CN111135839A - Iron oxide modified attapulgite/bismuth molybdate composite photocatalyst and preparation method and application thereof - Google Patents
Iron oxide modified attapulgite/bismuth molybdate composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN111135839A CN111135839A CN201911386147.8A CN201911386147A CN111135839A CN 111135839 A CN111135839 A CN 111135839A CN 201911386147 A CN201911386147 A CN 201911386147A CN 111135839 A CN111135839 A CN 111135839A
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- attapulgite
- iron oxide
- photocatalyst
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- tetracycline hydrochloride
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 98
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 98
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 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 claims abstract description 17
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 10
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002900 Bi2MoO6 Inorganic materials 0.000 claims abstract description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000000593 degrading effect Effects 0.000 claims abstract 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 230000015556 catabolic process Effects 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 229910015667 MoO4 Inorganic materials 0.000 claims description 9
- 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 claims description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 230000004043 responsiveness Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 238000010335 hydrothermal treatment Methods 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 229940088710 antibiotic agent Drugs 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
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- 239000011550 stock solution Substances 0.000 description 1
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- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
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- 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
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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
- B01J37/0201—Impregnation
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Abstract
The invention belongs to the field of preparation of photocatalytic materials, and particularly relates to an iron oxide modified attapulgite/bismuth molybdate composite photocatalyst as well as a preparation method and application thereof. According to the invention, the attapulgite is firstly acidified, then the iron element is loaded in the attapulgite structure through impregnation, iron generates iron oxide quantum dots in the pores of the attapulgite during the heat treatment process to obtain the iron oxide modified attapulgite, so that the light responsiveness of the attapulgite is improved; then useThe modified attapulgite is used as a framework as a catalyst carrier sodium molybdate to ensure that Bi2MoO6The nanocrystalline grows along the attapulgite skeleton to obtain the composite photocatalytic material, and the invention promotes the generated Bi2MoO6The crystal grows in situ on the attapulgite, and the crystal forms a heterojunction with the attapulgite and the ferric oxide to obtain high-efficiency photocatalytic performance, and has outstanding application effect in degrading tetracycline hydrochloride.
Description
Technical Field
The invention belongs to the field of preparation of composite materials, and particularly relates to application of an iron oxide modified attapulgite/bismuth molybdate composite photocatalyst and a preparation method thereof.
Background
Antibiotics are widely applied to human medical treatment and agricultural production, and with the increase of the dosage of the antibiotics, environmental pollution is becoming serious day by day and even poses serious threat to human health. Therefore, the removal of antibiotics from wastewater has attracted attention and is a hot topic in the field. Nowadays, a large number of methods are used for removing antibiotics, such as biological methods, physical methods, chemical methods, and the like, and in particular, photocatalytic degradation has the advantages of simple operation, high efficiency, low cost, and the like, and is considered to be an ideal technology for antibiotic treatment.
The attapulgite is a natural one-dimensional nano mineral material containing water and rich in magnesium and aluminum, but the attapulgite does not have photoresponse, so that the attapulgite is modified in the prior art to achieve the effect of visible light response, and the attapulgite is used as a photocatalyst to expand the application of the attapulgite in the field of photocatalysis.
The invention firstly uses hydrochloric acid to remove impurities and then soaks the solution containing Fe3+The solution is stirred and evaporated, and Fe (OH) is generated due to hydrolysis of iron3. High temperature calcination conditions → Fe2O3Loaded in the attapulgite structure, the photoresponse of the material is improved.
Also prepared and assembled herein as Bi2MoO6And mixing it with modified attapulgite, Fe2O3The heterojunction formed between the particles can separate oxidation and reduction reaction sites from space, and a network structure consisting of common-angle octahedrons is beneficial to carrier transmission, so that the utilization rate of photo-generated electrons and holes is effectively improved, and high-efficiency photocatalysis performance is obtained.
