CN111185210B - Titanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst and preparation method and application thereof - Google Patents

Titanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst and preparation method and application thereof Download PDF

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CN111185210B
CN111185210B CN202010042527.6A CN202010042527A CN111185210B CN 111185210 B CN111185210 B CN 111185210B CN 202010042527 A CN202010042527 A CN 202010042527A CN 111185210 B CN111185210 B CN 111185210B
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black phosphorus
phosphorus nanosheet
titanium dioxide
composite photocatalyst
trititanium
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CN111185210A (en
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邵彬彬
刘智峰
童设华
龚维友
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Hunan Dalong Environmental Technology Co ltd
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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
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
    • 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 composite photocatalyst of tricotitanium dicarbonide/titanium dioxide/black phosphorus nanosheet and a preparation method and application thereof. The composite photocatalyst is prepared by using a black phosphorus nanosheet as a carrier, modifying the surface of the black phosphorus nanosheet with a few layers of tricotitanium dicarbonide and growing titanium dioxide in situ in the few layers of the tricotitanium dicarbonide. The preparation method comprises the steps of preparing a black phosphorus nanosheet suspension, preparing few-layer trititanium dicarbonate, and adding the few-layer trititanium dicarbonate into the black phosphorus nanosheet suspension for hydrothermal reaction to obtain a product. The composite photocatalyst has the advantages of strong light absorption capacity, low photoproduction electron-hole recombination rate, good photocatalytic performance, good stability, simple preparation method, easily controlled conditions and low cost, and is suitable for large-scale industrial production. The composite photocatalyst can be used for degrading antibiotic wastewater, and has the advantages of high degradation efficiency, good removal effect, high safety, no secondary pollution and good practical application prospect.

Description

Titanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalysis, relates to a composite photocatalyst, and particularly relates to a composite photocatalyst of titanium carbide triticum dicarbonide/titanium dioxide/black phosphorus nanosheet and a preparation method and application thereof.
Background
With the development and progress of society, antibiotic drugs have been widely used, and their overuse and incomplete metabolism make antibiotics often detected in natural water, sewage, soil and other environmental media, and these unmetabolized antibiotics are likely to affect the development of biological cells, the circulation of ecosystem and promote the propagation of drug-resistant pathogenic bacteria, thereby adversely affecting the ecological environment and human health. At present, common methods for removing antibiotics in water environments at home and abroad comprise a biological method, a physicochemical method, an electrochemical method and a filtration method. Although the biological method is low in cost, the required time is long, and the removal effect is interfered by multiple factors. The electrochemical method has high unit treatment cost for low-concentration pollutants, and is difficult to use on a large scale. Filtration simply transfers contaminants from one phase to another and does not mineralize them into carbon dioxide and water. Photocatalytic degradation in physicochemical methods can be seen as an effective and environmentally friendly method. However, in the previous studies, the following problems still remain in the photocatalyst used for photocatalytic degradation: the method has the advantages of low light utilization efficiency, fast photoproduction electron-hole recombination, poor photocatalytic performance, poor stability and the like, and greatly limits the wide application of photocatalytic degradation due to a large number of defects of the photocatalyst. Therefore, how to comprehensively improve the problems and defects in the existing photocatalytic degradation technology to obtain a photocatalyst with strong light absorption capability, low photoproduction electron-hole recombination rate, high photocatalytic performance and good stability is of great significance for popularizing the application of the photocatalytic degradation technology in treating antibiotics.
