CN115228490A - Iron phosphide/iron monoatomic Fenton photocatalyst and preparation method and application thereof - Google Patents
Iron phosphide/iron monoatomic Fenton photocatalyst and preparation method and application thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 205
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 102
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000004098 Tetracycline Substances 0.000 claims abstract description 48
- 229960002180 tetracycline Drugs 0.000 claims abstract description 48
- 229930101283 tetracycline Natural products 0.000 claims abstract description 48
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 48
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- 238000004108 freeze drying Methods 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 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 claims abstract description 11
- 229940072172 tetracycline antibiotic Drugs 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 32
- 239000003344 environmental pollutant Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 231100000719 pollutant Toxicity 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 238000005286 illumination Methods 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 2
- 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 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 31
- 238000006731 degradation reaction Methods 0.000 abstract description 31
- 239000003054 catalyst Substances 0.000 abstract description 27
- 229910052723 transition metal Inorganic materials 0.000 abstract description 8
- 150000003624 transition metals Chemical class 0.000 abstract description 8
- 230000003115 biocidal effect Effects 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 20
- 230000000694 effects Effects 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001994 activation Methods 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- -1 ferric nitrate nonahydrate ions Chemical class 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- 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
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Abstract
The invention relates to the technical field of antibiotic tetracycline wastewater treatment, in particular to an iron phosphide/iron monoatomic Fenton photocatalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding an aqueous solution of ferric nitrate nonahydrate into an aqueous solution of graphene oxide, and sequentially stirring, washing and freeze-drying to obtain iron monoatomic atoms; and mixing and dissolving iron phosphide and iron monoatomic compound in water, and sequentially stirring, washing and freeze-drying to obtain the iron phosphide/iron monoatomic Fenton-like photocatalyst. In the catalyst, the nonmetal phosphorus and the transition metal iron both have the characteristics of multiple valence states, and electrons circulate among the multiple valence states, so that the utilization rate of hydrogen peroxide is obviously improved; due to the introduction of the monoatomic iron active site, the distribution of the active sites of the heterogeneous catalyst is improved, and the active efficiency of hydrogen peroxide is further improved; when the catalyst is used for treating tetracycline antibiotic wastewater, the degradation efficiency of the antibiotic tetracycline wastewater is obviously improved.
Description
Technical Field
The invention relates to the technical field of antibiotic tetracycline waste water treatment, in particular to an iron phosphide/iron monoatomic Fenton photocatalyst and a preparation method and application thereof.
Background
The Fenton oxidation reaction is used as a large class of advanced oxidation technology, and has important application prospects in environmental management and restoration and remediation. The traditional Fenton oxidation is that ferrous iron reacts with hydrogen peroxide to generate hydroxyl free radicals with strong oxidation capacity, so that organic pollutants are degraded. However, the traditional Fenton oxidation has the problems of low activation utilization rate of hydrogen peroxide, secondary pollution of water caused by iron mud, great influence of pH, incapability of recycling a homogeneous catalyst and the like. Therefore, there is an urgent need to develop a heterogeneous fenton-like catalyst having a high active site to solve the above problems.
Transition metal phosphide is an important multifunctional catalyst material, and is widely applied to the fields of electrocatalysis, thermocatalysis, photocatalysis and the like in recent years. The iron phosphide is a phosphide with low cost and excellent performance, and on one hand, the iron phosphide has wide optical absorption and can be used as a visible light or even near infrared light catalyst; on the other hand, the transition metal iron can be used as an active site in the hydrogen peroxide activation process and used for activating the hydrogen peroxide. Meanwhile, because the nonmetal phosphorus and the transition metal iron both have the characteristic of multiple valence states, the circulation among multiple valence states can be realized, the transfer conversion efficiency of electrons in the catalyst is improved, and the utilization rate of hydrogen peroxide is further improved. Therefore, the iron phosphide can be used as an excellent Fenton-like photocatalyst to be applied to the field of organic wastewater treatment.
However, the conventional iron phosphide particles have small specific surface area and relatively few surface exposed iron active sites, and cannot deal with rapid degradation of refractory organic pollutants.
