CN115888846B - Composite photocatalyst and preparation method and application thereof - Google Patents
Composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002356 single layer Substances 0.000 claims abstract description 48
- 239000010936 titanium Substances 0.000 claims abstract description 48
- 238000004729 solvothermal method Methods 0.000 claims abstract description 31
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 24
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims abstract description 10
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 238000001035 drying Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 16
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 230000004298 light response Effects 0.000 abstract description 3
- 239000004098 Tetracycline Substances 0.000 description 10
- 229960002180 tetracycline Drugs 0.000 description 10
- 229930101283 tetracycline Natural products 0.000 description 10
- 235000019364 tetracycline Nutrition 0.000 description 10
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 9
- -1 physical adsorption Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001291 vacuum drying Methods 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
- 230000004044 response Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention provides a composite photocatalyst, a preparation method and application thereof, and belongs to the technical field of photocatalysts. The invention firstly uses a single layer of Nb 2 C is dispersed in N, N-dimethylformamide to obtain a single-layer Nb 2 C dispersion; mixing 2-amino terephthalic acid and a titanium source in a solvent to obtain a mixed solution; finally, a single layer of Nb 2 C, mixing the dispersion liquid with the mixed solution, and performing solvothermal reaction to obtain NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst. The photocatalyst prepared by the invention has higher specific surface area and larger pores, provides more active sites, has stronger visible light response and narrower band gap, and has higher adsorption capacity and degradation capacity on tetracycline hydrochloride.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a composite photocatalyst, a preparation method and application thereof.
Background
Tetracycline (TC) hydrochloride is an effective antibiotic and has been widely used in the fields of medicine, animal husbandry, aquaculture, agricultural production, etc., and the discharge or residue in water or soil poses a serious threat to the ecological environment and human health. Therefore, many methods have been devised to remove antibiotics from water, such as physical adsorption, membrane separation, biodegradation, and chemical oxidation techniques. The degradation process of the method has fatal defects such as large energy consumption, low efficiency, possibility of secondary pollution and the like. The photocatalysis technology is one of the emerging means capable of effectively treating organic pollutants, almost has good degradation and mineralization effects on most of the organic pollutants, does not generate secondary pollution, and is simple to operate, low in process cost and the like. Therefore, the photocatalysis technology is a very effective technical means for directly treating antibiotics in wastewater.
NH as a novel metal organic framework photocatalyst 2 MIL-125 (Ti) is widely applied to the field of photocatalysis due to the characteristics of unique energy band structure, good chemical stability, low cost, easy obtainment and the like. But NH 2 MIL-125 (Ti) has poor response to visible light and low electron and hole separation efficiency, so that the application of MIL-125 in practice is limited. It is often necessary to modify the porous material by doping, ligand functionalization, complexing with other semiconductors, annealing to obtain a derivative porous material, etc. to increase its photocatalytic efficiency.
Nb 2 CMxene is an emerging two-dimensional material with graphene-like structure, which has a higher specific surfaceThe advantages of excellent conductivity and the like are obtained, the catalyst is compounded with other materials to be used as a catalyst promoter for improving the photocatalytic performance, and the catalyst promoter and NH are not reported at present 2 MIL-125 (Ti) is compounded to improve the photocatalytic performance.
Disclosure of Invention
The invention aims to provide a composite photocatalyst, a preparation method and application thereof, which aim to solve the problem of NH in the prior art 2 The MIL-125 (Ti) catalyst has poor response to visible light and low separation efficiency of electrons and holes.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a composite photocatalyst, which comprises the following steps:
(1) To a single layer of Nb 2 C is dispersed in N, N-dimethylformamide to obtain a single-layer Nb 2 C dispersion;
(2) Mixing 2-amino terephthalic acid and a titanium source in a solvent to obtain a mixed solution;
(3) To a single layer of Nb 2 C, mixing the dispersion liquid with the mixed solution obtained in the step (2), and performing solvothermal reaction to obtain NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst.
Preferably, in the step (1), a single layer of Nb 2 The preparation method of C comprises the following steps: to be multi-layer Nb 2 Dispersing C in tetrabutylammonium hydroxide solution, stirring, centrifuging, ultrasonic treating, centrifuging, and drying to obtain single-layer Nb 2 C。
Preferably, the tetrabutylammonium hydroxide solution has a concentration of 20 to 30wt%.
