CN108927182B - Eu-doped Bi4O5I2Composite nano photocatalyst and preparation method thereof - Google Patents
Eu-doped Bi4O5I2Composite nano photocatalyst and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 51
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 12
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 235000009518 sodium iodide Nutrition 0.000 claims abstract description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 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 abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
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- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 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 abstract description 12
- 229960004989 tetracycline hydrochloride Drugs 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
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- 239000011148 porous material Substances 0.000 description 4
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- 238000001228 spectrum Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 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
- B01J27/06—Halogens; Compounds thereof
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/613—
-
- B01J35/635—
-
- B01J35/647—
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses Eu-doped Bi4O5I2The composite nano photocatalyst is prepared by taking bismuth nitrate, sodium iodide and europium nitrate as raw materials and reacting by a hydrothermal method. The preparation method comprises the following steps: s1, dissolving bismuth nitrate in a nitric acid aqueous solution to form a solution A, and dissolving NaI in another nitric acid aqueous solution to form a solution B; s2, slowly dripping the solution B into the solution A, and stirring to obtain a dark red BiOI solution; s3, adding alkali liquor into the BiOI solution to adjust the pH to 10 to obtain a white solution; s4, adding europium nitrate and sodium dodecyl benzene sulfonate into the white solution, and stirring until the europium nitrate and the sodium dodecyl benzene sulfonate are completely dissolved to obtain a mixed solution; s5, transferring the mixed solution into a Teflon reaction kettle, heating to 120 ℃ and 180 ℃, reacting for 6-24h to generate yellow precipitate, and drying to obtain yellow precipitated powder; s6, heating the yellow precipitated powder to 400 ℃ under the vacuum condition, and calcining for 3h to obtain Eu/Bi4O5I2A photocatalyst. The catalyst has high catalytic performance under visible light, and can degrade tetracycline hydrochloride by photocatalysis.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to Eu-doped Bi with high catalytic capability under visible light4O5I2A composite nano photocatalyst and a preparation method thereof.
Background
In recent years, semiconductor photocatalysts have been widely used in environmental treatments such as air purification, water disinfection, treatment of toxic wastes and degradation of organic matter. In order to develop anisotropic semiconductor photocatalysts with high photocatalytic activity, researchers have done thisA great deal of research has been conducted. Research results show that the form, the grain size, the crystal orientation, the crystallinity, the oxygen defect and the structure type of the semiconductor play a key role in changing the photodegradation performance. Among various semiconductor photocatalysts, Bi4O5I2The photocatalyst is a novel photocatalyst which can be widely applied to environmental management, and is nontoxic and easy to prepare because of the narrow forbidden band width, better visible light response capability, good conductivity and effective oxygen ion conductivity. However, from a practical and commercial point of view, it has some disadvantages and drawbacks such as a high electron-hole recombination rate. Thus Bi4O5I2Must be further enhanced.
Disclosure of Invention
The purpose of the invention is to provide Bi4O5I2The defect of degrading organic matters under visible light and high electron-hole recombination rate, provides Eu-doped Bi4O5I2The composite nano photocatalyst of (1).
Another object of the present invention is to provide a Eu-doped Bi4O5I2The preparation method of the composite nanometer photocatalyst.
In order to achieve the objects of the present invention, the present invention provides a Eu-doped Bi4O5I2The composite nano photocatalyst is prepared by taking bismuth nitrate, sodium iodide and europium nitrate as raw materials and reacting by a hydrothermal method. The molar ratio of Eu element to Bi element in the catalyst is 0.01-0.1.
Preferably, the molar ratio of Eu element to Bi element in the catalyst is 0.05.
Eu-doped Bi4O5I2The preparation method of the composite nano photocatalyst comprises the following steps:
s1, dissolving bismuth nitrate in a nitric acid aqueous solution to form a solution A, and dissolving NaI in another nitric acid aqueous solution to form a solution B, wherein the nitric acid aqueous solution is formed by mixing concentrated nitric acid and water according to the volume ratio of 1: 1;
s2, slowly dripping the solution B into the solution A, and stirring to obtain a dark red BiOI solution;
s3, adding alkali liquor into the BiOI solution to adjust the pH to 10 to obtain a white solution;
s4, adding europium nitrate and sodium dodecyl benzene sulfonate into the white solution, and stirring until the sodium dodecyl benzene sulfonate is completely dissolved to obtain a mixed solution;
s5, transferring the mixed solution into a Teflon reaction kettle, heating to 120 ℃ and 180 ℃, reacting at constant temperature for 6-24h to generate yellow precipitate, drying, and separating to obtain yellow precipitated powder;
s6, heating the yellow precipitated powder to 400 ℃ under vacuum condition, calcining for 3h at the heating rate of 10 ℃/min to obtain Eu/Bi4O5I2A photocatalyst.
