CN117563581A - Dy single-atom-loaded TiO 2 Photocatalyst, preparation method and application thereof - Google Patents

Dy single-atom-loaded TiO 2 Photocatalyst, preparation method and application thereof Download PDF

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CN117563581A
CN117563581A CN202311172410.XA CN202311172410A CN117563581A CN 117563581 A CN117563581 A CN 117563581A CN 202311172410 A CN202311172410 A CN 202311172410A CN 117563581 A CN117563581 A CN 117563581A
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tio
solution
photocatalyst
atom
monoatomic
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叶盛
刘梦梦
刘璐璐
秦渝沣
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Anhui Agricultural University AHAU
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Anhui Agricultural University AHAU
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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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • C02F2101/306—Pesticides
    • 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
    • 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
    • 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
    • C02F2103/36—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 manufacture of organic compounds
    • 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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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
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Abstract

The invention discloses a Dy single-atom-loaded TiO 2 A photocatalyst, a preparation method and application thereof. The Dy single-atom-loaded TiO 2 The photocatalyst comprises the following components in parts by weight: tiO (titanium dioxide) 2 100 parts of dysprosium nitrate hexahydrate and 0.01 to 1 part of dysprosium nitrate hexahydrate. The preparation method comprises (1) mixing titanium source with hydrofluoric acid for hydrothermal reaction to obtain TiO 2 A nanosheet; (2) TiO is mixed with 2 Adding the nano-sheet into the mixed solution to obtain a solution I; (3) adding dysprosium nitrate hexahydrate into the solution to obtain a solution II; (4) adding the solution II into the solution I to react to obtain a solution III; and (5) filtering, drying and heat treating the solution III to obtain the product. Dy single-atom-loaded TiO of the invention 2 The photocatalyst can effectively degrade glyphosate pesticide pollutants, has higher photocatalytic degradation performance under ultraviolet light, and is relative to TiO 2 The reaction kinetics of the degradation of the nano-sheet is improved by 15 times, and a new idea is provided for the problem of increasingly serious pesticide pollution.

Description

Dy single-atom-loaded TiO 2 Photocatalyst, preparation method and application thereof
Technical Field
The invention belongs to the field of environmental photocatalysis, and in particular relates to Dy single-atom-loaded TiO 2 A photocatalyst, a preparation method and application thereof.
Background
Glyphosate is a non-selective and post-emergence herbicide that is ubiquitous in the world agricultural arts, and several studies have shown that glyphosate affects the physiological metabolism of animals and plants. Therefore, there is a need to develop an efficient and low cost method for removing glyphosate from water.
At present, many methods for treating glyphosate wastewater exist, such as physical technology, chemical technology and biodegradation. However, most of these techniques are costly, inefficient, or require stringent conditions, which can result in secondary pollution of the water. Compared with the traditional pesticide treatment methods, the advanced oxidation method has great advantages in the aspect of treating pesticide pollutants in the environment, can realize complete mineralization, and has excellent application prospect. The photocatalysis technology is an environment-friendly and efficient method for converting pesticides into micromolecular nontoxic products by using solar energy. Solar energy is a renewable energy source, and photocatalysts driven by light are more promising. In recent decades, photocatalytic technology has been widely studied and applied in the field of wide environmental remediation, such as heavy metal ion reduction, pollutant degradation, and air purification.
Photocatalysts are an important component of photocatalytic technology. Semiconductor metal oxides are widely used as photocatalytically active catalysts due to their availability and low cost. TiO (titanium dioxide) 2 Is a widely used adsorption and photocatalyst. In the last decades, tiO 2 Photocatalysts are receiving extensive attention because of their obvious advantages of good chemical stability, rich elements, easy synthesis, no toxicity, etc. Particularly, physical and chemical properties capable of achieving various functions have been attracting extensive research interest.
The use of Rare Earth (RE) elements in heterogeneous catalysis has attracted attention, rare earth elements playing an important role in heterogeneous catalysis as active metals or supports. The rich orbitals and electrons of the RE element can provide strong coordination bonds with anions in the catalyst support material, thereby promoting the formation of rare earth monoatomic catalysts (RE-SAC). Due to the electronic nature of rare earth atoms, they generally form stable, highly coordinated structures with at least four ligands. Meanwhile, RE-SAC is used for catalytic reaction, and a large-scale local coordination environment leads to strong atom-carrier interaction, suppresses thermomigration, and has excellent activity, selectivity and longer catalyst life.