Preferably, the stirring time is 20-30 hours; the ultrasonic treatment time is 1-3 hours; the rotational speed of the centrifugation is 3000-4000 r/min, and the centrifugation time is 0.5-1.5 h; the drying temperature is 50-70 ℃, and the drying time is 20-30 h.
Preferably, in the step (1), a single layer of Nb 2 The concentration of the dispersion liquid C is 1-5 mg/mL.
Preferably, in the step (2), the mass-volume ratio of the 2-amino terephthalic acid, the titanium source and the solvent is 0.5-0.7 g, 0.4-0.6 mL and 20-40 mL.
Preferably, in the step (2), the solvent is a mixture of N, N-dimethylformamide and methanol, wherein the volume ratio of the N, N-dimethylformamide to the methanol is 1-3:1-3; the titanium source is tetrabutyl titanate and/or isopropyl titanate.
Preferably, in the step (3), the temperature of the solvothermal reaction is 140-160 ℃, and the time of the solvothermal reaction is 70-100 h;
the single layer Nb 2 The mass ratio of the C to the 2-amino terephthalic acid is 2-10 mg/0.5-0.7 g.
The invention provides an NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst.
The invention provides an NH 2 MIL-125 (Ti) composite Nb 2 The application of the CMXene photocatalyst in adsorbing and degrading tetracycline hydrochloride in wastewater.
The invention has the beneficial effects that:
(1) NH prepared by the invention 2 MIL-125 (Ti) composite Nb 2 The CMXene photocatalyst has higher specific surface area and larger pores, provides more active sites and has higher adsorption and catalysis effects on tetracycline hydrochloride (TC).
(2) NH prepared by the invention 2 MIL-125 (Ti) composite Nb 2 The CMXene photocatalyst has stronger visible light response and narrower band gap, and improves the utilization rate of sunlight.
(3) NH prepared by the invention 2 MIL-125 (Ti) composite Nb 2 The CMXene photocatalyst has higher photo-generated electron-hole separation efficiency, and improves the photocatalytic degradation efficiency.
(4) NH prepared by the invention 2 MIL-125 (Ti) composite Nb 2 The CMXene photocatalyst has excellent adsorption performance and good photocatalytic degradation capability on tetracycline hydrochloride.
Drawings
FIG. 1 shows the results of examples 1 to 4NH of (C) 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst and NH produced in comparative example 1 2 MIL-125 (Ti) photocatalyst, monolayer Nb 2 XRD pattern of C;
FIG. 2 shows NH produced in examples 1 to 4 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst and NH produced in comparative example 1 2 MIL-125 (Ti) photocatalyst, monolayer Nb 2 C, an ultraviolet diffuse reflection spectrogram;
FIG. 3 shows NH groups obtained in examples 1 to 4 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst and NH produced in comparative example 1 2 Taucplots plot of MIL-125 (Ti) photocatalyst;
FIG. 4 shows NH groups obtained in examples 1 to 4 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst and NH produced in comparative example 1 2 -transient photocurrent response plot of MILs-125 (Ti) photocatalyst;
FIG. 5 is a NH group obtained in example 3 2 MIL-125 (Ti) composite Nb 2 The ultraviolet visible absorption spectrum of CMXene photocatalyst for degrading tetracycline hydrochloride (TC) is plotted against illumination time.
Detailed Description
The invention provides a preparation method of a composite photocatalyst, which comprises the following steps:
(1) To a single layer of Nb 2 C is dispersed in N, N-dimethylformamide to obtain a single-layer Nb 2 C dispersion;
(2) Mixing 2-amino terephthalic acid and a titanium source in a solvent to obtain a mixed solution;
(3) To a single layer of Nb 2 C, mixing the dispersion liquid with the mixed solution obtained in the step (2), and performing solvothermal reaction to obtain NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst.
In the present invention, in the step (1), a single layer of Nb 2 The preparation method of C comprises the following steps: to be multi-layer Nb 2 Dispersing C in tetrabutylammonium hydroxide solution, stirring, centrifuging, ultrasonic treating, centrifuging, and drying to obtain single-layer Nb 2 C。
In the present invention, the concentration of the tetrabutylammonium hydroxide solution is 20 to 30wt%, preferably 22 to 28wt%, and more preferably 25wt%.
