CN115193439A - Three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 Preparation method and application of photocatalyst - Google Patents
Three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 Preparation method and application of photocatalyst Download PDFInfo
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- CN115193439A CN115193439A CN202210420370.5A CN202210420370A CN115193439A CN 115193439 A CN115193439 A CN 115193439A CN 202210420370 A CN202210420370 A CN 202210420370A CN 115193439 A CN115193439 A CN 115193439A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 24
- 239000004005 microsphere Substances 0.000 claims abstract description 22
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- 238000000034 method Methods 0.000 claims abstract description 18
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 150000002603 lanthanum Chemical class 0.000 claims abstract description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 229920002223 polystyrene Polymers 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002351 wastewater Substances 0.000 claims description 12
- -1 iron ions Chemical class 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000003980 solgel method Methods 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 150000002505 iron Chemical class 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 34
- 229910017771 LaFeO Inorganic materials 0.000 description 24
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 3
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
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- YREOLPGEVLLKMB-UHFFFAOYSA-N 3-methylpyridin-1-ium-2-amine bromide hydrate Chemical compound O.[Br-].Cc1ccc[nH+]c1N YREOLPGEVLLKMB-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- 238000007210 heterogeneous catalysis Methods 0.000 description 1
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- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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Abstract
The invention relates to a three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A method of preparing a photocatalyst, comprising: s1, dispersing polystyrene and/or polymethyl methacrylate microspheres in anhydrous lower alcohol to obtain a dispersion liquid; dissolving soluble lanthanum salt, cerium salt, iron salt and complexing agent inObtaining a metal salt mixed solution in water; s2, mixing the dispersion liquid with the metal salt mixed solution, carrying out ultrasonic treatment, evaporating at the temperature of less than or equal to 90 ℃ to obtain a gel-like substance, and drying to obtain the three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A precursor; s3, mixing 3DOMLa 0.4 Ce 0.6 FeO 3 Roasting the precursor at multi-stage temperature in air atmosphere to obtain the three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A photocatalyst. The invention takes Polystyrene (PS) microspheres as a template, and then combines a sol-gel method to dope specific types and specific proportions of active metals to prepare the three-dimensional ordered macroporous structure material, which can obviously improve the activity of photocatalytic degradation of methylene blue and the removal rate of COD and TOC, and improve the utilization rate of hydrogen peroxide.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A preparation method and application of the photocatalyst.
Background
The printing and dyeing wastewater has the characteristics of large discharge amount, high content of refractory organic matters, strong alkalinity and the like, so that the treatment difficulty is extremely high. Methylene blue is an azo dye, and is difficult to degrade by traditional methods such as biochemical methods, chemical oxidation and the like because the aromatic structure of the dye is not easy to damage. The advanced oxidation technology utilizes external energy (light energy, electric energy, etc.) and substance (O) 3 、H 2 O 2 Etc.) through a series of physicochemical processes, hydroxyl radicals (. OH) are generated. Since OH oxidation potential is as high as 2.8V, most organic matters in the wastewater can be oxidized, so the advanced oxidation technology has wide application prospect. The photo-fenton technique and the photocatalytic technique are commonly used advanced oxidation techniques.The two technologies can realize the efficient degradation of pollutants by absorbing light radiation to generate free radicals with strong oxidizability, and have the advantages of mild reaction conditions, wide application range, high treatment efficiency, thorough damage to pollutants and the like. The traditional homogeneous photocatalyst has high catalytic activity, but has the problems of narrow pH adaptation range, difficult recovery, large iron mud generation amount and the like, so the heterogeneous photocatalyst becomes a research hotspot. Commonly used photocatalysts such as TiO 2 Ultraviolet light is required for excitation, and the ultraviolet light accounts for only about 5% of natural light, which limits the efficient operation under sunlight.
The perovskite type oxide is a perovskite (CaTiO) with nature 3 ) The compound oxide with the same cubic crystal structure has a chemical general formula of ABO 3 The A and B positions may be substituted by ions of the same or different valency, with A 1-x A′ x B 1-y B′ y O 3+δ And (4) showing. The perovskite type oxide has wide application prospect in the field of heterogeneous catalysis due to the stable crystal structure, high catalytic activity and great flexibility of lattice adaptation cation substitution. However, in the prior art, the perovskite catalyst prepared by the traditional sol-gel method and the coprecipitation method mostly exists in the form of nano-scale particles, the particle aggregation degree is high, the specific surface area is small, the exposure of active sites is not facilitated, and the application of the perovskite catalyst in the catalysis field is limited.