In CN109529805A, a preparation method of a rare earth doped modified nano titanium oxide photocatalyst for degrading organophosphorus pesticides is disclosed, wherein an ultraviolet lamp is used as a light source, oxygen is provided by magnetic stirring in an air environment, the organophosphorus pesticides can be degraded by photocatalysis, and the organophosphorus pesticides can be effectively degraded without causing secondary pollution. But the degradation efficiency is low. The invention of a rare earth doped nano TiO in CN102783484A 2 Wettable powder and preparation method thereof, the provided wettable powder is suitable for photocatalytic degradation of pesticides, and nano TiO after spraying 2 Can be adsorbed on a target object, and can generate more electron holes after full irradiation of ultraviolet rays, thereby improving the photocatalytic activity and realizing degradation. However, the prior art generally has the problem of low degradation efficiency, and the pesticide cannot be well degraded with high efficiency. Therefore, in order to overcome the defects of the prior art, the research of a simple preparation method of the rare earth monoatomic photocatalyst is developed by aiming at constructing a high-efficiency photocatalyst by utilizing the unique property of the rare earth monoatomic, and a catalyst capable of being efficiently degraded is found.
Disclosure of Invention
Aiming at the problem of low degradation efficiency in the prior art, one aim of the invention is to provide a TiO loaded with Dy monoatoms 2 A photocatalyst. Another object of the present invention is to provide Dy monoatomic-supported TiO 2 A preparation method of a photocatalyst. A third object of the present invention is to provide the Dy monoatomic-supported TiO 2 The application of the photocatalyst in degrading organic pesticide pollutant.
Dy monoatomic-supported TiO as described in the present invention 2 Photocatalyst and Dy-TiO 2 Monoatomic photocatalysts represent the same meaning.
In order to achieve the above purpose, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides Dy monoatomic-supported TiO 2 The photocatalyst comprises the following components in parts by weight: tiO (titanium dioxide) 2 :100 parts of dysprosium nitrate hexahydrate: 0.01-1 part.
Further, the Dy single-atom-loaded TiO 2 The photocatalyst comprises the following components in parts by weight: tiO (titanium dioxide) 2 :100 parts of dysprosium nitrate hexahydrate: 0.1 part.
In a second aspect, the present invention provides the Dy monoatomic-supported TiO as described above 2 The preparation method of the photocatalyst comprises the following steps:
(1) Mixing a titanium source with hydrofluoric acid to obtain uniform mixed solution, and performing hydrothermal reaction on the mixed solution to obtain TiO 2 A nanosheet;
(2) TiO in the step (1) 2 The nano-sheets are dispersed in a mixed solution of deionized water and glycol to obtain a solution I;
(3) Dispersing dysprosium nitrate hexahydrate in an ethylene glycol solution to obtain a solution II;
(4) Adding the solution II in the step (3) into the solution I, and reacting to obtain a solution III;
(5) Centrifugally washing, drying and heat treating the solution III obtained in the step (4) to obtain Dy single-atom-loaded TiO 2 A photocatalyst.
Further, the titanium source in step (1) is a hydrolyzable titanium-containing compound.
Preferably, the titanium source in step (1) is tetrabutyl titanate.
Further, the volume ratio of tetrabutyl titanate to hydrofluoric acid in the step (1) is (1:1) - (25:1).
Preferably, the volume ratio of tetrabutyl titanate to hydrofluoric acid is 5:1.
Further, the hydrothermal reaction temperature in the step (1) is 150-200 ℃ and the reaction time is 2-12h.
Further, the white precipitate obtained by the hydrothermal reaction in the step (1) is dried and ground to obtain TiO 2 A nano-sheet.
Preferably, the drying temperature in step (1) is 60 ℃ and the time is 12 hours.
Further, in the step (2), the volume ratio of deionized water to ethylene glycol is (1:9) - (9:1).