In the present invention, the stirring time is 20 to 30 hours, preferably 22 to 28 hours, and more preferably 24 to 26 hours; the ultrasonic treatment time is 1 to 3 hours, preferably 1.5 to 2.5 hours, and more preferably 2 hours; the rotational speed of the centrifugation is 3000-4000 r/min, preferably 3200-3800 r/min, and more preferably 3500r/min; the centrifugation time is 0.5 to 1.5 hours, preferably 0.8 to 1.2 hours, and more preferably 1 hour; the drying temperature is 50-70 ℃, preferably 55-65 ℃, and more preferably 60 ℃; the drying time is 20 to 30 hours, preferably 22 to 28 hours, and more preferably 24 to 26 hours.
In the present invention, the single layer Nb 2 The preparation method of C is preferably as follows: to be multi-layer Nb 2 C is dissolved in 10mL tetrabutylammonium hydroxide solution with the concentration of 25wt percent and stirred for 24 hours at the temperature of 25 ℃ to obtain Nb 2 Sol-state solution of C, then to Nb 2 C, centrifuging the sol solution, wherein the centrifuging speed is 3500r/min, the centrifuging time is 1h, then adding 100mL of ultrapure water, and carrying out ultrasonic treatment for 2h under the protection of inert gas, wherein in the ultrasonic treatment process, in order to avoid the condition that the temperature is too high due to the ultrasonic treatment, the performance of MXene is influenced, and the ultrapure water can be replaced every 20-30 min; performing centrifugal treatment again after ultrasonic treatment, wherein the centrifugal speed is 3500r/min, the centrifugal time is 1h, to obtain colloid solution, and finally drying the colloid solution at 60deg.C for 24h to obtain single-layer Nb 2 C。
In the present invention, in the step (1), a single layer of Nb 2 The concentration of the C dispersion is 1 to 5mg/mL, preferably 2 to 4mg/mL, and more preferably 2mg/mL.
In the present invention, in the step (2), the mass-volume ratio of the 2-amino terephthalic acid, the titanium source and the solvent is 0.5 to 0.7g:0.4 to 0.6mL:20 to 40mL, preferably 0.55 to 0.65g:0.42 to 0.58mL:25 to 35mL, and more preferably 0.627 g:0.45 to 0.55mL:30mL.
In the invention, in the step (2), the solvent is a mixture of N, N-dimethylformamide and methanol, wherein the volume ratio of the N, N-dimethylformamide to the methanol is 1-3:1-3, preferably 1:1; the titanium source is tetrabutyl titanate and/or isopropyl titanate, preferably isopropyl titanate.
In the present invention, in the step (3), the temperature of the solvothermal reaction is 140 to 160 ℃, preferably 145 to 155 ℃, and more preferably 150 ℃; the solvothermal reaction time is 70-100 h, preferably 75-95 h, and more preferably 80-90 h;
the single layer Nb 2 The mass ratio of C to 2-amino terephthalic acid is 2-10 mg/0.5-0.7 g, preferably 3-9 mg/0.55-0.65 g, more preferably 4-8 mg/0.6278 g.
The invention provides an NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst.
