CN115318329A - Titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dot/(001) surface as well as preparation method and application thereof - Google Patents
Titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dot/(001) surface as well as preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002096 quantum dot Substances 0.000 title claims abstract description 55
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 33
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 238000000034 method Methods 0.000 claims abstract description 21
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
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- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- SCKYRAXSEDYPSA-UHFFFAOYSA-N ciclopirox Chemical compound ON1C(=O)C=C(C)C=C1C1CCCCC1 SCKYRAXSEDYPSA-UHFFFAOYSA-N 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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Abstract
The invention provides a titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dots/(001) surface and a preparation method and application thereof, wherein the method comprises the following steps of dispersing titanium dioxide/titanium carbide MXene powder with exposed (001) surface in ethanol to obtain a suspension, irradiating the suspension under ultraviolet light, and adding g-C 3 N 4 Quantum dot solution, g-C 3 N 4 Quantum dot and (001) plane exposed titanium dioxide/titanium carbideThe mass ratio of MXene powder is (2.5-10): 50, obtaining a mixed system; irradiating the mixed system under ultraviolet light to obtain a reaction solution; and (3) sequentially drying the precipitates in the reaction liquid to obtain the titanium dioxide/titanium carbide MXene with the exposed carbon nitride quantum dot/(001) surface. The method is low in cost and simple to operate, and can be used for degrading antibiotic pollutant ciprofloxacin through a full spectrum.
Description
Technical Field
The invention belongs to the field of preparation of semiconductor photocatalytic functional materials, and particularly relates to titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dots/(001) surface, and a preparation method and application thereof.
Background
In recent years, semiconductor photocatalysis technology has a wide application prospect in the aspect of environmental pollution treatment, and is receiving wide attention.
Block g-C 3 N 4 The specific surface area is small and cannot be matched with TiO 2 The photocatalytic performance is affected by establishing an efficient electron transport interface, and the interface defects of the electron transport interface become recombination centers of photon-generated carriers, so that the photocatalytic performance is affected. Thus, the g-C is reduced 3 N 4 Dimensionality is an effective method for increasing the specific surface area of a material, a graphite phase carbon nitride quantum dot (g-C) 3 N 4 QDs) have been widely used due to their advantages of good water solubility and stability, low toxicity, etc. g-C 3 N 4 QDs has higher fluorescence quantum efficiency than Graphene Quantum Dots (GQDs) and Carbon Quantum Dots (CQDs). By aligning blocks g-C 3 N 4 Subjecting to ultrasonic treatment, chemical treatment or hydrothermal corrosion, pulverizing and decomposing carbon nitride to obtain g-C 3 N 4 QDs。g-C 3 N 4 The unique physicochemical properties of QDs enable them toThe photocatalytic activity of the semiconductor can be obviously improved after the photocatalyst is compounded with the semiconductor.
g-C in the form of quantum dots 3 N 4 g-C as a zero-dimensional material with larger specific surface area and more active sites, but in the form of quantum dots 3 N 4 With TiO 2 After the recombination, the photoresponse is not high enough, and the separation of photon-generated carriers is not ideal.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the titanium dioxide/titanium carbide MXene with the exposed carbon nitride quantum dot/(001) surface, the preparation method and the application thereof, the cost is low, the operation is simple, and the method can be used for degrading antibiotic pollutant ciprofloxacin through a full spectrum.
The invention is realized by the following technical scheme:
the preparation method of the titanium dioxide/titanium carbide MXene with the exposed carbon nitride quantum dot/(001) surface comprises the following steps,
dispersing the titanium dioxide/titanium carbide MXene powder exposed on the (001) surface in ethanol to obtain a suspension, irradiating the suspension under ultraviolet light, and adding g-C 3 N 4 Quantum dot solution, g-C 3 N 4 The mass ratio of the quantum dots to the titanium dioxide/titanium carbide MXene powder exposed on the (001) surface is (2.5-10): 50, obtaining a mixed system;
irradiating the mixed system under ultraviolet light to obtain a reaction solution; and (3) sequentially drying the precipitates in the reaction liquid to obtain the titanium dioxide/titanium carbide MXene with the exposed carbon nitride quantum dot/(001) surface.
Preferably, said g-C 3 N 4 The quantum dot solution is carried out according to the following processes:
firstly, porous g-C 3 N 4 Dispersing in ammonia water, performing hydrothermal reaction at 170-190 ℃ for 10-14 h to obtain reaction liquid, separating and cleaning products in the reaction liquid to obtain porous g-C 3 N 4 Nanosheets prepared by mixing porous g-C 3 N 4 Dispersing the nano-sheets in deionized water, and finally carrying out ultrasonic crushing for 2.5-3.5 h under 800-1200W to obtain g-C 3 N 4 A quantum dot solution.
Further, the porous g-C 3 N 4 The method comprises the following steps:
calcining urea at 500-600 ℃ for 3.5-4.5 h to obtain g-C 3 N 4 G to C 3 N 4 Stirring the mixture for 1.5 to 2.5 hours at room temperature in the mixed solution of concentrated sulfuric acid and concentrated nitric acid to obtain mixed solution, washing the mixed solution by deionized water, and filtering the solid in the mixed solution to obtain porous g-C 3 N 4 Ultrasonication to give g-C 3 N 4 A quantum dot solution.
Preferably, in the suspension, the proportion of the titanium dioxide/titanium carbide MXene powder exposed from the (001) surface to the ethanol is (45-55) mg: (25-35) mL.
Preferably, the suspension is irradiated for 3.5 to 4.5 hours under ultraviolet light, and then g-C is added 3 N 4 A quantum dot solution.
