CN110721679A - Preparation method of photocatalyst - Google Patents
Preparation method of photocatalyst Download PDFInfo
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- CN110721679A CN110721679A CN201911058608.9A CN201911058608A CN110721679A CN 110721679 A CN110721679 A CN 110721679A CN 201911058608 A CN201911058608 A CN 201911058608A CN 110721679 A CN110721679 A CN 110721679A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 239000000243 solution Substances 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004327 boric acid Substances 0.000 claims abstract description 7
- 150000003672 ureas Chemical class 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 6
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- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 34
- 239000002131 composite material Substances 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229910000161 silver phosphate Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 4
- 229940019931 silver phosphate Drugs 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000005303 weighing Methods 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
- QDZOEBFLNHCSSF-PFFBOGFISA-N (2S)-2-[[(2R)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-1-[(2R)-2-amino-5-carbamimidamidopentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-(1H-indol-3-yl)propanoyl]amino]-N-[(2R)-1-[[(2S)-1-[[(2R)-1-[[(2S)-1-[[(2S)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]amino]-1-oxo-3-phenylpropan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]pentanediamide Chemical compound C([C@@H](C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](N)CCCNC(N)=N)C1=CC=CC=C1 QDZOEBFLNHCSSF-PFFBOGFISA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102100024304 Protachykinin-1 Human genes 0.000 description 1
- 101800003906 Substance P Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a preparation method of a photocatalyst, which specifically comprises the following steps: mixing a proper amount of tetrabutyl titanate and absolute ethyl alcohol to form a solution A; adding a proper amount of acetic acid, a saturated urea solution, deionized water and boric acid into absolute ethyl alcohol in sequence, and stirring and uniformly mixing to form a solution B; slowly adding the solution B into the solution A, mixing and stirring for reaction for a period of time, and drying, grinding and calcining a product to obtain a catalyst A; adding polyethylene glycol, absolute ethyl alcohol and AgNO into a proper amount of catalyst A3Irradiating the solution under an ultraviolet lamp for a period of time, centrifuging and collecting a reaction product, and washing and drying the reaction product to obtain the catalyst B. The catalyst obtained by the technical scheme of the invention has a larger photoresponse range, has good absorption in an ultraviolet visible light region of 200-800 nm, and has high photocatalytic degradation efficiency on dye rhodamine B under the reaction condition of visible light excitation without adding other synergistic reagents.
Description
The technical field is as follows:
the invention relates to the field of photocatalytic oxidation, in particular to a preparation method of a photocatalyst.
Background art:
the photocatalytic oxidation method is a green and efficient environmental pollution treatment technology, the photocatalytic degradation process can lead organic pollutants to be completely mineralized and decomposed so as to achieve the purposes of decontamination, bleaching and deodorization, and secondary pollution can not be brought; secondly, photocatalysis has general applicability to the degradation of organic pollutants; the reaction process is simple and convenient to operate, can be carried out at normal temperature and normal pressure, and has low energy consumption.
TiO2As the most commonly used semiconductor photocatalytic material, the photocatalyst can remove harmful pollutants which are difficult to degrade in water, but TiO2The photocatalyst has shortcomings in practical application. First TiO 22Forbidden band width of 3.2eV and TiO2The energy band structure of the solar cell determines that the solar cell can only utilize ultraviolet light irradiated on the ground, the ultraviolet light only accounts for 3-5% of the sunlight, the utilization rate of the sunlight energy is greatly limited, secondly, the recombination probability of photoproduction electron-hole pairs is high, the quantum efficiency is low, and therefore TiO is caused2The photocatalytic efficiency is low. Therefore, the TiO can be subjected to noble metal deposition, nonmetal doping and the like2Modified to improve TiO2The photocatalytic performance of (a).
C. N, F, S, P and other different non-metal elements are doped into TiO in different forms2The structure and energy band change caused by the lattice, the radius of S atom is too large, and more energy is needed to effectively replace TiO2Oxygen atoms in the crystal lattice; C. the energy band formed after P doping is deeper, so that the effective migration of photon-generated carriers cannot be ensured; whereas F doping does not alter TiO2The forbidden band width of (c). Thus N, B doping is to promote TiO2The most efficient way visible light responds.
