CN117582977A - LCQDs/Bi for degrading tetracycline 2 MoO 6 Preparation method and application of spherical flower-shaped composite photocatalyst - Google Patents
LCQDs/Bi for degrading tetracycline 2 MoO 6 Preparation method and application of spherical flower-shaped composite photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004098 Tetracycline Substances 0.000 title claims abstract description 9
- 229960002180 tetracycline Drugs 0.000 title claims abstract description 9
- 229930101283 tetracycline Natural products 0.000 title claims abstract description 9
- 235000019364 tetracycline Nutrition 0.000 title claims abstract description 9
- 150000003522 tetracyclines Chemical class 0.000 title claims abstract description 8
- 230000000593 degrading effect Effects 0.000 title claims description 4
- 229920005610 lignin Polymers 0.000 claims abstract description 47
- 239000003513 alkali Substances 0.000 claims abstract description 43
- 238000004729 solvothermal method Methods 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 35
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 21
- 235000015393 sodium molybdate Nutrition 0.000 claims description 21
- 239000011684 sodium molybdate Substances 0.000 claims description 21
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 16
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004809 Teflon Substances 0.000 claims description 7
- 229920006362 Teflon® Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229940072172 tetracycline antibiotic Drugs 0.000 claims description 7
- 238000000502 dialysis Methods 0.000 claims description 6
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000013032 photocatalytic reaction Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 238000001782 photodegradation Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 239000003242 anti bacterial agent Substances 0.000 abstract description 3
- 229940088710 antibiotic agent Drugs 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002800 charge carrier Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
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- 230000006798 recombination Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 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 description 16
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 241001198704 Aurivillius Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 241001530121 Trollius Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 238000005424 photoluminescence Methods 0.000 description 1
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Classifications
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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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of degradation of antibiotics by photocatalytic materials, and particularly relates to LCQDs/Bi 2 MoO 6 A preparation method of a spherical flower-shaped composite photocatalyst and application of the spherical flower-shaped composite photocatalyst in the field of photocatalytic degradation of tetracycline in water bodies. In this context, LCQDs are obtained by solvothermal methods with alkali lignin as a carbon source; successfully preparing Bi by using solvothermal method 2 MoO 6 A photocatalyst; adding LCQDs solution to Bi 2 MoO 6 Growing LCQDs in spherical Bi by in-situ precipitation in the suspension 2 MoO 6 Surface to obtain LCQDs/Bi 2 MoO 6 Novel composite photocatalysts. LCQDs serve as charge carriers, promote separation and migration of photo-generated carriers, prevent electron-hole pair recombination, and further improve single Bi 2 MoO 6 Photocatalytic activity of semiconductor materials. LCQDs/Bi prepared by the invention 2 MoO 6 The spherical flower-shaped composite photocatalyst has high chemical stability, simple preparation process, low cost and environmental protection. Under the irradiation of visible light, the tetracycline waste water shows better photodegradation effect, and after 180min of irradiation, the degradation rate of the tetracycline can reach 99.47%.
Description
Technical Field
The invention relates to the field of photocatalytic material degradation of tetracycline antibiotics, in particular to an LCQDs/Bi 2 MoO 6 A spherical flower-shaped composite photocatalyst and a preparation method thereof.
Background
In recent years, the pollution problem of antibiotics to water environment is urgently solved. However, the traditional activated sludge method and the nitrification/denitrification process cannot effectively remove the tetracycline antibiotics in the water body. Therefore, the tetracycline is degraded by utilizing an environment-friendly photocatalysis technology, and has important significance in the field of water environment restoration.