The invention is provided in view of the above.
Disclosure of Invention
The invention aims to provide an iron phosphide/iron monoatomic Fenton photocatalyst and a preparation method and application thereof, wherein in the catalyst, nonmetal phosphorus and transition metal iron both have multiple valence state characteristics, and electrons circulate among multiple valence states, so that the utilization rate of hydrogen peroxide is obviously improved; due to the introduction of the monoatomic iron active site, the distribution of the active sites of the heterogeneous catalyst is improved, and the active efficiency of hydrogen peroxide is further improved; when the catalyst is used for treating tetracycline antibiotic wastewater, the degradation efficiency of the antibiotic tetracycline wastewater is obviously improved.
The invention provides a preparation method of an iron phosphide/iron monoatomic Fenton photocatalyst, which comprises the following steps:
adding an aqueous solution of ferric nitrate nonahydrate into an aqueous solution of graphene oxide, and sequentially stirring, washing and freeze-drying to obtain iron monatomic; and mixing and dissolving iron phosphide and iron monatomic in water, and sequentially stirring, washing and freeze-drying to obtain the iron phosphide/iron monatomic Fenton photocatalyst.
According to the invention, firstly, graphene oxide with ultrahigh specific surface area is used as a carrier, a monoatomic dispersed iron monoatomic atom is prepared through coordination chelation and reducibility between ferric nitrate nonahydrate ions and residual oxygen of the graphene oxide, and then phosphide nanoparticles and the iron monoatomic Fenton photocatalyst are compounded through an electrostatic attraction-immersion compounding method by using positive charges on the surface of iron phosphide and negative charges on the surface of the iron monoatomic atom to obtain the iron phosphide/iron monoatomic Fenton photocatalyst. Researches show that the catalyst has wider optical adsorption performance, can realize visible and near infrared light catalysis, and the non-metal phosphorus and the transition metal iron in the catalyst have multiple valence state characteristics, and the electron circulation among multiple valence states improves the utilization rate of hydrogen peroxide, while the introduction of the active site of the monatomic iron further improves the activity of the hydrogen peroxide. When the catalyst is used for treating tetracycline antibiotic wastewater, the degradation efficiency of the antibiotic tetracycline wastewater is obviously improved.
Researches show that the catalyst can achieve 100% of tetracycline degradation rate under visible-near infrared light irradiation, and the tetracycline degradation efficiency can still achieve 94% after the catalyst is recycled for 6 times.
The specific proportioning and using amount of the graphene oxide and the ferric nitrate nonahydrate are not strictly limited, but in order to ensure that iron atoms can be uniformly loaded on the surface of the graphene oxide and high exposure of active sites of the iron atoms, the mass concentration of the graphene oxide with the mass concentration of 1-2mg/mL corresponds to the ferric nitrate nonahydrate is 0.5-1mg/L; similarly, the mass ratio of the iron phosphide to the iron atom is not strictly limited, but in order to ensure the matching degree between the positive charges on the surface of the iron phosphide and the negative charges on the surface of the iron atom and improve the utilization rate of raw materials, the mass ratio of the iron phosphide to the iron monoatomic is controlled to be (50-100): (5-10).
In addition, the invention does not strictly limit the specific technological parameters of stirring, centrifuging and freeze drying for preparing the iron atom and iron phosphide/iron monoatomic Fenton photocatalyst, and takes full stirring, washing and impurity content reduction as the criteria. Specifically, when the iron monatomic is prepared, the stirring time is controlled to be 20-28h, and after the stirring is finished, deionized water is used for centrifugal washing for 3-4 times, and then freeze drying is carried out; preferably, the stirring speed is controlled to be 100-150rpm during stirring; and when the ferric phosphate/iron monatomic Fenton photocatalyst is prepared, the stirring time is controlled to be 10-14h, and after stirring is finished, deionized water is used for centrifugal washing for 3-4 times, and then freeze drying is carried out.
The iron phosphide/iron monoatomic Fenton-like photocatalyst prepared according to the preparation method also belongs to the protection scope of the invention.