Is commonly used in TiO2The modified noble metal is Au, Ru, Pt, Ag, Pd, etc. When noble metal is deposited on TiO, the Fermi level of the noble metal is different from that of the semiconductor2On the surface, redistribution of photogenerated carriers occurs, electrons from the high fermi level TiO2And (4) flowing to the noble metal with lower Fermi level until the Fermi levels are equal. When Ag is deposited on the surface of the catalyst, the metal surface obtains excessive negative charges, the semiconductor obtains excessive holes, the recombination of electrons and holes can be inhibited, and the visible light response range and the photocatalytic activity of the catalyst are improved.
At present, many research and development reports about composite visible-light-driven photocatalyst exist, but the problems of small photoresponse range exist to different degrees, and some defects of high preparation cost, complex process, high raw material toxicity and the like exist.
A preparation method of a composite visible light catalyst (CN 106914263A) discloses a preparation method of a composite visible light catalyst, wherein a titanium source and a nitrogen source are uniformly dispersed in ethanol, and then water is dripped into the ethanol to obtain a mixed material; evaporating the mixed material to dryness under a stirring state to obtain a precursor; then transferring the prepared precursor into a muffle furnace, and calcining for 0.5-12 h at 300-800 ℃ in the muffle furnace to obtain TiO2/g-C3N4And compounding the visible light catalyst. The preparation method is simple and convenient, but the photoresponse range of the prepared catalyst is not obviously changed, and the visible light region is not obviously improved, so that the application of the catalyst is limited.
A preparation method of a composite visible-light-driven photocatalyst (CN 107029796A) is provided, which comprises the steps of firstly preparing a simple substance P and AgNO3The molar ratio is 1:3 weighing P and AgNO in proportion3(ii) a Then according to Zr4+With Ag+ZrCl is weighed according to the molar ratio of (1-10) to 14Then according to terephthalic acid and ZrCl4Weighing terephthalic acid according to the molar ratio of (1-1.2) to 1; dispersing the raw materials into an N, N-dimethylformamide solvent, adding acetic acid, controlling the reaction temperature to be 160-180 ℃, and synthesizing Ag for 20-24 h3PO4the/Uio-66 composite visible light catalyst. Although the catalyst has good effect, the preparation process takes a long time, and the raw materials are complex, so that the catalyst is not beneficial to large-scale production.
A silver phosphate-based visible light composite photocatalyst (CN 105642362A) discloses a silver phosphate-based visible light composite photocatalyst. The obtained visible light composite photocatalyst is formed by compounding two materials of silver phosphate and poly-3-hexylthiophene, wherein a small amount of poly-3-hexylthiophene is coated on the surface of silver phosphate particles with the particle size of 200-300 nm, and the obtained visible light composite photocatalyst Ag3PO4The structure of the/P3 HT is controllable and the morphology is regular. The catalysisThe effect of the agent in a visible light region is good, but nitrogen is needed to be used as protective gas during preparation, the process is complicated, and the catalyst dosage is large during treatment of rhodamine B, so that the actual engineering application is not facilitated.
A visible light type composite photocatalyst and a preparation method thereof (CN 105833890A) disclose a visible light type composite photocatalyst, and the photocatalyst is prepared from SrCO3And g-C3N4The photocatalyst is formed by compounding and is light yellow powder, and SrCO in the photocatalyst3And g-C3N4The mass ratio of (A) to (B) is 1: 0.2-1: 4. The catalyst has good effect under visible light, but the raw material SrCO3The cost is high, and melamine is involved in the preparation process, which belongs to carcinogenic substances and causes adverse effects on the environment and health.
The invention content is as follows:
in view of the above problems, an object of the present invention is to provide a method for preparing a photocatalyst, wherein the prepared photocatalyst has a wider photoresponse range and higher catalytic efficiency, and the preparation process is simpler and more environment-friendly.
The technical scheme of the invention is as follows:
1) mixing a proper amount of tetrabutyl titanate and absolute ethyl alcohol to form a solution A;
2) adding a proper amount of acetic acid, a saturated urea solution, deionized water and boric acid into absolute ethyl alcohol in sequence, and stirring and uniformly mixing to form a solution B;
3) slowly adding the solution B into the solution A, wherein the volume ratio of the solution B to the solution A is 1: 1.5-1: 2, mixing, stirring and reacting for a period of time, drying and grinding a reaction product, and calcining for 2 hours at 300-500 ℃ to obtain a catalyst A;
4) putting a proper amount of catalyst A into a container, and respectively adding polyethylene glycol, absolute ethyl alcohol and AgNO3Irradiating the solution under an ultraviolet lamp for a period of time, centrifugally collecting reaction products, and washing and drying the reaction products in sequence to obtain the catalyst B (product).