Preferably, said g-C 3 N 4 The concentration of the quantum dot solution is 0.15-0.25 mg/mL, g-C 3 N 4 The volume ratio of the quantum dot solution to the ethanol is (25-100): (25 to 35).
Preferably, the mixed system is irradiated under ultraviolet light for 1-4 h to obtain a reaction solution.
Preferably, the precipitate in the reaction solution is respectively washed by deionized water and absolute ethyl alcohol for 2 to 5 times, and is dried in vacuum for 10 to 14 hours at the temperature of between 60 and 70 ℃ to obtain the titanium dioxide/titanium carbide MXene with the exposed carbon nitride quantum dots/(001) surface.
The carbon nitride quantum dot/(001) -plane-exposed titanium dioxide/titanium carbide MXene prepared by the preparation method of the carbon nitride quantum dot/(001) -plane-exposed titanium dioxide/titanium carbide MXene.
An application of titanium dioxide/titanium carbide MXene exposed on a carbon nitride quantum dot/(001) surface in degrading ciprofloxacin under visible light and near infrared light is disclosed.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of titanium dioxide/titanium carbide MXene with exposed (001) plane of carbon nitride quantum dots, which is characterized in that (001) crystal plane TiO is exposed 2 /Ti 3 C 2 MXene is dispersed in ethanol to prepare suspension, and the suspension is irradiated under ultraviolet light and subjected to TiO precipitation 2 Under the action of surface heterojunction of (2), tiO 2 The electrons on the valence bands of the (001) crystal face and the (101) crystal face are excited to jump to the corresponding conduction bands, meanwhile, holes are left on the valence bands, and under the action of a built-in electric field of the surface heterojunction, the photogenerated electrons with negative charges are promoted to TiO 2 Moves to the (101) plane of (A), and the positively charged photogenerated holes move to TiO 2 After the (001) plane of (A) is migrated, negatively charged g-C is added 3 N 4 Quantum dot solution, performing a photo-deposition reaction under UV irradiation, negatively charged g-C 3 N 4 QDs and TiO 2 The positively charged holes on the (001) crystal face are compounded together under the action of electrostatic attraction to combine g-C 3 N 4 QDs deposited on inlaid Ti 3 C 2 TiO between MXene surface and interlayer 2 Exposing the (001) crystal face, separating the product and drying to obtain g-C 3 N 4 QDs/(001)TiO 2 /Ti 3 C 2 MXene photocatalyst. The invention adopts a photo-deposition method to prepare g-C 3 N 4 Quantum dots supported on TiO 2 g-C on the surface of (001) plane of (C) 3 N 4 QDs/(001)TiO 2 /Ti 3 C 2 MXene photocatalyst. The invention is in g-C 3 N 4 QDs and TiO 2 (001) Electrostatic field formed at crystal face interface, tiO 2 Built-in electric field formed by surface heterojunction, tiO 2 (101) Crystal face and Ti 3 C 2 Built-in electric field of Schottky junction formed by MXene and plasma Ti 3 C 2 Under the combined action of LSPR effect of MXene, the light absorption characteristic in the full spectrum range of 200-2200nm is enhanced, wherein Ti 3 C 2 Transverse surface plasmon resonance (TE) and longitudinal surface plasmon resonance (TM) of MXene such that g-C 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 MXene also has strong light absorption in the near infrared spectrum range when the g-C 3 N 4 QDs loading on exposed (001) plane/TiO 2 /Ti 3 C 2 When on MXene, the full spectrum absorption is obviously enhanced,can enhance the exposure of (001) crystal face/TiO 2 /Ti 3 C 2 MXene has high utilization rate of solar energy, photoproduction electrons and holes are effectively separated in space, the photocatalytic degradation performance is enhanced, and ciprofloxacin CIP can be effectively degraded under visible light and near infrared light.
g-C of the invention 3 N 4 QDs/(001)TiO 2 /Ti 3 C 2 The MXene photocatalyst has a high degradation rate on ciprofloxacin under visible light, can effectively degrade ciprofloxacin under near infrared light, and has a good application prospect.
Drawings
FIG. 1 is an XRD pattern of the products prepared in comparative example 1, example 1 to example 4 of the present invention.
FIG. 2 shows g-C 3 N 4 SEM images of QDs before dispersion.
FIG. 3 shows g-C 3 N 4 TEM image of QDs.
FIG. 4 is an SEM photograph of a product prepared in example 2 of the present invention.
FIG. 5 is an enlarged SEM photograph of the product of example 2 of the present invention.
FIG. 6 is an EDS diagram of the product prepared in example 2 of the present invention.
FIG. 7 is a graph of UV-vis-NIR DRS of the products prepared in comparative example 1, example 2 and example 4 of the present invention.
FIG. 8 is a graph of degradation of the products prepared in comparative example 1, example 1 to example 4 of the present invention versus cycloxabexarotene under simulated visible light.
FIG. 9 is a graph showing degradation of the products prepared in comparative example 1, example 1 to example 4 of the present invention to ciclopirox under simulated near infrared light.
FIG. 10 is a plot of the photocurrents i-t under visible light for the products prepared in comparative example 1, example 2 and example 4 of the present invention.
FIG. 11 is a graph showing photocurrents i-t under near infrared light for the products prepared in comparative example 1, example 2 and example 4 of the present invention.
FIG. 12 shows g-C prepared according to the present invention 3 N 4 QDs/(001)TiO 2 /Ti 3 C 2 The photocatalytic degradation mechanism diagram of the MXene photocatalyst.
