CN115069280A - Bismuth tungstate/titanium carbide quantum dot composite material and preparation method and application thereof - Google Patents

Bismuth tungstate/titanium carbide quantum dot composite material and preparation method and application thereof Download PDF

Info

Publication number
CN115069280A
CN115069280A CN202210759537.0A CN202210759537A CN115069280A CN 115069280 A CN115069280 A CN 115069280A CN 202210759537 A CN202210759537 A CN 202210759537A CN 115069280 A CN115069280 A CN 115069280A
Authority
CN
China
Prior art keywords
quantum dot
composite material
titanium carbide
dot composite
bismuth tungstate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210759537.0A
Other languages
Chinese (zh)
Other versions
CN115069280B (en
Inventor
孙彬
李华鹏
周国伟
刘德法
高婷婷
董旭晟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qilu University of Technology
Original Assignee
Qilu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN202210759537.0A priority Critical patent/CN115069280B/en
Publication of CN115069280A publication Critical patent/CN115069280A/en
Application granted granted Critical
Publication of CN115069280B publication Critical patent/CN115069280B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the technical field of advanced materials, relates to a photocatalyst, and particularly relates to a bismuth tungstate/titanium carbide quantum dot composite material as well as a preparation method and application thereof. Bi 2 WO 6 Dispersing the nano-sheets into a solvent, adding Ti under the stirring condition 3 C 2 Stirring the quantum dot solution in an inert atmosphere, and filtering and drying the stirred material to obtain the quantum dot solution. The invention is prepared by mixing Ti 3 C 2 Quantum dots and Bi 2 WO 6 The nano-sheets are compounded, so that the specific surface area of the composite material can be increased to provide more surface active sites, adsorption and degradation reactions on amoxicillin are promoted, and meanwhile, Ti 3 C 2 QuantumThe dots can capture electrons and are beneficial to promoting Bi 2 WO 6 The separation of the photo-generated electron hole pairs improves the photocatalytic performance of the photo-generated electron hole pairs.