Further, dysprosium nitrate hexahydrate and TiO in step (4) 2 The mass ratio of (1:100) - (0.01:100).
Preferably, dysprosium nitrate hexahydrate and TiO in step (4) 2 The mass ratio of (2) is 0.1:100.
Further, the reaction condition in the step (4) is 60-80 ℃ and is protected from light for 10-12h.
Preferably, the reaction condition in the step (4) is 60 ℃ and the water bath is protected from light for 10 hours.
In a third aspect, the present invention provides the Dy monoatomic-supported TiO as described above 2 The application of the photocatalyst in degrading organic pesticide pollutant.
The Dy single-atom-loaded TiO 2 The photocatalyst can degrade organic pesticide pollutants under the irradiation of light with the power of 50-1000W and the wavelength range of 320-1100nm, which is mainly due to the Dy single-atom-loaded TiO provided by the invention 2 The photocatalyst is prepared by mixing TiO 2 Mixing the nano-sheet with dysprosium nitrate hexahydrate, and performing heat treatment to obtain TiO 2 The O element on the surface of the nano-sheet coordinates with Dy ions to realize that Dy monoatoms are in TiO 2 On the surface of the nanoplateletsAnchoring load, dy single atom-loaded TiO prepared by the method 2 The photocatalyst improves the separation of photo-generated carriers, increases the number of active sites, and further enhances the performance of photocatalytic degradation of organic pesticide pollutants.
Further, the organic pesticide pollutant is glyphosate, and the concentration of the glyphosate is 5-100ppm.
Compared with the prior art, the invention has the beneficial effects that:
(1) Dy single-atom-loaded TiO prepared by the invention 2 The photocatalyst can realize complete degradation of organic pesticide pollutants, has higher photocatalytic degradation performance under ultraviolet light, and provides a new thought for solving the pesticide pollution problem in the environment;
(2) The preparation method provided by the invention has the advantages of simple process, abundant raw materials and low price, and has a realistic application prospect.
Drawings
FIG. 1 is a diagram of TiO in example 1 2 Field Emission Scanning Electron Microscope (FESEM) of nanoplatelets, FIG. 1, tiO at 500nm 2 Field Emission Scanning Electron Microscope (FESEM) of nanoplatelets, FIG. 1, tiO at 200nm b 2 Field Emission Scanning Electron Microscope (FESEM) of nanoplatelets, FIG. 1, tiO at 100nm 2 Field Emission Scanning Electron Microscope (FESEM) of nanoplatelets, FIG. 1, tiO at 50nm d 2 A Field Emission Scanning Electron Microscope (FESEM) image of the nanoplatelets;
FIG. 2 is a diagram of TiO in example 1 2 High Resolution Transmission Electron Microscopy (HRTEM) image of nanoplatelets, tiO at 200nm in FIG. 2 2 High Resolution Transmission Electron Microscopy (HRTEM) image of nanoplatelets, tiO at 50nm in FIG. 2 2 High Resolution Transmission Electron Microscopy (HRTEM) image of nanoplatelets, tiO at 10nm in FIG. 2 2 High Resolution Transmission Electron Microscopy (HRTEM) image of nanoplatelets, tiO at 2nm in FIG. 2 2 High Resolution Transmission Electron Microscopy (HRTEM) images of nanoplatelets;
FIG. 3 is a diagram of TiO in example 1 2 Degradation performance of the nanoplatelets is shown in FIG. 3, wherein a is the concentration of the fixed catalyst, and the degradation performance of the glyphosate concentration is changed, and FIG. 3b is a linear fit of a in fig. 3, c in fig. 3 is a fixed glyphosate concentration, degradation performance at varying catalyst concentrations, and d in fig. 3 is a linear fit of c in fig. 3;
FIG. 4 is a diagram of TiO in example 2 2 Nanoplatelets and Dy 0.1％ -TiO 2 XRD pattern of single-atom photocatalyst;
FIG. 5 is a diagram of TiO in example 2 2 Nanoplatelets and Dy 0.1％ -TiO 2 Raman diagram of single-atom photocatalyst;