Disclosure of Invention
Technical problem to be solved
In view of the above disadvantages and shortcomings of the prior art, the present invention provides a three-dimensionally ordered macroporous La 0.4 Ce 0.6 FeO 3 The preparation method and the application of the photocatalyst solve the problems of narrow pH application range, high particle aggregation degree, small specific surface area, less exposure of active sites, high iron mud yield and unfavorable recovery and separation of the traditional homogeneous catalyst.
(II) technical scheme
In order to achieve the purpose, the invention adopts the following main technical scheme:
in a first aspect, the invention provides a three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A method of preparing a photocatalyst, comprising:
s1, dispersing polystyrene and/or polymethyl methacrylate microspheres in anhydrous lower alcohol to obtain a dispersion liquid; dissolving soluble lanthanum salt, cerium salt, ferric salt and a complexing agent in water to obtain a metal salt mixed solution;
s2, mixing the dispersion liquid with the metal salt mixed solution, carrying out ultrasonic treatment, evaporating at the temperature of less than or equal to 90 ℃ to obtain a gel-like substance, and drying to obtain the three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A precursor;
s3, mixing 3DOMLa 0.4 Ce 0.6 FeO 3 Roasting the precursor at multi-stage temperature in air atmosphere to obtain the three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A photocatalyst.
According to a preferred embodiment of the invention, in S1, the polystyrene microspheres are placed in absolute ethyl alcohol and stirred for at least 30min to obtain a dispersion; the mass ratio of the polystyrene microspheres to the absolute ethyl alcohol is 2. In addition, the polystyrene microspheres may be replaced with polymethyl methacrylate microspheres or a mixture of both. Both microspheres can be thoroughly removed by roasting, have the specific gravity close to that of water, and can be suspended in a system under the stirring or ultrasonic condition, so that the three-dimensional ordered macroporous structure is distributed in the whole catalyst material.
According to a preferred embodiment of the present invention, in S1, the molar ratio of lanthanum ions, cerium ions and iron ions in the metal salt mixed solution is 0.4:0.59-0.61:0.99-1.02; preferably, the ratio of 0.4:0.6:1.
according to a preferred embodiment of the present invention, in S1, the complexing agent in the metal salt mixed solution is citric acid, and the total molar ratio of citric acid to metal ions is 1.
According to the preferred embodiment of the present invention, in S1, the molar concentration of lanthanum ions in the metal salt mixed solution is 0.029-0.0306mol/L, and the concentration of cerium ions is 0.0445-0.045mol/L,0.074-0.075mol/L.
According to the preferred embodiment of the present invention, in S2, the gel-like material is dried at 80-100 deg.C for 6-12h.
According to the preferred embodiment of the invention, in S3, the temperature rise speed of the multi-stage temperature roasting is 70-80 ℃/h; and the roasting is divided into three stages: the first stage is as follows: heating to 180-250 deg.C (preferably 200 deg.C) in air atmosphere, and calcining for 1.5-2.5 hr, second stage: heating to 350-450 deg.C (preferably 300 deg.C), calcining for 1.5-2.5 hr, and calcining at 750-850 deg.C (preferably 800 deg.C) for 2.5-3.5 hr. In the multi-stage temperature roasting process, PS is burnt and removed, three-dimensional macropores are left, meanwhile, after high-temperature roasting, solid solution is formed among metal elements, ce plays a better doping role, and the photocatalytic activity is improved.
In a second aspect, the invention provides a three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A photocatalyst produced by the method of any one of the above examples.
In a third aspect, the invention also provides a three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 The application of the photocatalyst in heterogeneous photo-Fenton catalytic degradation of methylene blue.
Preferably, the method comprises the steps of:
step 1: subjecting three-dimensionally ordered macroporous La 0.4 Ce 0.6 FeO 3 Adding the photocatalyst into the wastewater containing methylene blue for dark adsorption, wherein the adding amount is>0.4g/L；
Step 2: turning on a light source, adding hydrogen peroxide, adjusting the pH to be 2-10, adjusting the wavelength of the light source to be 400-460 nm, and adding the hydrogen peroxide in an amount of 0.1-0.5mL/L.
