CN111135839B - 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 PDF

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CN111135839B
CN111135839B CN201911386147.8A CN201911386147A CN111135839B CN 111135839 B CN111135839 B CN 111135839B CN 201911386147 A CN201911386147 A CN 201911386147A CN 111135839 B CN111135839 B CN 111135839B
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attapulgite
iron oxide
photocatalyst
oxide modified
tetracycline hydrochloride
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CN111135839A (en
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姚超
尹克诚
左士祥
李霞章
刘文杰
吴凤芹
严向玉
王灿
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Jiangsu Naou New Materials Co ltd
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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
    • B01J35/39—
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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 taking the modified attapulgite as a framework as a catalyst carrier sodium molybdate to ensure that Bi is 2 MoO 6 The nanocrystalline grows along the attapulgite skeleton to obtain the composite photocatalytic material, and the invention promotes the generated Bi 2 MoO 6 The 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

Iron oxide modified attapulgite/bismuth molybdate composite photocatalyst and preparation method and application thereof
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 impregnates the mixture containing Fe 3+ The solution is stirred and evaporated, and Fe (OH) is generated due to hydrolysis of iron 3 . High temperature calcination conditions → Fe 2 O 3 Loaded in the attapulgite structure, the photoresponse of the material is improved.
This paper also prepares Bi 2 MoO 6 And making it and modified attapulgite react with Fe 2 O 3 The 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
To make full use of the sunThe invention provides an iron oxide modified attapulgite/bismuth molybdate composite photocatalytic material, which solves the problem of low utilization rate of sunlight due to the fact that most visible light is contained in light energy, and an iron element is loaded in an attapulgite structure through an immersion method, so that on one hand, iron oxide quantum dots generated in the heat treatment process of iron are placed in pores of the attapulgite to improve the light responsiveness of the attapulgite; on the other hand, the attapulgite framework is used as a catalyst carrier, and Bi 2 MoO 6 The 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 a hydrochloric acid solution to prepare dispersed slurry, and carrying out hydrothermal stirring at 80 ℃ for 24 hours to obtain an 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 dispersion 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 minerals 2+ 、Mg 2+ 、Al 3+ Plasma; for subsequent Fe 3+ The modification provides a new location. The optimal acidification concentration is 4M, and the acidification treatment time is 24h.
(2) Adding a certain amount of bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O) is dispersed into 40mL of glycol solution, and is magnetically stirred for 20-30min until 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) 2 MoO 4 ·2H 2 O) 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/Mo is 2; bi 2 MoO 6 Accounts for 15 to 100 percent of the weight of the iron oxide modified attapulgite; pre-impregnating, and adsorbing MoO by using the pore canal on attapulgite 4 2- So that the subsequently formed bismuth molybdate crystals can grow along the attapulgite framework, the heterojunction can be favorably formed, the binding force is improved, and the bismuth molybdate crystals cannot grow along the attapulgite framework and are difficult to form if the bismuth molybdate crystals are not pre-impregnated.
(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 160-180 ℃ for 10-24h, 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 has the advantages of low price, easy obtainment, better adsorption performance and more active sites, and can be used as an excellent carrier of the catalyst after the acidification treatment and the impregnation treatment. The light responsiveness of the attapulgite is improved by entering the iron oxide into the attapulgite structure for heat treatment to generate the iron oxide quantum dots (the iron oxide quantum dots refer to the iron oxide quantum dots with the size smaller than or close to the exciton Bohr radius, and the general diameter is not more than 10 nm). Then loading Bi thereon 2 MoO 6 Nanocrystalline, fe 2 O 3 And Bi 2 MoO 6 And a heterojunction is formed, and the carrier separation efficiency is synergistically improved.
Mixing sodium molybdate (Na) 2 MoO 4 ·2H 2 O) and attapulgite modified by ferric oxide are ultrasonically dispersed together, and the aim is to pre-disperse MoO 4 2- Ions are pre-combined with the ferric oxide quantum dots in the modified attapulgite pore structure, so that Bi is convenient 2 MoO 6 Heterojunction formed between crystals grown in situ on attapulgite to effectively increase carrierEfficiency of fluid separation.
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-power image of FIG. 1 (d), the lattice lines of iron oxide and bismuth molybdate are clearly seen, and the two are tightly combined.
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 conventional products which are not indicated by manufacturers and are commercially available.
The degradation performance test used in the experiments was,
the experiment takes tetracycline hydrochloride as a degradation object and takes a 300W high-pressure mercury lamp as a light source. 0.10g of the catalyst was weighed and charged into the photochemical reactor, and the prepared tetracycline hydrochloride solution (20 mg/L,100 mL) was further added thereto at 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-A t /A 0 )×100％
wherein: eta is degradation rate (%) and A 0 As absorbance of stock solution, A t As absorbance 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 of attapulgite into 40mL of hydrochloric acid solution (4M) to prepare dispersed slurry, and carrying out hydrothermal stirring at 80 ℃ for 12h to obtain an 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 ·5H 2 O) 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) 2 MoO 4 ·2H 2 O) and 1496.2mg of iron oxide modified attapulgite are placed in deionized water for ultrasonic dispersion for 30min to obtain 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 3h 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 of attapulgite into 40mL of hydrochloric acid solution (4M) to prepare dispersed slurry, and carrying out hydrothermal stirring at 80 ℃ for 24h to obtain an 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 ·5H 2 O) is dispersed into 40mL of glycol solution, and is magnetically stirred for 30min until clear transparent solution is formed;
(3) 1mmol of sodium molybdate (Na) 2 MoO 4 ·2H 2 O) and 1795.5mg oxidationPlacing the iron-modified attapulgite in deionized water, and ultrasonically dispersing 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 50%.
After 3h 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 10nm; and the surface of the attapulgite is coated with compact bismuth molybdate crystals. If loaded, produce Bi 2 MoO 6 The crystal is loaded with ferric oxide and bismuth molybdate with larger grain diameter, bi is prepared first 2 MoO 6 The crystals are easy to block the pores dissolved out by acidification treatment in advance, the subsequent tight combination of the iron oxide semiconductor material and the attapulgite main body structure is not facilitated, and the structural stability of the catalyst is poor.
Example 3
(1) Firstly, preparing the iron oxide modified attapulgite: adding 1.0g of attapulgite into 40mL of hydrochloric acid solution (4M) to prepare dispersed slurry, and carrying out hydrothermal stirring at 80 ℃ for 12h to obtain an 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) Adding 2mmol of bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O) is dispersed into 40mL of glycol solution, and is magnetically stirred for 30min until clear transparent solution is formed;
(3) Adding 1mmol of sodium molybdate (Na) 2 MoO 4 ·2H 2 O) and 897.8mg of iron oxide modified attapulgite are placed in deionized water for ultrasonic dispersion for 30min to obtain 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 of attapulgite into 40mL of hydrochloric acid solution (4M) to prepare dispersed slurry, and carrying out hydrothermal stirring at 80 ℃ for 24h to obtain an acidified attapulgite material; heat treatment is carried out for 2h at 500 ℃ to obtain the acidified attapulgite material.
(2) 1mmol of bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O) is dispersed into 40mL of glycol solution, and is magnetically stirred for 30min until clear transparent solution is formed;
(3) Adding 0.5mmol of sodium molybdate (Na) 2 MoO 4 ·2H 2 O) 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 of attapulgite into 40mL of hydrochloric acid solution (6M) to prepare dispersed slurry, and carrying out hydrothermal stirring at 80 ℃ for 12h to obtain an 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) 1mmol of bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O) 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) 2 MoO 4 ·2H 2 O) and 1496.2mg of iron oxide modified attapulgite are placed in deionized waterUltrasonically dispersing for 30min to obtain 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 3h of photocatalytic degradation, the tetracycline hydrochloride degradation efficiency of the catalyst is measured as follows: and (3.02).
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 made to the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.