FIG. 6 shows Dy in example 2 0.1％ -TiO 2 Field Emission Scanning Electron Microscope (FESEM) of single atom photocatalyst, dy at 500nm in FIG. 6 0.1％ -TiO 2 Field Emission Scanning Electron Microscope (FESEM) of single atom photocatalyst, dy at 200nm in FIG. 6 0.1％ -TiO 2 Field Emission Scanning Electron Microscope (FESEM) of single atom photocatalyst, dy at 100nm in FIG. 6 0.1％ -TiO 2 Field Emission Scanning Electron Microscope (FESEM) of single atom photocatalyst, dy at d of 50nm in FIG. 6 0.1％ -TiO 2 A Field Emission Scanning Electron Microscope (FESEM) image of a single atom photocatalyst;
FIG. 7 shows Dy in example 2 0.1％ -TiO 2 High Resolution Transmission Electron Microscope (HRTEM) image of monoatomic photocatalyst, dy at 200nm in FIG. 7 0.1％ -TiO 2 High Resolution Transmission Electron Microscope (HRTEM) image of monoatomic photocatalyst, dy at 50nm in FIG. 7 0.1％ -TiO 2 High Resolution Transmission Electron Microscope (HRTEM) image of monoatomic photocatalyst, dy at 10nm in FIG. 7 0.1％ -TiO 2 High Resolution Transmission Electron Microscope (HRTEM) image of monoatomic photocatalyst, dy at d of 2nm in FIG. 7 0.1％ -TiO 2 High Resolution Transmission Electron Microscope (HRTEM) images of monoatomic photocatalyst;
FIG. 8 shows Dy in example 2 0.1％ -TiO 2 Spherical aberration electron microscope (HAADF-STEM) diagram and element distribution (EDS Mapping) diagram of single-atom photocatalyst, dy at 2nm in FIG. 8 0.1％ -TiO 2 Spherical aberration electron microscope (HAADF-STEM) diagram of single-atom photocatalyst, dy at 100nm in FIG. 8 b 0.1％ -TiO 2 Element distribution (EDS Mapping) diagram of single-atom photocatalyst;
FIG. 9 shows Dy in example 2 0.1％ -TiO 2 The synchrotron radiation of the monoatomic photocatalyst is shown as Dy L in FIG. 9 a 3 -side X-ray near side absorption spectrum (XANES), dy in fig. 9 b 0.1％ -TiO 2 And Dy 2 O 3 L of medium Dy 3 Edge k 3 Weighted fourier transform diagram, c in fig. 9 and d in fig. 9 are Dy, respectively 0.1％ -TiO 2 And Dy 2 O 3 Is a wavelet transform of (1);
FIG. 10 is a diagram of TiO in example 2 2 Nanoplatelets and Dy 0.1％ -TiO 2 Ultraviolet visible spectrum of single-atom photocatalyst;
FIG. 11 shows Dy-single-atom-supported TiO of different Dy contents in examples 2-6 2 Degradation performance diagram of photocatalyst, dy 0.01％ -TiO 2 Dysprosium nitrate hexahydrate and TiO in monoatomic photocatalyst 2 The mass ratio of the nano-sheets is 0.01:100, dy 0.05％ -TiO 2 Dysprosium nitrate hexahydrate and TiO in monoatomic photocatalyst 2 The mass ratio of the nano-sheets is 0.05:100, dy 0.1％ -TiO 2 Dysprosium nitrate hexahydrate and TiO in monoatomic photocatalyst 2 The mass ratio of the nano-sheets is 0.1:100, dy 0.5％ -TiO 2 Dysprosium nitrate hexahydrate and TiO in monoatomic photocatalyst 2 The mass ratio of the nano-sheets is 0.5:100, dy 1％ -TiO 2 Dysprosium nitrate hexahydrate and TiO in monoatomic photocatalyst 2 The mass ratio of the nano-sheets is 1:100;
FIG. 12 shows dysprosium nitrate hexahydrate, la in comparative example 1 and comparative example 2 0.1％ -TiO 2 Monoatomic photocatalyst and Dy 0.1％ -TiO 2 The degradation performance of the monoatomic photocatalyst is compared with that of the monoatomic photocatalyst, and a in fig. 12 is a comparison graph of degradation performance, and b in fig. 12 is a linear fitting graph of a in fig. 12.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Preparation of photocatalyst
Example 1:
preparation of TiO 2 Nanosheets:
preparation of anatase TiO by typical hydrothermal method 2 A nano-sheet. 1mL of hydrofluoric acid was added dropwise to 5mL of tetrabutyl titanate precursor, and mixed with stirring (400 rpm) at room temperature. Transferring the solution into a 100mL high-temperature high-pressure hydrothermal reaction kettle, reacting at 180 ℃ for 5 hours, centrifuging, collecting white precipitate, repeatedly washing with ethanol and water, drying at 60 ℃ for 12 hours, finally obtaining white powder, and preparing the TiO 2 A nano-sheet. FIG. 1 shows a TiO according to the prior invention 2 Nanosheets Field Emission Scanning Electron Microscopy (FESEM), FIG. 2 is a TiO of the prior invention 2 High Resolution Transmission Electron Microscopy (HRTEM) pictures of nanoplatelets from which the morphology of the material is seen as nanoplatelets and the extended lattice spacing of 0.24nm is seen under high resolution transmission electron microscopy.