Preferably, the three-dimensionally ordered macroporous La 0.4 Ce 0.6 FeO 3 The adding amount of the photocatalyst is 0.5g/L; the light source wavelength is 420nm.
Preferably, the reaction time in step 2 is more than or equal to 60min.
Wherein, the concentration of the treated methylene blue is 50-100mg/L, and the COD is 50-200mg/L.
(III) advantageous effects
(1) The invention takes Polystyrene (PS) microspheres as a template to prepare the three-dimensional ordered macroporous structure material, and the special structure of the material can obviously improve the specific surface area of the catalyst, expose more active sites and greatly increase the number of the active sites on the surface of the catalyst, thereby effectively improving the catalytic activity of the photocatalyst. Compared with the traditional perovskite catalyst, the three-dimensional ordered macroporous structure has rich pore channels and larger specific surface area, and the pore channels have the characteristics of large pore diameter, uniform distribution and ordered arrangement height. The abundant pore structure can increase the specific surface area of the catalyst, is favorable for the contact of reactants and active sites, and further improves the activity of the catalyst.
(2) According to the invention, on the basis of taking Polystyrene (PS) microspheres as a template, a sol-gel method is combined to dope specific types and specific proportions of active metals, so that the catalytic effect is greatly improved. The doped Ce increases the light absorption capacity, and can obviously improve the catalytic methylene blue removal rate, the COD removal rate and the TOC removal rate.
(3) The preparation method is simple, has good industrial application prospect, can greatly improve the catalytic performance through multi-stage calcination treatment, and is a reliable photocatalyst preparation process in the field of water treatment.
Drawings
FIG. 1 is a graph of the product prepared in example 1 and 3DOMLa prepared in example 2 0.4 Ce 0.6 FeO 3 Fourier transform infrared spectrogram of photocatalyst.
FIG. 2 shows the product of example 1 and 3DOMLa of example 2 0.4 Ce 0.6 FeO 3 X-ray diffraction pattern of the photocatalyst.
FIG. 3 is an SEM image of PS microspheres.
FIG. 4 is bulk La prepared in example 1 0.4 Ce 0.6 FeO 3 SEM image of (d).
FIG. 5 and FIG. 6 are 3DOMLa of three-dimensional ordered macroporous structure under different multiples 0.4 Ce 0.6 FeO 3 SEM image of (d).
FIG. 7 is a diagram of LaFeO observed by an X-ray photoelectron spectrometer 3 、La 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.4 Ce 0.6 FeO 3 、La 0.2 Ce 0.8 FeO 3 And 3DOMLa 0.4 Ce 0.6 FeO 3 Map one of the valence state of the surface active component element.
FIG. 8 is a diagram of LaFeO observed by an X-ray photoelectron spectrometer 3 、La 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.4 Ce 0.6 FeO 3 、La 0.2 Ce 0.8 FeO 3 And 3DOMLa 0.4 Ce 0.6 FeO 3 And a second map of the valence state of the surface active component element.
FIG. 9 is a schematic diagram of LaFeO observed by using the ultraviolet-visible diffuse reflection technique 3 、La 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.4 Ce 0.6 FeO 3 、La 0.2 Ce 0.8 FeO 3 And 3DOMLa 0.4 Ce 0.6 FeO 3 Absorption spectrum of the catalyst.
FIG. 10 shows La at different initial pH values 0.4 Ce 0.6 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.8 Ce 0.2 FeO 3 、La 0.2 Ce 0.8 FeO 3 、LaFeO 3 And 3DOMLa 0.4 Ce 0.6 FeO 3 And the decolorization of methylene blue by ferrous sulfate heptahydrate is compared with the removal rate of COD and TOC; the effect of initial pH on decolorization, (b) the effect of initial pH on COD, and (c) the effect of initial pH on TOC (total organic carbon).
FIG. 11 shows La in different amounts of hydrogen peroxide 0.4 Ce 0.6 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.8 Ce 0.2 FeO 3 、La 0.2 Ce 0.8 FeO 3 、LaFeO 3 And 3DOMLa 0.4 Ce 0.6 FeO 3 And the decolorization of methylene blue by ferrous sulfate heptahydrate is compared with the removal rate of COD and TOC; the influence of the added amount of hydrogen peroxide on the decolorization rate, (b) the influence of the added amount of hydrogen peroxide on COD, and (c) the influence of the added amount of hydrogen peroxide TOC (total organic carbon).
