrading PPCPs in water Download PDFInfo
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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
-
- B01J35/39—
-
- 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
-
- 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
-
- 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 ternary composite photocatalytic material, a preparation method thereof and a method for degrading PPCPs in water, wherein the ternary composite photocatalytic material comprises titanium dioxide, graphitized carbon nitride and an iron nano tube, wherein the graphitized carbon nitride is used as a carrier, the iron nano tube and part of the titanium dioxide are loaded on the graphitized carbon nitride, and the rest part of the titanium dioxide is attached to the iron nano tube. By doping the titanium dioxide with the iron nano tube, the absorption performance of the ternary composite photocatalytic material on visible light is promoted, and the catalytic activity of the ternary composite photocatalytic material on small-molecule intermediates is improved, so that the degree of mineralization is greatly improved; meanwhile, the graphitized carbon nitride has narrower band gap energy and more negative conduction band position, so that TiO2Coupled with it, heterogeneous charge transfer can occur, which is beneficial to photogenerationThe separation of the sub-cavity and the cavity greatly improves the catalytic performance of the material in a visible light area, so that the prepared ternary composite photocatalytic material has good cycle stability and photocatalytic activity.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a ternary composite photocatalytic material, a preparation method thereof and a method for degrading PPCPs in water.
Background
The medicines and personal care products (PPCPs) are a new type of pollutants appearing in recent years, and the pollutants are low in concentration, complex in structure, high in biological activity and not negligible in potential harm, so that the PPCPs are increasingly concerned. Of these, Carbamazepine (CBZ), a typical antiepileptic drug, is the most representative of PPCPs. Due to its widespread use, carbamazepine is emitted in large quantities into the environment. In addition, it is important to study the environmental behavior and removal of carbamazepine and its derivatives in humans because of their metabolic effects in vivo and the degradation of the carbamazepine parent in the environment to produce a variety of derivatives (i.e., small molecule intermediates) which may be more toxic than the parent compound and are more difficult to degrade.
The photocatalytic advanced oxidation technology using semiconductor photocatalyst is increasingly paid attention to the degradation of PPCPs, and more novel catalysts are developed in succession. The principle of the semiconductor photocatalyst in water body treatment application is that electrons are transited due to the excitation of light to the photocatalyst, so that electrons and holes of photon-generated carriers are generated, and then active substances are generated to attack PPCPs, so that the effect of degrading the PPCPs is achieved.
In recent years, graphitized carbon nitride (g-C)3N4) The photocatalytic activity of (A) has attracted a great deal of attention, mainly due to the fact that g-C3N4Has the advantages of good chemical stability, direct utilization of visible light and the like, thereby having wide prospect in the aspects of photocatalytic oxidation of environmental pollutants and the like. But due to electronsThe holes are easy to recombine, so that the photocatalytic activity of the photocatalyst is low.
Disclosure of Invention
The invention mainly aims to provide a ternary composite photocatalytic material, a preparation method thereof and a method for degrading PPCPs in water, and aims to solve the problem that electrons and holes of the existing photocatalyst are easy to recombine.
In order to achieve the purpose, the invention provides a ternary composite photocatalytic material, which comprises titanium dioxide, graphitized carbon nitride and an iron nano tube, wherein the graphitized carbon nitride is used as a carrier, the iron nano tube and part of the titanium dioxide are loaded on the graphitized carbon nitride, and the rest part of the titanium dioxide is attached to the iron nano tube.
Further, the invention also provides a preparation method of the ternary composite photocatalytic material, which comprises the following steps:
s10, mixing Fe (NO)3)2·6H2Mixing O and melamine uniformly, crushing to obtain mixed powder, heating the mixed powder under the protection of nitrogen or inert gas, heating to 600-800 ℃, calcining for 1-2 h, cooling to obtain a crude product, and purifying the crude product to obtain an iron nano tube;
s20, dispersing the graphitized carbon nitride, the titanium dioxide and the iron nano tube in absolute ethyl alcohol to obtain a suspension, and drying the suspension to obtain a solid intermediate product;
s30, crushing the intermediate product, heating to T1 for calcining for 30-60 min in an inert gas or nitrogen atmosphere, and then continuously heating to T2 for calcining for 1-2 h to obtain a ternary composite photocatalytic material;
wherein the T1 is 200-300 ℃, the T2 is 300-500 ℃, and T1 is less than T2.
Optionally, before step S20, the method further includes the following steps:
and calcining the melamine at 500-600 ℃ for 3-8 h, and then crushing the melamine into powder to obtain the graphitized carbon nitride.