Example 2:
dy preparation 0.1％ -TiO 2 Monoatomic photocatalyst:
dysprosium nitrate hexahydrate and TiO 2 The mass ratio of (2) is 0.1:100. 100mg of TiO 2 The nanosheets are dispersed in 9mL of deionized water and 1mL of glycol mixed solution to prepare solution I with the concentration of 10 mg/mL; adding 20mg of dysprosium nitrate hexahydrate into 20mL of glycol solution to prepare solution II with the concentration of 1 mg/mL; adding 0.1mL of the solution II into the solution I to obtain a solution III; carrying out centrifugal washing on the solution III after being subjected to light-shielding water bath for 10 hours at the temperature of 60 ℃ to obtain a product; the obtained product is then subjected to heat treatment, and the specific parameters are as follows: heating rate is 2 ℃/min; argon is treated for 1h at 140 ℃ to obtain Dy 0.1％ -TiO 2 Monoatomic photocatalyst.
FIG. 4 is a diagram of TiO 2 Nanoplatelets and Dy 0.1％ -TiO 2 XRD patterns of monoatomic photocatalysts, from which it can be seen that Dy monoatoms are added without affecting TiO 2 A crystal structure of (a); FIG. 5 is a diagram of TiO 2 Nanoplatelets and Dy 0.1％ -TiO 2 Raman spectrum of single-atom photocatalyst, after Dy single atom is added, dy 0.1％ -TiO 2 The Raman spectrum of the monoatomic photocatalyst shifts to a low wave number; FIG. 6 is Dy 0.1％ -TiO 2 A Field Emission Scanning Electron Microscope (FESEM) of the monoatomic photocatalyst, from which it can also be seen that the morphology and structure of the photocatalyst have not changed after Dy monoatomic is introduced; nanoplatelets of Dy can be observed from the High Resolution Transmission Electron Microscope (HRTEM) of FIG. 7 0.1％ -TiO 2 Monoatomic photocatalyst, and no obvious metal particles are present; in the spherical aberration electron microscope (HAADF-STEM) diagram in fig. 8, the bright spots in the circles are Dy single atoms, and the element distribution (EDS Mapping) diagram in fig. 8 b can observe that Ti, O and Dy are uniformly dispersed; the synchrotron radiation results of FIG. 9 show Dy 0.1％ -TiO 2 Only Dy-O bond exists in the rare earth element, which indicates that Dy element is single atom and Dy particles are not present. FIG. 10 is a diagram of TiO 2 Nanoplatelets and Dy 0.1％ -TiO 2 The ultraviolet visible spectrum of the single-atom photocatalyst shows that after rare earth atoms are loaded, the light absorption characteristic of the sample has a certain blue shift, and the blue shift amplitude is relatively smaller due to the lower loading.