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present embodiments of the invention, which are illustrated in the accompanying drawings.
Example 1
LaFeO is prepared according to the following steps 3 、La 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.4 Ce 0.6 FeO 3 、La 0.2 Ce 0.8 FeO 3 。
(1) Dissolving lanthanum nitrate hexahydrate, cerium nitrate hexahydrate, 1.0000g ferric nitrate nonahydrate and 1.0403g citric acid in 100ml deionized water, and stirring for 30min on a magnetic stirrer to obtain a mixed solution;
(2) Evaporating the mixed solution at 80 ℃ to form gel, and drying the gel at 80-100 ℃ for 6-12h to obtain a precursor;
(3) And (3) placing the precursor in a tubular heating furnace, heating to 200 ℃ at a constant speed for 3h, roasting for 2h, heating to 400 ℃ at a constant speed for 3h, roasting for 2h, heating to 750 ℃ at a constant speed for 3h, and roasting for 3h to obtain a target product.
By controlling the molar amounts of lanthanum nitrate hexahydrate, cerium nitrate hexahydrate and iron nitrate nonahydrate in step (1), the molar ratio of lanthanum, cerium and iron elements in the mixed solution is 1 3 、La 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.4 Ce 0.6 FeO 3 、La 0.2 Ce 0.8 FeO 3 。
The photocatalytic activity of the products as a photocatalyst for degrading methylene blue in wastewater is tested by adopting the following method:
the photocatalyst LaFeO prepared in the above way is added under the condition that the pH is =3 3 、La 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.4 Ce 0.6 FeO 3 、La 0.2 Ce 0.8 FeO 3 Adding into methylene blueThe wastewater is absorbed in dark for 30min, a light source is turned on, meanwhile, hydrogen peroxide is added, the dosage of a catalyst is 0.5g/L, the wavelength of the light source is 420nm, the dosage of the hydrogen peroxide is 0.5mL/L, and the reaction time is 60min. In the wastewater, the concentration of methylene blue is 50mg/L, and the COD is 200mg/L.
The results are shown in Table 1.
TABLE 1
| Catalyst and process for preparing same | Methylene blue removal rate/%) | COD removal rate/%) |
| LaFeO 3 | 62.33 | 45.66 |
| La 0.8 Ce 0.2 FeO 3 | 75.42 | 54.89 |
| La 0.6 Ce 0.4 FeO 3 | 80.26 | 61.24 |
| La 0.4 Ce 0.6 FeO 3 | 95.89 | 85.46 |
| La 0.2 Ce 0.8 FeO 3 | 85.46 | 78.55 |
As can be seen from Table 1, it is found that the crystal structure is relatively similar to LaFeO 3 (undoped Ce) photocatalyst, la 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.4 Ce 0.6 FeO 3 And La 0.2 Ce 0.8 FeO 3 The catalyst has higher methylene blue removal rate and COD removal rate, which shows that the doping of Ce can obviously improve LaFeO 3 The catalytic activity of (3). La 0.4 Ce 0.6 FeO 3 The highest methylene blue degradation efficiency is achieved in the test range, so that the optimal doping ratio is selected to be La: ce =0.4:0.6. thus in the following experiments, three-dimensionally ordered macroporous La was prepared 0.4 Ce 0.6 FeO 3 。
Example 2
This example prepares La with a three-dimensional ordered macroporous structure 0.4 Ce 0.6 FeO 3 The preparation method of the photocatalyst comprises the following steps:
(1) 2.0g of Polystyrene (PS) microspheres were placed in 10mL of absolute ethanol, and placed on a magnetic stirrer and stirred for 60min to obtain a dispersion.
(2) 1.2862g of lanthanum nitrate hexahydrate, 1.9346g of cerium nitrate hexahydrate, 3.0000g of ferric nitrate nonahydrate and 3.1206g of citric acid are weighed and dissolved in 100ml of deionized water, and the mixture is placed on a magnetic stirrer to be stirred for 30min, so that a metal mixed solution is obtained.
(3) Mixing the dispersion solution and the metal mixed solution, performing ultrasonic treatment, mixing, evaporating at 80 deg.C to gel, drying the gel at 80-100 deg.C for 6-12 hr to obtain 3DOM (three-dimensionally ordered macroporous structure) La 0.4 Ce 0.6 FeO 3 And (3) precursor.
