CN115318329B - Titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dot/(001) surface, and preparation method and application thereof - Google Patents
Titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dot/(001) surface, and 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 55
- 239000002096 quantum dot Substances 0.000 title claims abstract description 45
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 27
- 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 27
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 31
- 230000001678 irradiating effect Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 17
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 14
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 6
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000008367 deionised water Substances 0.000 claims description 51
- 229910021641 deionized water Inorganic materials 0.000 claims description 51
- 239000000047 product Substances 0.000 claims description 38
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- 235000019441 ethanol Nutrition 0.000 claims description 30
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- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 239000002135 nanosheet Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002064 nanoplatelet Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 abstract description 5
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- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000003242 anti bacterial agent Substances 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 133
- 239000013078 crystal Substances 0.000 description 104
- 229910010413 TiO 2 Inorganic materials 0.000 description 93
- 239000011941 photocatalyst Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- 229910020808 NaBF Inorganic materials 0.000 description 9
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- 230000005012 migration Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 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
- 239000011521 glass Substances 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000002198 surface plasmon resonance spectroscopy Methods 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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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- KHOITXIGCFIULA-UHFFFAOYSA-N Alophen Chemical compound C1=CC(OC(=O)C)=CC=C1C(C=1N=CC=CC=1)C1=CC=C(OC(C)=O)C=C1 KHOITXIGCFIULA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000503 bisacodyl Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 238000002484 cyclic voltammetry Methods 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 239000000428 dust Substances 0.000 description 1
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- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical class [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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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- 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
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dot/(001) surface, 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 then adding g-C 3 N 4 The quantum dot solution is uniformly mixed, 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 (3) sequentially drying the precipitate in the reaction liquid to obtain the titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dots/(001) surface. The invention has low cost and simple operation, and can be used for degrading the ciprofloxacin which is an antibiotic pollutant under the 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, a preparation method and application thereof.
Background
In recent years, semiconductor photocatalysis technology has been widely concerned with the prospect of environmental pollution control.
Block g-C 3 N 4 The specific surface area is small and can not be matched with TiO 2 And establishing an efficient electron transmission interface to influence the photocatalytic performance, wherein interface defects of the electron transmission interface become recombination centers of photogenerated carriers to influence the photocatalytic performance. Thus, g-C is reduced 3 N 4 The dimension is an effective method for improving the specific surface area of the material, and the graphite phase carbon nitride quantum dot (g-C 3 N 4 QDs) have been widely used due to their good water solubility and stability, low toxicity, and the like. g-C 3 N 4 QDs have higher fluorescence quantum efficiencies than Graphene Quantum Dots (GQDs) and Carbon Quantum Dots (CQDs). By aligning the blocks g-C 3 N 4 Performing 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 physical and chemical properties of the QDs enable the QDs to be compounded with a semiconductor so as to obviously improve the photocatalytic activity of the semiconductor.
g-C in the form of quantum dots 3 N 4 As a zero-dimensional material with a larger specific surface area and more active sites, but in the form of quantum dots 3 N 4 With TiO 2 The photo-response after recombination is not high enough and the separation of photo-generated carriers is not ideal enough.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dots/(001) surface, and a preparation method and application thereof, which have low cost and simple operation, and can be used for degrading antibiotic pollutants ciprofloxacin under full spectrum.
The invention is realized by the following technical scheme:
the preparation method of the titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dot/(001) surface comprises the following steps,
titanium dioxide/titanium carbide MXene powder with exposed (001) surfaceDispersing the obtained mixture in ethanol to obtain suspension, irradiating the suspension with ultraviolet light, and adding g-C 3 N 4 The quantum dot solution is uniformly mixed, 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 (3) sequentially drying the precipitate in the reaction liquid to obtain the titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dots/(001) surface.
Preferably, said g-C 3 N 4 The quantum dot solution is prepared according to the following steps:
porous g-C 3 N 4 Dispersing in ammonia water, performing hydrothermal reaction at 170-190 ℃ for 10-14 h to obtain a reaction solution, separating and cleaning a product in the reaction solution to obtain porous g-C 3 N 4 Nanoplatelets, porous g-C 3 N 4 Dispersing the nano-sheets in deionized water, and finally performing ultrasonic crushing for 2.5-3.5 hours under 800-1200W to obtain g-C 3 N 4 Quantum dot solution.
Further, the porous g-C 3 N 4 The method comprises the following steps:
calcining urea at 500-600 deg.c for 3.5-4.5 hr to obtain g-C 3 N 4 g-C 3 N 4 Stirring for 1.5-2.5 h at room temperature in a mixed solution of concentrated sulfuric acid and concentrated nitric acid to obtain a mixed solution, washing the mixed solution with deionized water, and filtering solids in the mixed solution to obtain porous g-C 3 N 4 Ultrasonic crushing to obtain g-C 3 N 4 Quantum dot solution.
Preferably, in the suspension, the ratio of the titanium dioxide/titanium carbide MXene powder with the (001) surface exposed to ethanol is (45-55) mg: (25-35) mL.
Preferably, the suspension is irradiated with ultraviolet light for 3.5 to 4.5 hours and then g-C is added 3 N 4 Quantum dot solution.
Preferably, the g-C 3 N 4 The concentration of the quantum dot solution is 0.15-0.25 mg/mL, g-C 3 N 4 Quantum dotThe volume ratio of the solution to the ethanol is (25-100): (25-35).