Description

Bismuth tungstate/titanium carbide quantum dot composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of advanced materials, relates to a photocatalyst, and particularly relates to a bismuth tungstate/titanium carbide quantum dot composite material as well as a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Amoxicillin is one of the most widely used antibiotics at present, which cannot be completely absorbed in human body, and residual components are often discharged out of body along with metabolism, thereby bringing interference of water pollution, soil pollution, biological drug resistance and the like to the natural environment ecosystem. The conventional sewage treatment technology at present cannot effectively remove amoxicillin residues; biodegradation is easily limited by biological drug resistance; physical adsorption is time consuming and ineffective. The semiconductor photocatalysis technology becomes an ideal way for solving the problem due to the advantages of greenness, high efficiency, mild reaction conditions and the like.
Bismuth tungstate (Bi) 2 WO 6 ) As a narrow band gap semiconductor photocatalytic material with a perovskite layered structure, the material has good visible light activity and strong oxidation capacity, and is widely applied to the field of photocatalysis. However, Bi 2 WO 6 The defects of fast recombination of photon-generated carriers, small specific surface area and the like exist, and the further application of the photo-generated carriers in the field of photocatalysis is limited. To solve the problem of Bi 2 WO 6 By constructing Bi 2 WO 6 /Ti 3 C 2 The composite material can improve the photocatalytic activity. However, the inventors of the present invention have found, through studies, that Ti 3 C 2 The composite material is a two-dimensional (2D) laminated structure, the interlamellar stacking of the composite material is easy to occur due to Van der Waals force, the specific surface area of the composite material is increased very limitedly, and the performance of degrading amoxicillin by photocatalysis is influenced.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a bismuth tungstate/titanium carbide quantum dot composite material and a preparation method and application thereof, wherein titanium carbide (Ti) 3 C 2 ) Quantum dots and Bi 2 WO 6 The nano-sheets are compounded, so that the specific surface area of the composite material can be increased to provide more surface active sites, adsorption and degradation reactions on amoxicillin are promoted, and meanwhile, Ti 3 C 2 The quantum dots can capture electrons and are favorable for promoting Bi 2 WO 6 The separation of the photo-generated electron hole pairs improves the photocatalytic performance of the photo-generated electron hole pairs.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the bismuth tungstate/titanium carbide quantum dot composite material comprises Bi 2 WO 6 Nanosheets and titanium carbide quantum dots, the Ti 3 C 2 Quantum dots attached to Bi 2 WO 6 The surface of the nanoplatelets.
On the other hand, a preparation method of bismuth tungstate/titanium carbide quantum dot composite material, Bi 2 WO 6 Dispersing the nano-sheets into a solvent, adding Ti under the stirring condition 3 C 2 Stirring the quantum dot solution in an inert atmosphere, and filtering and drying the stirred material to obtain the quantum dot solution.
In a third aspect, the photocatalyst comprises an active ingredient and a carrier, wherein the active ingredient is the bismuth tungstate/titanium carbide quantum dot composite material.
In a fourth aspect, the bismuth tungstate/titanium carbide quantum dot composite material is applied to photocatalytic degradation of amoxicillin.
The invention has the beneficial effects that:
(1) bi prepared by the invention 2 WO 6 /Ti 3 C 2 The quantum dot composite material adopts a self-assembly strategy, is simpler, more efficient and energy-saving compared with other composite material preparation methods, has stable structure, is not easy to fall off among components, and can shorten the photon-generated carrier due to the close combination of interfacesThe transmission distance.
(2) The invention provides Bi 2 WO 6 /Ti 3 C 2 The quantum dot composite material has single Bi 2 WO 6 The obviously increased specific surface area can provide more reactive sites, and is beneficial to the adsorption and degradation reaction of reactants. At the same time, a specific content of Ti 3 C 2 The quantum dots are used as a cocatalyst, and the high conductivity of the quantum dots is favorable for promoting Bi 2 WO 6 The separation of photon-generated carriers, and research shows that the prepared Bi 2 WO 6 /Ti 3 C 2 The degradation efficiency of the quantum dot composite material on amoxicillin is obviously superior to that of single Bi 2 WO 6 And has selectivity to the photocatalytic degradation of amoxicillin.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows Bi prepared in examples 1 to 4 of the present invention 2 WO 6 And Bi 2 WO 6 /Ti 3 C 2 An X-ray diffraction pattern (XRD) of the quantum dot composite.