Disclosure of Invention
Bismuth molybdate (Bi) 2 MoO 6 ) Bi as one of the important Aurivillius oxides, compared to other semiconductor photocatalysts 2 MoO 6 Has ferroelectric property, and the spontaneous polarization electric field existing inside the material can enhance the photocatalytic activity. CN 111974376A discloses a Bi 2 MoO 6 Respectively testing Bi after secondary calcination at different temperatures 2 MoO 6 Photocatalytic degradation rate for ciprofloxacin antibiotics. But the single Bi prepared 2 MoO 6 The light capturing property is poor, the light energy utilization rate is low, the electrons and the holes are difficult to separate, and the optical performance of the light-emitting diode is still required to be further optimized. The prior art mainly aims at Bi by means of constructing heterojunction, doping noble metal and the like 2 MoO 6 The semiconductor material is modified, but the problem of high cost is not neglected. In recent years, CN115779889A discloses a lignin carbon/bismuth molybdate composite photocatalyst, which is prepared into a large-particle lignin carbon material composite semiconductor by a pyrolysis method, and Bi is improved by utilizing the conductivity of the large-particle lignin carbon material composite semiconductor 2 MoO 6 The electron transfer rate of the semiconductor surface, thereby degrading the dye wastewater. Compared to conventional large particle biomass charcoal materials, however, alkali lignin carbon quantum dots (Alkaline lignin carbon quantum dots,LCQDs) is a zero-dimensional carbon-based material with the particle size smaller than 10nm, holes are formed in the surface, and the LCQDs have stronger photoluminescence characteristics, good water solubility and higher sensitivity. Can serve as charge carriers to promote carrier separation, is a potential promoter, but the research reports of alkali lignin carbon quantum dots in the field of photocatalysis are less at present.
Compared with the prior art, the method is green and efficient, is simple to operate and lower in cost, and the used catalyst can be recycled, so that secondary pollution is avoided.
The invention aims to provide the LCQDs/BMO spherical composite photocatalyst which has the advantages of good photocatalytic degradation effect, environmental protection, simple operation and low toxicity.
The second purpose of the invention is to provide a preparation method of the LCQDs/BMO spherical flower-shaped composite photocatalyst and application thereof in degradation of tetracycline antibiotics.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention relates to an LCQDs/BMO spherical flower-shaped composite photocatalyst and a preparation method thereof, comprising the following steps:
preparing an alkali Lignin Carbon Quantum Dot (LCQDs) solution:
adding a certain amount of alkali lignin into an absolute ethyl alcohol solution, performing ultrasonic treatment, adding a certain amount of ethylenediamine as a nitrogen source, stirring for 30min, transferring a reaction system into a polytetrafluoroethylene (Teflon) reaction kettle, and continuously reacting for 12h at 180 ℃ in an oven to obtain an alkali lignin carbon quantum dot solution; cooling to room temperature after the reaction is finished, filtering the alkali lignin carbon quantum dot solution through a 0.22 mu m microporous filter membrane to remove undispersed large-particle carbon, and dialyzing the filtered supernatant for 48 hours by using a dialysis bag with a molecular weight cut-off of 3000Da to obtain a purified alkali lignin carbon quantum dot solution;
step (II) Bi 2 MoO 6 Preparation of the photocatalyst:
bi (NO) 3 ) 3 ·5H 2 Adding O into glycol solution, stirring until the O is completely dissolved to obtain bismuth nitrate solution, and marking the bismuth nitrate solution as solution A; na is mixed with 2 MoO 4 ·2H 2 Adding O into glycol, stirring until the O is completely dissolved to obtain a sodium molybdate solution, and marking the sodium molybdate solution as a solution B; fully mixing A, B solution, continuously stirring for 1h, transferring into a polytetrafluoroethylene Teflon reaction kettle for solvothermal reaction, cooling to room temperature after the reaction is finished, and centrifuging, suction filtering and drying to obtain Bi 2 MoO 6 A photocatalyst.
Preparing a spherical flower-shaped composite photocatalyst of alkali lignin carbon quantum dots/bismuth molybdate (LCQDs/BMO):
bi (NO) 3 ) 3 ·5H 2 Adding O into glycol solution, stirring until the O is completely dissolved to obtain bismuth nitrate solution, and marking the bismuth nitrate solution as solution A; na is mixed with 2 MoO 4 ·2H 2 Adding O into glycol, stirring until the O is completely dissolved to obtain a sodium molybdate solution, and marking the sodium molybdate solution as a solution B; and (3) fully mixing A, B solution, adding the LCQDs solution obtained in the step (A), continuously stirring for 1h, transferring to a polytetrafluoroethylene Teflon reaction kettle for solvothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, filtering and drying to obtain the alkali lignin carbon quantum dot/bismuth molybdate spherical flower-shaped composite photocatalyst (LCQDs/BMO) by an in-situ coprecipitation method.