The invention also discloses an application of the iron phosphide/iron monatomic Fenton photocatalyst in the treatment of tetracycline antibiotic wastewater, and the application also belongs to the protection scope of the invention.
Specifically, the method for treating the tetracycline antibiotic wastewater by using the iron phosphide/iron monoatomic Fenton photocatalyst comprises the following steps of:
adding the iron phosphide/iron monoatomic Fenton photocatalyst into a pollutant solution containing tetracycline, adding hydrogen peroxide after adsorption balance is achieved, and reacting under visible-near infrared light irradiation.
Preferably, in the present embodiment, the tetracycline: the mass concentration ratio of the iron phosphide/iron monoatomic Fenton photocatalyst to the hydrogen peroxide is (20-50): (0.02-0.05): (0.025-0.625).
In the technical scheme, when the catalyst is used for treating tetracycline antibiotic wastewater, the degradation effect of the catalyst on tetracycline is better when the concentration of the pollutant solution is 10-50mg/L, and the treatment effect is optimal when the concentration is 20 mg/L.
The intensity of the visible-near infrared illumination is not strictly limited in the invention, but in order to further improve the photoactivity of the catalyst, the light intensity of the visible-near infrared illumination is 100-200mW/cm 2 And preferably 200mW/cm 2 。
The iron phosphide/iron monoatomic Fenton photocatalyst at least has the following technical effects:
1. according to the method, graphene oxide with an ultrahigh specific surface area is used as a carrier, and a monoatomic iron monoatomic atom is prepared through coordination chelation and reducibility between ferric ions and residual oxygen of the graphene oxide;
2. the invention also utilizes the positive charges on the surface of the iron phosphide and the negative charges on the surface of the iron monatomic catalyst to compound phosphide nano-particles and the iron monatomic catalyst by an electrostatic attraction-impregnation compounding method, thereby preparing the iron phosphide/iron monatomic Fenton photocatalyst. The iron phosphide/iron monatomic Fenton photocatalyst prepared by the method is stable and efficient.
3. Compared with the traditional Fenton and Fenton-like catalysts, the iron phosphide/iron monoatomic Fenton-like photocatalyst provided by the invention has the following advantages: excellent wide optical absorption performance, and can realize catalysis of visible light and near infrared light; the nonmetal phosphorus and the transition metal iron both have the characteristic of multiple valence states, and electrons circulate among the multiple valence states, so that the utilization rate of hydrogen peroxide is obviously improved; the introduction of the active site of the monatomic iron improves the distribution of the active sites of the heterogeneous catalyst, thereby improving the active efficiency of the hydrogen peroxide;
4. the iron phosphide/iron monatomic Fenton photocatalyst provided by the invention can be used for remarkably improving the degradation efficiency of antibiotic tetracycline wastewater, solving the problems of low Fenton oxidation efficiency, secondary iron mud pollution, incapability of recycling homogeneous catalysts and the like in the traditional Fenton oxidative degradation of organic pollutants by transition metals, and having wide application prospects in the fields of treatment of pharmaceutical factory organic wastewater, hospital organic wastewater, breeding wastewater and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a TEM image and a spherical aberration electron micrograph of a sample prepared in example 1 of the present invention (both (a) and (b) are TEM images, and (c) is a spherical aberration electron micrograph);
FIG. 2 is an XRD pattern of a sample prepared in example 1 of the present invention;
FIG. 3 is an XPS plot of an iron phosphide/iron monatomic catalyst prepared in example 1 of the present invention;
FIG. 4 is a UV-Vis plot of a sample prepared in example 1 of the present invention;
FIG. 5 is a graph showing the degradation effect of tetracycline by activated hydrogen peroxide in different samples according to test example 1 of the present invention;
FIG. 6 is a graph showing the degradation effect of iron phosphide/iron monatomic catalyst of test example 2 of the present invention in degrading tetracycline under different experimental conditions;