Preferably, the mixed system is illuminated for 1-4 hours under ultraviolet light to obtain a reaction solution.
Preferably, the precipitate in the reaction liquid 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 60 to 70 ℃ to obtain the titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dots/(001) surface.
The carbon nitride quantum dot/(001) -surface-exposed titanium dioxide/titanium carbide MXene prepared by the preparation method of any one of the carbon nitride quantum dot/(001) -surface-exposed titanium dioxide/titanium carbide MXene.
The application of titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dot/(001) surface in degrading ciprofloxacin under visible light and near infrared light is provided.
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 carbon nitride quantum dots/(001) surface, which exposes (001) crystal face TiO 2 /Ti 3 C 2 Dispersing MXene in ethanol to obtain suspension, and irradiating with ultraviolet light to obtain TiO 2 Under the action of surface heterojunction of (2) TiO 2 Electrons on the (001) and (101) crystal plane valence bands are excited to transition to the corresponding conduction band, holes are left on the valence band, and negatively charged photo-generated electrons are promoted to TiO under the action of a built-in electric field of a surface heterojunction 2 (101) crystal plane migration, and positively charged photo-generated holes to TiO 2 (001) crystal plane migration followed by addition of negatively charged g-C 3 N 4 Carrying out light deposition reaction on the quantum dot solution under ultraviolet irradiation, and carrying out g-C with negative electricity 3 N 4 QDs and TiO 2 Positive holes of the (001) crystal face are combined together under the action of electrostatic attraction to form g-C 3 N 4 QDs are deposited on the surface embedded in Ti 3 C 2 TiO between MXene surfaces and layers 2 On the exposed (001) crystal face, and drying the product after separation to obtain g-C 3 N 4 QDs/(001)TiO 2 /Ti 3 C 2 MXene lightA catalyst. The invention adopts a photo-deposition method to prepare the g-C 3 N 4 The quantum dots are loaded on TiO 2 g-C on the (001) crystal plane surface 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 by crystal interface and TiO 2 Built-in electric field formed by surface heterojunction and 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 whole spectrum range of 200-2200nm is enhanced, wherein Ti 3 C 2 Transverse surface plasmon resonance (TE) and longitudinal surface plasmon resonance (TM) effects of MXene such that g-C 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 MXene also has strong light absorption in the near infrared spectrum, when g-C 3 N 4 QDs Supported on exposed (001) crystal face/TiO 2 /Ti 3 C 2 When MXene is added, the full spectrum absorption is obviously enhanced, and the exposure (001) crystal face/TiO can be enhanced 2 /Ti 3 C 2 The MXene has high solar energy utilization rate, the space between the photo-generated electrons and the holes is effectively separated, the photocatalytic degradation performance is enhanced, and the CIP of the 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 higher degradation rate on ciprofloxacin under visible light, can effectively degrade ciprofloxacin under near infrared light, and has good application prospect.
Drawings
FIG. 1 shows XRD patterns of the products prepared in comparative example 1 and examples 1 to 4 according to the present invention.
FIG. 2 is g-C 3 N 4 SEM image of QDs before dispersion.
FIG. 3 is g-C 3 N 4 TEM image of QDs.
FIG. 4 is an SEM image of the product of example 2 of the present invention.
FIG. 5 is an enlarged SEM image 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 UV-vis-NIR DRS graph of the products prepared in comparative example 1, example 2 and example 4 of the present invention.
FIG. 8 is a graph showing the degradation of the products prepared in comparative example 1, examples 1 to 4 according to the present invention to the cyclic bisaxacin under simulated visible light.
FIG. 9 is a graph showing the degradation of the products prepared in comparative example 1 and examples 1 to 4 according to the present invention to the cyclic bisacodyl under the simulated near infrared light.
FIG. 10 is a graph showing photocurrent i-t in the visible light of the products prepared in comparative example 1, example 2 and example 4 according to the present invention.
FIG. 11 is a graph showing photocurrent i-t in near infrared light of the products prepared in comparative example 1, example 2 and example 4 according to 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 Photocatalytic degradation mechanism diagram of MXene photocatalyst.
FIG. 13 is an electrochemical impedance plot of the products prepared in comparative example 1, example 2 and example 4 of the present invention.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
Since the surface active site and the electronic structure depend on the special crystal face structure, the crystal face engineering plays a very key role in the photocatalysis process, and the high-activity TiO is exposed 2 The semiconductor crystal face can be used for improving the photocatalytic activity of the material. Controlling NaBF in crystal face 4 Under the action of (A) TiO 2 The crystal is easier to expose the (001) crystal face with high activity, and TiO with the (001) crystal face exposed 2 At Ti 3 C 2 Growing in situ on the substrate to make TiO 2 With Ti 3 C 2 Has an intimate contact interface, and TiO when excited by light 2 The (001) crystal face with high activity can generate photo-generated electron hole pairs with high efficiencyAt the same time Ti 3 C 2 The rapid capture of photogenerated holes greatly facilitates the separation of carriers to expose the (001) crystal plane TiO 2 /Ti 3 C 2 Based on composite material, through the g-C with zero-dimensional material quantum dot form 3 N 4 The photocatalyst constructs heterojunction, which can further improve visible light (lambda)>400 nm) and near infrared light (lambda>800 nm) facilitating further separation of photogenerated carriers. Thus, a g-C of the invention 3 N 4 QDs/exposed (001) crystal face TiO 2 /Ti 3 C 2 The preparation of the MXene photocatalyst was carried out as in the following examples.