FIG. 2 shows Bi prepared in example 2 of the present invention 2 WO 6 /Ti 3 C 2 Transmission Electron Microscopy (TEM) of quantum dot composites.
FIG. 3 shows Bi prepared in example 2 of the present invention 2 WO 6 /Ti 3 C 2 Scanning Electron Microscopy (SEM) images of the quantum dot composites.
FIG. 4 shows Bi prepared in example 2 of the present invention 2 WO 6 /Ti 3 C 2 An element energy distribution surface scanning spectrum (EDS mapping) of the quantum dot composite material.
FIG. 5 shows Bi prepared in examples 1 to 4 of the present invention 2 WO 6 And Bi 2 WO 6 /Ti 3 C 2 A performance diagram of photocatalytic degradation of amoxicillin of the quantum dot composite material.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background, Ti is currently used 3 C 2 The bismuth tungstate/titanium carbide quantum dot composite material has a 2D structure, and has the problems that stacking is easy to occur among sheets, the surface area of a composite material system is improved to a limited extent, surface active sites are few, and the like, so that the photocatalytic degradation performance of amoxicillin needs to be improved.
A typical embodiment of the invention provides a bismuth tungstate/titanium carbide quantum dot composite material, which comprises Bi 2 WO 6 Nanosheets and titanium carbide quantum dots, the Ti 3 C 2 Quantum dots attached to Bi 2 WO 6 The surface of the nanoplatelets.
In some examples of this embodiment, the Ti is 3 C 2 The size of the quantum dots is within 10 nm. Further improvement of the specific surface area of the composite material can be ensured.
In another embodiment of the invention, a preparation method of the bismuth tungstate/titanium carbide quantum dot composite material is provided, and Bi 2 WO 6 Dispersing the nano-sheets into a solvent, adding Ti under the stirring condition 3 C 2 Stirring the quantum dot solution in an inert atmosphere, and filtering and drying the stirred material to obtain the quantum dot solution.
The invention is stirred under inert atmosphere to avoid oxidation.
In some embodiments of this embodiment, Bi 2 WO 6 Nanosheet and Ti 3 C 2 The mass ratio of the quantum dots is 100: 1.0-8.0. When the mass ratio is 100: 3.0-7.0, especially 100: 3.0-4.0, the prepared composite material has better performance of photocatalytic degradation of amoxicillin.
In some examples of this embodiment, the stirring time is 6 to 12 hours. Preferably 11-12 h. Contributes to obtaining firm interface bonding and Ti 3 C 2 Bi with uniformly distributed quantum dots 2 WO 6 /Ti 3 C 2 A quantum dot composite material.
Bi 2 WO 6 The nanosheets may be prepared by existing methods in order to render Bi 2 WO 6 Nanosheet and Ti 3 C 2 Better combination of quantum dots, some examples of this embodiment are Bi obtained by hydrothermal reaction of tungstate with bismuth salt 2 WO 6 Nanosheets.
Tungstate in the context of the invention refers to compounds in which the anion is tungstate anion, e.g. Na 2 WO 4 、K 2 WO 4 And the like.
The bismuth salt in the present invention refers to a compound in which the cation is a bismuth ion, such as bismuth nitrate, bismuth chloride, bismuth acetate, and the like.
In one or more embodiments, the temperature of the hydrothermal reaction of the tungstate and the bismuth salt is 120-180 ℃ and the time is 12-24 hours. The temperature is preferably 120-130 ℃, and the time is preferably 23-25 h.
In one or more embodiments, cetyltrimethylammonium bromide is added to the hydrothermal reaction.
Ti of the invention 3 C 2 The quantum dots can be prepared by various methods in the prior art (e.g., hydrothermal-solvent method, mechanical milling method, etc.). To prepare Ti 3 C 2 The quantum dots are uniform in size and yield, and in some examples of this embodiment, the Ti is etched using HF 3 AlC 2 Obtaining Ti 3 C 2 Under inert atmosphere, using dimethyl sulfoxideSulfone (DMSO) vs. Ti 3 C 2 Intercalation assisted ultrasonic stripping to obtain few-layer Ti 3 C 2 MXene, small layer of Ti 3 C 2 MXene is subjected to hydrothermal treatment to obtain Ti 3 C 2 And (4) quantum dots. The method adopts a hydrothermal method to prepare Ti 3 C 2 The quantum dots are simple, efficient, good in reproducibility, uniform in size and within 10nm on average.
In one or more embodiments, Ti 3 AlC 2 The adding ratio of the HF solution to the solution is 1: 3-30 g: mL. When Ti is present 3 AlC 2 The addition ratio of the Ti to the HF solution is 1: 19-21, and when the addition ratio of the HF solution to the HF solution is 1: 19-21 g: mL 3 AlC 2 The etching effect is better.