A large number of materials have been found to have photocatalytic properties to date, which mainly include metal-based photocatalytic materials and non-metal-based photocatalytic materials. Compared with a metal-based photocatalyst, the nonmetal-based photocatalyst has more advantages, such as low price, no secondary pollution, simple preparation method and the like. In recent years, various non-metallic photocatalysts have been widely studied, such as graphite-phase carbon nitride, hexagonal boron nitride, black phosphorus, and the like. Among them, black phosphorus is the simplest non-metallic photocatalyst, which contains only one element, phosphorus. Through research, the black phosphorus has various excellent characteristics, such as adjustable band gap (0.3 eV-2.1 eV), high-efficiency carrier transport capacity and good response to light. Compared with the massive black phosphorus crystal, the black phosphorus nanosheet has better photocatalytic performance. However, since black phosphorus nanoplates are easily oxidized, there are many challenges to be directly applied to practical use. In order to improve the practical application possibility, various methods have been developed to modify the semiconductor device, such as doping elements, constructing a heterojunction, etc. The heterojunction is constructed by compounding the black phosphorus nanosheet with other materials to form a heterojunction photocatalytic system, and the heterojunction system can obviously improve the stability of the black phosphorus nanosheet and can accelerate the photoproduction electron-hole separation speed at the same time, so that the photocatalytic performance of the photocatalyst is improved. However, the existing black phosphorus-based heterojunction photocatalytic material still has the problems of weak light absorption capacity, slow photoproduction electron-hole separation rate and the like, which limits the photocatalytic performance of the material. Therefore, how to comprehensively solve the problems of weak light absorption capacity, slow photoproduction electron-hole separation rate, poor photocatalysis performance and the like in the existing black phosphorus-based heterojunction material, the composite photocatalyst with strong light absorption capacity, low photoproduction electron-hole recombination rate, high photocatalysis performance and good stability and the preparation method of the composite photocatalyst matched with the composite photocatalyst with simple process, easily controlled conditions and low cost are obtained, and the method has important significance for further expanding the application range of the photocatalysis technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the tricotitanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst with strong light absorption capacity, low photoproduction electron-hole recombination rate, high photocatalytic performance and good stability, also provides a preparation method of the tricotitanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst with simple process, easily controllable conditions and low cost, and correspondingly provides the application of the tricotitanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst in photocatalytic degradation of antibiotics.
In order to solve the technical problems, the invention adopts the following technical scheme:
a composite photocatalyst of tricotitanium dicarbonide/titanium dioxide/black phosphorus nanosheet is prepared by using the black phosphorus nanosheet as a carrier, modifying a few layers of tricotitanium dicarbonide on the surface of the black phosphorus nanosheet, and growing titanium dioxide in situ in the few layers of the tricotitanium dicarbonide.
Preferably, the mass ratio of the few-layer tricotitanium dicarbonide to the black phosphorus nanosheet is 1-3: 10-20.
As a general technical concept, the invention also provides a preparation method of the composite photocatalyst of the titanium tricarboxide/titanium dioxide/black phosphorus nanosheet, which is characterized by comprising the following steps:
and S1, adding the black phosphorus crystal block into water, and carrying out continuous ultrasonic treatment under the conditions of inert gas and ice-water bath to obtain the black phosphorus nanosheet suspension.
S2, etching titanium aluminum carbide in acid liquor, and then performing ultrasonic intercalation on the etching product in ethanol to obtain few-layer trititanium dicarbonide;
s3, adding the few-layer trititanium dicarbonate obtained in the step S2 into the black phosphorus nanosheet suspension obtained in the step S1 to perform hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 120-150 ℃, and the time of the hydrothermal reaction is 3-6 hours, so that the trititanium dicarbonate/titanium dioxide/black phosphorus nanosheet composite photocatalyst is obtained.
Preferably, in the step S3, the concentration of the black phosphorus nanosheet suspension is 0.1mg/mL to 0.2mg/mL, and the mass-to-volume ratio of the few-layer tricontanium carbide to the black phosphorus nanosheet suspension is 1mg to 3 mg: 100 mL.
Preferably, in the step S1, the mass-to-volume ratio of the black phosphorus crystal block to water is 30 mg-60 mg: 100 mL-200 mL, the water is deoxidized ultrapure water, the inert gas is nitrogen, the continuous ultrasonic time is 12 h-24 h, and the composite photocatalyst is centrifuged at 2000 rpm-3000 rpm after the continuous ultrasonic is completed.
In the above preparation method of the trititanium dicarbocarbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst, preferably, in step S3, the hydrothermal reaction is performed under the conditions of no acid, no alkali and no reducing agent.
In the preparation method of the trititanium dicarbonide/titanium dioxide/black phosphorus nanosheet composite photocatalyst, preferably, in the step S2, the number of the few layers of trititanium dicarbonide is 1-5, and more preferably 1-3.
The preparation method of the composite photocatalyst of the titanium carbide/titanium dioxide/black phosphorus nanosheet is preferable, in the step S2, the mass-volume ratio of the titanium aluminum carbide to the acid solution is 2 g-3 g: 40 mL-60 mL, the acid solution is obtained by the reaction of lithium fluoride and hydrochloric acid solution, the mass volume ratio of the lithium fluoride to the hydrochloric acid solution is 6-8 g: 100mL, the concentration of the hydrochloric acid solution is 9-10 mol/L, the particle size of the titanium aluminum carbide is 200-400 meshes, the etching is carried out for 24-48 h under the stirring at the temperature of 40-60 ℃, then centrifuging at 6000 rpm-8000 rpm, washing until the pH value is 6-7, wherein the time of ultrasonic intercalation is 3 h-6 h, then centrifuging at 3000 rpm-4000 rpm to obtain upper suspension, centrifuging the upper suspension at 11000 rpm-12000 rpm, and vacuum drying to obtain the low-layer trititanium carbide.