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 performing HF to Ti 3 AlC 2 Carrying out acid etching reaction, after the reaction is finished, washing the product centrifugally separated from the reaction liquid by 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 the multilayer Ti 3 C 2 I.e. ML-Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the ML-Ti is added at a concentration of 25mg/L 3 C 2 Dispersing the powder in 40mL deionized water, ultrasonically crushing for 1h, centrifuging, and vacuum drying the product at 60 ℃ for 12h to obtain a few-layer Ti 3 C 2 MXene。
Step 2, 200mg of Ti 3 C 2 MXene powder was dispersed in 30mL of 1mol/L HCl solution, and 0.33g of NaBF as a crystal face control agent was added 4 Stirring for 30min, ultrasonic treating for 10min, transferring to a hydrothermal reaction kettle of polytetrafluoroethylene, reacting at 160deg.C for 12 hr, cooling the reaction liquid to room temperature, cleaning with deionized water and ethanol respectively for 3 times, and vacuum drying at 60deg.C for 12 hr 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 for 2h at room temperature in a mixture of 20mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, and washing the mixture with 1L of deionized water for 3 times to obtain porous g-C 3 N 4 100mg of porous g-C was taken again 3 N 4 Dispersing in 30mL28% ammonia water, hydrothermal reacting at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanometer sheet, finally 10mg of porous g-C is taken 3 N 4 Dispersing the nanosheets in 100mL deionized water, ultrasonically crushing for 3 hours at high energy of 1000W by using an XM-1000T ultrasonic crusher, and dispersing the porous g-C by using cavitation of ultrasonic waves 3 N 4 Stirring and crushing the nano-sheet agglomerated particles into g-C 3 N 4 QDs to give g-C at a concentration of 0.1mg/mL 3 N 4 QDs solution;
step 4, 50mg of the exposed (001) crystal face TiO 2 /Ti 3 C 2 MXene powder was dispersed in 30mL of ethanol to prepare a suspension and irradiated with ultraviolet light for 3 hours, followed by addition of 25mL of g-C having a concentration of 0.1mg/mL 3 N 4 The QDs solution is uniformly mixed to obtain a mixed system, and g-C is obtained at the moment 3 N 4 QDs and exposed (001) crystal plane TiO 2 /Ti 3 C 2 The mass ratio of MXene is 2.5:50;
step 5, irradiating the mixed system for 2 hours under ultraviolet irradiation to carry out a photo-deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and absolute ethanol for 2 times, vacuum drying at 60deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) crystal face 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 reaction solution with the concentration of 0.1g/mL, stirring at room temperature for 27h to perform acid etching reaction, washing the centrifugally separated product of the reaction solution with deionized water and ethanol until the pH value of the solution is greater than 6.5, centrifugally separating the solution, and vacuum drying the product at 60 ℃ for 12h to obtain ML-Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the ML-Ti is added at a concentration of 25mg/L 3 C 2 Dispersing the powder in 40mL deionized water, ultrasonically crushing for 1h, centrifuging, and vacuum drying the product at 60 ℃ for 12h to obtain a few-layer Ti 3 C 2 MXene。
Step 2, 200mg of Ti 3 C 2 MXene powder was dispersed in 30mL of 1mol/L HCl solution, and 0.33g of NaBF as a crystal face control agent was added 4 Stirring for 30min, ultrasonic treating for 10min, transferring to a hydrothermal reaction kettle of polytetrafluoroethylene, reacting at 160deg.C for 12 hr, cooling the reaction liquid to room temperature, cleaning with deionized water and ethanol respectively for 3 times, and vacuum drying at 60deg.C for 12 hr 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 for 2h at room temperature in a mixture of 20mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, and washing the mixture with 1L of deionized water for 3 times to obtain porous g-C 3 N 4 100mg of porous g-C was taken again 3 N 4 Dispersing in 30mL27% ammonia water, hydrothermal reacting at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanometer sheet, finally 10mg of porous g-C is taken 3 N 4 Dispersing the nanosheets in 100mL deionized water, and performing ultrasonic crushing for 3 hours under high energy of 1000W by using an XM-1000T ultrasonic crusher to obtain g-C with the concentration of 0.1mg/mL 3 N 4 QDs solution;
step 4, 50mg of the exposed (001) crystal face TiO 2 /Ti 3 C 2 Dispersing MXene powder in 30mL ethanol to obtain suspension, irradiating with ultraviolet light for 3 hr, and adding 50mL g-C with concentration of 0.1mg/mL 3 N 4 The QDs solution is uniformly mixed to obtain a mixed system, and g-C is obtained at the moment 3 N 4 QDs and exposed (001) crystal plane TiO 2 /Ti 3 C 2 The mass ratio of MXene is 5:50;
step 5, irradiating the mixed system for 2 hours under ultraviolet irradiation to carry out a photo-deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and absolute ethanol for 2 times, vacuum drying at 60deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) crystal face TiO 2 /Ti 3 C 2 MXene photocatalyst.