In one or more embodiments, the HF etches Ti 3 AlC 2 The temperature is 25-50 ℃, and the etching time is 24-64 h. When the etching temperature is 34-36 ℃ and the etching time is 47-49 h, the Al layer can be completely etched.
In one or more embodiments, the HF etches Ti 3 AlC 2 Then, the mixture was washed with water and then freeze-dried. Unreacted HF is removed. Freeze drying is beneficial to maintaining Ti 3 C 2 The morphology of (2). Washing with water to pH>6。
In one or more embodiments, Ti 3 C 2 The adding ratio of the DMSO to the DMSO is 1: 3-30, and g: mL. When Ti is present 3 C 2 The addition ratio of the surfactant to DMSO is 1: 9-11, and when g: mL, a better intercalation effect can be obtained, and the detergent is easy to wash.
In one or more embodiments, there will be fewer layers of Ti 3 C 2 MXene is dispersed uniformly, and is subjected to hydrothermal treatment after ammonia water is added. More specifically, the temperature of the hydrothermal treatment is 100-150 ℃ and the time is 6-12 h. When the temperature of the hydrothermal treatment is 100-105 ℃ and the time is 11-13 h, Ti with uniform dispersion and size within 10nm can be ensured 3 C 2 Quantum dots, and preventing oxidation thereof.
The preferred steps are:
firstly, 1-3 g of Ti 3 AlC 2 Adding the powder into 10-30 mL of HF solution to form uniform suspension;
② continuously stirring for 24-64 h at 25-50 ℃, centrifuging the obtained suspension, washing with deionized water to pH>6, freeze drying to obtain black Ti 3 C 2 Powder;
③ mixing 1-3 g of black Ti 3 C 2 Dispersing the powder in 10-30 mL of DMSO (dimethylsulfoxide), stirring for 24h under the protection of Ar, centrifugally washing to remove DMSO, dispersing black precipitate in 100mL of deionized water to form black suspension, and performing ultrasonic treatment for 3h under the protection of Ar;
fourthly, the turbid liquid is filled into a reaction kettle with a polytetrafluoroethylene lining, ammonia water is dripped to adjust the pH value to be approximately 9, and then hydrothermal treatment is carried out for 6-12 h at the temperature of 100-150 ℃; finally filtering the obtained suspension with a filter membrane of 220 μm, taking the lower solution, and preparing Ti with concentration of 1mg/mL after cold drying 3 C 2 A quantum dot solution.
In a third embodiment of the invention, a photocatalyst is provided, which comprises an active ingredient and a carrier, wherein the active ingredient is the bismuth tungstate/titanium carbide quantum dot composite material.
The fourth embodiment of the invention provides an application of the bismuth tungstate/titanium carbide quantum dot composite material or the photocatalyst in photocatalytic degradation of amoxicillin.
Specifically, the bismuth tungstate/titanium carbide quantum dot composite material is added into an amoxicillin solution for dispersion, and then illumination is performed. Research shows that the degradation rate of amoxicillin by 2 hours of illumination is close to 70%.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1:
bi 2 WO 6 The preparation method of the nanosheet comprises the following steps: 0.9701g of Bi (NO) 3 ) 3 ·5H 2 Dissolving O in 40mL of deionized water, stirring at room temperature for 1h to uniformly disperse the O, and marking the solution as a solution A; 0.2507g of Na 2 WO 4 ·2H 2 O and 0.05g cetyltrimethylammonium bromide (CTAB) were dissolved in 40mL deionized water, stirred at room temperature for 1h to disperse uniformly, and labeled as suspendedAnd (4) turbid liquid B. The solution A is dropwise added into the suspension B, and the mixture is magnetically stirred for 1 hour at room temperature until a white suspension is formed. The suspension was transferred to a teflon lined reactor and subjected to hydrothermal treatment in an oven at 120 ℃ for 24 h. Naturally cooling to room temperature, centrifuging, washing, drying and grinding the obtained precipitate to obtain Bi 2 WO 6 Nanosheets.
Bi 2 WO 6 /Ti 3 C 2 The preparation method of the quantum dot composite material (marked as BTQDs-1%) comprises the following steps:
mixing 1g of Ti 3 AlC 2 The powder was added to 20mL of 40% HF solution to form a uniform suspension. Stirring continuously for 48h at 35 deg.C, centrifuging the obtained suspension, and washing with deionized water to pH>6, freeze drying to obtain black Ti 3 C 2 And (3) powder. 1g of black Ti 3 C 2 Dispersing the powder in 10mL of DMSO, stirring for 24h under the protection of Ar, centrifugally washing to remove the DMSO, dispersing black precipitate in 100mL of deionized water to form black suspension, carrying out ultrasonic treatment for 3h under the protection of Ar, putting the suspension into a reaction kettle with a polytetrafluoroethylene lining, dropwise adding ammonia water to adjust the pH to be approximately 9, and then carrying out hydrothermal treatment at 100 ℃ for 12 h. Finally filtering the obtained suspension with a filter membrane of 220 μm, taking the lower solution, and preparing Ti with concentration of 1mg/mL after cold drying 3 C 2 A quantum dot solution.