Example 3:
dy preparation 0.01％ -TiO 2 Monoatomic photocatalyst:
dysprosium nitrate hexahydrate and TiO 2 The mass ratio of (2) is 0.01:100. 100mg of TiO 2 The nanosheets are dispersed in 9mL of deionized water and 1mL of glycol mixed solution to prepare solution I with the concentration of 10 mg/mL; adding 20mg of dysprosium nitrate hexahydrate into 20mL of glycol solution to prepare solution II with the concentration of 1 mg/mL; adding 0.01mL of the solution II into the solution I to obtain a solution III; carrying out centrifugal washing on the solution III after being subjected to light-shielding water bath for 10 hours at the temperature of 60 ℃ to obtain a product; the obtained product is then subjected to heat treatment, and the specific parameters are as follows: heating rate is 2 ℃/min; argon is treated for 1h at 140 ℃ to obtain Dy 0.01％ -TiO 2 Monoatomic photocatalyst.
Example 4:
dy preparation 0.05％ -TiO 2 Monoatomic photocatalyst:
dysprosium nitrate hexahydrate and TiO 2 The mass ratio of (2) is 0.05:100. 100mg of TiO 2 The nanosheets are dispersed in 9mL of deionized water and 1mL of glycol mixed solution to prepare solution I with the concentration of 10 mg/mL; adding 20mg of dysprosium nitrate hexahydrate into 20mL of glycol solution to prepare solution II with the concentration of 1 mg/mL; adding 0.05mL of the solution II into the solution I to obtain a solution III; carrying out centrifugal washing on the solution III after being subjected to light-shielding water bath for 10 hours at the temperature of 60 ℃ to obtain a product; the obtained product is then subjected to heat treatment, and the specific parameters are as follows: heating rate is 2 ℃/min; argon is treated for 1h at 140 ℃ to obtain Dy 0.05％ -TiO 2 Monoatomic photocatalyst.
Example 5:
dy preparation 0.5％ -TiO 2 Monoatomic photocatalyst:
dysprosium nitrate hexahydrate and TiO 2 The mass ratio of (2) is 0.5:100. 100mg of TiO 2 The nanosheets are dispersed in 9mL of deionized water and 1mL of glycol mixed solution to prepare solution I with the concentration of 10 mg/mL; adding 20mg of dysprosium nitrate hexahydrate into 4mL of glycol solution to prepare solution II with the concentration of 5 mg/mL; adding 0.1mL of the solution II into the solution I to obtain a solution III; carrying out centrifugal washing on the solution III after being subjected to light-shielding water bath for 10 hours at the temperature of 60 ℃ to obtain a product; the obtained product is then subjected to heat treatment, and the specific parameters are as follows: heating rate is 2 ℃/min; argon is treated for 1h at 140 ℃ to obtain Dy 0.5％ -TiO 2 Monoatomic photocatalyst.
Example 6:
dy preparation 1％ -TiO 2 Monoatomic photocatalyst:
dysprosium nitrate hexahydrate and TiO 2 The mass ratio of (2) is 1:100. 100mg of TiO 2 The nanosheets are dispersed in 9mL of deionized water and 1mL of glycol mixed solution to prepare solution I with the concentration of 10 mg/mL; adding 20mg of dysprosium nitrate hexahydrate into 2mL of glycol solution to prepare solution II with the concentration of 10 mg/mL; adding 0.1mL of the solution II into the solution I to obtain a solution III; carrying out centrifugal washing on the solution III after being subjected to light-shielding water bath for 10 hours at the temperature of 60 ℃ to obtain a product; along with itAnd then carrying out heat treatment on the obtained product, wherein the specific parameters are as follows: heating rate is 2 ℃/min; argon is treated for 1h at 140 ℃ to obtain Dy 1％ -TiO 2 Monoatomic photocatalyst.
Comparative example 1:
dysprosium nitrate hexahydrate was used only as a photocatalyst.
Comparative example 2:
preparation of La-monoatomic-supported TiO 2 And (3) a photocatalyst:
lanthanum nitrate hexahydrate and TiO 2 The mass ratio of the nano-sheets is 0.1:100. TiO is mixed with 2 The nanosheets are dispersed in 9mL of deionized water and 1mL of glycol mixed solution to prepare solution I with the concentration of 10 mg/mL; adding 20mg of lanthanum nitrate hexahydrate into 20mL of glycol solution to prepare solution II with the concentration of 1 mg/mL; adding 0.1mL of the solution II into the solution I to obtain a solution III; carrying out centrifugal washing on the solution III after being subjected to light-shielding water bath for 10 hours at the temperature of 60 ℃ to obtain a product; the obtained product is then subjected to heat treatment, and the specific parameters are as follows: heating rate is 2 ℃/min; argon is treated for 1h at 140 ℃ to obtain La 0.1％ -TiO 2 Monoatomic photocatalyst.
