CN112058291A - Microspherical composite visible-light-driven photocatalyst and rapid preparation method and application thereof - Google Patents
Microspherical composite visible-light-driven photocatalyst and rapid preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 230000015556 catabolic process Effects 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000004005 microsphere Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229910052797 bismuth Inorganic materials 0.000 description 8
- 230000000593 degrading effect Effects 0.000 description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
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- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 239000002800 charge carrier Substances 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
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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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B01J35/39—
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- 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
- B01J37/04—Mixing
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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
- B01J37/08—Heat treatment
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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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
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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
- C02F2101/345—Phenols
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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
Abstract
The invention relates to a microspherical composite visible-light-driven photocatalyst, a rapid preparation method and application thereof, and the prepared microspherical BiVO4/g‑C3N4The composite visible light catalyst is BiVO4Adding citric acid and urea into the precursor solution, adjusting the pH value to be alkaline, and controlling the appearance to be microspherical BiVO4And with melamine as g-C3N4Calcining the precursor at high temperature, and dissolving the microspherical BiVO in ethanol4And g-C3N4Mixing and oscillating according to a certain mass ratio to form a composite catalyst precursor solution, and calcining at a low temperature to obtain a target product. Compared with the prior art, the microspherical BiVO synthesized by the invention4/g‑C3N4The composite visible light catalyst has the advantages of simple synthesis process, short operation flow, low material cost, mild reaction conditions, good visible light performance and the like, and the prepared microspherical BiVO4/g‑C3N4The catalyst is in an ellipsoidal shape, has large specific surface area, pore volume and uniform granularity, has excellent photocatalysis performance, and has very wide application prospect in the field of environmental organic matter degradation.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a microspherical composite visible-light-driven photocatalyst, and a rapid preparation method and application thereof.
Background
The promotion of urbanization improves the industrial level of cities, the population is greatly increased, and the emission of pollution sources is increased. Photocatalysis has become a very promising pollutant treatment process. The principle of photocatalysis is that a semiconductor material such as titanium dioxide is excited by light, and electrons and holes generated by the semiconductor material participate in oxidation-reduction reactions. When light with energy greater than or equal to the energy gap is irradiated on the semiconductor nano-particle, electrons in the valence band are excited to jump to the conduction band, and relatively stable holes are left on the valence band, so that electron-hole pairs are formed. Due to the presence of a large number of defects and dangling bonds in the nanomaterial, these defects and dangling bonds can trap electrons or holes and prevent the recombination of electrons and holes. These trapped electrons and holes diffuse to the surface of the particles, respectively, and a strong redox potential is generated.
Bismuth vanadate (BiVO)4) As a novel semiconductor material, the organic light-emitting diode can be directly excited by visible light, so that solar energy is more effectively utilized, and mineralization of organic pollutants is realized, thus forming one of the hotspots in the research field of recent photocatalytic materials. However, due to the defects of low mobility of the photo-generated carriers, difficult separation and recombination of the photo-generated charge carriers, low catalytic utilization rate, low amplified spectral response range and the like of the general bismuth vanadate, the bismuth vanadate has a bottleneck in performance when being applied to a photocatalyst for pollutant treatment, and meanwhile, because the existing photocatalysts all need harsh preparation conditions, the existing photocatalysts cannot be industrially amplified in the preparation process, and are difficult to industrially popularize.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a microspherical composite visible-light-driven photocatalyst, a rapid preparation method and application thereof3N4. Obtaining microspherical BiVO through simple mixed heat treatment4/g- C3N4A composite binary photocatalyst. The prepared composite photocatalyst has good visible light photocatalytic activity and excellent stability, and has a very wide application prospect in the fields of degradation and control of environmental pollutants, energy sources and the like.
The purpose of the invention can be realized by the following technical scheme:
the rapid preparation method of the microspherical composite visible-light-driven photocatalyst comprises the following steps:
s1: g-C is prepared by calcining melamine as raw material3N4；
S2: adding Bi (NO)3)3·5H2Adding O into the nitric acid solution, then adding citric acid and urea, and fully stirring to dissolve the O to obtain a Bi solution; taking NH4VO3Adding the mixture into ammonia water to prepare a solution,then adding citric acid, and fully stirring and dissolving to obtain a V solution;
s3: and mixing the Bi solution and the V solution according to the ratio of Bi: mixing V-1: 1 molar ratio to obtain a mixed solution, stirring, adjusting the mixed solution to be alkaline by ammonia water, and stirring to obtain microspherical BiVO4A precursor solution;
s4: subjecting the microspheric BiVO4Drying and calcining the precursor solution to obtain microspherical BiVO4；
S5: g to C3N4And microspheric BiVO4Grinding and mixing to obtain microspherical BiVO4/g-C3N4And (c) a complex.