Further, in the first step, the volume ratio of the mass of the alkali lignin to the absolute ethyl alcohol is 1g to 94mL.
Further, in the first step, the volume ratio of the mass of the alkali lignin to the ethylenediamine is 1 g/6 mL. And ethylenediamine is used as a nitrogen source for modifying the alkali lignin carbon quantum dots.
Further, bi (NO 3 ) 3 ·5H 2 O and Na 2 MoO 4 ·2H 2 The molar ratio of O was 2:1.
Further, in the second and third steps, ethylene glycol was used as a base solvent in an amount of 30ml.
Further, in the third step, the addition amounts of the alkali lignin carbon quantum dot solution are respectively 0ml, 4ml, 7ml and 10ml. The corresponding composite catalysts are named BMO/LCQDs-0, BMO/LCQDs-1, BMO/LCQDs-2 and BMO/LCQDs-4 respectively.
Further, the solvothermal reaction temperature in the second step and the third step is 160 ℃.
Further, the solvothermal reaction time in the second step and the third step is 12h.
Further, the drying conditions in the second step and the third step are vacuum conditions, and the drying is continuously carried out for 8 hours at 80 ℃.
The invention also provides the photodegradation application of the obtained LCQDs/BMO spherical flower-shaped composite photocatalyst in the photodegradation field, in particular to the photodegradation application in the wastewater containing tetracycline antibiotics.
Photocatalytic activity detection: adding 50ml of 50mg/L tetracycline hydrochloride (TCH) simulated wastewater into a photocatalysis reaction instrument, adding 50mg of BMO/LCQDs photocatalyst, performing dark reaction for 30min under the action of a magnetic stirrer, starting photocatalysis reaction under the action of a 300W xenon lamp after adsorption balance is achieved, sampling 5ml at intervals of 30min, filtering by a 0.22 mu m microporous membrane to obtain a sample to be tested, and obtaining the maximum absorption wavelength of tetracycline hydrochlorideλ max At 363nm, sample absorbance was measured using a T600A uv-vis spectrophotometer and determined by the formula: degradation rate (%) = [ (C) 0 -C t )/C 0 ]×100%=[(A 0 -A t )/A 0 ]X 100%, where C 0 To achieve the initial concentration of tetracycline hydrochloride solution at adsorption equilibrium, C t For the instantaneous concentration at reaction time t, A 0 To achieve the initial absorbance of the tetracycline hydrochloride solution at adsorption equilibrium, A t Is the instantaneous absorbance at reaction time t.
The invention has the beneficial effects that:
the invention adopts a solvothermal method, and takes alkali lignin, sodium molybdate and bismuth nitrate as main raw materials to synthesize the LCQDs/BMO spherical composite photocatalyst. The composite material is used as a photocatalysis material, can degrade tetracycline antibiotics, expands the photoresponse range, obviously enhances the photocatalytic reduction activity and has good repeated use performance.
The degradation rate of the BMO/LCQDs spherical composite photocatalyst prepared by the invention to TCH is up to 99.47% when illuminated by a xenon lamp for 180min, and the degradation rate is that of undoped LCQDsSingle Bi 2 MoO 6 The photocatalyst is 1.8 times.
The method is environment-friendly, low in cost, simple and easy to operate and high in yield.
Drawings
FIG. 1 is an X-ray powder diffraction pattern (XRD) of the LCQDs/BMO spherical composite photocatalyst of the example;
FIG. 2 shows Bi in the example 2 MoO 6 Scanning Electron Microscopy (SEM) of the globeflower semiconductor material;
FIG. 3 is a Transmission Electron Microscope (TEM) of the LCQDs and LCQDs/BMO spherical flower-shaped composite photocatalyst according to the example, wherein: (a) is a TEM image of the prepared LCQDs; (b) TEM images of the LCQDs/BMO spherical composite photocatalyst obtained in examples 1-3.
FIG. 4 is a photodegradation chart of TCH by LCQDs/BMO balloon-like composite photocatalyst in example, wherein: (a) Is a photodegradation diagram of the prepared LCQDs/BMO spherical flower-shaped composite photocatalyst with different proportions for TCH; (b) Is the removal rate of TCH by different photocatalysts and the first order dynamics fitting.
Detailed Description
The following examples of the present invention are described in detail, and are provided by taking the technical scheme of the present invention as a premise, and the detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following examples.