Alternatively, in step S10:
the purification treatment comprises the following steps: and soaking the crude product in concentrated hydrochloric acid for 20-28 h, and then washing the crude product with water for multiple times to obtain the iron nano tube.
Alternatively, in step S10:
said Fe (NO)3)2·6H2The mass ratio of the O to the melamine is 0.5-2: 0.5 to 6; and/or the presence of a gas in the gas,
and in the process of heating to 600-800 ℃, the heating rate is 2-20 ℃/min.
Alternatively, in step S20:
the mass-volume ratio of the graphitized carbon nitride to the titanium dioxide to the iron nanotube to the absolute ethyl alcohol is 1.5-3.2 g: 2.4-6.3 g: 0.03g to 0.15 g: 90-110 mL.
Optionally, step S20 includes:
uniformly mixing the graphitized carbon nitride, titanium dioxide, the iron nano tube and absolute ethyl alcohol, and then performing ultrasonic dispersion for 20-40 min to obtain a suspension;
and (3) stirring the suspension and drying at a constant temperature of 50-70 ℃ to obtain a solid intermediate product.
Alternatively, in step S30:
in the process of heating to T1, the heating rate is 3-5 ℃/min; and/or the presence of a gas in the gas,
and in the process of heating to T2, the heating rate is 3-5 ℃/min.
In addition, the invention also provides a method for degrading PPCPs in water, namely, the aqueous solution containing the PPCPs is treated by using the ternary composite photocatalytic material.
Optionally, the PPCPs comprise carbamazepine.
In the technical scheme provided by the invention, the ternary composite photocatalytic material comprises titanium dioxide, graphitized carbon nitride and an iron nano tube, the iron nano tube and part of the titanium dioxide are loaded on the graphitized carbon nitride, the rest part of the titanium dioxide is attached to the iron nano tube, and the crystal structure, surface functional groups, surface hydroxyl groups and the like of the titanium dioxide are changed by doping the iron nano tube to the titanium dioxideThe surface characteristics promote the absorption performance of the ternary composite photocatalytic material on visible light, and simultaneously improve the catalytic activity of the ternary composite photocatalytic material on micromolecule intermediates obtained after the PPCPs are primarily degraded, so that the mineralization degree of the treated aqueous solution is greatly improved; meanwhile, the graphitized carbon nitride has narrower band gap energy and more negative conduction band position, so that TiO2Coupled with the material, heterogeneous charge transfer can be generated, which is beneficial to the separation of photo-generated electrons and holes, thereby greatly improving the catalytic performance of the material in a visible light region and leading the prepared ternary composite photocatalytic material to have good cycle stability and photocatalytic activity.
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 an SEM image of an embodiment of a three-component composite photocatalytic material provided by the invention;
FIG. 2 is a TEM image of the three-component composite photocatalytic material prepared in example 1 of the present invention;
FIG. 3 is a Fourier infrared image of the three-component composite photocatalytic material prepared in example 1 of the present invention;
FIG. 4 is a graph showing the degradation effect of the photocatalytic materials prepared in the examples and comparative examples of the present invention on carbamazepine under visible light;
FIG. 5 is a graph showing the stability of the photocatalytic material prepared in example 1 of the present invention in degrading carbamazepine;
FIG. 6 is a graph showing the stability of the photocatalytic material prepared in comparative example 2 according to the present invention in degrading carbamazepine.
The reference numbers illustrate:
| reference numerals | Name (R) | Reference numerals | Name (R) |
| 1 | |
2 | Titanium dioxide |
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.
In recent years, the photocatalytic activity of graphitized carbon nitride (g-C3N4) has attracted much attention, mainly because g-C3N4 has the advantages of good chemical stability, direct utilization of visible light and the like, and thus has a wide prospect in the aspect of photocatalytic oxidation of environmental pollutants and the like. But its application is limited due to its low light utilization and easy recombination of electron-hole.
In view of this, the present invention proposes a three-way composite photocatalytic material comprising titanium dioxide (TiO)2) Graphitized carbon nitride (g-C)3N4) And iron nano tubes (CNFe), wherein the graphitized carbon nitride is used as a carrier, the iron nano tubes and part of the titanium dioxide are loaded on the graphitized carbon nitride, and the rest part of the titanium dioxide is attached to the iron nano tubes.