Example 3:
step 1, weighing 10g of Ti 3 AlC 2 Slowly add 100mL of HF solution with mass fraction of 40%Obtaining a reaction solution with the concentration of 0.1g/mL, stirring the reaction solution at room temperature for 27h to carry out acid etching reaction, washing a product centrifugally separated from the reaction solution by deionized water and ethanol until the pH value of the solution is more than 6.5 after the reaction is finished, centrifugally separating the solution, and drying the product at 60 ℃ in vacuum for 12h to obtain ML-Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the ML-Ti is added at a concentration of 25mg/L 3 C 2 Dispersing the powder in 40mL deionized water, ultrasonically crushing for 1h, centrifuging, and vacuum drying the product at 60 ℃ for 12h to obtain a few-layer Ti 3 C 2 MXene。
Step 2, 200mg of Ti 3 C 2 MXene powder was dispersed in 30mL of 1mol/L HCl solution, and 0.33g of NaBF as a crystal face control agent was added 4 Stirring for 30min, ultrasonic treating for 10min, transferring to a hydrothermal reaction kettle of polytetrafluoroethylene, reacting at 160deg.C for 12 hr, cooling the reaction liquid to room temperature, cleaning with deionized water and ethanol respectively for 3 times, and vacuum drying at 60deg.C for 12 hr 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 for 2h at room temperature in a mixture of 20mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, and washing the mixture with 1L of deionized water for 3 times to obtain porous g-C 3 N 4 100mg of porous g-C was taken again 3 N 4 Dispersing in 30mL26% ammonia water, hydrothermal reacting at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanometer sheet, finally 10mg of porous g-C is taken 3 N 4 Dispersing the nanosheets in 100mL deionized water, and performing ultrasonic crushing for 3 hours under high energy of 1000W by using an XM-1000T ultrasonic crusher to obtain g-C with the concentration of 0.1mg/mL 3 N 4 QDs solution;
step 4, 50mg of the exposed (001) crystal face TiO 2 /Ti 3 C 2 Dispersing MXene powder in 30mL ethanol to obtain suspension, irradiating with ultraviolet light for 3 hr, and adding 75mL g-C with concentration of 0.1mg/mL 3 N 4 The QDs solution is uniformly mixed to obtain a mixed system, and g-C is obtained at the moment 3 N 4 QDs and exposed (001) crystal plane TiO 2 /Ti 3 C 2 The mass ratio of MXene is 7.5：50；
Step 5, irradiating the mixed system for 2 hours under ultraviolet irradiation to carry out a photo-deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and absolute ethanol for 2 times, vacuum drying at 60deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) crystal face 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 reaction solution with the concentration of 0.1g/mL, stirring at room temperature for 27h to perform acid etching reaction, washing the centrifugally separated product of the reaction solution with deionized water and ethanol until the pH value of the solution is greater than 6.5, centrifugally separating the solution, and vacuum drying the product at 60 ℃ for 12h to obtain ML-Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the ML-Ti is added at a concentration of 25mg/L 3 C 2 Dispersing the powder in 40mL deionized water, ultrasonically crushing for 1h, centrifuging, and vacuum drying the product at 60 ℃ for 12h to obtain a few-layer Ti 3 C 2 MXene。
Step 2, 200mg of Ti 3 C 2 MXene powder was dispersed in 30mL of 1mol/L HCl solution, and 0.33g of NaBF as a crystal face control agent was added 4 Stirring for 30min, ultrasonic treating for 10min, transferring to a hydrothermal reaction kettle of polytetrafluoroethylene, reacting at 160deg.C for 12 hr, cooling the reaction liquid to room temperature, cleaning with deionized water and ethanol respectively for 3 times, and vacuum drying at 60deg.C for 12 hr 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 for 2h at room temperature in a mixture of 20mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, and washing the mixture with 1L of deionized water for 3 times to obtain porous g-C 3 N 4 100mg of porous g-C was taken again 3 N 4 Dispersing in 30mL25% ammonia water, hydrothermal reacting at 180deg.C for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanometer sheet, finally 10mg of porous g-C is taken 3 N 4 Dispersing the nanosheets in 100mL deionized water, and using an XM-1000T ultrasonic crusherUltrasonic crushing at high energy of 1000W for 3h to obtain g-C with concentration of 0.1mg/mL 3 N 4 QDs solution;
step 4, 50mg of the exposed (001) crystal face TiO 2 /Ti 3 C 2 Dispersing MXene powder in 30mL ethanol to obtain suspension, irradiating with ultraviolet light for 3 hr, and adding 100mL g-C with concentration of 0.1mg/mL 3 N 4 The QDs solution is uniformly mixed to obtain a mixed system, and g-C is obtained at the moment 3 N 4 QDs and exposed (001) crystal plane TiO 2 /Ti 3 C 2 The mass ratio of MXene is 10:50;
step 5, irradiating the mixed system for 2 hours under ultraviolet irradiation to carry out a photo-deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and absolute ethanol for 5 times, vacuum drying at 60deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) crystal face TiO 2 /Ti 3 C 2 MXene photocatalyst.