Example 1: the preparation of the LCQDs/BMO-1 spherical flower-shaped composite photocatalyst is as follows:
preparing alkali Lignin Carbon Quantum Dots (LCQDs):
adding 1g of alkali lignin into 94mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min, adding 6mL of ethylenediamine, stirring for 30min, transferring the reaction system into a polytetrafluoroethylene Teflon reaction kettle, and performing solvothermal reaction at 180 ℃ for 12h to obtain an alkali lignin carbon quantum dot solution; cooling to room temperature after the reaction is finished, filtering the alkali lignin carbon quantum dot solution through a 0.22 mu m microporous filter membrane, removing undispersed large-particle carbon, dialyzing the filtered supernatant for 48 hours by using a dialysis bag with a molecular weight cut-off of 3000Da, and filtering again by using the 0.22 mu m microporous filter membrane to obtain the purified alkali lignin carbon quantum dot solution.
Step (II) Bi 2 MoO 6 Preparation of the photocatalyst:
bi (NO) of 1.94 g 3 ) 3 ·5H 2 Adding O into 30mL of glycol solution, stirring until the solution is completely dissolved, and obtaining bismuth nitrate solution, namely solution A; will be 0.48 g Na 2 MoO 4 ·2H 2 Adding O into 30mL of ethylene glycol, stirring until the O is completely dissolved to obtain a sodium molybdate solution, and marking the sodium molybdate solution as a B solution; fully mixing A, B solution, continuously stirring for 1h, transferring into a reaction kettle for solvothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, filtering, and vacuum drying at 80 ℃ for 8h to obtain Bi 2 MoO 6 A photocatalyst.
And (3) preparing the LCQDs/BMO-1 spherical flower-shaped composite photocatalyst:
bi (NO) of 1.94 g 3 ) 3 ·5H 2 Adding O into 30mL of glycol solution, stirring until the solution is completely dissolved, and obtaining bismuth nitrate solution, namely solution A; will be 0.48 g Na 2 MoO 4 ·2H 2 Adding O into 30mL of ethylene glycol, stirring until the O is completely dissolved to obtain a sodium molybdate solution, and marking the sodium molybdate solution as a B solution; and (3) fully mixing A, B solutions, then adding 4mL of LCQDs solution respectively, continuously stirring for 1h, transferring to a reaction kettle for solvothermal reaction, cooling to room temperature after the reaction is finished, centrifuging and filtering, and vacuum drying at 80 ℃ for 8h to obtain the LCQDs/BMO-1 spherical flower-shaped composite photocatalyst.
Example 2: the preparation of the LCQDs/BMO-2 spherical flower-shaped composite photocatalyst is as follows:
preparing alkali Lignin Carbon Quantum Dots (LCQDs):
adding 1g of alkali lignin into 94mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min, adding 6mL of ethylenediamine, stirring for 30min, transferring the reaction system into a polytetrafluoroethylene Teflon reaction kettle, and performing solvothermal reaction at 180 ℃ for 12h to obtain an alkali lignin carbon quantum dot solution; cooling to room temperature after the reaction is finished, filtering the alkali lignin carbon quantum dot solution through a 0.22 mu m microporous filter membrane, removing undispersed large-particle carbon, dialyzing the filtered supernatant for 48 hours by using a dialysis bag with a molecular weight cut-off of 3000Da, and filtering again by using the 0.22 mu m microporous filter membrane to obtain the purified alkali lignin carbon quantum dot solution.
Step (II) Bi 2 MoO 6 Preparation of the photocatalyst:
bi (NO) of 1.94 g 3 ) 3 ·5H 2 Adding O into 30mL of glycol solution, stirring until the solution is completely dissolved, and obtaining bismuth nitrate solution, namely solution A; will be 0.48 g Na 2 MoO 4 ·2H 2 Adding O into 30mL of ethylene glycol, stirring until the O is completely dissolved to obtain a sodium molybdate solution, and marking the sodium molybdate solution as a B solution; fully mixing A, B solution, continuously stirring for 1h, transferring into a reaction kettle for solvothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, filtering, and vacuum drying at 80 ℃ for 8h to obtain Bi 2 MoO 6 A photocatalyst.