FIG. 7 is a graph showing the degradation effect of an iron phosphide/iron monatomic catalyst under visible-near infrared light irradiation on tetracycline degradation by activated hydrogen peroxide in test example 3 of the present invention under different initial pH conditions;
FIG. 8 is a graph showing the degradation effect of iron phosphide/iron monatomic catalyst of test example 4 of the present invention in degrading tetracycline by activating hydrogen peroxide repeatedly under visible-near infrared light irradiation.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1) Weighing 40mg of graphene oxide and 10mg of ferric nitrate nonahydrate, respectively dissolving in 20mL of deionized water to obtain a graphene oxide aqueous solution and a ferric nitrate nonahydrate aqueous solution, slowly adding the ferric nitrate nonahydrate aqueous solution into the graphene oxide aqueous solution, stirring the mixed solution at the rotation speed of 150rpm for 24 hours, centrifugally washing with deionized water at the rotation speed of 14000rpm for 4 times, and freeze-drying to obtain iron monoatomic ions;
2) Weighing 50mg of iron phosphide and 5mg of iron monatomic in a 25mL beaker, adding 20mL of deionized water, stirring at the rotating speed of 150rpm for 12 hours, centrifuging and washing at the rotating speed of 14000rpm for 4 times, and freeze-drying to obtain the iron phosphide/iron monatomic Fenton photocatalyst.
Example 2
1) Weighing 30mg of graphene oxide and 15mg of ferric nitrate nonahydrate, respectively dissolving in 20mL of deionized water to obtain a graphene oxide aqueous solution and a ferric nitrate nonahydrate aqueous solution, slowly adding the ferric nitrate nonahydrate aqueous solution into the graphene oxide aqueous solution, stirring the mixed solution at the rotating speed of 150rpm for 24 hours, centrifugally washing with deionized water at the rotating speed of 14000rpm for 4 times, and freeze-drying to obtain iron single atoms;
2) 70mg of iron phosphide and 10mg of iron monatomic are weighed in a 25mL beaker, 20mL of deionized water is added, the mixture is stirred for 12 hours at the rotating speed of 150rpm, then the mixture is centrifugally washed for 4 times at the rotating speed of 14000rpm, and finally the iron phosphide/iron monatomic Fenton photocatalyst is obtained through freeze drying.
Therefore, the microscopic morphology and the crystal structure of the iron phosphide/iron monatomic Fenton photocatalyst prepared in example 1 and the absorption conditions of light in different wave bands are researched by adopting a TEM (transmission electron microscope), a spherical aberration electron microscope, an XRD (X-ray diffraction), an XPS (X-ray diffraction) and an ultraviolet visible absorption spectrometer.
As can be seen from FIGS. 1-4, the present invention successfully prepared the above samples, and the above samples have a wide light absorption range, and have absorption in the 400-2000nm band.
Test example 1
In this test example, tetracycline was selected as a representative of the contaminant, and experiments for degrading tetracycline by activated hydrogen peroxide were performed using iron phosphide, iron monatomic, and iron phosphide/iron monatomic, respectively.
200mL of 20mg/L tetracycline solution is prepared, and 40mL of tetracycline solution is measured and placed in a beaker; weighing 6mg of iron phosphide, iron monatomic powder and iron phosphide/iron monatomic powder, respectively adding the weighed materials into the pollutant solution, and uniformly stirring the materials to achieve adsorption balance; then measuring 12 mu L of hydrogen peroxide, adding the hydrogen peroxide into the pollutant solution, and taking 1mL of reaction solution at fixed intervals to test the tetracycline content.
FIG. 5 is a graph showing the degradation effect of activated hydrogen peroxide on tetracycline by iron phosphide, molybdenum phosphide, iron monatomic and iron phosphide/iron monatomic powders in this test example. As can be seen from the figure, tetracycline is not degraded within 30min by independently adding hydrogen peroxide, and iron phosphide, molybdenum phosphide, iron monatomic and iron phosphide/iron monatomic powder are used for respectively activating the hydrogen peroxide, so that degradation rates of 16%, 7%, 31% and 78% are respectively achieved within 30min, thereby showing that iron circulation in the iron phosphide/iron monatomic catalyst can be effectively used for activating the hydrogen peroxide, and the synergy of the iron monatomic and the iron phosphide can effectively promote the activation of the hydrogen peroxide so as to degrade the tetracycline.