Preferably, the bismuth nitrate is Bi (NO)3)3·5H2O, europium nitrate is Eu (NO)3)3·6H2O。Bi(NO3)3·5H2O、NaI、 Eu(NO3)3·6H2The molar ratio of O is 20:20: 1.
Preferably, step S5 is specifically: transferring the mixed solution to a Teflon reaction kettle, heating to 120 ℃, reacting for 12 hours at constant temperature to generate yellow precipitate, centrifugally separating out the yellow precipitate, washing with distilled water and absolute ethyl alcohol in sequence, and drying for 6 hours at 80 ℃ to obtain yellow precipitated powder.
The invention has the advantages that:
in the presence of Bi4O5I2Eu is doped and introduced into the photocatalyst, and the Eu and the photocatalyst form a local electromagnetic field to promote the transfer and separation of photo-generated charges. Eu as an electron-capturing agent to make Bi4O5I2Electrons of conduction band are enriched on Eu and cannot react with Bi4O5I2Hole recombination of valence band, thus realizing Bi4O5I2Electron-hole separation of (1), so that the prepared Eu/Bi4O5I2The composite nano material has high visible light degradation capability.
Drawings
FIG. 1, Eu/Bi at different Eu addition levels4O5I2The degradation effect of the photocatalyst on tetracycline hydrochloride.
FIG. 2, pure Bi4O5I2And Eu/Bi4O5I2XRD spectrum of photocatalyst material.
FIG. 3, pure Bi4O5I2And Eu/Bi4O5I2SEM and TEM testing of the photocatalyst material.
FIG. 4, Eu/Bi4O5I2XPS plot of the sample.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
Preparation of Eu/Bi4O5I2The photocatalyst preparation method comprises the following steps:
(1) mixing concentrated nitric acid and water at a volume ratio of 1:1 to prepare 50% nitric acid aqueous solution, weighing two 30ml nitric acid aqueous solutions, and mixing 2mmol Bi (NO)3)3·5H2Dissolving O and 2mmol NaI in two parts of nitric acid water solution respectively to obtain a solution A and a solution B respectively; (2) the solution B (NaI solution) was slowly added dropwise to the solution A (Bi (NO) with magnetic stirring3)3Solution) to obtain a dark red BiOI solution; (3) adjusting the pH value of the BiOI solution to 10 by using a NaOH solution to change the solution into a white solution; (4) adding 0.1mmol Eu (NO) to the white solution3)3·6H2O and 1g of sodium dodecyl benzene sulfonate are continuously stirred until the sodium dodecyl benzene sulfonate is completely dissolved to obtain a mixed solution; (5) transferring the mixed solution into a 100ml Teflon reaction kettle, and reacting for 12 hours at 120 ℃ to generate yellow precipitate; collecting yellow precipitate after centrifugal separation, washing with distilled water and anhydrous ethanol for several times, and drying at 80 deg.C for 6 hr to obtain yellow precipitated powder; (6) placing the yellow precipitated powder in a muffle furnace, heating to 400 deg.C under vacuum, calcining at constant temperature for 3 hr, and heating to obtain powderThe temperature rate is 10 ℃/min to obtain Eu/Bi4O5I2A photocatalyst.
Example 2
Respectively placing 6 parts of 0.97g of pentahydrate bismuth nitrate and 6 parts of 0.34g of KI into 6 beakers, adding 25ml of nitric acid aqueous solution (the nitric acid aqueous solution is formed by mixing concentrated nitric acid and water according to the volume ratio of 1: 1) into each beaker, uniformly mixing under magnetic stirring to obtain a deep red BiOI solution, and adjusting the pH value of the BiOI solution to 10 by using NaOH; then 0, 0.002mmol, 0.006mmol, 0.01mmol, 0.014mmol and 0.02mmol of Eu (NO) were weighed out3)3·6H2Adding O into the 6 parts of solution in sequence, and mixing uniformly; transferring each mixed solution into a 100ml reaction kettle respectively, heating to 120 ℃, and keeping the temperature for 12 hours; cooling the reaction kettle to room temperature, removing supernatant, centrifuging, repeatedly washing the generated yellow precipitate with ethanol and distilled water, drying at 80 deg.C for 6 hr in a vacuum drying oven, grinding the dried product into fine powder with agate mortar, heating to 400 deg.C under vacuum condition, and calcining for 3 hr to obtain Eu/Bi4O5I2A composite photocatalyst sample.