As a general technical concept, the invention also provides an application of the tricotitanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst or the tricotitanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst prepared by the preparation method in degradation of antibiotic wastewater.
The above application, preferably, comprises the steps of: mixing the tricotitanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst with antibiotic wastewater, stirring under a dark condition, carrying out photocatalytic reaction under an illumination condition after adsorption balance is achieved, and finishing the treatment of antibiotics.
In the application, preferably, the antibiotic in the antibiotic wastewater is tetracycline hydrochloride, the concentration of the tetracycline hydrochloride is 10 mg/L-20 mg/L, and the composition is carried outThe mass volume ratio of the photocatalyst to the tetracycline hydrochloride is 0.5-1 g: 1L, the stirring speed is 400-600 rpm, and the stirring time is 30-60 min; the photocatalytic reaction is carried out under the irradiation of a xenon lamp, and the intensity of visible light irradiated by the xenon lamp is 100mW cm-2～120mW cm-2The time of the photocatalytic reaction is 60-120 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a tricotitanium dicarbonide/titanium dioxide/black phosphorus nanosheet composite photocatalyst, which is prepared by using a black phosphorus nanosheet as a carrier, modifying a few layers of tricotitanium dicarbonide on the surface of the black phosphorus nanosheet and growing titanium dioxide in situ in the few layers of the tricotitanium dicarbonide; the composite photocatalyst has the advantages of strong light absorption capacity, low photoproduction electron-hole recombination rate, good photocatalytic performance, good stability and the like, is a novel photocatalytic material, and has good application prospect in the fields of energy and environment.
According to the invention, the black phosphorus nanosheet and the few-layer tricopeptide carbide are compounded, titanium dioxide is generated in the few-layer tricopeptide carbide to form a ternary heterojunction structure, a Schottky junction can be formed between the titanium dioxide and the tricopeptide carbide, and the stability and the photocatalytic performance of the composite photocatalyst are obviously improved through the synergistic effect of the titanium dioxide and the tricopeptide carbide. The few-layer trititanium carbide is an excellent conductive material, can quickly transfer photogenerated electrons on the surface of the black phosphorus nanosheet, has a photosensitive characteristic, can enhance the response of the composite photocatalyst to visible light, can inhibit the problem that the black phosphorus nanosheet is easily oxidized when exposed in the air, obviously improves the stability of the black phosphorus nanosheet, and further improves the stability of the composite photocatalyst. Meanwhile, the Schottky junction formed between the few layers of the titanium carbide and the titanium dioxide can change the transmission path of electrons, remarkably accelerate the separation efficiency of photoproduction electrons and holes and reduce the recombination of the photoproduction electrons and the holes. Compared with multilayer titanium dicarbonide, the few-layer titanium dicarbonide has larger specific surface area, more exposed reactive active sites, more abundant functional groups at surface terminals, and less layers, which are more beneficial to the migration of electrons, thereby being beneficial to improving the catalytic performance of the material. Meanwhile, the few-layer tricotitanium dicarbonide is obtained by ultrasonic stripping of multiple layers of tricotitanium dicarbonide, certain metal defects or oxygen defects can be caused on the surface of the tricotitanium dicarbonide in the stripping process, the formation of the defects can also increase the response of materials to light, improve the separation efficiency of photoproduction electrons and holes, increase reaction active sites, and is beneficial to the photocatalysis process. The excellent characteristics enable the photocatalytic performance of the composite photocatalyst to be obviously improved.
In the research, the inventor finds that although the black phosphorus nanosheet and the titanium carbide/titanium dioxide have high response to visible light, the removal effect of the black phosphorus nanosheet and the titanium carbide/titanium dioxide on antibiotics under the irradiation of the visible light is poor, and the inventor repeatedly researches and combines two catalysts with poor removal effects to obtain a composite photocatalyst with a good removal effect on the antibiotics under the irradiation of the visible light, so that an unexpected technical effect is achieved.