0.1g of Bi is weighed 2 WO 6 Adding 50mL of deionized water into the nanosheet, and performing ultrasonic treatment for 1h to uniformly disperse the nanosheet. Under the condition of introducing Ar and continuously stirring, 1mL of prepared Ti is dripped into the solution 3 C 2 A quantum dot solution. After stirring for 12h, the product was collected by suction filtration and dried under vacuum at 60 ℃ for 12 h.
Example 2:
this example provides a Bi 2 WO 6 /Ti 3 C 2 The preparation method of the quantum dot composite material (marked as BTQDs-3%) comprises the following steps:
mixing 1g of Ti 3 AlC 2 The powder was added to 20mL of 40% HF solution to form a uniform suspension. Stirring at 35 deg.C for 48 hr, centrifuging the obtained suspension, and removingWashing with ionized water to pH>6, freeze drying to obtain black Ti 3 C 2 And (3) powder. 1g of black Ti 3 C 2 Dispersing the powder in 10mL of DMSO, stirring for 24h under the protection of Ar, centrifugally washing to remove the DMSO, dispersing black precipitate in 100mL of deionized water to form black suspension, carrying out ultrasonic treatment for 3h under the protection of Ar, putting the suspension into a reaction kettle with a polytetrafluoroethylene lining, dropwise adding ammonia water to adjust the pH to be approximately 9, and then carrying out hydrothermal treatment at 100 ℃ for 12 h. Finally filtering the obtained suspension with a filter membrane of 220 μm, taking the lower solution, and preparing Ti with concentration of 1mg/mL after cold drying 3 C 2 A quantum dot solution.
0.1g of Bi is weighed 2 WO 6 Adding 50mL of deionized water into the nanosheet, and performing ultrasonic treatment for 1h to uniformly disperse the nanosheet. 3.1mL of pre-prepared Ti was added dropwise with stirring while introducing Ar 3 C 2 A quantum dot solution. After stirring for 12h, the product was collected by suction filtration and dried under vacuum at 60 ℃ for 12 h.
Example 3:
this example provides a Bi 2 WO 6 /Ti 3 C 2 The preparation method of the quantum dot composite material (marked as BTQDs-5%) comprises the following steps:
mixing 1g of Ti 3 AlC 2 The powder was added to 20mL of 40% HF solution to form a uniform suspension. Stirring continuously for 48h at 35 deg.C, centrifuging the obtained suspension, and washing with deionized water to pH>6, freeze drying to obtain black Ti 3 C 2 And (3) powder. 1g of black Ti 3 C 2 Dispersing the powder in 10mL DMSO, stirring for 24h under the protection of Ar, centrifugally washing to remove DMSO, dispersing black precipitate in 100mL deionized water to form black suspension, performing ultrasonic treatment for 3h under the protection of Ar, putting the suspension into a polytetrafluoroethylene-lined reaction kettle, dropwise adding ammonia water to adjust the pH to be approximately 9, and performing hydrothermal treatment at 100 ℃ for 12 h. Finally filtering the obtained suspension with a filter membrane of 220 μm, taking the lower solution, and preparing Ti with concentration of 1mg/mL after cold drying 3 C 2 A quantum dot solution.
0.1g of Bi is weighed 2 WO 6 Adding 50mL of deionized water into the nanosheet, and performing ultrasonic treatment for 1h to uniformly disperse the nanosheet. Under the condition of introducing Ar and continuously stirring5.3mL of pre-prepared Ti was added dropwise thereto 3 C 2 A quantum dot solution. After stirring for 12h, the product was collected by suction filtration and dried under vacuum at 60 ℃ for 12 h.
Example 4:
this example provides a Bi 2 WO 6 /Ti 3 C 2 The preparation method of the quantum dot composite material (marked as BTQDs-7%) comprises the following steps:
mixing 1g of Ti 3 AlC 2 The powder was added to 20mL of 40% HF solution to form a uniform suspension. Stirring continuously for 48h at 35 deg.C, centrifuging the obtained suspension, and washing with deionized water to pH>6, freeze drying to obtain black Ti 3 C 2 And (3) powder. 1g of black Ti 3 C 2 Dispersing the powder in 10mL of DMSO, stirring for 24h under the protection of Ar, centrifugally washing to remove the DMSO, dispersing black precipitate in 100mL of deionized water to form black suspension, carrying out ultrasonic treatment for 3h under the protection of Ar, putting the suspension into a reaction kettle with a polytetrafluoroethylene lining, dropwise adding ammonia water to adjust the pH to be approximately 9, and then carrying out hydrothermal treatment at 100 ℃ for 12 h. Finally filtering the obtained suspension with a filter membrane of 220 μm, taking the lower solution, and preparing Ti with concentration of 1mg/mL after cold drying 3 C 2 A quantum dot solution.