And (3) preparing the LCQDs/BMO-1 spherical flower-shaped composite photocatalyst:
bi (NO) of 1.94 g 3 ) 3 ·5H 2 Adding O into 30mL of glycol solution, stirring until the solution is completely dissolved, and obtaining bismuth nitrate solution, namely solution A; will be 0.48 g Na 2 MoO 4 ·2H 2 Adding O into 30mL of ethylene glycol, stirring until the O is completely dissolved to obtain a sodium molybdate solution, and marking the sodium molybdate solution as a B solution; and (3) fully mixing A, B solutions, then adding 7mL of LCQDs solution respectively, continuously stirring for 1h, transferring to a reaction kettle for solvothermal reaction, cooling to room temperature after the reaction is finished, centrifuging and filtering, and vacuum drying at 80 ℃ for 8h to obtain the LCQDs/BMO-2 spherical flower-shaped composite photocatalyst.
Example 3: the preparation of the LCQDs/BMO-4 spherical flower-shaped composite photocatalyst is as follows:
preparing alkali Lignin Carbon Quantum Dots (LCQDs):
adding 1g of alkali lignin into 94mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min, adding 6mL of ethylenediamine, stirring for 30min, transferring the reaction system into a polytetrafluoroethylene Teflon reaction kettle, and performing solvothermal reaction at 180 ℃ for 12h to obtain an alkali lignin carbon quantum dot solution; cooling to room temperature after the reaction is finished, filtering the alkali lignin carbon quantum dot solution through a 0.22 mu m microporous filter membrane, removing undispersed large-particle carbon, dialyzing the filtered supernatant for 48 hours by using a dialysis bag with a molecular weight cut-off of 3000Da, and filtering again by using the 0.22 mu m microporous filter membrane to obtain the purified alkali lignin carbon quantum dot solution.
Step (II) Bi 2 MoO 6 Preparation of the photocatalyst:
bi (NO) of 1.94 g 3 ) 3 ·5H 2 Adding O into 30mL of glycol solution, stirring until the solution is completely dissolved, and obtaining bismuth nitrate solution, namely solution A; will be 0.48 g Na 2 MoO 4 ·2H 2 Adding O into 30mL of ethylene glycol, stirring until the O is completely dissolved to obtain a sodium molybdate solution, and marking the sodium molybdate solution as a B solution; fully mixing A, B solution, continuously stirring for 1h, transferring into a reaction kettle for solvothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, filtering, and vacuum drying at 80 ℃ for 8h to obtain Bi 2 MoO 6 A photocatalyst.
And (3) preparing the LCQDs/BMO-1 spherical flower-shaped composite photocatalyst:
bi (NO) of 1.94 g 3 ) 3 ·5H 2 Adding O into 30mL of glycol solution, stirring until the solution is completely dissolved, and obtaining bismuth nitrate solution, namely solution A; will be 0.48 g Na 2 MoO 4 ·2H 2 Adding O into 30mL of ethylene glycol, stirring until the O is completely dissolved to obtain a sodium molybdate solution, and marking the sodium molybdate solution as a B solution; and (3) fully mixing A, B solutions, then adding 10mL of LCQDs solution respectively, continuously stirring for 1h, transferring to a reaction kettle for solvothermal reaction, cooling to room temperature after the reaction is finished, centrifuging and filtering, and vacuum drying at 80 ℃ for 8h to obtain the LCQDs/BMO-4 spherical flower-shaped composite photocatalyst.