Fig. 13 is a graph of electrochemical impedance of the products prepared in comparative example 1, example 2 and example 4 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Because the surface active sites and the electronic structure both depend on special crystal face structures, the crystal face engineering plays a very key role in the photocatalysis process, and high-activity TiO is exposed 2 The semiconductor crystal face can improve the photocatalytic activity of the material. Crystal face control agent NaBF 4 Under the action of (2), tiO 2 The crystal is easier to expose the (001) crystal face with high activity, and the TiO crystal face with the (001) crystal face is exposed 2 At Ti 3 C 2 In situ growth of TiO 2 With Ti 3 C 2 Has a close contact interface between them, and TiO is excited by light 2 The high-activity (001) crystal face can efficiently generate photo-generated electron-hole pairs, and Ti simultaneously 3 C 2 The rapid trapping of photogenerated holes greatly facilitates the separation of carriers to expose (001) crystal plane TiO 2 /Ti 3 C 2 Based on composite materials, by mixing with g-C in the form of zero-dimensional material quantum dots 3 N 4 The photocatalyst constructs a heterojunction, and can further improve visible light (lambda)>400 nm) and near infrared light (. Lamda.))>800 nm) to promote further separation of photogenerated carriers. Thus a g-C of the invention 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 The preparation of MXene photocatalyst was carried out as follows.
Example 1:
step 1, weighing 10g of Ti 3 AlC 2 Slowly adding 100mL of HF solution with the mass fraction of 40% to obtain a reaction solution with the concentration of 0.1g/mL, stirring at room temperature for 27h, and reacting Ti with HF 3 AlC 2 Performing acid etching reaction, washing the product obtained by centrifugally separating the reaction solution after the reaction is finished with deionized water and ethanol until the pH value of the solution is more than 6.5, centrifugally separating the solution, and vacuum-drying the product at 60 ℃ for 12 hours to obtain a multilayer Ti 3 C 2 I.e. ML-Ti 3 C 2 (ii) a At a concentration of 25mg/L, adding ML-Ti 3 C 2 Dispersing the powder in 40mL of deionized water, carrying out ultrasonic crushing for 1h, centrifuging, and carrying out vacuum drying on the product at 60 ℃ for 12h to obtain few-layer Ti 3 C 2 MXene。
Step 3, calcining the urea at 550 ℃ for 4 hours to obtain g-C 3 N 4 Taking 1g of g-C 3 N 4 Stirring the mixture for 2 hours at room temperature in a mixed solution of 20mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, and washing the mixed solution for 3 times by using 1L of deionized water to obtain porous g-C 3 N 4 Taking 100mg of porous g-C 3 N 4 Dispersing in 30mL of 28% ammonia water, carrying out hydrothermal reaction at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanosheets, finally 10mg of porous g-C 3 N 4 Dispersing the nano-sheets in 100mL of deionized water, carrying out ultrasonic crushing for 3h under high energy of 1000W by using an XM-1000T ultrasonic crusher, and dispersing porous g-C by using the cavitation of ultrasonic waves 3 N 4 The nano-sheet aggregated particles are stirred and crushed into g-C 3 N 4 QDs, to give g-C at a concentration of 0.1mg/mL 3 N 4 Solutions of QDs;
step 5, mixing the system into purpleIrradiating for 2 hours under external illumination to carry out a light deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and anhydrous ethanol for 2 times, and vacuum drying at 60 deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 MXene photocatalyst.
Example 2:
step 1, weighing 10g of Ti 3 AlC 2 Slowly adding 100mL of HF solution with the mass fraction of 40% to obtain a reaction solution with the concentration of 0.1g/mL, stirring at room temperature for 27h for acid etching reaction, washing a product obtained by centrifugally separating the reaction solution with deionized water and ethanol until the pH value of the solution is more than 6.5, centrifugally separating the solution, and vacuum-drying the product at 60 ℃ for 12h to obtain ML-Ti 3 C 2 (ii) a At a concentration of 25mg/L, adding ML-Ti 3 C 2 Dispersing the powder in 40mL of deionized water, carrying out ultrasonic crushing for 1h, centrifuging, and carrying out vacuum drying on the product at 60 ℃ for 12h to obtain few-layer Ti 3 C 2 MXene。
Step 3, calcining urea at 550 ℃ for 4 hours to obtain g-C 3 N 4 Taking 1g of g-C 3 N 4 Stirring the mixture for 2 hours at room temperature in a mixed solution of 20mL concentrated sulfuric acid and 20mL concentrated nitric acid, washing the mixed solution for 3 times by using 1L deionized water to obtain porous g-C 3 N 4 Taking 100mg of porous g-C 3 N 4 Dispersing in 30mL of 27% ammonia water, carrying out hydrothermal reaction at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanosheets, finally 10mg of porous g-C 3 N 4 Dispersing the nano-sheets in 100mL of deionized water, and ultrasonically crushing for 3h by using an XM-1000T ultrasonic crusher under high energy of 1000W to obtain g-C with the concentration of 0.1mg/mL 3 N 4 Solutions of QDs;
step 5, irradiating the mixed system under ultraviolet illumination for 2 hours to carry out a light deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and anhydrous ethanol for 2 times, and vacuum drying at 60 deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 MXene photocatalyst.