Example 5:
step 1, weighing 10g of Ti 3 AlC 2 Slowly adding 100mL of HF solution with the mass fraction of 40% to obtain reaction solution with the concentration of 0.1g/mL, stirring at room temperature for 27h to perform acid etching reaction, washing the centrifugally separated product of the reaction solution with deionized water and ethanol until the pH value of the solution is greater than 6.5, centrifugally separating the solution, and vacuum drying the product at 60 ℃ for 12h to obtain ML-Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the ML-Ti is added at a concentration of 25mg/L 3 C 2 Dispersing the powder in 40mL deionized water, ultrasonically crushing for 1h, centrifuging, and vacuum drying the product at 60 ℃ for 12h to obtain a few-layer Ti 3 C 2 MXene。
Step 2, 200mg of Ti 3 C 2 MXene powder was dispersed in 30mL of 1mol/L HCl solution, and 0.33g of NaBF as a crystal face control agent was added 4 Stirring for 30min, ultrasonic treating for 10min, transferring to a hydrothermal reaction kettle of polytetrafluoroethylene, reacting at 160deg.C for 12 hr, cooling the reaction liquid to room temperature, cleaning with deionized water and ethanol respectively for 3 times, and vacuum drying at 60deg.C for 12 hr to obtain exposed (001) crystal face TiO 2 /Ti 3 C 2 MXene；
Step 3, calcining urea at 550 DEG CBurning for 4h to obtain g-C 3 N 4 Taking 1g of g-C 3 N 4 Stirring for 2h at room temperature in a mixture of 20mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, and washing the mixture with 1L of deionized water for 3 times to obtain porous g-C 3 N 4 100mg of porous g-C was taken again 3 N 4 Dispersing in 30mL28% ammonia water, hydrothermal reacting at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanometer sheet, finally 10mg of porous g-C is taken 3 N 4 Dispersing the nanosheets in 100mL deionized water, and performing ultrasonic crushing for 3 hours under high energy of 1000W by using an XM-1000T ultrasonic crusher to obtain g-C with the concentration of 0.1mg/mL 3 N 4 QDs solution;
step 4, 50mg of the exposed (001) crystal face TiO 2 /Ti 3 C 2 Dispersing MXene powder in 30mL ethanol to obtain suspension, irradiating with ultraviolet light for 3 hr, and adding 50mL g-C with concentration of 0.1mg/mL 3 N 4 The QDs solution is uniformly mixed to obtain a mixed system, and g-C is obtained at the moment 3 N 4 QDs and exposed (001) crystal plane TiO 2 /Ti 3 C 2 The mass ratio of MXene is 5:50;
step 5, irradiating the mixed system for 1h under ultraviolet irradiation to carry out a photo-deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and absolute ethanol for 3 times, vacuum drying at 60deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) crystal face 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 reaction solution with the concentration of 0.1g/mL, stirring at room temperature for 27h to perform acid etching reaction, washing the centrifugally separated product of the reaction solution with deionized water and ethanol until the pH value of the solution is greater than 6.5, centrifugally separating the solution, and vacuum drying the product at 60 ℃ for 12h to obtain ML-Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the ML-Ti is added at a concentration of 25mg/L 3 C 2 Dispersing the powder in 40mL deionized water, ultrasonically crushing for 1h, centrifuging, and vacuum drying the product at 60 ℃ for 12h to obtain a few-layer Ti 3 C 2 MXene。
Step 2, 200mg of Ti 3 C 2 MXene powder was dispersed in 30mL of 1mol/L HCl solution, and 0.33g of NaBF as a crystal face control agent was added 4 Stirring for 30min, ultrasonic treating for 10min, transferring to a hydrothermal reaction kettle of polytetrafluoroethylene, reacting at 160deg.C for 12 hr, cooling the reaction liquid to room temperature, cleaning with deionized water and ethanol respectively for 3 times, and vacuum drying at 60deg.C for 12 hr 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 for 2h at room temperature in a mixture of 20mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, and washing the mixture with 1L of deionized water for 3 times to obtain porous g-C 3 N 4 100mg of porous g-C was taken again 3 N 4 Dispersing in 30mL26% ammonia water, hydrothermal reacting at 180 ℃ for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanometer sheet, finally 10mg of porous g-C is taken 3 N 4 Dispersing the nanosheets in 100mL deionized water, and performing ultrasonic crushing for 3 hours under high energy of 1000W by using an XM-1000T ultrasonic crusher to obtain g-C with the concentration of 0.1mg/mL 3 N 4 QDs solution;
step 4, 50mg of the exposed (001) crystal face TiO 2 /Ti 3 C 2 Dispersing MXene powder in 30mL ethanol to obtain suspension, irradiating with ultraviolet light for 3 hr, and adding 50mL g-C with concentration of 0.1mg/mL 3 N 4 The QDs solution is uniformly mixed to obtain a mixed system, and g-C is obtained at the moment 3 N 4 QDs and exposed (001) crystal plane TiO 2 /Ti 3 C 2 The mass ratio of MXene is 5:50;