Comparative example
The comparative example is the preparation of LCQDs/BMO-0 spherical flower-shaped composite photocatalyst:
preparing alkali Lignin Carbon Quantum Dots (LCQDs):
adding 1g of alkali lignin into 94mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min, adding 6mL of ethylenediamine, stirring for 30min, transferring the reaction system into a polytetrafluoroethylene Teflon reaction kettle, and performing solvothermal reaction at 180 ℃ for 12h to obtain an alkali lignin carbon quantum dot solution; cooling to room temperature after the reaction is finished, filtering the alkali lignin carbon quantum dot solution through a 0.22 mu m microporous filter membrane, dialyzing the filtered supernatant for 48 hours by using a dialysis bag with a molecular weight cut-off of 3000Da, filtering again by using the 0.22 mu m microporous filter membrane, and removing undispersed large-particle carbon to obtain a purified alkali lignin carbon quantum dot solution;
preparing the LCQDs/BMO-0 spherical flower-shaped composite photocatalyst:
bi (NO) of 1.94 g 3 ) 3 ·5H 2 Adding O into 30mL of glycol solution, stirring until the solution is completely dissolved, and obtaining bismuth nitrate solution, namely solution A; will be 0.48 g Na 2 MoO 4 ·2H 2 Adding O into 30mL of ethylene glycol, stirring until the O is completely dissolved to obtain a sodium molybdate solution, and marking the sodium molybdate solution as a B solution; and (3) fully mixing A, B solution, continuously stirring for 1h, transferring to a reaction kettle for solvothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, filtering, and vacuum drying at 80 ℃ for 8h to obtain the LCQDs/BMO-0 photocatalyst.
Characterization of
In examples 1-3, the XRD patterns of the resulting products are shown in FIG. 1. By combining fig. 1 with a standard PDF card (Bi 2 MoO 6 PDF # 21-0102) control analysis showed that the products obtained in each example had the same peak pattern without significant change, in which the load of LCQDs did not change Bi 2 MoO 6 The original crystal structure, in addition, no obvious diffraction peak of LCQDs is observed, mainly due to the fact that the content of the introduced LCQDs is low, the dispersity is high, and the crystallinity is low.
FIG. 2 shows Bi in the example 2 MoO 6 SEM image of spherical semiconductor material, from FIG. 2a, it can be seen that Bi is produced 2 MoO 6 The crystal grains are arranged regularly and compactly in a spherical structure. From FIG. 2b, it can be seen that Bi 2 MoO 6 The spherical surface presents a layer flower structure, has larger specific surface area, and has larger reaction contact area and higher refractive index to visible light.
FIG. 3 is a TEM image of alkali Lignin Carbon Quantum Dots (LCQDs) and alkali lignin carbon quantum dot composite bismuth molybdate (LCQDs/BMO) photocatalyst, and it can be seen from FIG. 3a that LCQDs are uniformly dispersed and have uniform size of between 5 and 10nm, indicating that LCQDs are successfully prepared. As shown in FIG. 3b, LCQDs are uniformly dispersed in Bi 2 MoO 6 The surface of the nanosphere shows that the LCQDs/BMO spherical flower-shaped composite photocatalyst is successfully prepared.
The tetracycline hydrochloride solution was degraded by using photocatalysis and its maximum absorption wavelength was 363nm measured in the wavelength range of 300-400nm, and its degradation rate was calculated by the formula.
Degradation rate (%) = [ (C) 0 -C t )/C 0 ]×100%=[(A 0 -A t )/A 0 ]×100%
Wherein C is 0 To achieve the initial concentration of tetracycline hydrochloride solution at adsorption equilibrium, C t For the instantaneous concentration at reaction time t, A 0 To achieve the initial absorbance of the tetracycline hydrochloride solution at adsorption equilibrium, A t Is the instantaneous absorbance at reaction time t. The specific method comprises the following steps:
LCQDs/BMO spherical photocatalyst (LCQDs/BMO-0, LCQDs/BMO-1, LCQDs/BMO-2, LCQDs/BMO-4) with different proportions is added to TCH solution with initial concentration of 50mg/L, and the sample addition amount is 1g/L. After the dark reaction reaches adsorption equilibrium for 30min, the photocatalysis reaction is carried out under the irradiation of a 300w xenon lamp serving as a light source, 5ml is sampled at intervals of 30min, and the reaction is continued for 180min.
FIG. 4 is a graph showing the comparison of photocatalytic degradation effects of LCQDs/BMO spherical composite photocatalysts of different ratios on TCH. As shown in FIG. 4a, the degradation rates of the BMO, LCQDs/BMO-1, LCQDs/BMO-2 and LCQDs/BMO-4 spherical composite photocatalyst for TCH are 53.97%,73.20%,99.47% and 86.76% respectively. It can be seen that the obtained LCQDs/BMO-2 spherical composite photocatalyst has the highest degradation efficiency for TCH when the input amount of LCQDs is 4ml. According to photodegradation TCH reaction, fitting by using a first-order kinetic model: ln (C) t /C 0 ) Kt, where C t And C 0 The instantaneous concentration and the initial concentration at the reaction time t, respectively, k being the rate constant. As can be seen from fig. 4b, LCThe QDs/BMO-2 reaction rate was 0.02903min -1 7.64 times that of a single BMO. The results further demonstrate that appropriate LCQDs loading facilitates enhanced photogenerated carrier separation and enhanced photocatalytic reactivity of LCQDs/BMO sphere flower-like composite photocatalysts. Therefore, the tetracycline antibiotics can be efficiently and environmentally degraded, and the method has wide development prospect in the field of water environment purification.