Example 3:
step 1, weighing 10g of Ti 3 AlC 2 Slowly adding 100mL of HF solution with the mass fraction of 40% to obtain reaction liquid with the concentration of 0.1g/mL, stirring at room temperature for 27h for acid etching reaction, washing a product obtained by centrifugally separating the reaction liquid with deionized water and ethanol after the reaction is finished until the pH value of the solution is more than 6.5, centrifugally separating the solution, and drying the product at 60 ℃ in vacuum for 12h to obtain ML-Ti 3 C 2 (ii) a At a concentration of 25mg/L, adding ML-Ti 3 C 2 Dispersing the powder in 40mL of deionized water, carrying out ultrasonic crushing for 1h, centrifuging, and carrying out vacuum drying on the product at 60 ℃ for 12h to obtain few-layer Ti 3 C 2 MXene。
Step 3, calcining the urea at 550 ℃ for 4 hours to obtain g-C 3 N 4 Taking 1g of g-C 3 N 4 Stirring the mixture for 2 hours at room temperature in a mixed solution of 20mL concentrated sulfuric acid and 20mL concentrated nitric acid, washing the mixed solution for 3 times by using 1L deionized water to obtain porous g-C 3 N 4 Taking 100mg of porous g-C 3 N 4 Dispersing in 30mL of 26% ammonia water, carrying out hydrothermal reaction at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanosheets, finally 10mg of porous g-C 3 N 4 Dispersing the nano-sheets in 100mL of deionized water, and ultrasonically crushing for 3h by using an XM-1000T ultrasonic crusher under high energy of 1000W to obtain g-C with the concentration of 0.1mg/mL 3 N 4 Solutions of QDs;
step 5, irradiating the mixed system under ultraviolet illumination for 2 hours to carry out a light deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and anhydrous ethanol for 2 times, and vacuum drying at 60 deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 MXene photocatalyst.
Example 4:
step 1, weighing 10g of Ti 3 AlC 2 Slowly adding 100mL of HF solution with the mass fraction of 40% to obtain a reaction solution with the concentration of 0.1g/mL, stirring at room temperature for 27h for acid etching reaction, washing a product obtained by centrifugally separating the reaction solution with deionized water and ethanol until the pH value of the solution is more than 6.5, centrifugally separating the solution, and vacuum-drying the product at 60 ℃ for 12h to obtain ML-Ti 3 C 2 (ii) a At a concentration of 25mg/L, adding ML-Ti 3 C 2 Dispersing the powder in 40mL of deionized water, carrying out ultrasonic crushing for 1h, centrifuging, and carrying out vacuum drying on the product at 60 ℃ for 12h to obtain few-layer Ti 3 C 2 MXene。
In the step 2, the step of mixing the raw materials,200mg of Ti 3 C 2 MXene powder was dispersed in 30mL of 1mol/L HCl solution, and 0.33g of NaBF crystal face controlling agent was added 4 Stirring for 30min, performing ultrasonic treatment for 10min, transferring to a poly (tetrachloroethylene) hydrothermal reaction kettle, performing hydrothermal reaction at 160 ℃ for 12h, cooling the reaction solution to room temperature, respectively cleaning with deionized water and ethanol for 3 times, and drying at 60 ℃ in vacuum for 12h to obtain exposed (001) crystal face TiO 2 /Ti 3 C 2 MXene；
Step 3, calcining urea at 550 ℃ for 4 hours to obtain g-C 3 N 4 Taking 1g of g-C 3 N 4 Stirring the mixture for 2 hours at room temperature in a mixed solution of 20mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, and washing the mixed solution for 3 times by using 1L of deionized water to obtain porous g-C 3 N 4 Taking 100mg of porous g-C 3 N 4 Dispersing in 30mL of 25% ammonia water, carrying out hydrothermal reaction at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanosheets, finally 10mg of porous g-C 3 N 4 Dispersing the nano-sheets in 100mL of deionized water, and ultrasonically crushing for 3h by using an XM-1000T ultrasonic crusher under high energy of 1000W to obtain g-C with the concentration of 0.1mg/mL 3 N 4 Solutions of QDs;
step 5, irradiating the mixed system under ultraviolet illumination for 2 hours for carrying out a light deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and anhydrous ethanol for 5 times, and vacuum drying at 60 deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 MXene photocatalyst.
Example 5:
step 1, weighing 10g of Ti 3 AlC 2 Slowly adding into 100mL HF solution with mass fraction of 40%Stirring the reaction solution with the concentration of 0.1g/mL at room temperature for 27h for acid etching reaction, washing a product obtained by centrifugally separating the reaction solution after the reaction is finished by using deionized water and ethanol until the pH value of the solution is more than 6.5, centrifugally separating the solution, and vacuum-drying the product at 60 ℃ for 12h to obtain ML-Ti 3 C 2 (ii) a At a concentration of 25mg/L, adding ML-Ti 3 C 2 Dispersing the powder in 40mL of deionized water, carrying out ultrasonic crushing for 1h, centrifuging, and carrying out vacuum drying on the product at 60 ℃ for 12h to obtain few-layer Ti 3 C 2 MXene。
Step 3, calcining the urea at 550 ℃ for 4 hours to obtain g-C 3 N 4 Taking 1g of g-C 3 N 4 Stirring the mixture for 2 hours at room temperature in a mixed solution of 20mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, and washing the mixed solution for 3 times by using 1L of deionized water to obtain porous g-C 3 N 4 Taking 100mg of porous g-C 3 N 4 Dispersing in 30mL of 28% ammonia water, carrying out hydrothermal reaction at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanosheets, finally 10mg of porous g-C 3 N 4 Dispersing the nano-sheets in 100mL of deionized water, and ultrasonically crushing for 3h by using an XM-1000T ultrasonic crusher under high energy of 1000W to obtain g-C with the concentration of 0.1mg/mL 3 N 4 Solutions of QDs;
step 5, irradiating the mixed system under ultraviolet illumination for 1h to perform a light deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and anhydrous ethanol for 3 times, and vacuum drying at 60 deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 MXene photocatalyst.