The La monoatomic-loaded TiO of the invention 2 Photocatalyst and La 0.1％ -TiO 2 Monoatomic photocatalysts have the same meaning.
Degradation experiments on organic pesticide pollutants:
TiO prepared in example 1 2 Degradation experiment of nanosheets on organic pesticide pollutants:
TiO 2 the nano-sheet is used as a photocatalyst to carry out degradation experiments on organic pesticide pollutants, the concentration of the fixed catalyst is 250mg/L, and the concentration of glyphosate is changed to be 5ppm,10ppm,25ppm,50ppm and 100ppm respectively; fixing the concentration of glyphosate to be 50ppm, and changing the concentration of the catalyst to be 50mg/L, 100mg/L, 250mg/L, 500mg/L and 1000mg/L respectively; the photocatalytic condition is a 300W xenon lamp, and the degradation experiment is carried out under the condition of full spectrum and constant temperature of 15 ℃. Fig. 3 a shows degradation performance graphs of the same catalyst concentration and different glyphosate concentrations, and fig. 3 c shows degradation performance graphs of the same glyphosate concentration and different catalyst concentrations. The result of the catalytic activity is obviousThe illustration is: under the condition of the same catalyst concentration, the time of complete degradation gradually decreases with the decrease of the concentration of the glyphosate; under the condition of the same glyphosate concentration, the degradation effect is better and better along with the increase of the catalyst concentration.
Dy monoatomic-supported TiO prepared in examples 2 to 6 2 Degradation experiment of photocatalyst on organic pesticide pollutant:
dy monoatomic-loaded TiO 2 The degradation experimental process of the photocatalyst comprises the following steps: the degradation experiment is carried out under the conditions that the catalyst concentration is 250mg/L, the glyphosate concentration is 50ppm, the photocatalysis condition is a 300W xenon lamp, the full spectrum is carried out, and the constant temperature is 15 ℃.
FIG. 11 shows Dy-monoatomic-supported TiO of varying dysprosium nitrate hexahydrate content 2 Degradation performance of photocatalyst, with dysprosium nitrate hexahydrate amount ranging from 0.01%, 0.05%, 0.1%, 0.5% to 1%, dy single atom-loaded TiO 2 The catalytic activity of the photocatalyst shows parabolic change, and the photocatalytic activity of the photocatalyst shows parabolic change in dysprosium nitrate hexahydrate and TiO 2 The catalytic activity is optimal when the mass ratio of the nano-sheets is 0.1:100, and the complete degradation of the glyphosate is realized within 75 min. FIG. 12 is a diagram of TiO 2 Nanoplatelets and Dy 0.1％ -TiO 2 The degradation performance of the single-atom photocatalyst is compared with that of a graph, and the result shows that: after Dy monoatoms are loaded, the degradation performance is improved by 15 times. From this, it can be seen that Dy prepared in accordance with the present invention 0.1％ -TiO 2 The single-atom photocatalyst has higher photocatalytic degradation effect on glyphosate under the full spectrum condition, and further proves that the Dy single-atom-loaded TiO provided by the invention 2 The photocatalyst has higher application value in the degradation of persistent organic pesticide pollutants, which provides a new idea for solving increasingly serious environmental problems.
Comparative example 1: degradation experiment of dysprosium nitrate hexahydrate on organic pesticide pollutants:
in the degradation experiment process of using dysprosium nitrate hexahydrate as a photocatalyst, the catalyst concentration is 250mg/L, the glyphosate concentration is 50ppm, the photocatalysis condition is a 300W xenon lamp, and the degradation experiment is carried out under the conditions of full spectrum and constant temperature of 15 ℃. The degradation performance results are shown in FIG. 12, in which dysprosium nitrate hexahydrate is degradedCan be far lower than Dy 0.1％ -TiO 2 Monoatomic photocatalyst, dy prepared by the invention 0.1％ -TiO 2 The monoatomic photocatalyst has higher photocatalytic degradation effect on glyphosate under the condition of full spectrum.