(4) Placing the precursor in a tubular heating furnace, heating to 200 ℃ at a constant speed for 3h, roasting to 2h, heating to 400 ℃ at a constant speed for 3h, roasting to 2h, heating to 750 ℃ at a constant speed for 3h, and roasting for 3h to obtain the 3DOMLa 0.4 Ce 0.6 FeO 3 A photocatalyst.
Test 3DOMLa according to the following method 0.4 Ce 0.6 FeO 3 Photocatalytic activity of photocatalyst for degrading methylene blue in wastewater:
photocatalyst 3DOMLa is added under the condition of pH =3 0.4 Ce 0.6 FeO 3 Adding into wastewater containing methylene blue, adsorbing for 30min in dark, turning on light source, simultaneously adding hydrogen peroxide, with catalyst amount of 0.5g/L, light source wavelength of 420nm, hydrogen peroxide addition amount of 0.5mL/L, and reaction time of 60min. In the wastewater, the concentration of methylene blue is 50mg/L, and the COD is 200mg/L. The experimental results are as follows: methylene blue removal rate/% =99.99%, and COD removal rate/% =92.55%.
La prepared in example 1 0.4 Ce 0.6 FeO 3 In contrast, the three-dimensional ordered macroporous structure 3DOMLa prepared in this example 0.4 Ce 0.6 FeO 3 The catalyst has significantly higher methyl blue removal rate, COD removal rate and TOC (total organic carbon) removal rate, because the three-dimensional ordered macroporous structure has rich pore channels, the specific surface area of the catalyst is improved, and the catalytic activity of the catalyst is further improved. Thus, it can be confirmed that 3DOMLa of the present invention 0.4 Ce 0.6 FeO 3 The photocatalyst has remarkable progress in the aspect of photocatalytic degradation of organic matters in water.
Product characterization
(1) The product prepared in example 1 was mixed with 3DOMLa prepared in example 2 0.4 Ce 0.6 FeO 3 The phase structure of each material is shown in figure 1-2 when the photocatalyst is observed by a Fourier transform infrared spectrum and an X-ray diffractometer.
In FIG. 1, the transmittance curve corresponds to LaFeO in order from top to bottom 3 、La 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.2 Ce 0.8 FeO 3 、La 0.4 Ce 0.6 FeO 3 、3DOMLa 0.4 Ce 0.6 FeO 3 。
In FIG. 2, the X-ray intensity curves correspond to 3DOMLa sequentially from top to bottom 0.4 Ce 0.6 FeO 3 、La 0.4 Ce 0.6 FeO 3 、La 0.2 Ce 0.8 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.8 Ce 0.2 FeO 3 、LaFeO 3 。
As shown in FIG. 1, 3DOMLa 0.4 Ce 0.6 FeO 3 、La 1-x Ce x FeO 3 (x =0.2,0.4,0.6, 0.8) and LaFeO 3 All spectral lines of (2) are at 540cm -1 An asymmetric stretching vibration absorption peak of Fe-O bond appears nearby and represents typical FeO 6 Octahedron clusters prove that the catalysts prepared by the experiment all have perovskite structures. As can be seen from FIG. 2, the XRD spectrum shows that doping Ce does not destroy the perovskite structure, and La 0.4 Ce 0.6 FeO 3 The diffraction peak of (a) is stronger and sharper, indicating that the doped catalyst has higher crystallinity when x = 0.6. 3DOMLa 0.4 Ce 0.6 FeO 3 The diffraction peak intensity and sharpness were significantly higher, indicating 3DOMLa 0.4 Ce 0.6 FeO 3 Has a ratio of La 0.4 Ce 0.6 FeO 3 Higher crystallinity and crystal stability.