Example 6:
step 1, weighing 10g of Ti 3 AlC 2 Slowly adding 100mL of HF solution with the mass fraction of 40% to obtain a reaction solution with the concentration of 0.1g/mL, stirring at room temperature for 27h for acid etching reaction, washing a product obtained by centrifugally separating the reaction solution with deionized water and ethanol until the pH value of the solution is more than 6.5, centrifugally separating the solution, and vacuum-drying the product at 60 ℃ for 12h to obtain ML-Ti 3 C 2 (ii) a At a concentration of 25mg/L, adding ML-Ti 3 C 2 Dispersing the powder in 40mL of deionized water, carrying out ultrasonic crushing for 1h, centrifuging, and carrying out vacuum drying on the product at 60 ℃ for 12h to obtain few-layer Ti 3 C 2 MXene。
Step 3, calcining the urea at 550 ℃ for 4 hours to obtain g-C 3 N 4 Taking 1g of g-C 3 N 4 Stirring the mixture for 2 hours at room temperature in a mixed solution of 20mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, and washing the mixed solution for 3 times by using 1L of deionized water to obtain porous g-C 3 N 4 Taking 100mg of porous g-C 3 N 4 Dispersing in 30mL of 26% ammonia water, carrying out hydrothermal reaction at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanosheets, finally 10mg of porous g-C 3 N 4 Dispersing the nano-sheets in 100mL of deionized water, and crushing the nano-sheets in high energy by using an XM-1000T ultrasonic crusherUltrasonic crushing for 3h under the condition of 1000W to obtain g-C with the concentration of 0.1mg/mL 3 N 4 Solutions of QDs;
step 5, irradiating the mixed system for 3 hours under ultraviolet illumination to perform a light deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and anhydrous ethanol for 4 times, and vacuum drying at 60 deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 MXene photocatalyst.
Example 7:
step 1, weighing 10g of Ti 3 AlC 2 Slowly adding 100mL of HF solution with the mass fraction of 40% to obtain reaction liquid with the concentration of 0.1g/mL, stirring at room temperature for 27h for acid etching reaction, washing a product obtained by centrifugally separating the reaction liquid with deionized water and ethanol after the reaction is finished until the pH value of the solution is more than 6.5, centrifugally separating the solution, and drying the product at 60 ℃ in vacuum for 12h to obtain ML-Ti 3 C 2 (ii) a At a concentration of 25mg/L, adding ML-Ti 3 C 2 Dispersing the powder in 40mL of deionized water, carrying out ultrasonic crushing for 1h, centrifuging, and carrying out vacuum drying on the product at 60 ℃ for 12h to obtain few-layer Ti 3 C 2 MXene。
Step 3, calcining urea at 550 ℃ for 4 hours to obtain ureag-C 3 N 4 Taking 1g of g-C 3 N 4 Stirring the mixture for 2 hours at room temperature in a mixed solution of 20mL concentrated sulfuric acid and 20mL concentrated nitric acid, washing the mixed solution for 3 times by using 1L deionized water to obtain porous g-C 3 N 4 Taking 100mg of porous g-C 3 N 4 Dispersing in 30mL of 25% ammonia water, carrying out hydrothermal reaction at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanosheets, finally 10mg of porous g-C 3 N 4 Dispersing the nano-sheets in 100mL of deionized water, and ultrasonically crushing for 3h by using an XM-1000T ultrasonic crusher under high energy of 1000W to obtain g-C with the concentration of 0.1mg/mL 3 N 4 Solutions of QDs;
step 5, irradiating the mixed system under ultraviolet illumination for 4 hours to carry out a light deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and anhydrous ethanol for 2 times, and vacuum drying at 60 deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 MXene photocatalyst.
Comparative example 1:
step 1, weighing 10g of Ti 3 AlC 2 Slowly adding 100mL of HF solution with the mass fraction of 40% to obtain a reaction solution with the concentration of 0.1g/mL, stirring at room temperature for 27h for acid etching reaction, washing a product obtained by centrifugally separating the reaction solution with deionized water and ethanol until the pH value of the solution is more than 6.5, centrifugally separating the solution, and vacuum-drying the product at 60 ℃ for 12h to obtain ML-Ti 3 C 2 (ii) a At a concentration of 25mg/L, adding ML-Ti 3 C 2 Dispersing the powder in 40mL of deionized water, carrying out ultrasonic crushing for 1h, centrifuging, and carrying out vacuum drying on the product at 60 ℃ for 12h to obtain few-layer Ti 3 C 2 MXene。
The above conclusions and mechanisms are specifically explained below.