Test example 2
In the test example, the degradation effect of iron phosphide/iron monatomic on tetracycline under visible-near infrared irradiation, visible light irradiation or hydrogen peroxide addition conditions was studied respectively.
200mL of 20mg/L tetracycline solution is prepared, and 40mL of tetracycline solution is respectively measured and put in a plurality of beakers; weighing 6mg of iron phosphide/iron monatomic powder, respectively adding the iron phosphide/iron monatomic powder into the pollutant solution, and uniformly stirring to achieve adsorption balance; then measuring 12 mu L of hydrogen peroxide, adding the hydrogen peroxide into the pollutant solution, and keeping the illumination intensity at 200mW/cm 2 The reaction was carried out under visible-near infrared irradiation, and 1mL of the reaction solution was taken at fixed intervals to test the tetracycline content.
FIG. 6 is a graph showing the effect of iron phosphide/iron monatomic powder activated hydrogen peroxide in degrading tetracycline in this test example. As can be seen from the figure, the single iron phosphide/iron single atom can only weakly adsorb tetracycline; under the conditions of visible-near infrared light irradiation, visible light irradiation or hydrogen peroxide addition, the degradation rates of the iron phosphide/iron monatomic powder can reach 51%, 20% and 78% within 30min respectively; and under the conditions of visible-near infrared light irradiation and simultaneous use of hydrogen peroxide, the degradation rate of the iron phosphide/iron monoatomic atoms to the tetracycline can reach 100%, so that the degradation efficiency of the tetracycline is greatly improved. Therefore, the iron phosphide/iron monatomic catalyst has excellent capability of catalyzing and activating hydrogen peroxide to degrade waste tetracycline under visible-near infrared light, and can obviously improve the degradation effect of the tetracycline.
Test example 3
In this test example, the degradation effect of the iron phosphide/iron monatomic catalyst on tetracycline degradation by activated hydrogen peroxide at different pH values of 3, 5, 7, 9 and 11 was studied.
Preparing 200mL of 20mg/L tetracycline solution, respectively measuring 40mL of the tetracycline solution in a plurality of beakers, and adjusting the pH values of the solutions to be 3, 5, 7, 9 and 11 respectively; weighing 6mg of iron phosphide/iron monatomic powder, respectively adding the iron phosphide/iron monatomic powder into the pollutant solution, and uniformly stirring to achieve adsorption balance; then measuring 12 mu L of hydrogen peroxide, adding the hydrogen peroxide into the pollutant solution, and keeping the illumination intensity at 200mW/cm 2 The reaction was carried out under the irradiation of visible-near infrared light, and 1mL of the reaction solution was taken at fixed intervals to test the tetracycline content.
FIG. 7 is a graph showing the degradation effect of iron phosphide/iron monatomic in visible-near infrared light irradiation activated hydrogen peroxide in the present test example on tetracycline degradation under different initial pH conditions. As can be seen from the figure, the degradation efficiency of activated hydrogen peroxide for degrading tetracycline is kept high under the irradiation of visible-near infrared light and in different pH environments, the degradation efficiency is hardly influenced by the pH of the solution, and the problem that the traditional Fenton is limited by the pH is effectively solved.
Test example 4
In the test example, the degradation effect of the iron phosphide/iron monoatomic compound on tetracycline degradation by activating hydrogen peroxide for multiple times circularly under near infrared light irradiation is studied.
200mL of 20mg/L tetracycline solution is prepared, and 40mL of tetracycline solution is respectively measured and placed in a plurality of beakers; weighing 6mg of iron phosphide/iron monatomic powder, respectively adding the iron phosphide/iron monatomic powder into the pollutant solution, and uniformly stirring to achieve adsorption balance; then measuring 12 mu L of hydrogen peroxide, adding the hydrogen peroxide into the pollutant solution, and keeping the illumination intensity at 200mW/cm 2 The reaction is carried out under the irradiation of visible-near infrared light, and 1mL of the reaction solution is taken at fixed intervals to carry out the tetracycline content test.