(2) According to the composite photocatalyst of the tricontanium carbide/titanium dioxide/black phosphorus nanosheet, the mass ratio of few layers of the tricontanium carbide to the black phosphorus nanosheet is controlled to be 5-15: 100, so that the composite photocatalyst has better photocatalytic performance. This is because the few layers of trititanium dicarbonide have a significant effect on the performance of the black phosphorus nanoplates. For example, when the mass ratio of the few-layer tricopeptide carbide to the black phosphorus nanosheet is higher than 15: 100, the excessive doping amount of the few-layer tricopeptide carbide can reduce the responsiveness of the black phosphorus nanosheet to visible light, because the excessive doping amount of the few-layer tricopeptide carbide can cause excessive titanium dioxide generated in a hydrothermal process, according to the research of the inventor, the titanium dioxide generated in the hydrothermal process is nonresponsive to visible light, and thus the photocatalytic performance of the composite photocatalyst is reduced; when the mass ratio of the few-layer tricotitanium dicarbonide to the black phosphorus nanosheet is lower than 5: 100, the doping amount of the few-layer tricotitanium dicarbonide is too small, so that a plurality of active sites of the black phosphorus nanosheet are exposed outside, the stability of the black phosphorus nanosheet is reduced, the photocatalytic performance of the black phosphorus nanosheet cannot be better exerted, and the photocatalytic performance of the composite material is reduced.
(3) The preparation process of the composite photocatalyst is simple, only a few layers of tricotitanium dicarbonide are added into the suspension of the black phosphorus nanosheet for hydrothermal reaction, so that the few layers of tricotitanium dicarbonide are modified on the surface of the black phosphorus nanosheet, simultaneously titanium dioxide is synchronously generated in the few layers of the tricotitanium dicarbonide, the reaction is completed in one step, the reaction is only carried out in water, and the acid or alkali environment and the later high-temperature treatment of the conventional hydrothermal reaction are not needed.
The preparation of the black phosphorus nanosheet suspension only needs continuous ultrasound in low-temperature oxygen-free water, and does not need to add ionic liquid, organic solvent and the like.
(4) The invention also provides the application of the tricotitanium dicarbonide/titanium dioxide/black phosphorus nanosheet composite photocatalyst in degrading antibiotic wastewater, and the method is simple in steps, high in degradation efficiency, high in safety, free of secondary pollution, good in reusability of the composite photocatalyst and good in practical application prospect.
Drawings
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 with reference to the drawings in the embodiments of the present invention.
FIG. 1 is an SEM image of a trititanium dicarbonate/titanium dioxide/black phosphorus nanosheet composite photocatalyst (TCTBP-15), a black phosphorus nanosheet (BP), a few-layer trititanium dicarbonate (TC) prepared in example 1 of the present invention, and a trititanium dicarbonate/titanium dioxide (TCT) prepared in comparative example 1, wherein A is BP, B is TC, C is TCT, and D is TCTBP-15.
FIG. 2 is a TEM image of a trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst (TCTBP-15) prepared in example 1 of the present invention, a black phosphorus nanosheet (BP), a few-layer Trititanium Carbide (TC), and a trititanium carbide/titanium dioxide (TCT) prepared in comparative example 1, wherein A is BP, B is TC, C is TCT, and D is TCTBP-15.
FIG. 3 is an XRD diagram of the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst (TCTBP-15, TCTBP-10, TCTBP-5), black phosphorus nanosheet (BP), few-layer Trititanium Carbide (TC) and trititanium carbide/titanium dioxide (TCT) prepared in examples 1, 2 and 3 of the present invention.
FIG. 4 is a UV-visible diffuse reflectance spectrum of the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst (TCTBP-15, TCTBP-10, TCTBP-5), black phosphorus nanosheet (BP), few-layer Trititanium Carbide (TC) and trititanium carbide/titanium dioxide (TCT) prepared in examples 1, 2 and 3 of the present invention.
Fig. 5 is a photoluminescence curve diagram of the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst (TCTBP-15) and the black phosphorus nanosheet (BP) prepared in example 1 of the present invention.
FIG. 6 is a graph showing the degradation effect of trititanium dicarbonate/titanium dioxide/black phosphorus nanosheet composite photocatalyst (TCTBP-15, TCTBP-10, TCTBP-5), black phosphorus nanosheet (BP) and trititanium dicarbonate/titanium dioxide (TCT) on tetracycline hydrochloride prepared in examples 1, 2 and 3 of the present invention.
Fig. 7 is a graph of the degradation effect of the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst (TCTBP-15) prepared in example 1 of the present invention when tetracycline hydrochloride solution is repeatedly treated.
Fig. 8 is a graph of the degradation effect of tetracycline hydrochloride after the capture agent is added when the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst (TCTBP-15) prepared in embodiment 1 of the present invention catalyzes and degrades tetracycline hydrochloride in a water body.
FIG. 9 is a catalytic degradation mechanism diagram of the composite photocatalyst of tricotitanium dicarbonide/titanium dioxide/black phosphorus nanosheet.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the examples of the present invention, the raw materials and instruments used are commercially available unless otherwise specified. The data obtained are the average of three or more replicates.