FIG. 1 shows g-C prepared according to the present invention 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 XRD pattern of MXene photocatalyst. Wherein a is the exposed (001) plane TiO synthesized in comparative example 1 2 /Ti 3 C 2 MXene photocatalyst, and b, C, d and e are g-C synthesized according to example 1, example 2, example 3 and example 4, respectively 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 MXene photocatalyst. As in fig. 1,2 θ =9.5 °, 19.2 °, 27.8 ° and 60.3 ° respectively correspond to Ti 3 C 2 Diffraction peak of MXene, ti 3 C 2 After MXene is subjected to hydrothermal oxidation treatment, the 2 theta =25.2 degrees, 37.0 degrees, 37.8 degrees, 38.6 degrees, 48.1 degrees, 53.9 degrees, 55.1 degrees and 62.7 degrees correspond to anatase phase TiO 2 (JCPDSNo. 21-1272) and (101), (103), (004), (112), (200), (105), (211) and (204). Under the load of g-C 3 N 4 TiO 2 θ =25.2 ° and 37.8 ° after QDs 2 The diffraction peaks of the (101) and (004) crystal planes of (A) are slightly weakened, while Ti 3 C 2 The diffraction peaks at 9.5 ℃ and 19.2 ℃ of MXene are significantly reduced and follow the g-C 3 N 4 Increase in QDs loading, the two diffraction peaks showing a reduced tendency, ti on examples 3 and 4 3 C 2 These two peaks of MXene almost disappeared, indicating that g-C 3 N 4 QDs is wrapped in Ti 3 C 2 MXene and TiO 2 On the surface, g-C is illustrated 3 N 4 Successful loading of QDs.
FIG. 2 shows g-C 3 N 4 SEM images of quantum dots before dispersion. From FIG. 2, it can be seen that the pores g-C are porous 3 N 4 The average size of the nanoplatelets before dispersion is about 38.79nm. FIG. 3 is g-C 3 N 4 The TEM image of the quantum dots shows that g-C is obtained under the ultrasonic crushing action of 1000W high energy of an XM-1000T ultrasonic crusher 3 N 4 The average size of QDs is about 15nm.
FIGS. 4 and 5 are g-C prepared according to the present invention 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 SEM image of MXene photocatalyst. Exposing (001) plane TiO 2 Lamellar Ti inlaid in sheet 3 C 2 On MXene, it can be seen that a small amount of g-C 3 N 4 Quantum dots supported on TiO 2 On the surface of the (001) plane, which indicates that g-C is present in the ternary complex system 3 N 4 The presence of quantum dots.
FIG. 6 shows g-C 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 EDS picture of MXene. The presence of Ti, C, O and N elements can be detected, which also proves that g-C in the ternary complex system 3 N 4 The presence of quantum dots.
FIG. 7 shows g-C prepared according to the present invention 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 And (3) a UV-vis-NIR diffuse reflection spectrum diagram of the MXene photocatalyst. Both 580nm and 960nm have two distinct absorption peaks, which are attributed to Ti 3 C 2 Transverse surface plasmon resonance (TE) and longitudinal surface plasmon resonance (TM) of MXene such that g-C 3 N 4 QDs/exposed (001) plane/TiO 2 /Ti 3 C 2 MXene also has strong light absorption in the near infrared spectral range. When g-C 3 N 4 QDs loading on exposed (001) plane/TiO 2 /Ti 3 C 2 Full spectrum absorption is significantly enhanced on MXene, and g-C synthesized in example 2 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 Light absorption intensity of MXene was slightly higher than that of g-C synthesized in example 4 3 N 4 QDs/exposed (001) plane/TiO 2 /Ti 3 C 2 MXene. To illustrate the appropriate g-C 3 N 4 QDs loading can enhance exposure to (001) crystal plane/TiO 2 /Ti 3 C 2 High utilization of solar energy by MXene.
FIG. 8 shows g-C prepared according to the present invention 3 N 4 QDs/exposed (001) plane/TiO 2 /Ti 3 C 2 Degradation profile of MXene photocatalyst to CIP under visible light. After 30min of adsorption and desorption balance, the exposed (001) crystal face/TiO synthesized in the comparative example 1 is irradiated by visible light for 120min 2 /Ti 3 C 2 Examples 1-4 g-C 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 The degradation rates of the photocatalyst to CIP are 31.58%, 35.23%, 36.73%, 40.11% and 37.03% respectively; the degradation rate constants K are respectively 0.00005min -1 、0.00074min -1 、0.00159min -1 、0.00076min -1 And 0.00077min -1 . The above results illustrate the g-C loading 3 N 4 After QDs, g-C 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 The degradation performance of CIP under visible light is improved.
FIG. 9 shows g-C prepared according to the present invention 3 N 4 QDs/exposed (001) plane/TiO 2 /Ti 3 C 2 Degradation profile of MXene photocatalyst to CIP under near infrared light. After dark reaction for 30min and near-infrared light illumination for 120min, the exposed (001) crystal face/TiO synthesized in comparative example 1 2 /Ti 3 C 2 Examples 1-4 g-C 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 The degradation rate of the photocatalyst to CIP is 34.98%, 49.92%, 48.59%, 47.86% and 49.85% respectively; the degradation rate constants k are respectively 0.00013min -1 、0.00076min -1 、0.00114min -1 、0.00042min -1 And 0.00084min -1 . The above results illustrate the g-C loading 3 N 4 After QDs, g-C 3 N 4 QDs/exposed (001) plane/TiO 2 /Ti 3 C 2 Specific exposure (001) crystal face/TiO 2 /Ti 3 C 2 The degradation performance of CIP under near infrared light is improved.
FIG. 10 shows g-C prepared according to the present invention 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 Transient time-current curve of photocatalyst under visible light. The photocurrent curves (i-t) were carried out on a CHI660E electrochemical workstation. The test system used a standard three-electrode system, working electrode (sample film plated on FTO glass), reference electrode (saturated AgCl/Ag electrode) and counter electrode (platinum). Preparing 0.1mol/LNa 2 SO 4 The solution is used as an electrolyte solution, a 300W xenon lamp is selected as a light source, a filter with a specific wavelength is used for carrying out visible light simulation, the testing time of a photocurrent curve is 280s, the testing voltage range of a photovoltage and cyclic voltammetry test is 0-1V, and the voltage amplification is 0.01V/s. The preparation process of the working electrode is the prior process: weighing 20mg of sample, dispersing the sample in a mixed solution of 1mL of absolute ethyl alcohol and 0.1mL of naphthol, uniformly coating the sample on an excited FTO glass substrate for several times by using a spin coating method after ultrasonic dispersion, wherein the excited FTO glass substrate is an FTO glass substrate irradiated by ultraviolet light for 25min, and can remove surface dust and organic matters, so that the FTO glass substrate has hydrophilicity, is convenient for uniform spin coating, and annealing at 150 ℃ for 25min to prepare a working electrode.