The invention provides an NH 2 MIL-125 (Ti) composite Nb 2 The application of the CMXene photocatalyst in adsorbing and degrading tetracycline hydrochloride in wastewater.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
To a single layer of Nb 2 C is dispersed in N, N-dimethylformamide to obtain single-layer Nb with the concentration of 2mg/mL 2 C dispersion; adding 0.6278 g of 2-amino terephthalic acid and 0.53mL of isopropyl titanate into a solvent, wherein the solvent is formed by mixing 15mL of methanol and 15mL of LDMF, and stirring for 30min at normal temperature to obtain a mixed solution; then 1.0mL of single-layer Nb with the concentration of 2mg/mL is added 2 Slowly dripping the C dispersion into the mixed solution and carrying out ultrasonic treatment for 1h, transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, carrying out solvothermal reaction, wherein the solvothermal reaction temperature is 150 ℃, the reaction time is 84h, washing the solvothermal reaction product with DMF and methanol for 3 times respectively, and then carrying out vacuum drying, wherein the drying temperature is 60 ℃, and the drying time is 24h to obtain NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst (designated NM/Nb 2 C1.0)。
Example 2
To a single layer of Nb 2 C is dispersed in N, N-dimethylformamide to obtain single-layer Nb with the concentration of 2mg/mL 2 C dispersion; adding 0.6278 g of 2-amino terephthalic acid and 0.53mL of isopropyl titanate into a solvent, wherein the solvent is formed by mixing 15mL of methanol and 15mL of LDMF, and stirring for 30min at normal temperature to obtain a mixed solution; then 3.0mL of single-layer Nb with the concentration of 2mg/mL is added 2 Slowly dripping the C dispersion into the mixed solution and carrying out ultrasonic treatment for 1h, transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, carrying out solvothermal reaction, wherein the solvothermal reaction temperature is 150 ℃, the reaction time is 84h, washing the solvothermal reaction product with DMF and methanol for 3 times respectively, and then carrying out vacuum drying, wherein the drying temperature is 60 ℃, and the drying time is 24h to obtain NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst (designated NM/Nb 2 C3.0)。
Example 3
To a single layer of Nb 2 C is dispersed in N, N-dimethylformamide to obtain single-layer Nb with the concentration of 2mg/mL 2 C dispersion; adding 0.6278 g of 2-amino terephthalic acid and 0.53mL of isopropyl titanate into a solvent, wherein the solvent is formed by mixing 15mL of methanol and 15mL of LDMF, and stirring for 30min at normal temperature to obtain a mixed solution; then 4.0mL of single-layer Nb with the concentration of 2mg/mL is added 2 Slowly dripping the C dispersion into the mixed solution and carrying out ultrasonic treatment for 1h, transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, carrying out solvothermal reaction, wherein the solvothermal reaction temperature is 150 ℃, the reaction time is 84h, washing the solvothermal reaction product with DMF and methanol for 3 times respectively, and then carrying out vacuum drying, wherein the drying temperature is 60 ℃, and the drying time is 24h to obtain NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst (designated NM/Nb 2 C4.0)。
Example 4
To a single layer of Nb 2 C is dispersed in N, N-dimethylformamide to obtain single-layer Nb with the concentration of 2mg/mL 2 C dispersion; 0.6278 g of 2-aminoterephthalic acid, 0.53mL of isopropyl titanate were added to a solvent consisting of 15mL of 15 mM MF and 15mL ofMixing methanol, and stirring at normal temperature for 30min to obtain mixed solution; then 5.0mL of monolayer Nb with concentration of 2mg/mL 2 Slowly dripping the C dispersion into the mixed solution and carrying out ultrasonic treatment for 1h, transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, carrying out solvothermal reaction, wherein the solvothermal reaction temperature is 150 ℃, the reaction time is 84h, washing the solvothermal reaction product with DMF and methanol for 3 times respectively, and then carrying out vacuum drying, wherein the drying temperature is 60 ℃, and the drying time is 24h to obtain NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst (designated NM/Nb 2 C5.0)。
Example 5
To a single layer of Nb 2 C was dispersed in N, N-dimethylformamide to give a single layer of Nb at a concentration of 1mg/mL 2 C dispersion; adding 0.5g of 2-amino terephthalic acid and 0.6mL of isopropyl titanate into a solvent, wherein the solvent is prepared by mixing 5mL of LDMF and 15mL of methanol, and stirring for 30min at normal temperature to obtain a mixed solution; then 5.0mL of single-layer Nb with the concentration of 1mg/mL is added 2 Slowly dripping the C dispersion into the mixed solution and carrying out ultrasonic treatment for 1h, transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, carrying out solvothermal reaction, wherein the solvothermal reaction temperature is 140 ℃, the reaction time is 100h, washing the solvothermal reaction product with DMF and methanol for 3 times respectively, and then carrying out vacuum drying, wherein the drying temperature is 60 ℃, and the drying time is 24h, thus obtaining NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst.