Further, the calcination in S1 was carried out under conditions of raising the temperature to 550 ℃ at a rate of 5 ℃/min and maintaining at that temperature for 3 hours.
Further, Bi (NO) in the Bi solution in S23)3·5H2The concentration of O is 0.1mol/L, the concentration of nitric acid is 4mol/L, citric acid, urea and Bi (NO)3)3·5H2The molar ratio of O in the Bi solution is 2:1: 2.
Further, NH in the V solution in S24VO3The concentration is 0.1mol/L, the ammonia water is 13.3mol/L to 14.79mol/L, and the citric acid and the NH are4VO3The molar ratio of the solution V is 1: 1.
Further, the stirring time in the S2 is 20-30 min;
the stirring time of each time in S3 is 25-35 min;
adjusting the alkalinity in S3 to pH 9-10 to obtain deep blue microspherical BiVO4A precursor liquid.
Further, the drying process in S4 is air blast drying, and the drying process is drying for 24h at 80 ℃.
Further, the calcination process in S4 is to use N2As calcination shielding gas, N2The flow rate is 75ml/min, the temperature is raised from room temperature to 300 ℃ at the temperature raising rate of 2 ℃/min during calcination, then is raised to 500 ℃ at the temperature raising rate of 3 ℃/min, the temperature is kept for 2h, and then is heated for 8h to obtain the microspherical yellow-green BiVO4And (5) producing the product.
Further, g-C was ground in S53N4And microspheric BiVO4As a powder, then as 1: placing the mixture in an ethanol solvent according to the mass ratio of 8, violently mixing the mixture in a shaking table, and then placing the solution in an oven for drying to obtain microspherical BiVO4/g-C3N4And (c) a complex.
The graphite-phase carbon nitride can decompose water under visible light to produce hydrogen, and has many excellent properties, such as large surface area, high thermal stability and chemical inertness.
The invention synthesizes microspherical bismuth vanadate by controlling the morphology of bismuth vanadate, and g-C taking melamine as a precursor3N4The mixed ethanol is subjected to low-temperature heat treatment to generate microspherical BiVO4/g-C3N4The binary photocatalyst is compounded, and the degradation rate of the phenol solution reaches 24.78% under illumination for 4 hours. The preparation method is simple and low in cost, and industrial amplification can be easily realized.
Compared with the prior art, the invention has the following advantages:
1) the invention prepares the microspherical BiVO for the first time4/g-C3N4The compound visible light catalyst regulates BiVO by adding citric acid and urea4The shape of the microsphere is changed into a microspherical BiVO by using an ethanol solvent4And g-C3N4Fully synthesizing microspherical BiVO by using a shaking bed4/g-C3N4The composite is visible light catalyzed. The method integrates the advantages of a calcining method and shaking table oscillation reaction, has the advantages of relatively simple preparation process, simple and convenient experimental operation, low equipment and instrument, low cost of raw materials, easy obtainment, good physicochemical stability, mild reaction conditions, high energy consumption avoidance, short preparation period, high yield of synthesized products, high quality, low pollution, environmental friendliness and the like.
2) Microspherical BiVO prepared by the invention4/g-C3N4A composite visible light catalyst, belongs to a microspherical BiVO4And binding of g-C3N4Powder of (2), microspherical BiVO4And g-C3N4Quality of bondingThe ratio is 8: 1. the composite photocatalyst has uniform and irregular ellipsoidal shape, large specific surface area and uniform particle size distribution. The microspheric BiVO provided by the invention4/g-C3N4BiVO (BiVO) can be well mixed by the composite visible-light-driven photocatalyst4And binding of g-C3N4The advantages and the disadvantages of the microsphere are mutually compensated, and the microspherical BiVO provided by the invention is proved to be tested by degrading target pollutants through photocatalysis4/g-C3N4The composite visible light catalyst has better photocatalytic performance, can be used for degrading organic matters, and has good application prospect in solving the decomposition problems of organic pollutants in water environment, VOCs (volatile organic compounds) in air and the like.