Eu/Bi prepared by the method4O5I2The photocatalytic performance of the composite photocatalyst is detected by degrading tetracycline hydrochloride through photocatalysis. The experimental procedure was as follows: Eu/Bi4O5I2The test of the sample for photocatalytic degradation of tetracycline hydrochloride is carried out under simulated sunlight in a laboratory, and the initial concentration of the tetracycline hydrochloride is 40 mg/L. The mass of the photocatalyst sample was maintained at 25mg for each test. Dark treatment was carried out for half an hour before the experiment. Before the simulated solar light irradiation, the tetracycline hydrochloride content of the solution was measured by an ultraviolet photometer (UV-A model, manufactured by North Master optoelectronic Instrument factory), and then the simulated visible light irradiation was started, while the solution was thoroughly mixed with the solid sample by stirring with a magnetic stirrer, and the absorbance was measured every 10 minutes. Eu/Bi4O5I2The photocatalytic activity of the sample can be quantitatively characterized by the degradation rate of tetracycline hydrochloride.
FIG. 1 shows Eu/Bi at different Eu addition levels4O5I2The degradation effect of the photocatalyst on tetracycline hydrochloride. It can be seen that Eu (0.05)/Bi4O5I2The composite photocatalyst has the best degradation effect on tetracycline hydrochloride, the degradation rate can reach 97 percent in 60 minutes, and the degradation rate is obviously higher than that of pure Bi4O5I2Degradation rate of tetracycline hydrochloride. These data indicate that Eu (0.05)/Bi4O5I2The composite photocatalyst can reduce the rate of photo-induced electron-hole recombination, and the photocatalytic activity is greatly enhanced. Eu (0.05)/Bi4O5I2In the chemical formula, 0.05 in parentheses represents that the molar ratio of the Eu element and the Bi element is 0.05. In fig. 1, the numerical meanings in parentheses in the other chemical formulae also represent the molar ratios of Eu element and Bi element.
Example 3
In order to examine the influence of the reaction time on the photocatalytic activity of the sample, the Eu addition was fixed at 0.01mmol, and the reaction conditions were exactly the same as in example 2 except that the reaction time was different. The reaction times of 6 parts of the reaction solution were set to 3 hours, 6 hours, 9 hours, 12 hours, 18 hours, and 24 hours, respectively. As a result, as shown in Table 1, when the reaction time was 3 hours, its photocatalytic activity was low by 73.1%, because the sample prepared at 3 hours had low crystallinity, and thus it showed relatively low photocatalytic activity. The photocatalytic activity of the sample was maximized as the reaction time increased to 12h, due to the maximum crystallinity, higher pore volume and smaller grain size. With further increase in the reaction temperature, the photocatalytic activity decreases, which is probably due to the increase in the grain size and the decrease in the specific surface area and pore volume. From the above results, it can be deduced that Eu/Bi having high crystallinity4O5I2The particles are more advantageous for photocatalytic applications.
TABLE 1 reaction time vs. Eu/Bi4O5I2Effect of the degradation Rate of Tetracycline hydrochloride of samples
Reaction time/h | 3 | 6 | 9 | 12 | 18 | 24 |
Percent of degradation/%) | 73.1 | 79.2 | 85.6 | 97.0 | 88.2 | 84.5 |
Example 4
In order to test the influence of the reaction temperature on the photocatalytic activity of the sample, the reaction conditions were as follows, except that the reaction temperature was varied: eu usage of 0.01mmol, reaction time of 12 hours, reaction temperature of 90 ℃, 120 ℃, 150 ℃ and 180 ℃. As a result, Eu/Bi formed at a reaction temperature of 120 ℃ is shown in Table 24O5I2The photocatalytic activity of the composite photocatalyst is the greatest because the crystallinity of the composite nano photocatalyst formed at a reaction temperature of 120 ℃ is the highest.