Preferably, in the step 1), the mass ratio of tetrabutyl titanate to absolute ethyl alcohol is 1: 1-1: 3; in the step 2), the mass ratio of the absolute ethyl alcohol to the acetic acid is 3: 1-5: 1, andthe mass ratio of the water ethanol to the saturated urea solution is 1: 0.5-1: 1.5, the mass ratio of the absolute ethanol to the deionized water is 3: 1-5: 1, and the mass ratio of the absolute ethanol to the boric acid is 25: 1-50: 1; in the step 4), the mass ratio of the catalyst A to the polyethylene glycol is 1: 1-1: 3, the mass ratio of the catalyst A to the absolute ethyl alcohol is 1: 3-1: 5, and the catalyst A to AgNO3The mass ratio of the solution is 8: 1-40: 1, AgNO3The concentration of the solution was 0.1 moL/L.
Further, the stirring reaction time of the tetrabutyl titanate and the absolute ethyl alcohol mixed in the step 1) is 2-4 h; in the step 4), the catalyst A, polyethylene glycol, absolute ethyl alcohol and AgNO3The time for irradiating the mixture of solutions under an ultraviolet lamp was 30 min.
On the basis of the technical scheme, the invention further provides a method for degrading rhodamine B in wastewater, which comprises the following steps: namely, according to the content of rhodamine B in the wastewater, adding a catalyst B which is 5-10 times of the content of rhodamine B into the wastewater according to the mass ratio, and reacting for 1h under visible light.
Compared with the prior art, the invention has the technical effects that:
1) the rhodamine B is degraded by using visible light, the photoresponse range of the catalyst B obtained by the technical scheme of the invention is wider, and the catalyst B has good absorption in an ultraviolet visible light region of 200-800 nm.
2) The catalyst B has very high photocatalytic activity, and has very high photocatalytic degradation efficiency on the dye rhodamine B under the reaction condition that other synergistic reagents are not required to be added and only the visible light is excited: for the rhodamine B solution with the concentration of 15mg/L, when the adding amount of the catalyst B is 0.1g/L, the degradation rate of the rhodamine in 1h reaches 98 percent.
3) The method provided by the invention is simple and feasible, the reagent cost is low, and no toxic substances are involved basically.
Description of the drawings:
FIG. 1TiO2Photocatalyst, TiO2XRD patterns of the composite photocatalyst and catalyst B prepared from example 1.
FIG. 2TiO2Photocatalyst, TiO2Composite photocatalyst and its preparationUV-visDRS profile of catalyst B prepared in example 1.
FIG. 3TiO2Photocatalyst, TiO2Comparison of the degradation rate of the composite photocatalyst and the degradation rate of the catalyst B prepared in example 1 on rhodamine B.
FIG. 4 is a comparison of the degradation rate of rhodamine B with different dosages of catalyst B.
The specific implementation mode is as follows:
the technical solution of the present invention is further described in detail by examples below.
Example 1
1) Taking 8mL of tetrabutyl titanate, adding 15mL of absolute ethyl alcohol into a dry and clean beaker, and fully stirring and uniformly mixing to form solution A. To mix the solution evenly, solution A may be stirred at 600r/min for 30 min.
2) Adding 7mL of absolute ethyl alcohol into a beaker, sequentially adding 1mL of acetic acid, 4mL of saturated urea solution, 1mL of deionized water and 0.106g of boric acid, and violently stirring and uniformly mixing to form a solution B. To mix the solution evenly, the solution B can be stirred at a speed of 600r/min for 30 min.
3) And slowly dripping the solution B into the solution A, controlling the flow rate to be 2mL/min, and fully stirring, mixing and reacting for 3h after the dripping is finished.
4) Drying the reacted product in a drying oven at 105 ℃ for 6h, grinding the dried product, putting the ground powder in a box-type resistance furnace, and calcining for 2h in an air atmosphere at 400 ℃ (the temperature rise speed at the beginning of calcining is controlled to be 2 ℃/min), thus obtaining the powdery catalyst A.