Comparative example 1 synthesized exposed (001) crystal plane/TiO 2 /Ti 3 C 2 10% of example 2 with the CNQDs/(001) TO/TC sample as C, 20% of example 4 with the CNQDs/(001) TO/TC sample as e, g-C prepared in all examples 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 Photocurrent response under visible light, and g-C synthesized in example 2 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 The photocatalyst possessed the maximum photocurrent, which indicates that g-C 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 The carrier can be generated in large quantity under the irradiation of visible light, and can be effectively transferred and separated. Exposed (001) crystal plane/TiO synthesized with comparative example 1 2 /Ti 3 C 2 Comparative, load g-C 3 N 4 The photocurrent increased significantly after QDs, thus also demonstrating g-C 3 N 4 The presence of QDs can significantly improve carrier separation and transport efficiency.
FIG. 11 g-C prepared according to the invention 3 N 4 QDs/exposed (001) crystal plane/TiO 2 /Ti 3 C 2 The transient time-current curve under near infrared light is the same as the test process of FIG. 10, the filter with specific wavelength is subjected to near infrared light simulation, and the exposed (001) crystal face/TiO synthesized in comparative example 1 2 /Ti 3 C 2 In case a, C in example 2 and e, g-C in example 4 3 N 4 QDs/exposed (001) plane/TiO 2 /Ti 3 C 2 The transient time-current curve in the near infrared also follows the same law in the visible, g-C 3 N 4 The existence of the quantum dots can also remarkably improve the separation and migration efficiency of carriers.
FIG. 12 shows g-C prepared according to the present invention 3 N 4 QDs/exposed (001) plane TiO 2 /Ti 3 C 2 MXene degrades the reaction mechanism of CIP under simulated sunlight. Two-dimensional Ti 3 C 2 The work function of MXene is about 1.8eV 2 Has a work function of about 6.58eV to form TiO with an exposed (001) plane 2 /Ti 3 C 2 When MXene is used, schottky barrier is built on the interface, and electrons are separated from two-dimensional Ti 3 C 2 Migration of MXene to TiO 2 In Ti 3 C 2 MXene forms positively charged domains in TiO 2 Forming a negatively charged region, forming a space charge region free of free carriers, generating free electrons from Ti 3 C 2 MXene directional TiO 2 Built-in electric field E of 2 . g-C under illumination 3 N 4 QDs、TiO 2 (101) Crystal face and TiO 2 (001) Electrons in the valence band of the crystal plane are excited to transition to the corresponding conduction band, leaving holes in the valence band. Electrostatic electric field E at the interface 3 And built-in electric field E of surface heterojunction 1 Under the action of TiO 2 Hole transporting TiO in the valence band of (101) plane 2 (001) Crystal face and continue to g-C 3 N 4 The valence band of QDs shifts. Followed byg-C 3 N 4 Holes in the valence band of QDs and TiO 2 The hole migrated on the (001) crystal face of (A) is oxidized together to degrade CIP; and g-C 3 N 4 Transfer of electrons in the QDs conduction band to TiO 2 (001) Crystal face re-migrating to TiO 2 On the (101) crystal plane of (1); migration to TiO 2 The electrons on the conduction band of the (101) crystal plane and the electrons themselves photoexcited due to the Schottky junction of the interface have an internal electric field E 2 To allow electrons to continue to migrate to Ti 3 C 2 MXene, supplement Ti 3 C 2 Hot electrons of MXene excited, ti 3 C 2 MXene photoexcited hot electron and O in system 2 Reacting to generate superoxide radical (. O) 2- )，·O 2- And CIP to effect degradation. In g-C 3 N 4 QDs and TiO 2 (001) Electrostatic electric field E of crystal surface interface 3 、TiO 2 Built-in electric field E of surface heterojunction 1 、TiO 2 Crystal plane of (101) and Ti 3 C 2 Built-in electric field E of MXene Schottky junction 2 And plasma Ti 3 C 2 The LSPR effect of MXene is combined to enhance the photodegradation and degradation performance.
FIG. 13 is an electrochemical impedance plot of the products prepared in comparative example 1, example 2 and example 4 of the present invention, from which it can be seen that the 10-cent CNQDs/(001) TO/TC sample of example 2 has the smallest arc radius, shows the smallest resistance value, and the presence of CNQDs makes the 10-cent CNQDs/(001) TO/TC sample exhibit the smallest charge transfer resistance and enhanced photo-generated electron-hole pair separation rate and carrier mobility.
The above description is only one embodiment of the present invention, and not all or only one embodiment, and any equivalent alterations to the technical solutions of the present invention, which are made by those skilled in the art through reading the present specification, are covered by the claims of the present invention.