TABLE 2 reaction temperature vs. Eu/Bi4O5I2Effect of the degradation Rate of Tetracycline hydrochloride of samples
Reaction temperature/. degree.C | 90 | 120 | 150 | 180 |
Percent of degradation/%) | 84.1 | 97.0 | 85.2 | 81.6 |
And (3) performance testing:
(1) to study pure Bi4O5I2Catalyst and Eu/Bi after doping Eu4O5I2The BET test was conducted on the change of the specific surface area of the composite catalyst. The test results are shown in table 3. Pure Bi without Eu and sodium dodecyl benzene sulfonate4O5I2Has a specific surface area of 38.1m2(ii)/g; Eu/Bi doped with Eu4O5I2The specific surface area is 72.4m2G, it can be seen that Eu/Bi4O5I2The specific surface area is obviously increased, and the photocatalytic performance of the photocatalyst is further improved.
TABLE 3 Bi4O5I2And Eu/Bi4O5I2Specific surface area (S) ofBET) Pore volume (V)Total) And pore diameter (D)average)
Sample (I) | SBET(m2/g) | VTotal(cm3/g) | Daverage(nm) |
Bi4O5I2 | 38.05 | 0.196 | 20.65 |
Eu(0.05)/Bi4O5I2 | 72.40 | 0.576 | 42.86 |
(2) FIG. 2 shows pure Bi4O5I2And Eu/Bi4O5I2XRD spectrum of photocatalyst material. Pure Bi4O5I2The peaks of (a) are located at 28.4 °, 31.5 °, 45.1 °, 49.3 ° and 54.4 ° in one-to-one correspondence with diffraction peaks (-4-11), (402), (422), (066) and (811), respectively. But because Eu/Bi4O5I2The Eu content in the composite material is low, and no characteristic peak of Eu is found. And Bi4O5I2In contrast, in Eu/Bi4O5I2A slight shift of some characteristic peaks to larger diffraction angles can be observed in the composite. This is due to the presence of Eu resulting in Bi4O5I2Lightness of characteristic peaksAnd (4) changing. Bi with increasing Eu content4O5I2Gradually decrease the characteristic peak of Eu, thus proving that Eu/Bi4O5I2The existence of Eu in the composite material has influence on the performance of the catalyst.
(3) In order to explore Bi4O5I2Change of Eu doped front and back topography for pure Bi4O5I2And Eu/Bi4O5I2The samples were tested by SEM and TEM. The test results are shown in fig. 3. Bi can be observed from the SEM images in FIGS. a, b and c4O5I2The ultrathin nanosheet structure of (a). These nanoplatelets have a width of about 158 to 263nm and a thickness of about 20 nm. As can be seen from FIG. d, Eu (0.05)/Bi4O5I2Has a small nanosheet structure, but because the size is too small, the morphology and size thereof are observed by means of a TEM test. FIGS. e and f are TEM images showing Eu (0.05)/Bi4O5I2Has a width in the range of 25nm to 100nm and a thickness of about 7 nm. And Bi4O5I2Compared with the Eu/Bi form of the Eu/Bi after adding Eu and sodium dodecyl benzene sulfonate4O5I2The size is thinner and smaller, so that the specific surface area is increased, and the catalytic performance is better.
(4) FIG. 4 shows Eu/Bi4O5I2XPS plot of sample for studying Eu/Bi4O5I2The presence of elements in the sample and their valences. All peak positions were calibrated by the C1 s peak at 284.6 eV. As can be seen from the map of FIG. 4(a), Eu/Bi4O5I2The samples consisted of Bi, O, I, but Eu/Bi is not shown4O5I2Element Eu. This is because the characteristic peak signal of Eu is too low to appear. In the high-resolution spectrum of Bi 4f in FIG. 4(b), two peaks at 157.9 eV and 163.2eV are respectively assigned to Bi 4f7/2And Bi 4f5/2And Bi3+The characteristic peaks of (a) are consistent. I3 d in the I3 d high resolution spectra in FIG. 4(c)5/2And I3 d3/2The peak binding energies were 618.1eV and 629.6eV, respectively, and the results demonstrated that I-Presence of (a).As shown in FIG. 4(d), O1s has a unique characteristic peak at the position 528.7eV, indicating that Bi4O5I2The oxygen element in (1) is derived from lattice oxygen. As can be seen from FIG. 4(e), in Eu/Bi4O5I2On the sample, the peak value of Eu 3p is 1135eV, which is shown in Bi4O5I2Eu is successfully introduced.