0.1g of Bi is weighed 2 WO 6 Adding 50mL of deionized water into the nanosheet, and performing ultrasonic treatment for 1h to uniformly disperse the nanosheet. 7.5mL of pre-prepared Ti was added dropwise with stirring while introducing Ar 3 C 2 A quantum dot solution. After stirring for 12h, the product was collected by suction filtration and dried under vacuum at 60 ℃ for 12 h.
FIG. 1 shows Bi prepared in examples 1 to 4 2 WO 6 And Bi 2 WO 6 /Ti 3 C 2 XRD spectrum of quantum dot composite material, and Bi 2 WO 6 The diffraction peak of the composite material shows Bi 2 WO 6 Characteristic peak and peak intensity with Ti 3 C 2 The phenomenon that the content of the quantum dots is gradually reduced by increasing shows that Bi 2 WO 6 And Ti 3 C 2 Quantum dot recombination does not change Bi 2 WO 6 The crystal structure of (1). However, the composite material does not contain Ti 3 C 2 Diffraction peak of quantum dot, which may be Ti 3 C 2 The content of quantum dots is less and the distribution is uniform in the system, and the results show that Bi is 2 WO 6 /Ti 3 C 2 Quantum dot composites were successfully prepared.
As can be seen from the TEM image of BTQDs-3% composite material in FIG. 2, Ti 3 C 2 The quantum dots are uniformly loaded on Bi 2 WO 6 On the surface of (a).
As can be seen from the SEM image of the BTQDs-3% composite material in FIG. 3, the composite material has an overall sheet structure, and stacking of sheets occurs due to van der Waals' force, but Ti with a smaller size cannot be observed due to SEM observation accuracy 3 C 2 And (4) quantum dots.
As can be seen from the EDS spectrum of the BTQDs-3% composite material in FIG. 4, the BTQDs-3% contains Bi, W, O, C and other elements, and a uniform and dense Ti element signal can be observed, which indicates that Bi 2 WO 6 /Ti 3 C 2 Successfully preparing the quantum dot composite material.
Example 5:
the obtained Bi 2 WO 6 /Ti 3 C 2 The quantum dot composite material is applied to photocatalytic degradation to prepare amoxicillin, and the experimental process is as follows:
adding 70mg of the photocatalyst prepared in the embodiment 1-4 into 70mL of 20mg/L amoxicillin solution, ultrasonically dispersing uniformly, transferring the suspension into a reactor, putting the reactor into a photocatalytic activity evaluation system, magnetically stirring in the dark for 1h in advance to establish absorption and desorption balance between the photocatalyst and amoxicillin molecules, irradiating the reactor by using a 300W xenon lamp as simulated sunlight, taking out about 7mL of the solution every 15min, and centrifuging to remove the catalyst to be further tested.
After the visible light is irradiated for 2 hours, the degradation effect of the photocatalyst prepared by the method on amoxicillin is shown in figure 5, and the prepared Bi is shown in figure 5 2 WO 6 /Ti 3 C 2 The degradation rate of the quantum dot composite material to amoxicillin is higher than that of pure Bi 2 WO 6 In particular example 2 preparationThe degradation rate of the BTQDs-3% to amoxicillin within 2h reaches 69.8%, and the degradation rate is about pure Bi 2 WO 6 2.1 times of (32.9%). With the increase of the loading amount, the degradation rate of the composite material to amoxicillin is reduced, which is probably due to the excessive loading of Ti 3 C 2 Quantum dot shields Bi 2 WO 6 The absorption of light leads to a reduction in its photocatalytic activity, and the above results show that Ti is optimized 3 C 2 The content of the quantum dots has important significance for improving the photocatalytic activity of the composite material.
Example 6:
the obtained Bi 2 WO 6 /Ti 3 C 2 The quantum dot composite material is applied to photocatalytic degradation of papermaking wastewater, and the experimental process is as follows:
100mg of Bi prepared in examples 1 to 4 were weighed 2 WO 6 And Bi 2 WO 6 /Ti 3 C 2 Adding the quantum dot composite material and 100mL of papermaking wastewater into a reactor, performing magnetic stirring in the dark for 1h in advance to establish absorption and desorption balance between the photocatalyst and papermaking wastewater pollutants, irradiating the reactor for 12h by using a 300W xenon lamp as simulated sunlight, taking out about 15mL of turbid liquid every 2h, centrifuging to remove the catalyst, taking supernatant, and measuring the chemical oxygen demand by adopting a potassium dichromate method.
After 12h of irradiation with visible light, the Bi prepared in examples 1-4 was measured by potassium dichromate emission 2 WO 6 And Bi 2 WO 6 /Ti 3 C 2 The quantum dot composite material has extremely low removal rate of chemical oxygen demand of papermaking wastewater, and represents that the photocatalyst prepared by the invention has no obvious effect on the degradation of the papermaking wastewater, so that the photocatalyst prepared by the invention has certain selectivity on the photocatalytic degradation of amoxicillin.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The bismuth tungstate/titanium carbide quantum dot composite material is characterized by comprising Bi 2 WO 6 Nanosheets and titanium carbide quantum dots, the Ti 3 C 2 Quantum dots attached to Bi 2 WO 6 The surface of the nanoplatelets.