Referring to fig. 1, in an embodiment, in the three-component composite photocatalytic material, since titanium dioxide 2 is a nanoparticle, titanium dioxide 2 is attached to both iron nanotube 1 and graphitized carbon nitride (not shown in the figure), and graphitized carbon nitride is the largest among the three and is in a sheet shape, so that titanium dioxide 2 and iron nanotube 1 are attached to the graphitized carbon nitride sheet layer. In fig. 1, the graphitized carbon nitride in the form of a sheet is located below the aggregated titanium dioxide, and therefore, is not shown.
The titanium dioxide is used as a typical semiconductor material, and has the advantages of readily available raw materials, low cost, good chemical property and high stability. The graphitized carbon nitride has the advantages of good chemical stability, direct utilization of visible light and the like, and has narrower band gap energy and more negative conduction band position than titanium dioxide, and the titanium dioxide can be coupled with the graphitized carbon nitride to generate heterogeneous charge transfer,
in the technical scheme provided by the invention, the ternary composite photocatalytic material comprises titanium dioxide, graphitized carbon nitride and an iron nanotube, the iron nanotube and part of the titanium dioxide are loaded on the graphitized carbon nitride, and the rest part of the titanium dioxide is attached to the iron nanotube, wherein the titanium dioxide is used as a typical semiconductor material and is originally attached to the iron nanotubeThe material is easy to obtain, the cost is low, the chemical property is good, and the stability is high. The graphitized carbon nitride has the advantages of good chemical stability, direct utilization of visible light and the like, and surface characteristics of a crystal structure, surface functional groups, surface hydroxyl groups and the like of titanium dioxide are changed by doping the titanium dioxide with the iron nano tube, so that the absorption performance of the ternary composite photocatalytic material on the visible light is promoted, and the catalytic activity of the ternary composite photocatalytic material on micromolecule intermediates obtained after PPCPs are primarily degraded is improved, so that the mineralization degree of a treated aqueous solution is greatly improved; in addition, the graphitized carbon nitride has narrower band gap energy and more negative conduction band position than titanium dioxide, so that TiO2Coupled with the material, heterogeneous charge transfer can be generated, which is beneficial to the separation of photo-generated electrons and holes, thereby greatly improving the catalytic performance of the material in a visible light region and leading the prepared ternary composite photocatalytic material to have good stability and photocatalytic activity.
Based on the above purpose, the present invention further provides a preparation method of the ternary composite photocatalytic material, and in an embodiment, the preparation method includes the following steps:
step S10, adding Fe (NO)3)2·6H2Mixing O and melamine uniformly, crushing to obtain mixed powder, heating the mixed powder under the protection of nitrogen or inert gas, heating to 600-800 ℃, calcining for 1-2 h, cooling to obtain a crude product, and purifying the crude product to obtain an iron nano tube;
wherein, Fe (NO)3)2·6H2The mass ratio of the O to the melamine is 0.5-2: 0.5-6, so that the prepared iron nano tube (CNFe) has good effect. Specifically, in the present embodiment, the temperature rise rate is 2-20 ℃/min in the process of raising the temperature to 600-800 ℃.
Specifically, the purification treatment comprises: and soaking the cooled crude product in concentrated hydrochloric acid for 20-28 h, and washing the crude product with water for multiple times to obtain the iron nano tube. As such, some metal ion impurities in the crude product may be removed by purification treatment. In order to ensure that the effect of removing impurities is better, the molar concentration of the concentrated hydrochloric acid is 2 mol/L-5 mol/L.
Step S20, dispersing the graphitized carbon nitride, the titanium dioxide and the iron nano tube in absolute ethyl alcohol to obtain a suspension, and drying the suspension to obtain a solid intermediate product;
the present invention is not limited to the source of the graphitized carbon nitride, and may be prepared by a conventional method, and in this embodiment, the graphitized carbon nitride is prepared as follows (that is, the following step is further included before step S20): and calcining the melamine at 500-600 ℃ for 3-8 h, and then crushing the melamine into powder to obtain the graphitized carbon nitride.
Specifically, the melamine is placed into an alumina crucible with a cover, then the alumina crucible is placed into a muffle furnace to be calcined for 3-8 hours at 500-600 ℃, then an agate mortar is used for grinding, powder is collected, and the graphitized carbon nitride (g-C) is obtained3N4). Pure graphitized carbon nitride is prepared by a high temperature calcination method, and volatilization loss at high temperature is reduced by putting melamine into an aluminum oxide crucible with a cover. Further, in the embodiment, the temperature is increased to 500-600 ℃ at a temperature increase rate of 2-10 ℃/min, so that the obtained graphitized carbon nitride has a good molding effect, that is, the prepared graphitized carbon nitride is in a strip shape, rather than in a strip shape which is intermittent from section to section, so that the finally prepared ternary composite photocatalytic material has good catalytic activity.