Disclosure of Invention
In order to fully utilize most visible light in sunlight energy and solve the problem of low utilization rate of sunlight, the invention provides an iron oxide modified attapulgite/bismuth molybdate composite photocatalytic material, iron element is loaded in an attapulgite structure by an immersion method, on one hand, iron oxide quantum dots generated in the heat treatment process of iron are in attapulgite pores, so that the light responsiveness of the attapulgite is improved; on the other hand, the attapulgite framework is used as a catalyst carrier, and Bi2MoO6The nano crystal grows on the surface of the reaction medium in situ, so that a good dispersion effect can be achieved, and the contact area between the nano crystal and the reaction medium is increased.
In addition, aiming at the defects in the prior art, the invention aims to disclose a preparation method of the iron oxide modified attapulgite/bismuth molybdate composite material, and the prepared catalyst is applied to catalytic degradation of antibiotics.
The purpose of the invention is realized by the following technical scheme that the iron oxide modified attapulgite/bismuth molybdate composite material is prepared by the following steps:
(1) firstly, preparing the iron oxide modified attapulgite: adding a certain amount of attapulgite into hydrochloric acid solution to prepare dispersed slurry, and stirring for 24h at 80 deg.C to obtain acidified attapulgite material; and then adding the acidified attapulgite into an iron chloride solution, soaking and stirring, evaporating to dryness at 80 ℃, and then carrying out heat treatment at 500 ℃ for 2h to obtain the iron oxide modified attapulgite. The concentration of the hydrochloric acid is preferably 1-8 mol/L, the solid content in the dispersed slurry is preferably 7-10%, and the concentration of the ferric chloride solution is preferably 2-6 mol/L.
Acidifying with hydrochloric acid to remove impurities and remove Ca in natural minerals2+、Mg2+、Al3+Plasma; for subsequent Fe3+The modification provides a new location. The optimal acidification concentration is 4M, and the acidification treatment time is 24 h.
(2) Adding a certain amount of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) dispersing into 40mL of glycol solution, and magnetically stirring for 20-30min until a clear transparent solution is formed; the mass concentration of the bismuth nitrate pentahydrate solution is preferably 0.020-0.050 g/mL.
(3) Adding a certain amount of sodium molybdate (Na)2MoO4·2H2O) and the attapulgite modified by the ferric oxide are placed in deionized water for ultrasonic dispersion for 30min to obtain a uniform suspension; wherein the molar ratio of Bi to Mo is 2: 1; bi2MoO6Accounts for 15 to 100 percent of the weight of the iron oxide modified attapulgite; pre-impregnating, and adsorbing MoO by using the pore channels on the attapulgite4 2-Therefore, the bismuth molybdate crystals formed subsequently can grow along the attapulgite framework, a heterojunction can be formed favorably, the binding force is improved, and the bismuth molybdate crystals cannot grow along the attapulgite framework and are difficult to form the heterojunction if the bismuth molybdate crystals are not soaked in advance.
(4) And (3) adding the suspension prepared in the step (3) into the step (2), transferring the suspension to a hydrothermal kettle, carrying out hydrothermal treatment for 10-24h at the temperature of 160-180 ℃, carrying out suction filtration, washing and drying to obtain the iron oxide modified attapulgite/bismuth molybdate composite material.
The invention has the beneficial effects that: the invention adopts a hydrothermal method to prepare the iron oxide modified attapulgite/bismuth molybdate composite material, and has the advantages of simple method, easy operation, low cost and the like.
The attapulgite utilized by the invention is cheap and easy to obtain, has better adsorption performance and more active sites, and can be used as an excellent carrier of the catalyst after being subjected to acidizing and dipping treatment. Iron oxide quantum dots (the size of the iron oxide quantum dots is smaller than or close to the exciton Bohr radius, and the general diameter is not more than 10nm) are generated after the iron oxide enters an attapulgite structure for heat treatment, so that the concave is improvedLight responsiveness of attapulgite. Then loading Bi thereon2MoO6Nanocrystalline, Fe2O3And Bi2MoO6And a heterojunction is formed, and the carrier separation efficiency is synergistically improved.