Example 1
The invention relates to a tricotitanium dicarbonide/titanium dioxide/black phosphorus nanosheet composite photocatalyst, which is prepared by using a black phosphorus nanosheet as a carrier, modifying a few layers of tricotitanium dicarbonide on the surface of the black phosphorus nanosheet and growing titanium dioxide in situ in the few layers of the tricotitanium dicarbonide.
The mass ratio of the few-layer titanium dicarbonide to the black phosphorus nanosheet used in this example was 15: 100.
The preparation method of the composite photocatalyst of trititanium dicarbocarbide/titanium dioxide/black phosphorus nanosheet of the embodiment includes the following steps:
(1) adding 30mg of black phosphorus crystal blocks into 100mL of deoxidized ultrapure water, continuously performing ultrasonic treatment for 12h under the protection of nitrogen, centrifuging at 3000rpm for 3min to remove the black phosphorus crystal blocks which are not ultrasonically stripped, and obtaining black phosphorus nanosheet suspension with the concentration of 0.2mg/mL, which is recorded as BP.
(2) 6g of lithium fluoride is dissolved in 100mL of hydrochloric acid solution with the concentration of 9mol/L to prepare acid solution, then 40mL of the acid solution is slowly added into 2g of titanium aluminum carbide powder with the size of 200-400 meshes, and then the mixture is stirred for 48 hours at the temperature of 40 ℃. The mixture was then centrifuged at 6000rpm for 5min to remove the acid solution and washed with deoxygenated ultrapure water several times until the pH was 6. The resulting black material was then transferred to 100mL absolute ethanol and sonication continued for 3 h. And centrifuging at 3000rpm for 5min to obtain an upper suspension, centrifuging at 11000rpm for 5min to obtain a black residue, and drying the obtained black residue in a vacuum drying oven at 60 ℃ for 12h to obtain a few-layer trititanium carbide, wherein the number of the few-layer trititanium carbide is 3 and the total thickness is about 4.7 nm.
(3) Adding 3mg of the few-layer trititanium dicarbonate obtained in the step (2) into 100mL of the black phosphorus nanosheet suspension obtained in the step (1), stirring for 1h under the protection of nitrogen, then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 3h at 120 ℃, filtering out the obtained substance after natural cooling, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain the trititanium dicarbonate/titanium dioxide/black phosphorus nanosheet composite photocatalyst which is marked as TCTBP-15.
Example 2
The preparation method of the composite photocatalyst of the invention is basically the same as the embodiment 1, and the difference is only that: in the step (3), the few-layer trititanium dicarbonide is 2mg, the mass ratio of the trititanium dicarbonide/titanium dioxide to the black phosphorus nanosheet is 10: 100, and the obtained trititanium dicarbonide/titanium dioxide/black phosphorus nanosheet composite photocatalyst is marked as TCTBP-10.
Example 3
The preparation method of the composite photocatalyst of the invention is basically the same as the embodiment 1, and the difference is only that: in the step (3), the few-layer trititanium dicarbonide is 1mg, the mass ratio of the trititanium dicarbonide/titanium dioxide to the black phosphorus nanosheet is 5: 100, and the obtained trititanium dicarbonide/titanium dioxide/black phosphorus nanosheet composite photocatalyst is marked as TCTBP-5.
Comparative example 1
A preparation method of trititanium dicarbocarbide/titanium dioxide comprises the following steps:
adding 2mg of the small-layer trititanium dicarbonide obtained in example 1 into 100mL of ultrapure water, stirring for 1h under the protection of nitrogen, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 3h at 120 ℃, filtering out the obtained substance after natural cooling, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain the trititanium dicarbonide/titanium dioxide photocatalyst which is marked as TCT.
FIG. 1 is an SEM image of a black phosphorus nanosheet BP, a few-layer trititanium dicarbonate TC, the trititanium dicarbonate/titanium dioxide TCT prepared in comparative example 1 and the trititanium dicarbonate/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15 prepared in example 1, wherein A is BP, B is TC, C is TCT, and D is TCTBP-15. FIG. 2 is a TEM image of a black phosphorus nanosheet BP, a few-layer trititanium dicarbonate TC, the trititanium dicarbonate/titanium dioxide TCT prepared in comparative example 1, and the trititanium dicarbonate/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15 prepared in example 1, wherein A is BP, B is TC, C is TCT, and D is TCTBP-15. As can be seen from fig. 1 and 2, BP, TC and TCT are all sheet structures, BP and TC are irregular structures, while TCT is a regular elliptical structure, and TCTBP-15 is an elliptical TCT formed by surface-to-surface contact with the sheet BP.