The invention also does not limit the source of the titanium dioxide, can be common purchased titanium dioxide, and can also be nano titanium dioxide, and the catalytic activity of the ternary composite photocatalytic material prepared by the nano titanium dioxide is better.
Wherein the mass-volume ratio of the graphitized carbon nitride to the titanium dioxide to the iron nanotube to the absolute ethyl alcohol is 1.5-3.2 g: 2.4-6.3 g: 0.03g to 0.15 g: 90-110 mL.
In specific implementation, step S20 includes:
step S21, uniformly mixing the graphitized carbon nitride, the titanium dioxide, the iron nano tube and the absolute ethyl alcohol, and then performing ultrasonic dispersion for 20-40 min to obtain a suspension;
the graphitized carbon nitride, the titanium dioxide and the iron nano tube have better dispersion effect in the absolute ethyl alcohol by an ultrasonic dispersion mode.
And step S22, stirring the suspension liquid and drying at constant temperature of 50-70 ℃ to obtain a solid intermediate product.
It can be understood that the inert gas includes argon, and the mixed powder is heated under the protection of nitrogen or inert gas, so that the phenomenon that the iron nano tube cannot be obtained due to carbonization of the mixed powder is avoided.
And S30, crushing the intermediate product, heating to T1 for calcining for 30-60 min in a nitrogen or argon atmosphere, and then continuously heating to T2 for calcining for 1-2 h to obtain the ternary composite photocatalytic material.
Wherein the temperature T1 is 200-300 ℃, the temperature T2 is 300-500 ℃, and the temperature T1<T2, the intermediate product can be molded when being calcined for 30-60 min at the temperature of T1 by means of gradient temperature rise and calcination at different temperatures for a period of time, and then the intermediate product is further calcined to enable the iron nano tube, graphitized carbon nitride and titanium dioxide in the ternary composite photocatalytic material to reach a better state, so that the ternary composite photocatalytic material (TCNCNFe) is enabled to be in a better state-500) Has excellent catalytic activity.
If the temperature rising rate is too fast, the calcination of the intermediate product is not uniform, the catalytic performance of the finally obtained photocatalytic material is affected, if the temperature rising rate is too slow, the time required for temperature rising is longer, and the performance of components such as the iron nano tube of the prepared photocatalytic material is not good, so that the catalytic activity of the photocatalytic material is affected. In the embodiment, in the process of heating to T1, the heating rate is 3-5 ℃/min; and/or in the process of heating to T2, the heating rate is 3-5 ℃/min, the intermediate product is uniformly calcined at the heating rate, the required time is appropriate, and the prepared ternary composite photocatalytic material has good catalytic activity.
In addition, the invention also provides a method for degrading PPCPs in water, namely, the aqueous solution containing the PPCPs is treated by using the ternary composite photocatalytic material. As can be understood, the ternary composite photocatalytic material has a certain degradation effect on PPCPs.
In specific implementation, an aqueous solution containing carbamazepine is added into a reactor, the pH value of the aqueous solution is regulated and controlled by 0.1M HCl or NaOH, then a ternary composite photocatalytic material and Peroxymonosulfate (PMS) are added, an adsorption experiment is carried out for 30min in the dark before illumination to realize full contact between CBZ and the photocatalyst to establish adsorption balance, and then visible light source is used for illumination to degrade the carbamazepine in the aqueous solution.
In the embodiment, the PPCPs comprise carbamazepine, the degradation effect of the ternary composite photocatalytic material on the carbamazepine is mainly verified, and the verification result shows that the degradation effect on the carbamazepine is good and the mineralization degree of a degraded aqueous solution is high. Specifically, in the ternary composite photocatalytic material, TiO is changed by doping the titanium dioxide with the iron nano tube2The crystal structure, the surface functional groups, the surface hydroxyl groups and other surface characteristics promote Peroxymonosulfate (PMS) to generate sulfate radicals and hydroxyl radicals in water, and simultaneously improve the catalytic activity of micromolecule intermediate products obtained by primary degradation of carbamazepine, thereby greatly improving the mineralization degree of the treated aqueous solution.