The reacted sample was recovered as a catalyst and the above procedure was repeated.
FIG. 8 is a graph showing the degradation effect of tetracycline by multiple cycles of activating hydrogen peroxide under irradiation of near-infrared light by iron phosphide/iron monatomic in this test example. As can be seen from the figure, after the iron phosphide/iron monatomic powder disclosed by the invention is circulated under visible-near infrared light irradiation for 6 times, the degradation efficiency of the iron phosphide/iron monatomic powder on tetracycline can still reach 94%, the higher tetracycline degradation efficiency is kept, and the iron phosphide/iron monatomic powder has excellent circulation practicability.
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 (10)
1. A preparation method of an iron phosphide/iron monoatomic Fenton photocatalyst is characterized by comprising the following steps:
adding an aqueous solution of ferric nitrate nonahydrate into an aqueous solution of graphene oxide, and sequentially stirring, washing and freeze-drying to obtain iron monatomic; and mixing and dissolving iron phosphide and iron monatomic in water, and sequentially stirring, washing and freeze-drying to obtain the iron phosphide/iron monatomic Fenton photocatalyst.
2. The preparation method according to claim 1, wherein the mass concentration of iron nitrate nonahydrate per 1-2mg/mL of graphene oxide is 0.5-1mg/L;
the mass ratio of the iron phosphide to the iron monoatomic is (50-100): (5-10).
3. The preparation method according to claim 1, wherein in the preparation of the iron monatomic, the stirring time is controlled to be 20-28h, and after the stirring is completed, the iron monatomic is subjected to freeze drying after being centrifugally washed for 3-4 times by using deionized water;
preferably, the stirring speed is controlled to be 100-150rpm when the stirring is carried out.
4. The preparation method of claim 1, wherein the preparation of the iron phosphide/iron monoatomic Fenton photocatalyst is performed by controlling the stirring time to be 10-14h, performing centrifugal washing with deionized water for 3-4 times after the stirring is completed, and performing freeze drying.
5. An iron phosphide/iron monoatomic Fenton-like photocatalyst prepared by the method of any one of claims 1 to 4.
6. Use of the iron phosphide/iron monoatomic Fenton-like photocatalyst according to claim 5 in the treatment of wastewater with tetracycline antibiotics.
7. The method for treating tetracycline antibiotic wastewater by the iron phosphide/iron monatomic Fenton-like photocatalyst as recited in claim 5, characterized by comprising the steps of:
adding an iron phosphide/iron monatomic Fenton photocatalyst into a pollutant solution containing tetracycline, adding hydrogen peroxide after adsorption balance is achieved, and reacting under visible-near infrared light irradiation.
8. The method of claim 7, wherein the tetracycline: the mass concentration ratio of the iron phosphide/iron monoatomic Fenton photocatalyst to the hydrogen peroxide is (20-50): (0.02-0.05): (0.025-0.625).
9. The method of claim 7, wherein the contaminant solution has a concentration of 10-50mg/L.
10. The method of claim 7, wherein the visible-near infrared illumination has an intensity of 100-200mW/cm 2 。
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| CN113600170A (en) * | 2021-07-16 | 2021-11-05 | 西安理工大学 | Transition metal monoatomic active catalyst and preparation method and application thereof |
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| CN111282590A (en) * | 2020-03-13 | 2020-06-16 | 武汉工程大学 | Metal monoatomic-supported nitrogen-doped porous graphene composite catalyst and preparation method thereof |
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| CN116351445A (en) * | 2023-02-28 | 2023-06-30 | 齐鲁工业大学(山东省科学院) | Core-shell phosphating zero-valent iron material and preparation method and application thereof |
| CN116351445B (en) * | 2023-02-28 | 2024-05-10 | 齐鲁工业大学(山东省科学院) | Core-shell phosphating zero-valent iron material and preparation method and application thereof |
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