Example 6
To a single layer of Nb 2 C was dispersed in N, N-dimethylformamide to give a single layer of Nb at a concentration of 5mg/mL 2 C dispersion; adding 0.7g of 2-amino terephthalic acid and 0.4mL of tetrabutyl titanate into a solvent, wherein the solvent is formed by mixing 16mL of LDMF and 24mL of methanol, and stirring for 30min at normal temperature to obtain a mixed solution; 1mL of monolayer Nb with a concentration of 5mg/mL was further added 2 Slowly dripping the dispersion liquid C into the mixed solution, carrying out ultrasonic treatment for 1h, and transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle to carry out solvothermal reaction, wherein the solvothermal reaction temperature isThe reaction time is 70h at 160 ℃, finally, the product of the solvothermal reaction is washed 3 times by DMF and methanol respectively, and then is dried in vacuum, wherein the drying temperature is 60 ℃ and the drying time is 24h, thus obtaining NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst.
Comparative example 1
Adding 0.6278 g of 2-amino terephthalic acid and 0.53mL of isopropyl titanate into a solvent, wherein the solvent is formed by mixing 15mL of DMF and 15mL of methanol, stirring for 30min at normal temperature to obtain a mixed solution, transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle for solvothermal reaction, wherein the solvothermal reaction temperature is 150 ℃ and the reaction time is 84h, washing the solvothermal reaction product with DMF and methanol for 3 times respectively, and then drying in vacuum, wherein the drying temperature is 60 ℃ and the drying time is 24h to obtain NH 2 MIL-125 (Ti) photocatalyst (designated NM).
Application example
NH produced in example 3 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst (NM/Nb) 2 C4.0 For removal of tetracycline hydrochloride (TC): 30mg of NH was weighed 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst (NM/Nb) 2 C4.0 5 parts of the components are weighed and added into TC solutions with different concentrations respectively, wherein the concentrations of the TC are 10mg/L, 20mg/L, 30mg/L, 40mg/L and 50mg/L respectively, the components are adsorbed for 1 hour in dark place, and a light source (a 300W xenon lamp with the wavelength) is turned on after the adsorption-desorption equilibrium is reached>420 nm) for 3 hours, taking the reaction liquid once every 30min, taking 4mL once, centrifuging at high speed twice, detecting a peak value at 356nm wavelength by an ultraviolet-visible light spectrophotometer, and calculating the tetracycline hydrochloride removal rate according to the following formula:
removal rate (%) = (C 0 -C t )/C 0 *100％
Wherein C is 0 C for the absorption peak of the initial solution at 356nm wavelength t Is the absorption peak of the solution at 356nm wavelength at different degradation times.
The test results are shown in FIG. 5, from which it can be seen that example 3 was preparedNM/Nb 2 The TC 4.0 catalyst has the TC removal rates of about 65.2%, 70.2%, 71.2%, 71% and 70.5% for 10mg/L, 20mg/L, 30mg/L, 40mg/L and 50mg/L respectively in 180min, and has very strong adsorption effect on low-concentration TC.
As can be seen from fig. 1, the diffraction peak shape of NM is completely consistent with that reported previously, and diffraction peaks at 6.9 °,9.8 °, and 11.7 ° correspond to (101), (200), and (221) crystal planes, respectively, indicating that NM preparation was successful. The diffraction peak of the composite material is highly consistent with NM, however, the intensity of the diffraction peak follows Nb 2 The amount of CMXene added increases and decreases, indicating a gradual decrease in the relative content of NM.
As can be seen from fig. 2, NM exhibits good absorptivity at 200 to 480NM, that is, it has the ability to absorb ultraviolet light and visible light. Due to Nb 2 C is black, so it has full spectral absorption. Introduction of Nb 2 After C, the absorption edge of the composite material is red shifted, and gradually enhanced absorption intensity can be observed in the visible light range of 480-800 nm, which is attributed to Nb 2 Black and full spectrum absorption of C.
As can be seen from FIG. 3, NM, NM/Nb 2 C1.0,NM/Nb 2 C3.0,NM/Nb 2 C4.0,NM/Nb 2 The Eg values of C5.0 were 2.66eV,2.65eV,2.64eV,2.62eV,2.59eV, respectively. The band gap energy of the composite material gradually decreases compared to NM, consistent with the results of the uv diffuse reflectance plot.
As can be seen from fig. 4, under the irradiation of the xenon lamp of 300W, the transient photocurrent of the composite material increases rapidly, and has better photocurrent response capability compared with pure NM. In Nb 2 The photocurrent is strongest when the introduced amount of C is 4.0mL, and Nb is added again 2 The current drops after the C content, possibly due to the excess Nb 2 C may impede carrier transfer.