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, putting the crucible into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, calcining for 5 hours at the temperature, grinding by using an agate mortar, and collecting powder to obtain g-C3N4。
(2) 2g Fe (NO) are weighed out3)2·6H2Mixing O and 2g of melamine uniformly, grinding to obtain mixed powder, heating the mixed powder under the protection of nitrogen, heating to 700 ℃ at the heating rate of 5 ℃/min, calcining for 1.5h, naturally cooling to room temperature to obtain a crude product, soaking the obtained crude product in 200mL of concentrated hydrochloric acid with the molar concentration of 3mol/L for 24h, slowly pouring out the concentrated hydrochloric acid, and washing the crude product with water for a plurality of times to obtain CNFe。
(3) 1.5g g-C3N4、2.4g TiO20.05mg of CNFe and 100mL of absolute ethyl alcohol are mixed evenly, then ultrasonic dispersion is carried out for 30min to obtain suspension, and the suspension is stirred and dried at constant temperature by a constant temperature heating stirrer at 60 ℃ to form a solid intermediate product.
(4) Grinding the prepared intermediate product into powder, heating to 300 ℃ at the heating rate of 3 ℃/min under the protection of nitrogen, calcining for 50min, then continuously heating to 500 ℃ at the heating rate of 3 ℃/min, and calcining for 2h to obtain nanoparticles, namely the ternary composite photocatalytic material.
Example 2
(1) 20g of melamine was placed in an alumina crucible with a lid, and then placed in a muffle furnace at a heating rate of 2 ℃/min to 550 ℃ and calcined at this temperature for 5h, and then ground with an agate mortar and the powder collected to give g-C3N 4.
(2) 0.5g Fe (NO) was weighed3)2·6H2Mixing O and 3g of melamine uniformly, grinding to obtain mixed powder, heating the mixed powder under the protection of argon, heating to 600 ℃ at the heating rate of 2 ℃/min, calcining for 2h, naturally cooling to room temperature to obtain a crude product, soaking the obtained crude product in 200mL of concentrated hydrochloric acid with the molar concentration of 2mol/L for 28h, slowly pouring out the concentrated hydrochloric acid, and washing the crude product with water for several times to obtain CNFe.
(3) 3.2g g-C3N4, 6.3g TiO20.03mg of CNFe and 110mL of absolute ethyl alcohol are mixed uniformly, then ultrasonic dispersion is carried out for 30min to obtain suspension, and the suspension is stirred and dried at constant temperature by a constant-temperature heating stirrer at 60 ℃ to form a solid intermediate product.
(4) Grinding the prepared intermediate product into powder, heating to 200 ℃ at the heating rate of 3 ℃/min under the protection of nitrogen, calcining for 60min, then continuously heating to 600 ℃ at the heating rate of 4 ℃/min, and calcining for 1h to obtain nanoparticles, namely the ternary composite photocatalytic material.
Example 3
(1) 20g of melamine are placed in the beltPutting into a covered alumina crucible, heating to 600 deg.C at a heating rate of 10 deg.C/min in a muffle furnace, calcining at the temperature for 5 hr, grinding with agate mortar, and collecting powder to obtain g-C3N4。
(2) 1g of Fe (NO) is weighed3)2·6H2And mixing O and 0.5g of melamine uniformly, grinding to obtain mixed powder, heating the mixed powder under the protection of nitrogen, heating to 800 ℃ at a heating rate of 20 ℃/min, calcining for 1h, naturally cooling to room temperature to obtain a crude product, soaking the obtained crude product in 200mL of concentrated hydrochloric acid with the molar concentration of 5mol/L for 20h, slowly pouring out the concentrated hydrochloric acid, and washing the crude product with water for several times to obtain the CNFe.
(3) 2.3g g-C3N4, 3.5g TiO20.15mg of CNFe and 90mL of absolute ethyl alcohol are mixed uniformly, then ultrasonic dispersion is carried out for 30min to obtain suspension, and the suspension is stirred and dried at constant temperature by a constant-temperature heating stirrer at 70 ℃ to form a solid intermediate product.
(4) Grinding the prepared intermediate product into powder, heating to 250 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen, calcining for 30min, then continuously heating to 400 ℃ at the heating rate of 5 ℃/min, and calcining for 1.5h to obtain nanoparticles, namely the ternary composite photocatalytic material.