(2) The PS microspheres, la prepared in example 1, were observed using a scanning electron microscope 0.4 Ce 0.6 FeO 3 And the three-dimensionally ordered macroporous structure 3DOMLa prepared in example 2 0.4 Ce 0.6 FeO 3 The surface topography of (2). As shown in fig. 3-6. FIG. 3 shows PS microspheres with regular morphology and uniformly distributed diameters of about 2 μm. FIG. 4 is bulk La prepared in example 1 0.4 Ce 0.6 FeO 3 In FIGS. 5-6, 3DOMLa of three-dimensionally ordered macroporous structure 0.4 Ce 0.6 FeO 3 SEM image of (d). As can be seen from FIGS. 4-6, the perovskite catalyst prepared by the conventional sol-gel method and the coprecipitation method mostly exists in the form of nano-scale particles, the particle aggregation degree is high, a block structure with a smooth surface is formed, the structure limits the specific surface area of the catalyst (FIG. 4), and 3DOMLa prepared by using PS microspheres as a template agent 0.4 Ce 0.6 FeO 3 The surface has a large number of pores (figure 5-6), the pore diameter is about 2 μm, the diameter is equivalent to that of PS microspheres, and the diameter is equivalent to that of La 0.4 Ce 0.6 FeO 3 Compared with the prior art, the 3DOM structure enables the specific surface area of the catalyst to be remarkably improved, and is beneficial to exposure of active sites, so that the activity of the catalyst is improved. In the preparation process, the microsphere dispersion liquid and the mixed salt solution are subjected to ultrasonic dispersion, the specific gravity of the PS microspheres is close to that of water, the PS microspheres can be suspended in a reaction system, and then the 3DOMLa is subjected to evaporation gelatinization and multi-stage roasting to ensure that the 3DOMLa is obtained 0.4 Ce 0.6 FeO 3 The pores on the surface are distributed very uniformly.
(3) Observing 3DOMLa by adopting specific surface area and porosity analyzer 0.4 Ce 0.6 FeO 3 And La 0.4 Ce 0.6 FeO 3 The texture properties of (a) are as follows in table 2:
TABLE 2
| Catalyst and process for preparing same | Specific surface area/m 2 ·g -1 |
| 3DOMLa 0.4 Ce 0.6 FeO 3 | 70.89 |
| La 0.4 Ce 0.6 FeO 3 | 5.231 |
Calculated, 3DOMLa 0.4 Ce 0.6 FeO 3 Has a specific surface area of La 0.4 Ce 0.6 FeO 3 13.55 times of the specific surface area, indicating that the 3DOM structure significantly increases the specific surface area of the catalyst.
(4) LaFeO observation by adopting X-ray photoelectron spectrometer 3 、La 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.4 Ce 0.6 FeO 3 、La 0.2 Ce 0.8 FeO 3 And 3DOMLa 0.4 Ce 0.6 FeO 3 The valency of the surface active component elements is shown in fig. 7-8.
As can be seen from FIG. 7, for Fe2p 3/2 The orbit is subjected to peak-splitting fitting, laFeO 3 In the Fe form of Fe 3+ The form exists. La 1-x Ce x FeO 3 In the presence of Fe 2+ Indicating that doping Ce promotes Fe in the crystal lattice 3+ To Fe 2+ And the conversion is carried out, so that the catalytic efficiency is improved. When x =0.6, fe 2+ The content is 100 percent, 3DOMLa 0.4 Ce 0.6 FeO 3 The middle Fe is also Fe 2+ The form exists.
As shown in FIG. 8, in 3DOMLa 0.4 Ce 0.6 FeO 3 And La 1-x Ce x FeO 3 In (Ce) 3+ And Ce 4+ Are co-present, at levels of around 15% and 85%. A large body of literature indicates Fe 2+ The catalytic activity in photo-Fenton is higher than that of Fe 3+ So doping Ce will significantly increase the activity of the perovskite catalyst.
(5) LaFeO observation by adopting ultraviolet visible diffuse reflection technology 3 、La 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.4 Ce 0.6 FeO 3 、La 0.2 Ce 0.8 FeO 3 And 3DOMLa 0.4 Ce 0.6 FeO 3 The light absorption characteristics of the catalyst. As shown in FIG. 9, the curves correspond to 3DOMLa from top to bottom in sequence 0.4 Ce 0.6 FeO 3 、La 0.4 Ce 0.6 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.8 Ce 0.2 FeO 3 、La 0.2 Ce 0.8 FeO 3 、LaFeO 3 。
LaFeO prepared by sol-gel method, as shown in FIG. 9 3 Has obvious absorption band in the wavelength range of 200-800nm, la 1-x Ce x FeO 3 The catalyst has a ratio LaFeO in the visible light region 3 Higher light absorption strength indicates that doping with Ce improvesLaFeO 3 The absorption capacity of the catalyst for light. La when x =0.6 0.4 Ce 0.6 FeO 3 The strong absorption intensity indicates that the light absorption capability is good. 3DOMLa 0.4 Ce 0.6 FeO 3 Has a ratio of La 0.4 Ce 0.6 FeO 3 Higher light absorption capacity shows that the 3DOM structure is beneficial to increasing the specific surface area of the catalyst, enhancing the light transmission, improving the light absorption capacity and further improving the photocatalytic activity.