step 5, irradiating the mixed system for 3 hours under ultraviolet irradiation to carry out a photo-deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and absolute ethanol for 4 times, and vacuum drying at 60deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) crystal face 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 solution with the concentration of 0.1g/mL, stirring at room temperature for 27h to perform acid etching reaction, washing the centrifugally separated product of the reaction solution with deionized water and ethanol until the pH value of the solution is greater than 6.5, centrifugally separating the solution, and vacuum drying the product at 60 ℃ for 12h to obtain ML-Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the ML-Ti is added at a concentration of 25mg/L 3 C 2 Dispersing the powder in 40mL deionized water, ultrasonically crushing for 1h, centrifuging, and vacuum drying the product at 60 ℃ for 12h to obtain a few-layer Ti 3 C 2 MXene。
Step 2, 200mg of Ti 3 C 2 MXene powder was dispersed in 30mL of 1mol/L HCl solution, and 0.33g of NaBF as a crystal face control agent was added 4 Stirring for 30min, ultrasonic treating for 10min, transferring to a hydrothermal reaction kettle of polytetrafluoroethylene, reacting at 160deg.C for 12 hr, cooling the reaction liquid to room temperature, cleaning with deionized water and ethanol respectively for 3 times, and vacuum drying at 60deg.C for 12 hr 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 for 2h at room temperature in a mixture of 20mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, and washing the mixture with 1L of deionized water for 3 times to obtain porous g-C 3 N 4 100mg of porous g-C was taken again 3 N 4 Dispersing in 30mL25% ammonia water, hydrothermal reacting at 180deg.C for 12h, and washing the filtered solid to obtain porous g-C 3 N 4 Nanometer sheet, finally 10mg of porous g-C is taken 3 N 4 Dispersing the nanosheets in 100mL deionized water, and performing ultrasonic crushing for 3 hours under high energy of 1000W by using an XM-1000T ultrasonic crusher to obtain g-C with the concentration of 0.1mg/mL 3 N 4 QDs solution;
step 4, 50mg of the exposed (001) crystal face TiO 2 /Ti 3 C 2 Dispersing MXene powder in 30mL ethanol to obtain suspension, irradiating with ultraviolet light for 3 hr, and adding 50mL g-C with concentration of 0.1mg/mL 3 N 4 The QDs solution is uniformly mixed to obtain a mixed system, and g-C is obtained at the moment 3 N 4 QDs and exposed (001) crystal planesTiO 2 /Ti 3 C 2 The mass ratio of MXene is 5:50;
step 5, irradiating the mixed system for 4 hours under ultraviolet irradiation to carry out a photo-deposition reaction to obtain a reaction solution; washing the precipitate with deionized water and absolute ethanol for 2 times, vacuum drying at 60deg.C for 12 hr to obtain g-C 3 N 4 QDs/exposed (001) crystal face 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 reaction solution with the concentration of 0.1g/mL, stirring at room temperature for 27h to perform acid etching reaction, washing the centrifugally separated product of the reaction solution with deionized water and ethanol until the pH value of the solution is greater than 6.5, centrifugally separating the solution, and vacuum drying the product at 60 ℃ for 12h to obtain ML-Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the ML-Ti is added at a concentration of 25mg/L 3 C 2 Dispersing the powder in 40mL deionized water, ultrasonically crushing for 1h, centrifuging, and vacuum drying the product at 60 ℃ for 12h to obtain a few-layer Ti 3 C 2 MXene。
Step 2, 200mg of Ti 3 C 2 MXene powder was dispersed in 30mL of 1mol/L HCl solution, and 0.33g of NaBF as a crystal face control agent was added 4 Stirring for 30min, ultrasonic treating for 10min, transferring to a hydrothermal reaction kettle of polytetrafluoroethylene, reacting at 160deg.C for 12 hr, cooling the reaction liquid to room temperature, cleaning with deionized water and ethanol respectively for 3 times, and vacuum drying at 60deg.C for 12 hr to obtain exposed (001) crystal face TiO 2 /Ti 3 C 2 MXene；
The above conclusions and mechanisms are explained in detail below.
FIG. 1 shows g-C prepared according to the invention 3 N 4 QDs/exposed (001) crystal face TiO 2 /Ti 3 C 2 XRD pattern of MXene photocatalyst. Wherein a is the exposed (001) crystal face 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) crystal face TiO 2 /Ti 3 C 2 MXene photocatalyst. As in fig. 1,2θ=9.5°, 19.2 °, 27.8 ° and 60.3 ° correspond to Ti, respectively 3 C 2 Diffraction peak of MXene, ti 3 C 2 After the MXene is subjected to hydrothermal oxidation treatment, 2θ=25.2°, 37.0 °, 37.8 °, 38.6 °, 48.1 °, 53.9 °, 55.1 °, 62.7 ° positions correspond to anatase phase TiO 2 Diffraction peaks of (101), (103), (004), (112), (200), (105), (211), (204) crystal planes of (JCPDSNo.21-1272). At load g-C 3 N 4 After QDs, 2θ=25.2° and 37.8 ° corresponding TiO 2 The diffraction peaks of the (101) and (004) crystal planes are slightly weakened, and Ti 3 C 2 Diffraction peaks at 9.5℃and 19.2℃for MXene were significantly reduced and with g-C 3 N 4 An increase in the QDs loading, the two diffraction peaks show a decreasing trend, ti on example 3 and example 4 3 C 2 These two peaks of MXene almost disappeared, indicating g-C 3 N 4 QDs is wrapped in Ti 3 C 2 MXene and TiO 2 On the surface, g-C is described 3 N 4 Successful loading of QDs.
FIG. 2 is g-C 3 N 4 SEM image of quantum dots before dispersion. From FIG. 2, it can be seen that porous g-C 3 N 4 The average size of the nanoplatelets before dispersion was about 38.79nm. FIG. 3 is g-C 3 N 4 TEM image of quantum dot shows that under the action of high-energy ultrasonic crushing of XM-1000T ultrasonic crusher 1000W, g-C is obtained 3 N 4 The average size of QDs is about 15nm.