From the above examples, the present invention provides a composite photocatalyst, a preparation method and applications thereof, and first a single layer of Nb 2 C is dispersed in N, N-dimethylformamide to obtain a single-layer Nb 2 C dispersion; mixing 2-amino terephthalic acid and a titanium source in a solvent to obtain a mixed solution; finally, singly takeLayer Nb 2 C, mixing the dispersion liquid with the mixed solution, and performing solvothermal reaction to obtain NH 2 MIL-125 (Ti) composite Nb 2 CMXene photocatalyst. The photocatalyst prepared by the invention has higher specific surface area and larger pores, provides more active sites, has stronger visible light response and narrower band gap, and has higher adsorption and degradation capability on tetracycline hydrochloride.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the composite photocatalyst is characterized by comprising the following steps of:
(1) To a single layer of Nb 2 C is dispersed in N, N-dimethylformamide to obtain a single-layer Nb 2 C dispersion;
(2) Mixing 2-amino terephthalic acid and a titanium source in a solvent to obtain a mixed solution;
(3) To a single layer of Nb 2 C, mixing the dispersion liquid with the mixed solution obtained in the step (2), and performing solvothermal reaction to obtain NH 2 MIL-125 (Ti) composite Nb 2 C MXene photocatalyst.
2. The method according to claim 1, wherein in the step (1), a single layer of Nb 2 The preparation method of C comprises the following steps: to be multi-layer Nb 2 Dispersing C in tetrabutylammonium hydroxide solution, stirring, centrifuging, ultrasonic treating, centrifuging, and drying to obtain single-layer Nb 2 C。
3. The preparation method according to claim 2, wherein the concentration of the tetrabutylammonium hydroxide solution is 20 to 30wt%.
4. A method of preparation according to claim 2 or 3, wherein the stirring time is 20 to 30 hours; the ultrasonic treatment time is 1-3 hours; the rotational speed of the centrifugation is 3000-4000 r/min, and the centrifugation time is 0.5-1.5 h; the drying temperature is 50-70 ℃, and the drying time is 20-30 h.
5. The method according to claim 1, wherein in the step (1), a single layer of Nb 2 The concentration of the dispersion liquid C is 1-5 mg/mL.
6. The process according to claim 5, wherein in the step (2), the mass/volume ratio of the 2-amino terephthalic acid, the titanium source and the solvent is 0.5 to 0.7 g/0.4 to 0.6 mL/20 to 40mL.
7. The method according to claim 1 or 5, wherein in the step (2), the solvent is a mixture of N, N-dimethylformamide and methanol, wherein the volume ratio of N, N-dimethylformamide to methanol is 1-3:1-3; the titanium source is tetrabutyl titanate and/or isopropyl titanate.
8. The method according to claim 7, wherein in the step (3), the solvothermal reaction is carried out at a temperature of 140 to 160 ℃ for a period of 70 to 100 hours;
the single layer Nb 2 The mass ratio of the C to the 2-amino terephthalic acid is 2-10 mg/0.5-0.7 g.
9. An NH produced by the production method of any one of claims 1 to 8 2 MIL-125 (Ti) composite Nb 2 C MXene photocatalyst.
10. An NH as claimed in claim 9 2 MIL-125 (Ti) composite Nb 2 The application of the C MXene photocatalyst in adsorbing and degrading tetracycline hydrochloride in wastewater.
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| EP1036593A1 (en) * | 1999-03-16 | 2000-09-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Titanium dioxide photocatalyst with Fe3+ ions added thereon |
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| WO2022270501A1 (en) * | 2021-06-22 | 2022-12-29 | 国立大学法人東北大学 | Hydrogen generation co-catalyst, photocatalyst, method for producing hydrogen, device for producing hydrogen, and semiconductor material |
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| JP2010115635A (en) * | 2008-06-05 | 2010-05-27 | Sumitomo Chemical Co Ltd | Photocatalyst dispersion, its method of manufacturing the same and application thereof |
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| EP1036593A1 (en) * | 1999-03-16 | 2000-09-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Titanium dioxide photocatalyst with Fe3+ ions added thereon |
| WO2022270501A1 (en) * | 2021-06-22 | 2022-12-29 | 国立大学法人東北大学 | Hydrogen generation co-catalyst, photocatalyst, method for producing hydrogen, device for producing hydrogen, and semiconductor material |
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