Example 4
(1) Putting 20g of melamine into an alumina crucible with a cover, putting the crucible into a muffle furnace, heating to 500 ℃ at a heating rate of 7 ℃/min, calcining for 5 hours at the temperature, grinding by using an agate mortar, and collecting powder to obtain g-C3N4。
(2) 2g Fe (NO) are weighed out3)2·6H2Mixing O and 6g of melamine uniformly, grinding to obtain mixed powder, heating the mixed powder under the protection of argon, heating to 700 ℃ at a heating rate of 10 ℃/min, calcining for 1.5h, naturally cooling to room temperature to obtain a crude product, soaking the obtained crude product in 200mL of concentrated hydrochloric acid with the molar concentration of 4mol/L for 25h, slowly pouring out the concentrated hydrochloric acid, and washing the crude product with water for several times to obtain CNFe.
(3) 2.7g g-C3N4, 4.5g TiO20.10mg of CNFe and 100mL of absolute ethyl alcohol are mixed uniformly, then ultrasonic dispersion is carried out for 30min to obtain suspension, and the suspension is stirred and dried at constant temperature under 50 ℃ through a constant-temperature heating stirrer to form a solid intermediate product.
(4) Grinding the prepared intermediate product into powder, heating to 300 ℃ at the heating rate of 4 ℃/min under the protection of nitrogen, calcining for 40min, then continuously heating to 500 ℃ at the heating rate of 4 ℃/min, and calcining for 1h to obtain nanoparticles, namely the ternary composite photocatalytic material (TCNCNFe)-500)。
Comparative example 1
Putting 20g of melamine into an alumina crucible with a cover, putting the crucible into a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, calcining for 5 hours at the temperature, grinding by using an agate mortar, and collecting powder to obtain graphitized carbon nitride (g-C)3N4)。
Comparative example 2
2g Fe (NO) are weighed out3)2·6H2Mixing O and 2g of melamine uniformly, grinding to obtain mixed powder, heating the mixed powder under the protection of nitrogen, heating to 700 ℃ at the heating rate of 5 ℃/min, calcining for 1.5h, naturally cooling to room temperature to obtain a crude product, soaking the obtained crude product in 200mL of concentrated hydrochloric acid with the molar concentration of 3mol/L for 24h, slowly pouring out the concentrated hydrochloric acid, and washing the crude product with water for several times to obtain the iron nano tube (CNFe).
Comparative example 3
(1) 5g g-C3N4、7.5g TiO2And 90mL of absolute ethyl alcohol are mixed uniformly, then ultrasonic dispersion is carried out for 30min to obtain suspension, and the suspension is stirred and dried at constant temperature at 70 ℃ by a constant-temperature heating stirrer to form a solid intermediate product.
(2) Grinding the prepared intermediate product into powder, heating to 300 ℃ at the heating rate of 4 ℃/min under the protection of nitrogen, calcining for 40min, then continuously heating to 500 ℃ at the heating rate of 4 ℃/min, and calcining for 1h to obtain nano particles, namely g-C3N4/TiO2A binary composite photocatalytic material.
Application example 1
(1) Adding 100mL of aqueous solution containing carbamazepine into a reactor, wherein the pH of the aqueous solution is regulated and controlled by 0.1M HCl or NaOH, the initial concentration of the carbamazepine is 5mg/L, and the pH value is 7;
(2) adding Peroxymonosulfate (PMS) and the three-way composite photocatalytic material prepared in the example 1 into a prepared aqueous solution containing carbamazepine, wherein the three-way composite photocatalytic material (TCNCNFe)-500) The adding amount of the catalyst is 0.50g/L, the adding amount of PMS is 2mM, and before illumination, an adsorption experiment is carried out for 30min in the dark to realize the full contact between the carbamazepine and the photocatalyst so as to establish adsorption balance;
(3) placing a 300W xenon lamp with a filter (400nm) horizontally outside the reactor as a visible light source, and measuring the average light intensity on the surface of the reaction solution in the reactor by a photon densitometer to be 200mW/cm2I.e. 2 standard solar intensities (AM 3G). To maintain a constant reaction temperature, a cooling water circulation system was applied around the reactor and the experiment was performed with slow magnetic stirring.
The concentration change of carbamazepine in the solution is monitored and analyzed by a high performance liquid chromatograph, the detection result is shown in figure 4, and figure 4 shows that TCNCNFe-500After the aqueous solution containing carbamazepine is treated for 5min, the residual rate of the carbamazepine (residual rate which is the residual amount of the carbamazepine/initial amount) is 0, namely the removal rate of the carbamazepine of the ternary composite photocatalytic material prepared in example 1 is as high as 100% after 5 min.