Drawings
FIG. 1 shows a microspherical BiVO prepared in example 1 of the present invention4/g-C3N4XRD pattern of composite visible light catalyst;
FIG. 2 shows a microspherical BiVO prepared in example 1 of the present invention4/g-C3N4SEM image of composite visible light photocatalyst, wherein (a) is at 50000 times magnification and (b) is at 100000 times magnification;
FIG. 3 shows a microspherical BiVO prepared in example 1 of the present invention4/g-C3N4EDS picture of the composite visible light catalyst, the selected magnification ratio is 20000 times;
FIG. 4 shows a microspherical BiVO prepared in example 1 of the present invention4/g-C3N4A degradation curve chart of the composite visible light catalyst for degrading phenol.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Step 1, weighing 10.0g of melamine in 50mL of alumina crucible; placing an alumina crucible with a cover in the center of a muffle furnace hearth, heating to 550 ℃ at the speed of 5 ℃/min, and keeping the temperature for 3 hours; after the calcining and sintering, the temperature in the chamber is reduced to room temperature, so that the combustion reaction between the overhigh temperature of the material and oxygen in the air is avoided. And (3) taking the yellow solid obtained in the crucible out of an oven at the temperature of 60 ℃, and drying for 8h for storage for later use.
And 3, mixing the Bi solution and the V solution according to the ratio of Bi: mixing at a molar ratio of 1:1, stirring for 25min, and adjusting the pH value of the mixed solution to 9 with 25-28% ammonia water. If the pH is acidic, the color of the mixed solution is orange yellow. Stirring for 30min to obtain deep blue microspherical BiVO4A precursor liquid.
Step 4, mixing the microspheric BiVO4The precursor solution is put into an electric heating constant temperature blast drying oven, dried for 24 hours at the temperature of 80 ℃, put into a tubular furnace again, and protected by N2The flow rate is 75ml/min, the temperature is raised from room temperature to 300 ℃ at the temperature raising rate of 2 ℃/min, the temperature is raised to 500 ℃ at the temperature raising rate of 3 ℃/min, the temperature is kept for 2h, and after the calcination is finished, the temperature in the chamber is lowered to room temperature, so that the combustion reaction between the overhigh temperature of the material and oxygen in the air is avoided. Heating for 8 hours after calcining to obtain microspherical yellow-green BiVO4And (3) sampling.
Step 5, grinding g-C with agate mortar3N4And microspheric BiVO4Is powder, and is prepared according to the following steps of 1: 8 mass percent of the mixture is placed in 30mL of analysis ethanol solvent, wherein the microspherical BiVO4The mass is 0.8g, g-C3N4The mass was 0.1g, the shaking frequency of the shaker was 180rad/min, and the mixture was vigorously mixed at 25 ℃. The mixed sample is put into an oven to be thoroughly dried for 12 hours at the temperature of 110 ℃ to obtain the yellow microspherical BiVO4/g-C3N4The composite samples.
The phase composition of the product obtained in example 1 was measured by XRD, and it can be seen from FIG. 1 that it can be prepared by the microwave hydrothermal methodOutput microspheric BiVO4/g-C3N4Composite photocatalyst, and BiVO4And C3N4The peaks of the standard substances correspond to each other, which shows that the synthesized composite photocatalyst is microspherical BiVO4/g-C3N4A composite photocatalyst is provided.
FIG. 2 shows the microspherical BiVO obtained in example 14/g-C3N4SEM picture of the composite photocatalyst, and the microspherical BiVO prepared from the SEM picture4/g-C3N4The composite photocatalyst is a regular microspherical structure.
FIG. 3 shows microspherical BiVO obtained in example 14/g-C3N4EDS picture of the composite photocatalyst, and the microspherical BiVO prepared from the EDS picture4/g-C3N4The composite photocatalyst is an irregular microspherical structure, and microspherical BiVO can be known through a graph4/g-C3N4The weight percentages C, N, O, V, Bi of the composite photocatalyst are respectively 02.84%, 01.96%, 08.49%, 14.49% and 72.22%; the atomic number percentage C, N, O, V, Bi is 15.39%, 09.09%, 34.54%, 18.50% and 22.48%, respectively.
FIG. 4 shows microspherical BiVO obtained in example 14/g-C3N4The degradation change curve of the composite photocatalyst for degrading phenol (10mg/L) under ultraviolet light is 97.6% within 16 h.
Microspherical BiVO prepared by the invention4/g-C3N4A composite visible light catalyst, belongs to a microspherical BiVO4And binding of g-C3N4Powder of (2), microspherical BiVO4And g-C3N4The combined mass ratio is 8: 1. the composite photocatalyst has uniform and irregular microspherical appearance, large specific surface area and uniform particle size distribution.
Comparative example 1
In this comparative example, only monoclinic phase BiVO was used4As the catalyst, the performance test of degrading phenol (10mg/L) was performed under ultraviolet light, and the degradation curve is shown in FIG. 4.
In comparison with comparative examplesMonoclinic phase BiVO4The effect of photodegradation is obviously inferior to that of BiVO prepared in example 14/g-C3N4Description of BiVO4/g-C3N4The photocatalytic activity of single bismuth vanadate is obviously improved.