Mixing sodium molybdate (Na)2MoO4·2H2O) and attapulgite modified by ferric oxide are ultrasonically dispersed together, and the aim is to pre-disperse MoO4 2-Ions are pre-combined with the ferric oxide quantum dots in the modified attapulgite pore structure, so that Bi is convenient2MoO6The crystal grows on the attapulgite in situ to form a heterojunction between the crystal and the attapulgite, so that the carrier separation efficiency is effectively improved.
Drawings
FIG. 1 is a TEM image of the iron oxide-modified attapulgite and the composite material of example 2;
FIGS. 1(a), (b) are iron oxide modified attapulgite materials from which it can be seen that iron oxide quantum dots are deposited on an attapulgite structure; FIG. 1(c) is an image of the composite material prepared in example 2, in which the compact bismuth molybdate crystals coated on the surface of attapulgite are seen, and in the high-order image of FIG. 1(d), the lattice lines of iron oxide and bismuth molybdate are clearly seen, and the two are tightly combined together.
FIG. 2 is a graph showing the degradation performance of tetracycline hydrochloride in examples 1 to 3 and comparative examples 1 to 2.
Detailed Description
Embodiments of the present invention will now be described in detail with reference to the following examples, which are intended to be illustrative of the present invention and should not be construed as limiting the scope of the invention. The examples were carried out under the conventional conditions, unless otherwise specified. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The degradation performance test used in the experiments was,
the experiment uses tetracycline hydrochloride as a degradation object and a 300W high-pressure mercury lamp as a light source. 0.10g of the catalyst was weighed into a photochemical reactor, and then a prepared tetracycline hydrochloride solution (20mg/L, 100mL) was added thereto, and the mixture was cooled to room temperature. Starting a magnetic stirring device, introducing air from the bottom of the bottle for bubbling, carrying out dark adsorption for 30min to ensure that the solution reaches adsorption and desorption balance, then starting a mercury lamp (carrying an optical filter, filtering out ultraviolet light, and measuring under the condition that the wavelength is more than 420 nm), periodically sampling for 10mL, taking supernatant after centrifugal separation, measuring the absorbance of the supernatant at the wavelength of 352nm on a UV-3600 type ultraviolet-visible spectrophotometer, and calculating the degradation rate by the following formula:
η＝(1-At/A0)×100％
wherein η is the degradation rate (%), A0As absorbance of stock solution, AtAbsorbance of the solution after t time
The preparation process of the iron oxide modified attapulgite/bismuth molybdate composite material comprises the following steps:
example 1
(1) Firstly, preparing the iron oxide modified attapulgite: adding 5.0g attapulgite into 40mL hydrochloric acid solution (4M) to prepare dispersed slurry, and stirring at 80 deg.C for 12 hr to obtain acidified attapulgite material; and then adding the acidified attapulgite into 80mL of ferric chloride solution (4M), soaking and stirring, evaporating to dryness at 80 ℃, and then carrying out heat treatment at 500 ℃ for 2h to obtain the iron oxide modified attapulgite.
(2) Adding 1mmol of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) is dispersed into 40mL of glycol solution, and is magnetically stirred for 30min until a clear transparent solution is formed;
(3) adding 0.5mmol of sodium molybdate (Na)2MoO4·2H2O) and 1496.2mg of iron oxide modified attapulgite are placed in deionized water for ultrasonic dispersion for 30min to obtain a uniform suspension;
(4) and (3) adding the suspension prepared in the step (3) into the step (2), transferring the suspension into a hydrothermal kettle, carrying out hydrothermal treatment at 160 ℃ for 12 hours, carrying out suction filtration, washing and drying to obtain the iron oxide modified attapulgite/bismuth molybdate composite material with the mass content of bismuth molybdate being 30%.
After 3 hours of photocatalytic degradation, the tetracycline hydrochloride degradation efficiency of the catalyst is measured as follows: 73.58 percent.
Example 2
(1) Firstly, preparing the iron oxide modified attapulgite: adding 5.0g attapulgite into 40mL hydrochloric acid solution (4M) to prepare dispersed slurry, and stirring at 80 deg.C for 24 hr to obtain acidified attapulgite material; and then adding the acidified attapulgite into 80mL of ferric chloride solution (4M), soaking and stirring, evaporating to dryness at 80 ℃, and then carrying out heat treatment at 500 ℃ for 2h to obtain the iron oxide modified attapulgite.