5) 0.2g of catalyst A is taken and respectively added with 10mL of 50g/L polyethylene glycol aqueous solution, 0.4mL of absolute ethyl alcohol and 1mL0.1mol/L AgNO3And (3) adding deionized water to a constant volume of 50mL, violently stirring and uniformly mixing, placing under an ultraviolet lamp for irradiating for 30min, centrifuging the mixed solution at 4000r/min for 10min, removing supernatant, repeatedly centrifuging the collected product with distilled water, and washing.
6) And (3) placing the washed product in a drying box, and drying at 105 ℃ for 2h to obtain a catalyst B.
Performance characterization experiments
1.TiO2Of photocatalystsPreparation:
1) to a dry clean beaker, add 8mL of tetrabutyl titanate and 15mL of absolute ethanol, and stir well to form solution a.
2) 7mL of absolute ethanol and 4mL of deionized water were mixed and stirred to form solution b.
3) And (3) placing the solution a on a magnetic stirrer, stirring at the rotating speed of 600r/min for 30min, then slowly dropwise adding the solution b into the solution a, controlling the flow rate to be 2mL/min, and fully stirring, mixing and reacting for 3h after the dropwise adding is finished.
4) Drying the reaction product in a drying oven at 105 deg.C for 6h, grinding the dried product, calcining in a box-type resistance furnace at 400 deg.C for 2h, and controlling the temperature rise rate at 2 deg.C/min to obtain TiO2A photocatalyst.
2.TiO2Preparing a composite photocatalyst:
1) taking 8mL of tetrabutyl titanate, adding 15mL of absolute ethyl alcohol into a dry and clean beaker, and fully stirring and uniformly mixing to form a solution a.
2) Adding 7mL of absolute ethyl alcohol into a beaker, sequentially adding 1mL of acetic acid, 4mL of saturated urea solution, 1mL of deionized water and 0.106g of boric acid, and vigorously stirring and uniformly mixing to form a solution b.
3) The solution a and the solution b are respectively placed on a magnetic stirrer and stirred for 30min at the rotating speed of 600 r/min.
4) And slowly dripping the solution B into the solution A, controlling the flow rate to be 2mL/min, and fully stirring, mixing and reacting for 3h after the dripping is finished.
5) Drying the reacted product in a drying oven at 105 deg.C for 6h, grinding the dried product, placing the ground powder in a box-type resistance furnace, calcining at 400 deg.C for 2h in air atmosphere, controlling the temperature rise rate at 2 deg.C/min to obtain TiO2A composite photocatalyst is provided.
Adding TiO into the mixture2Photocatalyst, TiO2The X-ray diffraction (XRD) analysis of the composite photocatalyst and catalyst B prepared in example 1 is shown in fig. 1. As can be seen from fig. 1, diffraction peaks appear at diffraction angles 2 θ of 25.3 °, 37.8 °, 48.1 °, 53.7 °, 55.1 °, and 62.6 °, respectively, and correspond to (101), (004), (200), (105), (211), (c), (d204) A crystal plane. The titanium dioxide contained in the prepared catalyst is proved to be anatase type titanium dioxide. N, B main diffraction peak of modified catalyst and pure TiO2Substantially the same indicates that the doping of N, B element did not alter the TiO2The crystal phase structure of (1). The diffraction peak of Ag in the figure is not obvious, mainly because silver ions enter TiO2In the crystal lattice.
Adding TiO into the mixture2Photocatalyst, TiO2The ultraviolet-visible diffuse reflectance (UV-visDRS) analysis of the composite photocatalyst and catalyst B prepared in example 1 is shown in figure 2. As can be seen from FIG. 2, pure TiO2The photocatalyst only responds to ultraviolet region of 200-400 nm, and the N, B element doped TiO2The composite photocatalyst responds to the ultraviolet visible light region of 200-500 nm, and the catalyst B prepared in the embodiment 1 has better light response in the ultraviolet visible light region of 200-800 nm, compared with the existing Ag/TiO2The photocatalyst (the photoresponse range is basically 200-600 nm), the visible light response range is remarkably enlarged, and the photocatalyst can be better suitable for degrading organic pollutants by visible light photocatalysis.