Microspherical BiVO prepared by the invention4/g-C3N4BiVO (BiVO) can be well mixed by the composite visible-light-driven photocatalyst4And binding of g-C3N4The advantages and the disadvantages of the BiVO are mutually compensated, and the microspherical BiVO provided by the invention is proved to be tested by degrading target pollutants through photocatalysis4/g-C3N4The composite visible light catalyst has better photocatalytic performance, can be used for degrading organic matters, and has good application prospect in solving the decomposition problems of organic pollutants in water environment, VOCs (volatile organic compounds) in air, organic pollutants difficult to degrade in soil and the like.
The embodiments described above are described to facilitate an understanding and appreciation of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (10)
1. A rapid preparation method of a microspherical composite visible-light-driven photocatalyst is characterized by comprising the following steps:
s1: g-C is prepared by calcining melamine as raw material3N4；
S2: adding Bi (NO)3)3·5H2Adding O into the nitric acid solution, then adding citric acid and urea, and fully stirring to dissolve the O to obtain a Bi solution; taking NH4VO3Adding the mixture into ammonia water, adding citric acid, and fully stirring and dissolving to obtain a V solution;
s3: and mixing the Bi solution and the V solution according to the ratio of Bi: mole ratio of V to 1:1Mixing at a certain ratio to obtain a mixed solution, stirring, adjusting the mixed solution to alkalinity with ammonia water, and stirring to obtain microspherical BiVO4A precursor solution;
s4: subjecting the microspheric BiVO4Drying and calcining the precursor solution to obtain microspherical BiVO4；
S5: g to C3N4And microspheric BiVO4Grinding and mixing to obtain microspherical BiVO4/g-C3N4And (c) a complex.
2. The method for rapidly preparing the microspherical composite visible-light catalyst as claimed in claim 1, wherein the calcination in S1 is carried out under a condition of raising the temperature to 550 ℃ at a rate of 5 ℃/min and maintaining the temperature for 3 hours.
3. The method for rapidly preparing a microspherical composite visible-light-driven photocatalyst as claimed in claim 1, wherein Bi (NO) in the Bi solution in S23)3·5H2The concentration of O is 0.1mol/L, the concentration of nitric acid is 4mol/L, citric acid, urea and Bi (NO)3)3·5H2The molar ratio of O in the Bi solution is 2:1: 2.
4. The method for rapidly preparing a microspherical composite visible-light-driven photocatalyst as claimed in claim 1, wherein NH in the V solution in S24VO3The concentration is 0.1mol/L, the ammonia water is 13.3mol/L to 14.79mol/L, and the citric acid and the NH are4VO3The molar ratio of the solution V is 1: 1.
5. The method for rapidly preparing the microspherical composite visible-light-driven photocatalyst according to claim 1, wherein the stirring time in S2 is 20-30 min;
the stirring time of each time in S3 is 25-35 min;
adjusting the alkalinity in S3 to pH 9-10 to obtain deep blue microspherical BiVO4A precursor liquid.
6. The method for rapidly preparing the microspherical composite visible-light-driven photocatalyst according to claim 1, wherein the drying process in S4 is forced air drying, and the drying process is drying at 80 ℃ for 24 h.
7. The method for rapidly preparing the microspherical composite visible-light-driven photocatalyst as claimed in claim 1, wherein the calcination process in S4 is carried out by using N2As calcination shielding gas, N2The flow rate is 75ml/min, the temperature is raised from room temperature to 300 ℃ at the temperature raising rate of 2 ℃/min during calcination, then is raised to 500 ℃ at the temperature raising rate of 3 ℃/min, the temperature is kept for 2h, and then is heated for 8h to obtain the microspherical yellow-green BiVO4And (5) producing the product.
8. The method for rapidly preparing the microspherical composite visible-light-driven photocatalyst as claimed in claim 1, wherein g-C is ground in S53N4And microspheric BiVO4As a powder, then as 1: placing the mixture into an ethanol solvent according to the mass ratio of 8, violently mixing the mixture in a shaking table, and then placing the solution into an oven to be dried to obtain microspherical BiVO4/g-C3N4And (c) a complex.
9. The microspherical composite visible-light-driven photocatalyst is characterized in that the visible-light-driven photocatalyst is microspherical BiVO4/g-C3N4A complex of said microspheroidal BiVO4/g-C3N4The composite is obtained by the preparation method of any one of claims 1 to 8.
10. Use of the microspherical composite visible-light-induced photocatalyst according to claim 9 for degradation of organic pollutants.
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