FIG. 3 is an XRD (X-ray diffraction) diagram of the tricotitanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15, TCTBP-10, TCTBP-5, black phosphorus nanosheet BP, few-layer tricotitanium carbide TC prepared in the examples 1, 2 and 3 of the invention and the tricotitanium carbide/titanium dioxide TCT prepared in the comparative example 1. As can be seen from fig. 3, BP exhibits (020), (021), (040), (060), (240) crystal face, TC exhibits (002), (004), (006), (105), (110) crystal face, and TCT has a peak of titanium dioxide in addition to a peak containing TC, and peaks of the trititanium dicarbocarbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15, TCTBP-10, and TCTBP-5 contain characteristic peaks of the above three monomer materials, which indicates that the trititanium dicarbocarbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst of the present invention is successfully synthesized.
FIG. 4 is a diagram of ultraviolet-visible diffuse reflection spectra of the tricontanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15, TCTBP-10, TCTBP-5, black phosphorus nanosheet BP, few-layer tricontanium carbide TC prepared in examples 1, 2 and 3 of the present invention and the tricontanium carbide/titanium dioxide TCT prepared in comparative example 1. As can be seen from fig. 4, each monomer and the composite photocatalyst have good light absorption for ultraviolet light and visible light, and particularly for TCT, the monomer and the composite photocatalyst have significant absorption for visible light, and when the TCT and the BP material form a trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst, the absorption of the composite material for visible light is significantly improved, so that the utilization rate of light is improved.
Fig. 5 is a photoluminescence curve graph of the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15 and the black phosphorus nanosheet BP prepared in example 1 of the present invention. As can be seen from fig. 5, the fluorescence intensity of the BP monomer material is relatively high, which indicates that the photogenerated electron-hole recombination of BP is fast. The fluorescence intensity of the composite photocatalyst of the tricontanium carbide/titanium dioxide/black phosphorus nanosheet is obviously reduced, which shows that the formed heterojunction system improves the separation efficiency of photo-generated electrons and holes and reduces the recombination of the photo-generated electrons and holes.
The results show that the titanium carbide/titanium dioxide/black phosphorus nanosheet prepared by the method has the advantages of strong light absorption capability, low photoproduction electron-hole recombination rate and the like.
Example 4
The performance of the composite photocatalyst for catalyzing and degrading the antibiotic wastewater by using the trititanium carbide/titanium dioxide/black phosphorus nanosheet is examined, and the method comprises the following steps:
taking examples 1, 2 and 3 of the present inventionRespectively taking 100mg of the tricotitanium dicarbonide/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15, TCTBP-10, TCTBP-5 and black phosphorus nanosheet BP prepared in the step (1) and the tricotitanium dicarbonide/titanium dioxide TCT prepared in the step (1), respectively adding the 100mL of tetracycline hydrochloride (TCH) solution with the concentration of 10mg/L, uniformly mixing, stirring and adsorbing the TCH under the dark condition of 30 ℃ and 500rpm, and basically achieving adsorption balance after 30 min; placing the mixed solution after reaching the adsorption balance at the average intensity of 100mW cm-2Xenon lamp (lambda)>420nm), and carrying out a photocatalytic reaction for 60min at the temperature of 30 ℃ and the rpm of 500 to finish the TCH treatment.
A TCH solution without any catalyst added was used as a blank.
FIG. 6 is a graph showing the effect of the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalysts TCTBP-15, TCTBP-10 and TCTBP-5 and black phosphorus nanosheet BP prepared in examples 1, 2 and 3 of the present invention on tetracycline hydrochloride degradation by the trititanium carbide/titanium dioxide TCT prepared in comparative example 1. As can be seen from fig. 6, compared with BP and TCT photocatalysts, the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15, TCTBP-10 and TCTBP-5 of the present invention has a very significant removing effect on TCH, particularly, the removing rate of TCTBP-15 on TCH reaches 92.7%, and in research, the inventors found that although BP and TCT both have high response to visible light (see fig. 4), the removing effect of TCH by using BP and TCT photocatalysts alone is very poor, and the removing rate is only 9.35% and 10.70%. Therefore, the composite photocatalyst of the tricotitanium dicarbonide/titanium dioxide/black phosphorus nanosheet has better photocatalytic performance, TCH in water can be removed more thoroughly, and other comparative photocatalysts BP and TCT cannot achieve the degradation effect.