Application comparative example 1
The procedure was as in application example 1, except that the three-way composite photocatalytic material obtained in example 1 in step (2) was replaced with graphitized carbon nitride obtained in comparative example 1 (in the same amount as the three-way composite photocatalytic material).
The concentration change of carbamazepine in the solution was monitored and analyzed by a high performance liquid chromatograph, and the detection result is shown in fig. 4, and fig. 4 shows that after 5min, the residue rate of carbamazepine was 98%, that is, the removal rate of the graphitized carbon nitride prepared in comparative example 1 to carbamazepine was only 3%.
Comparative application example 2
The procedure was the same as in application example 1, except that the ternary composite photocatalytic material obtained in example 1 in step (2) was replaced with the iron nanotubes obtained in comparative example 2 (the amount of the iron nanotubes added was the same as that of the ternary composite photocatalytic material).
The concentration change of carbamazepine in the solution was monitored and analyzed by a high performance liquid chromatograph, and the experimental result is shown in fig. 4, and fig. 4 shows that after 5min, the residue rate of carbamazepine was 0, that is, the removal rate of the iron nanotubes prepared in comparative example 2 to carbamazepine was only 100%.
Comparative application example 3
The procedure was as in application example 1, except that the ternary composite photocatalytic material obtained in example 1 in step (2) was replaced with g-C obtained in comparative example 33N4/TiO2(the input amount is the same as that of the ternary composite photocatalytic material).
The concentration change of carbamazepine in the solution was monitored and analyzed by HPLC, and the detection results are shown in FIG. 4. FIG. 4 shows that after 5min, the residual rate of carbamazepine was 80%, i.e., g-C prepared in comparative example 33N4/TiO2The removal rate of carbamazepine was only 20%.
Application comparative example 4
The procedure is the same as in application example 1, except that the ternary composite photocatalytic material prepared in step (2) in example 1 is replaced with commercially available ordinary titanium dioxide nanoparticles (the amount of the added particles is the same as that of the ternary composite photocatalytic material).
The concentration change of the carbamazepine in the solution is monitored and analyzed by a high performance liquid chromatograph, the detection result is shown in figure 4, and figure 4 shows that after 5min, the residue rate of the carbamazepine is 98%, and the removal rate of common titanium dioxide nanoparticles to the carbamazepine after 5min is only about 2%.
Meanwhile, the degree of mineralization in the aqueous solution of carbamazepine was measured by a Total Organic Carbon (TOC) analyzer, and the results are shown in table 1.
TABLE 1 mineralization Capbamazepine capable of being obtained in various applications
As can be seen from Table 1, the mineralization degree of the carbamazepine by the application comparative examples is lower, while the mineralization degree of the ternary composite photocatalytic material prepared in the embodiment 1 of the invention is better.
The ternary composite photocatalytic material prepared in example 1 was observed by a Scanning Electron Microscope (SEM), and the result is shown in fig. 1; while it was observed with a Transmission Electron Microscope (TEM), the result is shown in fig. 2; the ternary composite photocatalytic material prepared in example 1 was detected by a fourier infrared spectrometer, and the result is shown in fig. 3.
As can be seen from FIG. 1, TiO modified by doping with Fe nanotubes2/g-C3N4The original sheet shape and particle shape are still maintained.
As can be seen from fig. 2, titanium dioxide can be uniformly distributed on the flake-shaped graphitized carbon nitride, and the agglomeration of titanium dioxide is obviously inhibited.
As can be seen from FIG. 3, the characteristic functional groups of both titanium dioxide and graphitized carbon nitride are in the ternary composite photocatalytic material (TCNCNFe)-500) Is also disclosed.
Further, the three-component composite photocatalytic material obtained in example 1 was subjected to the cycle stability test according to the method of application example 1, and the results are shown in fig. 5, and the iron nanotubes obtained in comparative example 2 were subjected to the cycle stability test according to the method of application example 1 (treatment time per cycle was 5 minutes), and the results are shown in fig. 6:
as can be seen from fig. 5, after 5 continuous cycles, after the aqueous solution containing carbamazepine is treated for 5min, the ternary composite photocatalytic material prepared in example 1 of the present invention has a residual rate of carbamazepine of only less than 10%, that is, the ternary composite photocatalytic material still has a removal rate of above 90% for carbamazepine. As can be seen from fig. 6, the iron nanotubes prepared in comparative example 2 according to the present invention had a 33% removal rate of carbamazepine after treating an aqueous solution containing carbamazepine for 5min at the 2 nd cycle, a 10% removal rate of carbamazepine at the 3 rd cycle, a 8% removal rate at the 4 th cycle, and a 1% removal rate at the 5 th cycle.