2. The bismuth tungstate/titanium carbide quantum dot composite material as claimed in claim 1, wherein the Ti is 3 C 2 The size of the quantum dots is within 10 nm.
3. The preparation method of the bismuth tungstate/titanium carbide quantum dot composite material is characterized in that Bi 2 WO 6 Dispersing the nano-sheets into a solvent, adding Ti under the stirring condition 3 C 2 Stirring the quantum dot solution in an inert atmosphere, and filtering and drying the stirred material to obtain the quantum dot solution.
4. The method for preparing bismuth tungstate/titanium carbide quantum dot composite material as claimed in claim 3, wherein Bi 2 WO 6 Nanosheet and Ti 3 C 2 The mass ratio of the quantum dots is 100: 1.0-8.0; preferably, the mass ratio is 100: 3.0-7.0; more preferably, the mass ratio is 100: 3.0-4.0.
5. The preparation method of the bismuth tungstate/titanium carbide quantum dot composite material as claimed in claim 3, wherein the stirring time is 6-12 hours; preferably 11-12 h.
6. The method of claim 3, wherein the bismuth tungstate and the bismuth salt are hydrothermally reacted to obtain Bi 2 WO 6 Nanosheets;
preferably, the temperature of the hydrothermal reaction of the tungstate and the bismuth salt is 120-180 ℃, and the time is 12-24 hours; the temperature is further preferably 120-130 ℃, and the time is further preferably 23-25 h;
preferably, cetyltrimethylammonium bromide is added to the hydrothermal reaction.
7. The method for preparing bismuth tungstate/titanium carbide quantum dot composite material as claimed in claim 3, wherein HF is used for etching Ti 3 AlC 2 Obtaining Ti 3 C 2 Under inert atmosphere, using dimethyl sulfoxide (DMSO) to Ti 3 C 2 Intercalation assisted ultrasonic stripping to obtain few-layer Ti 3 C 2 MXene, small layer of Ti 3 C 2 MXene is subjected to hydrothermal treatment to obtain Ti 3 C 2 Quantum dots;
preferably, Ti 3 AlC 2 The adding ratio of the HF solution to the solution is 1: 3-30, and g: mL; further preferably, Ti 3 AlC 2 The adding ratio of the HF solution to the HF solution is 1: 19-21, and g: mL;
preferably, the HF etches Ti 3 AlC 2 The temperature of the etching solution is 25-50 ℃, and the etching time is 24-64 h; further preferably, the etching temperature is 34-36 ℃, and the etching time is 47-49 h;
preferably, the HF etches Ti 3 AlC 2 Then washing with water, and then freeze-drying;
preferably, Ti 3 C 2 The adding ratio of the DMSO to the DMSO is 1: 3-30, and g: mL; further preferably, Ti 3 C 2 The adding ratio of the DMSO to the DMSO is 1: 9-11, and g: mL;
preferably, a few Ti layers are formed 3 C 2 MXene is uniformly dispersed, and is subjected to hydrothermal treatment after ammonia water is added; further preferably, the temperature of the hydrothermal treatment is 100-150 ℃ and the time is 6-12 h; more preferably, the temperature of the hydrothermal treatment is 100 to 105 ℃ and the time is 11 to 13 hours.
8. A photocatalyst comprises an active component and a carrier, and is characterized in that the active component is the bismuth tungstate/titanium carbide quantum dot composite material as claimed in claim 1 or 2 or the bismuth tungstate/titanium carbide quantum dot composite material obtained by the preparation method as claimed in any one of claims 3 to 7.
9. An application of the bismuth tungstate/titanium carbide quantum dot composite material as claimed in claim 1 or 2 or the bismuth tungstate/titanium carbide quantum dot composite material obtained by the preparation method as claimed in any one of claims 3 to 7 or the photocatalyst as claimed in claim 8 in photocatalytic degradation of amoxicillin.
10. The application of the bismuth tungstate/titanium carbide quantum dot composite material as claimed in claim 9 is characterized in that the bismuth tungstate/titanium carbide quantum dot composite material is added into an amoxicillin solution for dispersion, and then illumination is carried out.
CN202210759537.0A 2022-06-30 2022-06-30 Bismuth tungstate/titanium carbide quantum dot composite material and preparation method and application thereof Active CN115069280B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210759537.0A CN115069280B (en) 2022-06-30 2022-06-30 Bismuth tungstate/titanium carbide quantum dot composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210759537.0A CN115069280B (en) 2022-06-30 2022-06-30 Bismuth tungstate/titanium carbide quantum dot composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115069280A true CN115069280A (en) 2022-09-20
CN115069280B CN115069280B (en) 2023-07-14