Claims (9)
1. LCQDs/Bi 2 MoO 6 The spherical flower-like composite photocatalyst is characterized in that the LCQDs/Bi 2 MoO 6 The LCQDs in the composite photocatalyst are added in the form of a solution.
2. An LCQDs/Bi as claimed in claim 1 2 MoO 6 The preparation method of the spherical flower-shaped composite photocatalyst is characterized by comprising the following steps of:
a. preparing alkali lignin carbon quantum dots: adding 1g of alkali lignin into an absolute ethyl alcohol solution containing 6ml of ethylenediamine, stirring for 30min, transferring a reaction system into a hydrothermal reaction kettle, and continuously reacting for 12h at 180 ℃ in an oven to obtain an alkali lignin carbon quantum dot solution; and cooling to room temperature after the reaction is finished, and filtering the alkali lignin carbon quantum dot solution through a 0.22 mu m microporous filter membrane to remove undispersed large-particle carbon. Dialyzing the filtered supernatant for 48 hours by using a dialysis bag with a molecular weight cut-off of 3000Da to obtain a purified alkali lignin carbon quantum dot solution;
b. alkali lignin carbon quantum dots/bismuth molybdate (LCQDs/Bi) 2 MoO 6 ) Preparing a spherical flower-shaped composite photocatalyst: bi (NO) 3 ) 3 ·5H 2 Adding O into glycol solution, stirring until the O is completely dissolved to obtain bismuth nitrate solution, and marking the bismuth nitrate solution as solution A; na is mixed with 2 MoO 4 ·2H 2 Adding O into glycol, stirring until the O is completely dissolved to obtain a sodium molybdate solution, and marking the sodium molybdate solution as a solution B; fully mixing A, B solution, proportionally adding the prepared LCQDs solution into A, B mixed solution, transferring into a polytetrafluoroethylene Teflon reaction kettle for solvothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, filtering and carrying outAfter drying, LCQDs/Bi is obtained 2 MoO 6 Spherical flower-shaped composite photocatalyst.
3. The method according to claim 2, wherein in step b, bi (NO 3 ) 3 ·5H 2 O and Na 2 MoO 4 ·2H 2 The molar ratio of O was 2:1.
4. The method according to claim 2, wherein the added amounts of the LCQDs in the step b are 0ml, 4ml, 7ml and 10ml, respectively.
5. The process of claim 2, wherein in step b, the solvothermal reaction temperature is 160 ℃ and the solvothermal reaction time is 12 hours.
6. The method according to claim 2, wherein in the step b, the drying condition is 80 ℃ and the reaction time is 8 hours.
7. The LCQDs/Bi as claimed in claim 1 2 MoO 6 The application of the spherical flower-shaped composite photocatalyst in degrading tetracycline antibiotic wastewater.
8. The use according to claim 7, characterized in that the method is as follows: adding LCQDs/Bi to tetracycline-containing wastewater 2 MoO 6 And (3) performing photocatalytic reaction by using the spherical flower-shaped composite photocatalyst.
9. The use according to claim 8, wherein the tetracycline waste water concentration is 50mg/L, LCQDs/Bi 2 MoO 6 The addition amount of the photocatalyst is 1g/L.
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| CN115779889A (en) * | 2022-11-10 | 2023-03-14 | 中国林业科学研究院林产化学工业研究所 | Lignin carbon/bismuth molybdate composite photocatalyst and preparation method and application thereof |
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| CN115779889B (en) * | 2022-11-10 | 2024-05-03 | 中国林业科学研究院林产化学工业研究所 | Lignin charcoal/bismuth molybdate composite photocatalyst and preparation method and application thereof |
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