From the above, it can be seen that the ternary composite photocatalytic material prepared in example 1 of the present invention has a photocatalytic activity higher than that of the graphitized carbon nitride, the common titanium dioxide nanoparticles and g-C of the comparative example3N4/TiO2The removal rate of the carbamazepine is better, the mineralization degree of the carbamazepine is better than that of the comparative examples 1-4, and although the iron nano tube provided by the comparative example 2 has better removal rate of the carbamazepine, the iron nano tube has poor cycle stability, namely, poor practicability and higher cost.
It should be noted that, since the principle of the ternary composite photocatalytic material of examples 2-4 is the same as that of example 1, the morphological structure and catalytic performance are similar to those of example 1, and are not described herein again.
In conclusion, the raw materials, the preparation steps and the preparation conditions are designed, so that the prepared ternary composite photocatalytic material has good catalytic rate and mineralization degree on carbamazepine, and has good cycle stability and photocatalytic activity and strong practicability.
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. The three-element composite photocatalytic material is characterized by comprising titanium dioxide, graphitized carbon nitride and an iron nano tube, wherein the graphitized carbon nitride is used as a carrier, the iron nano tube and part of the titanium dioxide are loaded on the graphitized carbon nitride, and the rest part of the titanium dioxide is attached to the iron nano tube.
2. A method for preparing the three-component composite photocatalytic material as recited in claim 1, comprising the steps of:
s10, mixing Fe (NO)3)2·6H2Mixing O and melamine uniformly, crushing to obtain mixed powder, heating the mixed powder under the protection of nitrogen or inert gas, heating to 600-800 ℃, calcining for 1-2 h, cooling to obtain a crude product, and purifying the crude product to obtain an iron nano tube;
s20, dispersing the graphitized carbon nitride, the titanium dioxide and the iron nano tube in absolute ethyl alcohol to obtain a suspension, and drying the suspension to obtain a solid intermediate product;
s30, crushing the intermediate product, heating to T1 for calcining for 30-60 min in an inert gas or nitrogen atmosphere, and then continuously heating to T2 for calcining for 1-2 h to obtain a ternary composite photocatalytic material;
wherein the T1 is 200-300 ℃, the T2 is 300-500 ℃, and T1 is less than T2.
3. The method for preparing a three-way composite photocatalytic material as set forth in claim 2, wherein before step S20, the method further comprises the steps of:
and calcining the melamine at 500-600 ℃ for 3-8 h, and then crushing the melamine into powder to obtain the graphitized carbon nitride.
4. The method for preparing a three-way composite photocatalytic material as set forth in claim 2, wherein in step S10:
the purification treatment comprises the following steps: and soaking the crude product in concentrated hydrochloric acid for 20-28 h, and then washing the crude product with water for multiple times to obtain the iron nano tube.
5. The method for preparing a three-way composite photocatalytic material as set forth in claim 2, wherein in step S10:
said Fe (NO)3)2·6H2The mass ratio of O to melamine is 0.5-2: 0.5 to 6; and/or the presence of a gas in the gas,
and in the process of heating to 600-800 ℃, the heating rate is 2-20 ℃/min.
6. The method for preparing a three-way composite photocatalytic material as set forth in claim 2, wherein in step S20:
the mass-volume ratio of the graphitized carbon nitride to the titanium dioxide to the iron nanotube to the absolute ethyl alcohol is 1.5-3.2 g: 2.4-6.3 g: 0.03g to 0.15 g: 90-110 mL.
7. The method for preparing a three-way composite photocatalytic material as set forth in claim 2, wherein step S20 includes:
uniformly mixing the graphitized carbon nitride, titanium dioxide, the iron nano tube and absolute ethyl alcohol, and then performing ultrasonic dispersion for 20-40 min to obtain a suspension;
and (3) stirring the suspension and drying at a constant temperature of 50-70 ℃ to obtain a solid intermediate product.
8. The method for preparing a three-way composite photocatalytic material as set forth in claim 2, wherein in step S30:
in the process of heating to T1, the heating rate is 3-5 ℃/min; and/or the presence of a gas in the gas,
and in the process of heating to T2, the heating rate is 3-5 ℃/min.
9. A method for degrading PPCPs in water, comprising treating an aqueous solution containing PPCPs with the three-way composite photocatalytic material of claim 1.
10. The method for degrading PPCPs in water of claim 9, wherein said PPCPs comprise carbamazepine.
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