Family

ID=83256724

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210759537.0A Active CN115069280B (en) 2022-06-30 2022-06-30 Bismuth tungstate/titanium carbide quantum dot composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115069280B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116943697A (en) * 2023-07-20 2023-10-27 辽宁大学 Two-dimensional self-assembled composite photocatalyst, preparation method thereof and application of two-dimensional self-assembled composite photocatalyst to coupling persulfate under visible light

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106902810A (en) * 2017-03-10 2017-06-30 湖南大学 Individual layer Bismuth tungstate nano-sheet composite photo-catalyst of carbon quantum dot modification and its preparation method and application
CN108199015A (en) * 2017-12-15 2018-06-22 同济大学 The preparation method and application of black phosphorus quantum dot/titanium carbide nanosheet composite material
CN109852349A (en) * 2018-12-09 2019-06-07 大连理工大学 A kind of conversion of optical and thermal energy and thermal energy storage stable phase change composite material and preparation method thereof
CN110002493A (en) * 2019-03-28 2019-07-12 盐城工学院 A kind of two dimension Ti3C2/TiO2-xThe preparation method of nanocomposite
CN110368968A (en) * 2019-07-15 2019-10-25 中国石油大学(北京) NiFe-LDH/Ti3C2/Bi2WO6Nano-chip arrays and preparation method and application
CN113831544A (en) * 2021-09-22 2021-12-24 同济大学 Non-linear nano hybrid material of titanium carbide quantum dots and vanadium metal organic framework and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106902810A (en) * 2017-03-10 2017-06-30 湖南大学 Individual layer Bismuth tungstate nano-sheet composite photo-catalyst of carbon quantum dot modification and its preparation method and application
CN108199015A (en) * 2017-12-15 2018-06-22 同济大学 The preparation method and application of black phosphorus quantum dot/titanium carbide nanosheet composite material
CN109852349A (en) * 2018-12-09 2019-06-07 大连理工大学 A kind of conversion of optical and thermal energy and thermal energy storage stable phase change composite material and preparation method thereof
CN110002493A (en) * 2019-03-28 2019-07-12 盐城工学院 A kind of two dimension Ti3C2/TiO2-xThe preparation method of nanocomposite
CN110368968A (en) * 2019-07-15 2019-10-25 中国石油大学(北京) NiFe-LDH/Ti3C2/Bi2WO6Nano-chip arrays and preparation method and application
CN113831544A (en) * 2021-09-22 2021-12-24 同济大学 Non-linear nano hybrid material of titanium carbide quantum dots and vanadium metal organic framework and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GUIMEI HUANG等: ""Ti3C2 MXene-Modified Bi2WO6 Nanoplates for Efficient Photodegradation of Volatile Organic Compounds"", 《APPLIED SURFACE SCIENCE》, pages 1 - 31 *
WANG JIAJIA等: ""0D/2D Interface Engineering of Carbon Quantum Dots Modified Bi2WO6 Ultrathin Nanosheets with Enhanced Photoactivity for Full Spectrum Light Utilization and Mechanism Insight"", pages 1 - 43 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116943697A (en) * 2023-07-20 2023-10-27 辽宁大学 Two-dimensional self-assembled composite photocatalyst, preparation method thereof and application of two-dimensional self-assembled composite photocatalyst to coupling persulfate under visible light

Also Published As

Publication number Publication date
CN115069280B (en) 2023-07-14

Similar Documents

Publication Publication Date Title
Ma et al. Effective photoinduced charge separation and photocatalytic activity of hierarchical microsphere-like C60/BiOCl
CN103480398B (en) Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof
CN108993550B (en) Surface oxygen vacancy modified bismuth oxybromide photocatalyst and preparation method thereof
Zhang et al. Facile hydrothermal synthesis and photocatalytic activity of rod-like nanosized silver tungstate
CN102580736B (en) Grapheme / silver vanadium oxide nanometer composite visible light catalyst and preparation method thereof
Jiang et al. Preparation of magnetically separable and recyclable carbon dots/NiCo 2 O 4 composites with enhanced photocatalytic activity for the degradation of tetracycline under visible light
Reheman et al. Facile photo-ultrasonic assisted reduction for preparation of rGO/Ag2CO3 nanocomposites with enhanced photocatalytic oxidation activity for tetracycline
CN103480399A (en) Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof
CN108187687B (en) Preparation method of photo-Fenton catalyst
Shi et al. The bifunctional composites of AC restrain the stack of g-C3N4 with the excellent adsorption-photocatalytic performance for the removal of RhB
CN111185210B (en) Titanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst and preparation method and application thereof
Zou et al. Enhanced photocatalytic activity of bismuth oxychloride by in-situ introducing oxygen vacancy
Altin CuO-TiO2/graphene ternary nanocomposite for highly efficient visible-light-driven photocatalytic degradation of bisphenol A
CN112521617B (en) Polyacid-based metal organic framework material for adsorbing antibiotics and preparation method and application thereof
CN111729682A (en) Photocatalyst g-C3N4/RGO/Bi2O3And method for preparing the same
CN107282134A (en) A kind of ZnO photocatalyst of graphene coated and preparation method thereof
CN114849748A (en) CoS/Ti 3 C 2 Preparation and application of MXene composite material
CN112619671A (en) Binary composite nano catalyst and preparation method and application thereof
CN112774718A (en) Cuprous oxide/tubular graphite-like phase carbon nitride composite catalyst and preparation method and application thereof
CN115069280A (en) Bismuth tungstate/titanium carbide quantum dot composite material and preparation method and application thereof
CN110227515B (en) Bi2MoO6/BiPO4P-n heterojunction photocatalyst, preparation method and application thereof
CN117383523B (en) Iodized crystal carbon nitride and preparation method and application thereof
CN111939944B (en) Preparation and application of cadmium selenide quantum dot/molybdenum disulfide composite photocatalyst
CN103521247B (en) A kind of preparation method of self assembly Silver-phosphate-bascomposite composite visible light photocatalytic material
CN108906093A (en) A kind of preparation method using carbon nanotube control silver orthophosphate crystal particle diameter

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP03 Change of name, title or address

Address after: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501

Patentee after: Qilu University of Technology (Shandong Academy of Sciences)

Country or region after: China

Address before: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501

Patentee before: Qilu University of Technology

Country or region before: China