In summary, the present invention is based on the prior Bi4O5I2Doping Eu in the photocatalyst, and preparing Eu/Bi by adopting a hydrothermal method4O5I2A composite nano photocatalyst. Eu and photocatalyst form a local electromagnetic field to promote the transfer and separation of photo-generated charges. Eu as an electron-capturing agent to make Bi4O5I2Electrons of conduction band are enriched on Eu and cannot react with Bi4O5I2Hole recombination of valence band, thus realizing Bi4O5I2Electron-hole separation of (1) to the prepared Eu/Bi4O5I2The composite nano material has high visible light degradation capability. The hydrothermal method is simple to operate, low in temperature, non-toxic and environment-friendly.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. Eu-doped Bi4O5I2The composite nano photocatalyst is characterized in that the catalyst is prepared by taking bismuth nitrate, sodium iodide and europium nitrate as raw materials and reacting the raw materials by a hydrothermal method, and the specific preparation method comprises the following steps:
s1, dissolving bismuth nitrate in a nitric acid aqueous solution to form a solution A, and dissolving NaI in another nitric acid aqueous solution to form a solution B;
s2, slowly dripping the solution B into the solution A, and stirring to obtain a dark red BiOI solution;
s3, adding alkali liquor into the BiOI solution to adjust the pH to 10 to obtain a white solution;
s4, adding europium nitrate and sodium dodecyl benzene sulfonate into the white solution, and stirring until the sodium dodecyl benzene sulfonate is completely dissolved to obtain a mixed solution;
s5, transferring the mixed solution into a Teflon reaction kettle, heating to 120 ℃ and 180 ℃, reacting at constant temperature for 6-24h to generate yellow precipitate, drying, and separating to obtain yellow precipitated powder;
s6, heating the yellow precipitated powder to 400 ℃ under the vacuum condition, and calcining for 3h to obtain Eu/Bi4O5I2A photocatalyst.
2. The Eu-doped Bi according to claim 14O5I2The composite nanometer photocatalyst is characterized in that the molar ratio of Eu element to Bi element in the catalyst is 0.01-0.1.
3. The Eu-doped Bi according to claim 24O5I2The composite nanometer photocatalyst is characterized in that the molar ratio of Eu element to Bi element in the catalyst is 0.05.
4. Eu-doped Bi according to any of claims 1 to 34O5I2The preparation method of the composite nano photocatalyst is characterized by comprising the following specific steps of:
s1, dissolving bismuth nitrate in a nitric acid aqueous solution to form a solution A, and dissolving NaI in another nitric acid aqueous solution to form a solution B;
s2, slowly dripping the solution B into the solution A, and stirring to obtain a dark red BiOI solution;
s3, adding alkali liquor into the BiOI solution to adjust the pH to 10 to obtain a white solution;
s4, adding europium nitrate and sodium dodecyl benzene sulfonate into the white solution, and stirring until the sodium dodecyl benzene sulfonate is completely dissolved to obtain a mixed solution;
s5, transferring the mixed solution into a Teflon reaction kettle, heating to 120 ℃ and 180 ℃, reacting at constant temperature for 6-24h to generate yellow precipitate, drying, and separating to obtain yellow precipitated powder;
s6, heating the yellow precipitated powder to 400 ℃ under the vacuum condition, and calcining for 3h to obtain Eu/Bi4O5I2A photocatalyst.
5. The Eu-doped Bi according to claim 44O5I2The preparation method of the composite nano photocatalyst is characterized in that in the step S1, the nitric acid aqueous solution is formed by mixing concentrated nitric acid and water according to the volume ratio of 1: 1.
6. The Eu-doped Bi according to claim 54O5I2The preparation method of the composite nano photocatalyst is characterized in that bismuth nitrate is Bi (NO)3)3·5H2O, europium nitrate is Eu (NO)3)3·6H2O,Bi(NO3)3·5H2O、NaI、Eu(NO3)3·6H2The molar ratio of O is 20:20: 1.
7. The Eu-doped Bi according to claim 44O5I2The preparation method of the composite nano photocatalyst is characterized in that the step S5 specifically comprises the following steps: transferring the mixed solution into a Teflon reaction kettle, heating to 120 ℃, reacting at constant temperature for 12h to generate yellow precipitate, drying, and separating to obtain yellow precipitated powder.
8. The Eu-doped Bi according to claim 74O5I2The preparation method of the composite nano photocatalyst is characterized in that in the step S5, yellow precipitate is separated by centrifugation, washed by distilled water and absolute ethyl alcohol in sequence, and then dried for 6 hours at 80 ℃ to obtain yellow precipitateStarch powder.
9. The Eu-doped Bi according to claim 44O5I2The preparation method of the composite nano photocatalyst is characterized in that in the step S6, the heating rate is 10 ℃/min.
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