FIGS. 4 and 5 show g-C prepared according to the present invention 3 N 4 QDs/exposed (001) crystal face TiO 2 /Ti 3 C 2 SEM image of MXene photocatalyst. Exposing (001) crystal face TiO 2 Inlaid with lamellar Ti 3 C 2 On MXene, it can be seen that a small amount of g-C 3 N 4 The quantum dots are loaded on TiO 2 On the (001) plane surface, which illustrates g-C in a ternary complex system 3 N 4 The presence of quantum dots.
FIG. 6 is g-C 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 EDS plot of MXene. The presence of Ti, C, O and N elements was detected, which also demonstrates the g-C in ternary complex systems 3 N 4 The presence of quantum dots.
FIG. 7 shows g-C prepared according to the invention 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 UV-vis-NIR diffuse reflectance spectra of MXene photocatalyst. There are two distinct absorption peaks at 580nm and 960nm due to Ti 3 C 2 Transverse surface plasmon resonance (TE) and longitudinal surface plasmon resonance (TM) effects of MXene such that g-C 3 N 4 QDs/exposed (001) crystal face/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 Supported on exposed (001) crystal face/TiO 2 /Ti 3 C 2 When MXene is added, the total spectrum absorption is obviously enhanced, and g-C synthesized in example 2 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 The light absorption intensity of MXene was slightly higher than that of the g-C synthesized in example 4 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 MXene. Description of the appropriate g-C 3 N 4 QDs loading can enhance exposure of the (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) crystal face/TiO 2 /Ti 3 C 2 Degradation profile of MXene photocatalyst for CIP under visible light. After adsorption and desorption equilibrium is carried out for 30min and visible light irradiation is carried out for 120min, the (001) crystal face/TiO synthesized in the comparative example 1 is exposed 2 /Ti 3 C 2 Example 1-example 4 synthetic g-C 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 The degradation rate of the photocatalyst to CIP is 31.58%, 35.23%, 36.73%, 40.11% and 37.03%, respectively; the degradation rate constant K value is 0.00005min -1 、0.00074min -1 、0.00159min -1 、0.00076min -1 And 0.00077min -1 . The above results illustrate the load g-C 3 N 4 g-C after QDs 3 N 4 QDs/exposed (001) crystal face/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) crystal face/TiO 2 /Ti 3 C 2 Graph of degradation of CIP by MXene photocatalyst under near infrared light. After a dark reaction for 30min and irradiation with near infrared light for 120min, the exposed (001) crystal face/TiO synthesized in comparative example 1 2 /Ti 3 C 2 Example 1-example 4 synthetic g-C 3 N 4 QDs/exposed (001) crystal face/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 constant k value is 0.00013min respectively -1 、0.00076min -1 、0.00114min -1 、0.00042min -1 And 0.00084min -1 . The above results illustrate the load g-C 3 N 4 g-C after QDs 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 Specific exposure of (001) crystal plane/TiO 2 /Ti 3 C 2 The degradation performance of CIP is improved under near infrared light.
FIG. 10 shows g-C prepared according to the present invention 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 Transient time-current curve of photocatalyst under visible light. Photocurrent curve (i-t) was performed on the CHI660E electrochemical workstation. The test system used a standard three electrode system, a working electrode (sample film plated on FTO glass), a reference electrode (saturated AgCl/Ag electrode) and a counter electrode (platinum). Preparation of 0.1mol/LNa 2 SO 4 The solution is used as electrolyte solution, a 300W xenon lamp is used as a light source, a specific wavelength filter is used for visible light simulation, the test time of a photocurrent curve is 280s, the test voltage range of photovoltage and cyclic voltammetry test is 0-1V, and the voltage increment is 0.01V/s. The preparation process of the working electrode is the existing process: weighing 20mg of sample, dispersing in a mixed solution of 1mL of absolute ethyl alcohol and 0.1mL of naphthol, and uniformly coating the mixture on the excited by adopting a spin coating method after ultrasonic dispersionThe excited FTO glass substrate is the FTO glass substrate irradiated by ultraviolet light for 25min, and surface dust and organic matters can be removed, so that the FTO glass substrate has hydrophilicity, is convenient for uniform spin coating, and is annealed at 150 ℃ for 25min to prepare the working electrode.
Comparative example 1 synthetic exposed (001) crystal face/TiO 2 /Ti 3 C 2 For a, 10% CNQDs/(001) TO/TC sample of example 2 is C, 20% CNQDs/(001) TO/TC sample of example 4 is e, g-C prepared in all examples 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 Photocurrent response in visible light, and g-C synthesized in example 2 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 The photocatalyst has the greatest photocurrent, which indicates g-C 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 A large number of carriers can be generated under irradiation of visible light, and can be efficiently transferred and separated. Exposed (001) crystal face/TiO synthesized with comparative example 1 2 /Ti 3 C 2 Comparison, 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 the separation and transport efficiency of carriers.