Claims (10)
1. The preparation method of the titanium dioxide/titanium carbide MXene with the exposed carbon nitride quantum dot/(001) surface is characterized by comprising the following steps of,
dioxygen exposing (001) faceDispersing titanium oxide/titanium carbide MXene powder in ethanol to obtain suspension, irradiating the suspension under ultraviolet light, and adding g-C 3 N 4 Quantum dot solution, g-C 3 N 4 The mass ratio of the quantum dots to the titanium dioxide/titanium carbide MXene powder with the exposed (001) surface is (2.5-10): 50, obtaining a mixed system;
irradiating the mixed system under ultraviolet light to obtain a reaction solution; and sequentially drying the precipitates in the reaction liquid to obtain the titanium dioxide/titanium carbide MXene with the exposed carbon nitride quantum dot/(001) surface.
2. The method for preparing carbon nitride quantum dots/(001) surface exposed titanium dioxide/titanium carbide MXene according to claim 1, wherein g-C is 3 N 4 The quantum dot solution is carried out according to the following processes:
porous g-C is firstly 3 N 4 Dispersing in ammonia water, performing hydrothermal reaction at 170-190 ℃ for 10-14 h to obtain reaction liquid, separating and cleaning products in the reaction liquid to obtain porous g-C 3 N 4 Nanosheets prepared by mixing porous g-C 3 N 4 Dispersing the nano-sheets in deionized water, and finally carrying out ultrasonic crushing for 2.5-3.5 h under 800-1200W to obtain g-C 3 N 4 A quantum dot solution.
3. The method for preparing carbon nitride quantum dots/(001) surface exposed titanium dioxide/titanium carbide MXene according to claim 2, wherein the porous g-C is 3 N 4 The method comprises the following steps:
calcining urea at 500-600 ℃ for 3.5-4.5 h to obtain g-C 3 N 4 G to C 3 N 4 Stirring the mixture for 1.5 to 2.5 hours at room temperature in the mixed solution of concentrated sulfuric acid and concentrated nitric acid to obtain mixed solution, washing the mixed solution by deionized water, and filtering the solid in the mixed solution to obtain porous g-C 3 N 4 Ultrasonication to obtain g-C 3 N 4 A quantum dot solution.
4. The method for preparing carbon nitride quantum dots/(001) plane exposed titanium dioxide/titanium carbide MXene according to claim 1, wherein the ratio of (001) plane exposed titanium dioxide/titanium carbide MXene powder to ethanol in the suspension is (45-55) mg: (25-35) mL.
5. The method for preparing carbon nitride quantum dots/(001) surface exposed titanium dioxide/titanium carbide MXene according to claim 1, wherein g-C is added after the suspension is irradiated under ultraviolet light for 3.5-4.5 h 3 N 4 A quantum dot solution.
6. The method for preparing carbon nitride quantum dots/(001) plane exposed titanium dioxide/titanium carbide MXene according to claim 1, wherein the g-C is 3 N 4 The concentration of the quantum dot solution is 0.15-0.25 mg/mL, g-C 3 N 4 The volume ratio of the quantum dot solution to the ethanol is (25-100): (25 to 35).
7. The method for preparing the titanium dioxide/titanium carbide MXene with the exposed carbon nitride quantum dot/(001) surface according to claim 1, wherein the mixed system is irradiated under ultraviolet light for 1-4 h to obtain a reaction solution.
8. The method for preparing carbon nitride quantum dots/(001) surface exposed titanium dioxide/titanium carbide MXene according to claim 1, wherein the precipitate in the reaction solution is washed with deionized water and absolute ethanol for 2-5 times, and vacuum dried at 60-70 ℃ for 10-14 h to obtain the carbon nitride quantum dots/(001) surface exposed titanium dioxide/titanium carbide MXene.
9. The carbon nitride quantum dot/(001) -surface exposed titanium dioxide/titanium carbide MXene prepared by the method for preparing the carbon nitride quantum dot/(001) -surface exposed titanium dioxide/titanium carbide MXene according to any one of claims 1 to 8.
10. Use of the carbon nitride quantum dot/(001) plane exposed titanium dioxide/titanium carbide MXene according to claim 9 for degrading ciprofloxacin under visible light and near infrared light.
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| CN106492867A (en) * | 2016-09-27 | 2017-03-15 | 浙江大学 | g‑C3N4Quantum dot sensitized TiO2The preparation method of nanotube |
| CN108772094A (en) * | 2018-07-12 | 2018-11-09 | 重庆交通大学 | A kind of nitridation carbon quantum dot/TiO 2 sol and preparation method thereof |
| CN109622013A (en) * | 2018-12-07 | 2019-04-16 | 陕西科技大学 | One type graphite phase carbon nitride-(110) crystal face pucherite Z-type heterojunction photocatalyst and its preparation method and application |
| CN113578355A (en) * | 2021-07-30 | 2021-11-02 | 陕西科技大学 | Titanium dioxide/titanium carbide nanosheet with exposed (001) crystal face as well as preparation method and application thereof |
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| CN106492867A (en) * | 2016-09-27 | 2017-03-15 | 浙江大学 | g‑C3N4Quantum dot sensitized TiO2The preparation method of nanotube |
| CN108772094A (en) * | 2018-07-12 | 2018-11-09 | 重庆交通大学 | A kind of nitridation carbon quantum dot/TiO 2 sol and preparation method thereof |
| CN109622013A (en) * | 2018-12-07 | 2019-04-16 | 陕西科技大学 | One type graphite phase carbon nitride-(110) crystal face pucherite Z-type heterojunction photocatalyst and its preparation method and application |
| CN113578355A (en) * | 2021-07-30 | 2021-11-02 | 陕西科技大学 | Titanium dioxide/titanium carbide nanosheet with exposed (001) crystal face as well as preparation method and application thereof |
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