Example 5
The stability of the composite photocatalyst for catalyzing and degrading the antibiotic wastewater by using the trititanium carbide/titanium dioxide/black phosphorus nanosheet is inspected, and the method comprises the following steps:
(1) 100mg of the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15 prepared in example 1 is added into 100mL of TCH solution with the concentration of 10mg/L, and the mixture is uniformly mixed with the TCH solutionTCH is stirred and adsorbed under the conditions of 30 ℃ and 500rpm, and the adsorption balance is basically achieved after 30 min; placing the mixed solution after reaching the adsorption balance at the average intensity of 100mW cm-2Xenon lamp (lambda)>420nm), and carrying out a photocatalytic reaction for 60min at the temperature of 30 ℃ and the rpm of 500 to finish the TCH treatment.
(2) And (3) after the treatment in the step (1) is finished, carrying out centrifugal separation on the mixed solution obtained after the degradation is finished at 6000rpm, removing the supernatant obtained by the centrifugal separation, adding 100mL of TCH solution with the concentration of 10mg/L, and repeatedly treating the TCH solution under the same condition as that in the step (1) for 4 times. The TCTBP-15 degradation efficiency on TCH was measured after each treatment and the results are shown in FIG. 7.
Fig. 7 is a diagram of the degradation effect of the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15 prepared in example 1 of the present invention when tetracycline hydrochloride solution is repeatedly treated. Fig. 7 shows that after 4 cycles of experiments, the trititanium dicarbonate/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15 of the present invention still exhibits a good degradation effect on TCH degradation, wherein the degradation rate on TCH after 4 cycles is still 82.59%, which indicates that the trititanium dicarbonate/titanium dioxide/black phosphorus nanosheet composite photocatalyst of the present invention has excellent stability.
Example 6
The method for investigating the generation condition of free radicals in the process of catalyzing and degrading the antibiotic wastewater by using the composite photocatalyst of the tricontanium carbide/titanium dioxide/black phosphorus nanosheet comprises the following steps:
(1) taking 4 parts of the trititanium dicarbocarbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15 prepared in example 1, adding 100mg of each part of the composite photocatalyst TCTBP-15 into 100mL of TCH solution with the concentration of 10mg/L, uniformly mixing, stirring and adsorbing TCH at 30 ℃ and 500rpm, and basically achieving adsorption balance after 30 min.
(2) To 4 parts of the mixture obtained in step (1) after adsorption equilibrium was reached, 1mmol of triethanolamine (TEA for trapping h) was added+) 1mmol of p-Benzoquinone (BQ) for trapping O2 -) 1mmol of isopropanol (IPA for OH capture) and a flow rate of 200mL/min pure nitrogen (N)2)。
(3) Placing each mixed solution obtained in the step (2) at an average intensity of 100mW cm-2Xenon lamp (lambda)>420nm), and carrying out a photocatalytic reaction for 60min at the temperature of 30 ℃ and the rpm of 500 to finish the TCH treatment.
Control group 1: no trapping agent is added, and the method specifically comprises the following steps: adding 100mg of the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15 prepared in example 1 into 100mL of TCH solution with the concentration of 10mg/L, uniformly mixing, adsorbing TCH at 30 ℃ and 500rpm, and basically achieving adsorption balance after 30 min; placing the mixed solution after reaching the adsorption balance at the average intensity of 100mW cm-2Xenon lamp (lambda)>420nm), and carrying out a photocatalytic reaction for 60min at the temperature of 30 ℃ and the rpm of 500 to finish the TCH treatment.
FIG. 8 is a graph showing the degradation effect of tetracycline hydrochloride after a capture agent is added when the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst TCTBP-15 prepared in example 1 of the present invention catalyzes and degrades tetracycline hydrochloride in a water body. As can be seen from FIG. 8, the degradation rate of TCH after addition of the scavenger was significantly reduced compared to that without addition of the radical scavenger, where the degradation rates of TCH after addition of triethanolamine, benzoquinone, isopropanol, and nitrogen were 87.82%, 47.39%, 70.16%, and 38.09%, respectively, indicating three radicals (h) and+，·O2 -OH) plays an important role in the photodegradation of TCH, where O2 -Has the greatest effect on TCH degradation, followed by OH, then h+And the dissolved oxygen in water plays an important role in the degradation system.