FIG. 3 is TiO2Photocatalyst, TiO2And (3) comparing the degradation efficiency of the composite photocatalyst and the degradation efficiency of the catalyst B to rhodamine B. In the experiment, the concentration of the degraded rhodamine B solution is 15mg/L, a 300W xenon lamp and a 420nm optical filter are used as light sources, the adding amount of the three catalysts is 0.1g/L, and the reaction time is 1 h. As can be seen from FIG. 3, the degradation rate of the catalyst B on rhodamine B reaches more than 95 percent, which is obviously higher than that of TiO2Photocatalyst and TiO2A composite photocatalyst is provided.
FIG. 4 shows the results of comparative experiments on the degradation efficiency of rhodamine B for different dosages of catalyst B (0.05g/L, 0.1g/L and 0.2 g/L). In the experiment, the concentration of the degraded rhodamine B solution is 15mg/L, a 300W xenon lamp and a 420nm optical filter are used as light sources, and the reaction time is 1 h. When the adding amount of the catalyst is 0.05g/L, the degradation rate of rhodamine B is 60 percent; when the adding amount is 0.075g/L, the degradation rate is 92%; when the adding amount is 0.1g/L, the degradation rate of rhodamine B reaches 98 percent. When the adding amount of the catalyst exceeds 0.1g/L, the degradation rate of rhodamine B is slightly reduced: when the adding amount is 0.15g/L and 0.2g/L, the degradation rate is respectively reduced to 93 percent and 90 percent, which may be caused by that when the adding amount of the catalyst is higher, the scattering effect of the catalyst particles suspended in the reaction system on ultraviolet light is enhanced, the light transmittance is reduced, and thus the reaction rate is reduced. It can be seen that the degradation rate of the catalyst B and the rhodamine B in the water body per unit volume is better when the mass ratio of the catalyst B to the rhodamine B is 5: 1-10: 1, and the degradation rate is over 90 percent.
Claims (4)
1. A preparation method of a photocatalyst is characterized by comprising the following steps:
1) mixing a proper amount of tetrabutyl titanate and absolute ethyl alcohol to form a solution A;
2) adding a proper amount of acetic acid, a saturated urea solution, deionized water and boric acid into absolute ethyl alcohol in sequence, and stirring and uniformly mixing to form a solution B;
3) slowly adding the solution B into the solution A, wherein the volume ratio of the solution B to the solution A is 1: 1.5-1: 2, mixing, stirring and reacting for a period of time, drying and grinding a reaction product, and calcining for 2 hours at 300-500 ℃ to obtain a catalyst A;
4) putting a proper amount of catalyst A into a container, and respectively adding polyethylene glycol, absolute ethyl alcohol and AgNO3Irradiating the solution under an ultraviolet lamp for a period of time, centrifugally collecting reaction products, and washing and drying the reaction products in sequence to obtain a catalyst B product.
2. The photocatalyst preparation method according to claim 1, characterized in that:
in the step 1), the mass ratio of tetrabutyl titanate to absolute ethyl alcohol is 1: 1-1: 3;
in the step 2), the mass ratio of the absolute ethyl alcohol to the acetic acid is 3: 1-5: 1, the mass ratio of the absolute ethyl alcohol to the saturated urea solution is 1: 0.5-1: 1.5, the mass ratio of the absolute ethyl alcohol to the deionized water is 3: 1-5: 1, and the mass ratio of the absolute ethyl alcohol to the boric acid is 25: 1-50: 1;
in the step 4), the mass ratio of the catalyst A to the polyethylene glycol is 1: 1-1: 3, the mass ratio of the catalyst A to the absolute ethyl alcohol is 1: 3-1: 5, and the catalyst A to AgNO3Mass ratio of the solution8:1 to 40:1, AgNO3The concentration of the solution was 0.1 moL/L.
3. The photocatalyst preparation method according to claim 2, characterized in that: the stirring reaction time of the tetrabutyl titanate and the absolute ethyl alcohol mixed in the step 1) is 2-4 h; in the step 4), the catalyst A, polyethylene glycol, absolute ethyl alcohol and AgNO3The time for irradiating the mixture of solutions under an ultraviolet lamp was 30 min.
4. A method for degrading rhodamine B in wastewater by using the catalyst B prepared by the method in claim 1 is characterized in that: adding a catalyst B which is 5-10 times of the rhodamine B content into the wastewater according to the mass ratio according to the rhodamine B content in the wastewater, and reacting for 1h under visible light.
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