FIG. 11 g-C prepared according to the invention 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 The transient time-current curve under near infrared light, similar to the test procedure of FIG. 10, was simulated by near infrared light for a specific wavelength filter, and the exposed (001) crystal face/TiO synthesized in comparative example 1 2 /Ti 3 C 2 A, example 2 is C, example 4 is e, g-C 3 N 4 QDs/exposed (001) crystal face/TiO 2 /Ti 3 C 2 The transient time-current curve in near infrared light also follows the same law in visible light, g-C 3 N 4 The existence of the quantum dots can also obviously 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) crystal face TiO 2 /Ti 3 C 2 MXene mimics the reaction mechanism of CIP degradation under sunlight. Two-dimensional Ti 3 C 2 MXene has a work function of about 1.8eV and TiO 2 The work function of the (101) crystal plane of (2) is about 6.58eV, forming an exposed (001) crystal plane TiO 2 /Ti 3 C 2 When MXene is used, a Schottky barrier is established at the interface, and electrons are generated from two-dimensional Ti 3 C 2 Migration of MXene to TiO 2 In Ti 3 C 2 Positively charged regions are formed in MXene in TiO 2 A negatively charged region is formed, a space charge region without free carriers is formed, and a secondary Ti is generated 3 C 2 MXene pointing to TiO 2 Built-in electric field E of (2) 2 . g-C when illuminated 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, while leaving holes in the valence band. Electrostatic field E at interface 3 Built-in electric field E with surface heterojunction 1 Under the action of TiO 2 Hole transporting TiO on the valence band on the (101) crystal face 2 (001) Crystal face and continue to g-C 3 N 4 The valence band of QDs migrates. Subsequently g-C 3 N 4 Holes and TiO on the valence band of QDs 2 The holes migrated on the (001) crystal face co-oxidize and degrade CIP; and g-C 3 N 4 Electrons on QDs guide bands migrate to TiO 2 (001) Crystal plane re-migration to TiO 2 (101) on the crystal plane; migration to TiO 2 Electrons on the conduction band of the (101) crystal plane and electrons photo-excited by themselves due to the electric field E built in the Schottky junction of the interface 2 To make the electrons continuously migrate to cause Ti 3 C 2 MXene, supplement Ti 3 C 2 Hot electrons generated by excitation of MXene, ti 3 C 2 MXene photo-excited hot electrons and O in the system 2 React to generate superoxide radical (O) 2- )，·O 2- Acts with CIP to effect degradation. In g-C 3 N 4 QDs and TiO 2 (001) Electrostatic field E of crystal face interface 3 、TiO 2 Built-in electric field E of surface heterojunction 1 、TiO 2 (101) crystal face and Ti 3 C 2 Built-in electric field E of MXene Schottky junction 2 Plasma Ti 3 C 2 The LSPR effect of MXene enhances the photodegradation degradation performance under the combined action.
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% CNQDs/(001) TO/TC sample of example 2 has the smallest arc radius, exhibits the smallest resistance value, and that the presence of CNQDs results in the 10% CNQDs/(001) TO/TC sample exhibiting the smallest charge transfer resistance and enhanced photo-generated electron-hole separation rate and carrier mobility.
The foregoing is merely one embodiment, not all or only one embodiment, and any equivalent modifications of the technical solution of the present invention by those skilled in the art after reading the present specification are intended to be encompassed by the claims of the present invention.
Claims (4)
1. The preparation method of the titanium dioxide/titanium carbide MXene with exposed carbon nitride quantum dots/(001) surface is characterized by comprising the following steps,
dispersing titanium dioxide/titanium carbide MXene powder with exposed (001) surface in ethanol to obtain a suspension, irradiating the suspension for 3.5-4.5 h under ultraviolet light, and adding g-C with the concentration of 0.15-0.25 mg/mL 3 N 4 The quantum dot solution is uniformly mixed, g-C 3 N 4 The volume ratio of the quantum dot solution to the ethanol is (25-100): (25-35), 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 for 1-4 hours under ultraviolet light to obtain a reaction solution; washing the precipitate in the reaction liquid with deionized water and absolute ethyl alcohol for 2-5 times respectively, and vacuum drying at 60-70 ℃ for 10-14 hours to obtain titanium dioxide/titanium carbide Mxene with exposed carbon nitride quantum dots/(001) surfaces;
said g-C 3 N 4 The quantum dot solution is prepared according to the following steps:
porous g-C 3 N 4 Dispersing in ammonia water, and performing hydrothermal reaction at 170-190 ℃ for 10-14 h to obtainSeparating the product in the reaction liquid, and then cleaning to obtain porous g-C 3 N 4 Nanoplatelets, porous g-C 3 N 4 Dispersing the nano-sheets in deionized water, and finally performing ultrasonic crushing for 2.5-3.5 hours at 800-1200W to obtain g-C 3 N 4 A quantum dot solution;
the porous g-C 3 N 4 The method comprises the following steps:
calcining urea at 500-600 ℃ for 3.5-4.5 hours to obtain g-C 3 N 4 g-C 3 N 4 Stirring for 1.5-2.5 h at room temperature in a mixed solution of concentrated sulfuric acid and concentrated nitric acid to obtain a mixed solution, washing the mixed solution with deionized water, and filtering solids in the mixed solution to obtain porous g-C 3 N 4 。
2. The method for preparing carbon nitride quantum dot/(001) surface-exposed titanium dioxide/titanium carbide MXene according to claim 1, characterized in that the ratio of (001) surface-exposed titanium dioxide/titanium carbide MXene powder to ethanol in the suspension is (45-55) mg: (25-35) mL.
3. The carbon nitride quantum dot/(001) -surface-exposed titanium dioxide/titanium carbide MXene prepared by the method for preparing a carbon nitride quantum dot/(001) -surface-exposed titanium dioxide/titanium carbide MXene according to any one of claims 1 to 2.
4. Use of carbon nitride quantum dot/(001) plane exposed titanium dioxide/titanium carbide MXene as claimed in claim 3 for degrading ciprofloxacin under visible and near infrared light.
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| 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 |
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