FIG. 9 is a degradation mechanism diagram of the composite photocatalyst of tricotitanium dicarbonide/titanium dioxide/black phosphorus nanosheet. As can be seen from FIG. 9, the efficient photocatalytic degradation of tetracycline hydrochloride by the trititanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst is due to the formation of a heterojunction structure, that is, under the illumination condition, electrons generated in a BP valence band are respectively transferred to a conduction band, so that a hole is generated. And the electrons in the BP conduction band are rapidly transferred to the conduction band of the titanium dioxide again, so that the electrons in the BP conduction band are rapidly transferred to the conduction band of the titanium dioxideThe conduction band of the titanium dioxide accumulates a large number of electrons. The electrons accumulated in the conduction band of titanium dioxide are further transferred to the titanium carbide. Meanwhile, the Schottky junction formed by the titanium tricarboxide and the titanium dioxide further prevents the backflow of electrons, so that the oxidability of the titanium tricarboxide is stronger and stronger, and oxygen can be converted into superoxide radical (O) with strong oxidability2 -) And further converted into a hydroxyl radical (. OH). Final tetracycline hydrochloride in O having strong oxidizing property2 -And OH, and a reducing cavity is degraded into carbon dioxide and water.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.

Claims (6)

1. A preparation method of a composite photocatalyst of tricotitanium carbide/titanium dioxide/black phosphorus nanosheet is characterized by comprising the following steps:
s1, adding the black phosphorus crystal block into water, and carrying out continuous ultrasonic treatment under the conditions of inert gas and ice-water bath to obtain a black phosphorus nanosheet suspension;
s2, etching titanium aluminum carbide in acid liquor, and then performing ultrasonic intercalation on the etching product in ethanol to obtain few-layer trititanium dicarbonide;
s3, adding the few-layer trititanium dicarbonate obtained in the step S2 into the black phosphorus nanosheet suspension obtained in the step S1 to perform hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 120-150 ℃, and the time of the hydrothermal reaction is 3-6 hours, so that the trititanium dicarbonate/titanium dioxide/black phosphorus nanosheet composite photocatalyst is obtained;
the composite photocatalyst is prepared by using a black phosphorus nanosheet as a carrier, modifying the surface of the black phosphorus nanosheet with a few layers of tricotitanium dicarbonide and growing titanium dioxide in situ in the few layers of the tricotitanium dicarbonide.
2. The preparation method of the trititanium dicarbonide/titanium dioxide/black phosphorus nanosheet composite photocatalyst as claimed in claim 1, wherein the mass ratio of the few-layer trititanium dicarbonide to the black phosphorus nanosheet is 1-3: 10-20.
3. The method for preparing the trititanium dicarbocarbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst according to claim 1, wherein in step S3, the concentration of the black phosphorus nanosheet suspension is 0.1mg/mL to 0.2mg/mL, and the mass-to-volume ratio of the few-layer trititanium dicarbocarbide to the black phosphorus nanosheet suspension is 1mg to 3 mg: 100 mL.
4. The method for preparing the composite photocatalyst of tricotitanium dicarbonide/titanium dioxide/black phosphorus nanosheet of claim 1, wherein in step S1, the mass-to-volume ratio of the black phosphorus crystal block to water is 30 mg-60 mg: 100 mL-200 mL, the water is deoxidized ultrapure water, the inert gas is nitrogen, the time of the continuous ultrasound is 12 h-24 h, and the centrifugation is performed at 2000 rpm-3000 rpm after the continuous ultrasound is completed.
5. The method for preparing the trititanium dicarbocarbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst as claimed in claim 1, wherein in step S3, the hydrothermal reaction is carried out in the absence of acid, alkali and a reducing agent;
and/or in the step S2, the number of the few-layer tricontanium carbide layers is 1-5.
6. The preparation method of the composite photocatalyst of tricontanium carbide/titanium dioxide/black phosphorus nanosheet according to any one of claims 1 to 5, wherein in step S2, the mass-to-volume ratio of the titanium aluminum carbide to the acid solution is 2g to 3 g: 40mL to 60mL, the acid solution is obtained by reacting lithium fluoride with a hydrochloric acid solution, the mass-to-volume ratio of the lithium fluoride to the hydrochloric acid solution is 6g to 8 g: 100mL, the concentration of the hydrochloric acid solution is 9mol/L to 10mol/L, the particle size of the titanium aluminum carbide is 200 to 400 meshes, the etching is performed by stirring at 40 ℃ to 60 ℃ for 24h to 48h, then centrifuging at 6000rpm to 8000rpm, washing to pH 6 to 7, the time of ultrasonic intercalation is 3h to 6h, then centrifuging at 3000rpm to 4000rpm to obtain an upper suspension, and centrifuging the upper layer suspension at 11000 rpm-12000 rpm, and drying in vacuum to obtain the few-layer trititanium carbide.
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