(2) Adding 2mmol of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) is dispersed into 40mL of glycol solution, and is magnetically stirred for 30min until a clear transparent solution is formed;
(3) adding 1mmol of sodium molybdate (Na)2MoO4·2H2O) and 1795.5mg of iron oxide modified attapulgite are placed in deionized water for ultrasonic dispersion for 30min to obtain a uniform suspension;
(4) and (3) adding the suspension prepared in the step (3) into the step (2), transferring the suspension into a hydrothermal kettle, carrying out hydrothermal treatment at 160 ℃ for 12 hours, carrying out suction filtration, washing and drying to obtain the iron oxide modified attapulgite/bismuth molybdate composite material with the mass content of bismuth molybdate of 50%.
After 3 hours of photocatalytic degradation, the tetracycline hydrochloride degradation efficiency of the catalyst is measured as follows: 92.09 percent.
As can be seen from figure 1, the iron oxide quantum dots are deposited on the attapulgite structure, and the particle size of the iron oxide is obviously less than 10 nm; and the surface of the attapulgite is coated with compact bismuth molybdate crystals. If loaded, Bi is generated2MoO6The crystal is loaded with ferric oxide and bismuth molybdate with larger grain diameter, and Bi is prepared firstly2MoO6The crystals are easy to block the pores dissolved out by the prior acidification treatment, are not favorable for the subsequent tight combination of the iron oxide semiconductor material and the attapulgite main body structure, and have poor structural stability of the catalyst.
Example 3
(1) Firstly, preparing the iron oxide modified attapulgite: adding 1.0g attapulgite into 40mL hydrochloric acid solution (4M) to prepare dispersed slurry, and stirring at 80 deg.C for 12 hr to obtain acidified attapulgite material; and then adding the acidified attapulgite into 80mL of ferric chloride solution (2M), soaking and stirring, evaporating to dryness at 80 ℃, and then carrying out heat treatment at 500 ℃ for 3h to obtain the iron oxide modified attapulgite.
(2) 2mmol bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) is dispersed into 40mL of glycol solution, and is magnetically stirred for 30min until a clear transparent solution is formed;
(3) adding 1mmol of sodium molybdate (Na)2MoO4·2H2O) and 897.8mg of iron oxide modified attapulgite are placed in deionized water for ultrasonic dispersion for 30min to obtain a uniform suspension;
(4) and (3) adding the suspension prepared in the step (3) into the step (2), transferring the suspension into a hydrothermal kettle, carrying out hydrothermal treatment for 18h at 160 ℃, carrying out suction filtration, washing and drying to obtain the iron oxide modified attapulgite/bismuth molybdate composite material with the mass content of bismuth molybdate being 100%.
After 3 hours of photocatalytic degradation, the tetracycline hydrochloride degradation efficiency of the catalyst is measured as follows: 81.84 percent.
Comparative example 1
(1) Firstly, preparing acidified attapulgite: adding 5.0g attapulgite into 40mL hydrochloric acid solution (4M) to prepare dispersed slurry, and stirring at 80 deg.C for 24 hr to obtain acidified attapulgite material; heat treatment is carried out for 2h at 500 ℃ to obtain the acidified attapulgite material.
(2) Adding 1mmol of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) is dispersed into 40mL of glycol solution, and is magnetically stirred for 30min until a clear transparent solution is formed;
(3) adding 0.5mmol of sodium molybdate (Na)2MoO4·2H2O) and 1496.2mg of acidified and modified attapulgite are placed in deionized water for ultrasonic dispersion for 30min to obtain a uniform suspension;
(4) and (3) adding the suspension prepared in the step (3) into the step (2), transferring the suspension into a hydrothermal kettle, carrying out hydrothermal treatment at 160 ℃ for 12 hours, carrying out suction filtration, washing and drying to obtain the modified attapulgite/bismuth molybdate composite material with the mass ratio of 30%.
After 3 hours of photocatalytic degradation, the tetracycline hydrochloride degradation efficiency of the catalyst is measured as follows: 56.04 percent.