Comparative example 1
Taking 0.6561g of commercial ferrous sulfate heptahydrate as a catalyst, adding the ferrous sulfate heptahydrate into wastewater containing methylene blue under a certain pH value range, carrying out dark adsorption for 30min, turning on a light source, simultaneously adding hydrogen peroxide, wherein the pH is 2-0, the dosage of the catalyst is 0.5g/L, the wavelength of the light source is 420nm, the adding amount of the hydrogen peroxide is 0.5mL/L, the reaction time is 60min, and detecting the Fe concentration of the water by adopting ICP-MS after the reaction is finished. In parallel, the La prepared in example 1 was also tested 0.4 Ce 0.6 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.8 Ce 0.2 FeO 3 、La 0.2 Ce 0.8 FeO 3 、LaFeO 3 And 3DOMLa prepared in example 2 0.4 Ce 0.6 FeO 3 Parallel comparative experiments were performed. The results of the experiment are shown in table 3 and fig. 10.
TABLE 3
| |
2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Fe/mg·L -1 | 0.45 | 0.32 | 0.25 | 0.20 | 0.19 | 0.06 | 0.02 | 0.00 | 0.00 |
FIG. 10 shows the effect of initial pH on decolorization, (b) on COD, and (c) on TOC (Total organic carbon).
As is clear from Table 3, the iron ion content 0.50mg/L was lower than that of ferrous sulfate heptahydrate (amount converted to iron 132 mg/L). As can be seen from FIG. 10, it is found that LaFeO is correlated with LaFeO 3 、La 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.2 Ce 0.8 FeO 3 And ferrous sulfate heptahydrate (bottom curve of each figure), 3DOMLa prepared by the present invention 0.4 Ce 0.6 FeO 3 The methylene blue removal rate, the COD removal rate and the TOC removal rate were all the highest in the range of pH =2 to 10 (corresponding to the uppermost curve of each graph), indicating that La having a morphology of 3DOM is present 0.4 Ce 0.6 FeO 3 Has wider pH application rangeLess iron mud is generated (within pH = 2-10).
Comparative example 2
0.6561g of commercial ferrous sulfate heptahydrate is taken as a catalyst, the catalyst and the ferrous sulfate heptahydrate are added into wastewater containing methylene blue at the pH value of 3, dark adsorption is carried out for 30min, a light source is turned on, hydrogen peroxide is simultaneously added, the adding amount of the catalyst is 0.5g/L, the wavelength of the light source is 420nm, the adding amount of the hydrogen peroxide is 0.1-0.5mL/L, and the reaction time is 60min. In parallel, the La prepared in example 1 was also tested 0.4 Ce 0.6 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.8 Ce 0.2 FeO 3 、La 0.2 Ce 0.8 FeO 3 、LaFeO 3 And 3DOMLa prepared in example 2 0.4 Ce 0.6 FeO 3 Parallel comparative experiments were performed. The results of the experiment are shown in FIG. 11.
As shown in fig. 11, (a) shows the influence of the amount of added hydrogen peroxide on the decoloring rate, (b) shows the influence of the amount of added hydrogen peroxide on COD, and (c) shows the influence of the amount of added hydrogen peroxide TOC (total organic carbon).