Claims (6)

1. A photocatalyst for degrading tetracycline hydrochloride is characterized in that: the photocatalyst is an iron oxide modified attapulgite/bismuth molybdate composite material, and the preparation steps comprise:
(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; then, adding the acidified attapulgite into a ferric chloride solution, soaking and stirring, evaporating to dryness, and performing heat treatment to obtain the iron oxide modified attapulgite;
(2) Dispersing bismuth nitrate pentahydrate into an ethylene glycol solution, and stirring the solution to obtain a clear transparent solution;
(3) Placing the attapulgite modified by sodium molybdate and ferric oxide in deionized water for ultrasonic dispersion to obtain a uniform suspension;
(4) 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; the mass ratio of the bismuth molybdate to the iron oxide modified attapulgite is 0.15-1.
2. The photocatalyst for degrading tetracycline hydrochloride according to claim 1, wherein: the step (1) is hydrothermal stirring at 80 ℃ for 24h, and the thermal treatment condition is thermal treatment at 500 ℃ for 2 h.
3. The photocatalyst for degrading tetracycline hydrochloride of claim 1, wherein: the molar ratio of Bi/Mo in the bismuth nitrate pentahydrate and the sodium molybdate is 2.
4. The photocatalyst for degrading tetracycline hydrochloride according to claim 1, wherein: the hydrothermal reaction conditions in the step (4) are as follows: carrying out hydrothermal reaction for 10-24h at 160-180 ℃.
5. The photocatalyst for degrading tetracycline hydrochloride according to claim 1, wherein: the attapulgite modified by the ferric oxide is characterized in that ferric oxide quantum dots are generated in an attapulgite structure, and the size of the ferric oxide is not more than 10nm.
6. Use of a photocatalyst as claimed in any one of claims 1 to 5 for the degradation of tetracycline hydrochloride.
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