Comparative example 2
(1) Firstly, preparing the iron oxide modified attapulgite: adding 10.0g attapulgite into 40mL hydrochloric acid solution (6M) to prepare dispersed slurry, and stirring at 80 deg.C for 12 hr to obtain acidified attapulgite material; and then adding the acidified attapulgite into 80mL of ferric chloride solution (2M), soaking and stirring, evaporating to dryness at 80 ℃, and then carrying out heat treatment at 500 ℃ for 5h to obtain the iron oxide modified attapulgite.
(2) Adding 1mmol of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) is dispersed into 40mL of glycol solution, and is magnetically stirred for 30min until a clear transparent solution is formed;
(3) adding 0.5mmol of sodium molybdate (Na)2MoO4·2H2O) and 1496.2mg of iron oxide modified attapulgite are placed in deionized water for ultrasonic dispersion for 30min to obtain a uniform suspension;
(4) and (3) adding the suspension prepared in the step (3) into the step (2), transferring the suspension into a hydrothermal kettle, carrying out hydrothermal treatment at 160 ℃ for 12 hours, carrying out suction filtration, washing and drying to obtain the iron oxide modified attapulgite/bismuth molybdate composite material with the mass ratio of 30%.
After 3 hours of photocatalytic degradation, the tetracycline hydrochloride degradation efficiency of the catalyst is measured as follows: 63.02 percent.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified. The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all modifications of the above embodiments made according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (8)
1. A photocatalyst for degrading tetracycline hydrochloride is characterized in that: the photocatalyst is an iron oxide modified attapulgite/bismuth molybdate composite material.
2. A method for preparing the photocatalyst for degrading tetracycline hydrochloride according to claim 1, wherein the preparation step comprises:
(1) adding attapulgite into a hydrochloric acid solution to prepare dispersion slurry, and carrying out hydrothermal stirring for a period of time to obtain an acidified attapulgite material; and then adding the acidified attapulgite into an iron chloride solution, soaking and stirring, evaporating to dryness, and performing heat treatment to obtain the iron oxide modified attapulgite.
(2) Adding bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) dispersing into the ethylene glycol solution, and stirring to obtain a clear transparent solution;
(3) mixing sodium molybdate (Na)2MoO4·2H2O) and the attapulgite modified by the ferric oxide are placed in deionized water for ultrasonic dispersion to obtain a uniform turbid liquid;
(4) and (3) adding the suspension prepared in the step (3) into the transparent solution prepared in the step (2), transferring the transparent solution to a hydrothermal kettle for hydrothermal reaction, and performing suction filtration, washing and drying after the reaction to prepare the iron oxide modified attapulgite/bismuth molybdate composite material.
3. The method for preparing the photocatalyst for degrading tetracycline hydrochloride according to claim 2, wherein: the step (1) is to stir the mixture for 24 hours in a hydrothermal way at the temperature of 80 ℃, and the heat treatment condition is to heat treat the mixture for 2 hours at the temperature of 500 ℃.
4. The method for preparing the photocatalyst for degrading tetracycline hydrochloride according to claim 2, wherein: in the bismuth nitrate pentahydrate and the sodium molybdate, the molar ratio of Bi/Mo is 2: 1.
5. The method for preparing the photocatalyst for degrading tetracycline hydrochloride according to claim 2, wherein: the Bi2MoO6The mass ratio of the attapulgite to the iron oxide modified attapulgite is 0.15-1: 1.
6. The method for preparing the photocatalyst for degrading tetracycline hydrochloride according to claim 2, wherein: the hydrothermal reaction conditions in the step (4) are as follows: carrying out hydrothermal reaction for 10-24h at 160-180 ℃.
7. The method for preparing the photocatalyst for degrading tetracycline hydrochloride according to claim 2, characterized in that: the iron oxide modified attapulgite is formed by generating iron oxide quantum dots in an attapulgite structure, wherein the size of the iron oxide is not more than 10 nm.
8. Use of a photocatalyst according to any one of claims 1 to 7 for the degradation of tetracycline hydrochloride.
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