Comparative example 2 prepared La 0.1％ -TiO 2 Degradation experiment of monoatomic photocatalyst on organic pesticide pollutants:
La 0.1％ -TiO 2 in the degradation experiment process of the monoatomic photocatalyst, the catalyst concentration is 250mg/L, the glyphosate concentration is 50ppm, the photocatalysis condition is a 300W xenon lamp, and the degradation experiment is carried out under the condition of full spectrum and constant temperature of 15 ℃. The degradation performance results are shown in FIG. 12, la 0.1％ -TiO 2 Monoatomic photocatalyst and Dy 0.1％ -TiO 2 The degradation performance of the single-atom photocatalyst is compared, and Dy prepared by the invention 0.1％ -TiO 2 The degradation performance of the single-atom photocatalyst is superior to that of La 0.1％ -TiO 2 Monoatomic photocatalyst, dy prepared by the invention 0.1％ -TiO 2 The monoatomic photocatalyst has higher photocatalytic degradation effect on glyphosate under the condition of full spectrum.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1. Dy single-atom-loaded TiO 2 The photocatalyst is characterized by comprising the following components in parts by weight: tiO (titanium dioxide) 2 :100 parts of dysprosium nitrate hexahydrate: 0.01-1 part.
2. The Dy monoatomic-supported TiO of claim 1 2 The photocatalyst is characterized by comprising the following components in parts by weight: tiO (titanium dioxide) 2 :100 parts of dysprosium nitrate hexahydrate: 0.1 part.
3. The Dy monoatomic-supported TiO of claim 1 2 The preparation method of the photocatalyst is characterized in that: the method comprises the following steps:
(1) Mixing a titanium source with hydrofluoric acid to obtain uniform mixed solution, and performing hydrothermal reaction on the mixed solution to obtain TiO 2 A nanosheet;
(2) TiO in the step (1) 2 Adding the nano-sheet into a mixed solution of water and glycol to obtain a solution I;
(3) Adding dysprosium nitrate hexahydrate into an ethylene glycol solution to obtain a solution II;
(4) Adding the solution II in the step (3) into the solution I, and reacting to obtain a solution III;
(5) Filtering and drying the solution III obtained in the step (4), and performing heat treatment to obtain Dy single-atom-loaded TiO 2 A photocatalyst.
4. A method of preparation according to claim 3, characterized in that: the titanium source in step (1) is selected from the group consisting of hydrolyzable titanium-containing compounds; the volume ratio of the titanium source to the hydrofluoric acid in the step (1) is (1:1) - (25:1).
5. A method of preparation according to claim 3, characterized in that: the temperature of the hydrothermal reaction in the step (1) is 150-200 ℃ and the reaction time is 2-12h.
6. A method of preparation according to claim 3, characterized in that: the volume ratio of deionized water to glycol in the mixed solution in the step (2) is (1:9) - (9:1).
7. A method of preparation according to claim 3, characterized in that: tiO in the solution I in the step (4) 2 And dysprosium nitrate hexahydrate in solution II in a mass ratio of (100:1) - (100:0.01).
8. A method of preparation according to claim 3, characterized in that: the reaction condition in the step (4) is 60-80 ℃ and is protected from light water bath for 10-12h.
9. A method of preparation according to claim 3, characterized in that: the heat treatment in the step (5) is as follows:
and under the argon atmosphere, the temperature rising speed is 2 ℃/min, the temperature rises to 140-150 ℃, and the temperature is kept for 1-2h.
10. The Dy monoatomic-supported TiO according to claim 1 or 2 2 Photocatalyst or Dy single atom-supported TiO prepared by the preparation method as claimed in any one of claims 3 to 9 2 The application of the photocatalyst in degrading organic pesticide pollutants; the organic pesticide pollutant is glyphosate.
CN202311172410.XA 2023-09-12 2023-09-12 Dy single-atom-loaded TiO 2 Photocatalyst, preparation method and application thereof Pending CN117563581A (en)

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