FIG. 11 shows that LaFeO is correlated with LaFeO 3 、La 0.8 Ce 0.2 FeO 3 、La 0.6 Ce 0.4 FeO 3 、La 0.2 Ce 0.8 FeO 3 And ferrous sulfate heptahydrate (second curve from top), 3DOMLa 0.4 Ce 0.6 FeO 3 (corresponding to the uppermost curves of the figures) the methylene blue removal rate, the COD removal rate and the TOC removal rate are highest within the range of 0.1-0.5mL/L of hydrogen peroxide, which shows that the 3DOMLa prepared by the invention 0.4 Ce 0.6 FeO 3 Has higher utilization rate of hydrogen peroxide.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (11)
1. Three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A method for producing a photocatalyst, comprising:
s1, dispersing polystyrene and/or polymethyl methacrylate microspheres in anhydrous lower alcohol to obtain a dispersion liquid; dissolving soluble lanthanum salt, cerium salt, ferric salt and a complexing agent in water to obtain a metal salt mixed solution;
s2, mixing the dispersion liquid with the metal salt mixed solution, carrying out ultrasonic treatment, evaporating at the temperature of less than or equal to 90 ℃ to obtain a gel-like substance, and drying to obtain the three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A precursor;
s3, mixing 3DOMLa 0.4 Ce 0.6 FeO 3 Roasting the precursor at multi-stage temperature in air atmosphere to obtain three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A photocatalyst.
2. The preparation method according to claim 1, wherein in S1, the polystyrene microspheres are placed in absolute ethanol and stirred for at least 30min to obtain a dispersion; the mass ratio of the polystyrene microspheres to the absolute ethyl alcohol is 2.
3. The method according to claim 1, wherein in the metal salt mixed solution in S1, the molar ratio of lanthanum, cerium and iron ions is 0.4:0.59-0.61:0.99-1.02.
4. The preparation method according to claim 1, wherein in S1, the complexing agent in the metal salt mixed solution is citric acid, and the total molar ratio of citric acid to metal ions is 1.
5. The preparation method according to claim 1, wherein in S1, the molar concentration of lanthanum ions in the metal salt mixed solution is 0.029-0.0306mol/L, and the concentration of cerium ions is 0.0445-0.045mol/L and 0.074-0.075mol/L.
6. The method according to claim 1, wherein the drying condition for the gel-like material in S2 is 80 to 100 ℃ for 6 to 12 hours.
7. The method according to claim 1, wherein in S3, the temperature increase rate of the multi-step temperature baking is 70-80 ℃/h; and the roasting is divided into three stages: the first stage is as follows: heating to 180-250 ℃ in air atmosphere, roasting for 1.5-2.5h, and performing a second stage: heating to 350-450 deg.C, calcining for 1.5-2.5h, and calcining at 750-850 deg.C for 2.5-3.5h in the third stage.
8. Three-dimensional ordered macroporous La 0.4 Ce 0.6 FeO 3 A photocatalyst produced by the production method according to any one of claims 1 to 7.
9. The three-dimensionally ordered macroporous La of claim 8 0.4 Ce 0.6 FeO 3 The application of the photocatalyst in heterogeneous photo-Fenton catalytic degradation of methylene blue.
10. Use according to claim 9, characterized in that the step of degrading methylene blue comprises: step 1: subjecting three-dimensionally ordered macroporous La 0.4 Ce 0.6 FeO 3 Adding the photocatalyst into the wastewater containing methylene blue for dark adsorption, wherein the adding amount is>0.4g/L；
Step 2: turning on a light source, adding hydrogen peroxide, adjusting the pH to be =2-10, adjusting the wavelength of the light source to be 400-460 nm, and adding the hydrogen peroxide in an amount of 0.1-0.5mL/L.
11. Use according to claim 10, characterized in that the three-dimensionally ordered macroporous La 0.4 Ce 0.6 FeO 3 The adding amount of the photocatalyst is 0.5g/L; the light source wavelength is 420nm.
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| CN102923811A (en) * | 2012-11-12 | 2013-02-13 | 青岛科技大学 | Method for catalytic degradation of high-concentrated organic wastewater by micro-wave cooperating with perovskite |
| CN105688918A (en) * | 2016-01-18 | 2016-06-22 | 常州大学 | Preparation method of clay-perovskite composite material and application thereof |
| CN106179369A (en) * | 2016-07-25 | 2016-12-07 | 牛和林 | Tool visible ray Fenton activity LaFeO3/ C carbon back perovskite semiconductor composite nano material and its preparation method and application |
| CN106492813A (en) * | 2016-09-21 | 2017-03-15 | 昆明理工大学 | A kind of three-dimensional ordered macroporous LaFeO of support type3/CeO2The preparation method of catalyst |
| CN110876938A (en) * | 2019-11-05 | 2020-03-13 | 天津大学 | Perovskite type composite metal oxide oxygen carrier and preparation method and application thereof |
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