CN113842929A - Preparation method of plasma resonance effect ternary nano sunlight catalytic material - Google Patents
Preparation method of plasma resonance effect ternary nano sunlight catalytic material Download PDFInfo
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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
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- B01J35/39—
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- B01J35/40—
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- B01J35/613—
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- B01J35/615—
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- B01J35/647—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
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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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
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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
Abstract
The invention discloses Ag/AgBr/BiOBr/TiO with a plasma resonance effect2The ternary nanometer photocatalytic material is used in degrading organic pollutant in water. The photocatalytic material can efficiently utilize sunlight to degrade pollutants in a water body, can be used for treating surface water pollution, and belongs to the field of water pollution control. The method mainly comprisesModified TiO by utilizing plasma resonance effect of Ag/AgBr and higher visible light utilization efficiency of BiOBr2So that the final material can efficiently utilize sunlight to generate free radicals to realize the efficient degradation of water pollutants. The material prepared by the method has the following advantages: (1) the plasma resonance effect of Ag/AgBr can effectively inhibit the recombination of photo-generated electron-hole pairs (reduce energy loss) in the catalytic process, and the doped BiOBr can make up for TiO2The visible light utilization rate is low, so that the high-efficiency sunlight utilization rate is realized, and the organic pollutants in the water body are efficiently removed under the conditions of energy conservation and environmental protection; (2) the material has high stability in water, is easy to recover, and reduces the generation of secondary pollution.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and relates to synthesis of Ag/AgBr/BiOBr/TiO with plasma resonance effect2The ternary nano photocatalytic material is used for catalyzing and degrading organic pollutants in surface water under sunlight.
Background
With the development of the social industry, the amount of wastewater discharged from industrial processes such as petroleum refining, mineral exploitation and manufacturing industry is increasing, and the wastewater contains various organic pollutants which are difficult to degrade, such as Polycyclic Aromatic Hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCN) and the like. However, the conventional wastewater treatment methods, i.e., the biological treatment method and the conventional advanced oxidation method, hardly achieve satisfactory treatment effects. Thus, the discharged wastewater still poses a potential threat to aquatic life and human health. In recent years, photocatalytic technology, an advanced oxidation technology (AOPs), has been developed for oxidizing and even mineralizing organic pollutants. The method is considered to be an organic pollutant treatment method with great application prospect due to the advantages of high efficiency, low secondary pollution, simple operation and low treatment cost.
Discovery of TiO from 1972 Fujishima2Can be made from photo-decomposed water, TiO2Due to the advantages of high stability, low cost, no toxicity and the like, the method has been widely and long-term concerned about the degradation of water pollutants. However, TiO2Has a wide band gap, low visible light responsivity and high electron generationThe hole recombination rate makes it impossible to effectively utilize sunlight to degrade pollutants. Therefore, the research on the photocatalyst with high visible light utilization rate and excellent catalytic efficiency has important significance for degrading organic wastewater. BiOBr has a narrow band gap and is compatible with TiO2The formed p-n heterojunction can effectively improve the visible light utilization capability of the material. In addition, the photocatalytic activity of the material is often related to the recombination rate of photogenerated electrons and holes, so that the development of the photocatalytic material with a lower photogenerated electron-hole recombination rate has a very positive effect on improving the performance of the material.
In this invention, we used BiOBr with TiO2Compositely constructing a p-n heterojunction, and loading Ag/AgBr as a photosensitizer on the surface of the material to synthesize high-activity Ag/AgBr/BiOBr/TiO2A photocatalytic material. The introduction of BiOBr obviously improves the visible light absorption capacity of the material, Ag/AgBr obviously produces very strong visible light absorption capacity and simultaneously reduces the recombination rate of photo-electrons, and TiO is effectively optimized2The band structure of (2) makes it more favorable for electron transfer and free radical formation. Combinations of these materials on TiO2The modification has a certain synergistic effect, greatly improves the efficiency of the material in degrading pollutants by photocatalysis, and is obviously superior to other catalysts of the same type.
Disclosure of Invention
The invention aims to provide Ag/AgBr/BiOBr/TiO with plasma resonance effect2A preparation method of a ternary nano photocatalytic material and a product prepared by the same. The material is titanyl sulfate (TiO)2The precursor of the bismuth nitrate pentahydrate (the precursor of the BiOBr), silver nitrate, acetic acid and potassium bromide are mixed in a water solvent, synthesized by a codeposition method, washed, dried and photo-reduced to obtain the final material.
In the preparation method, a certain amount of titanyl sulfate and urea (the mass ratio is 3: 2) are uniformly mixed in a water solvent, are continuously stirred for 10-30 min, are transferred into a Teflon high-pressure reaction kettle and are continuously heated for 8-24 h at the temperature of 140-.
In the preparation method, the mixture obtained after the hydrothermal reaction is subjected to supernatant removal, and then the residual solid is washed to remove the interference of impurity ions. The washing is ultrapure water washing, then solid-liquid separation is carried out by centrifugation (the rotating speed is 5000 r/min), the centrifugation time is 15 min, and the washing is continuously carried out for a plurality of times.
The solid obtained in the above preparation method is uniformly mixed with water. Stirring the solution of bismuth nitrate pentahydrate, silver nitrate, acetic acid and water in the dark for 10-60 min, pouring into a certain amount of potassium bromide solution for codeposition, stirring for 10-60 min, and aging for 1-5 h. The aged suspension was poured into the mixture of solid and water obtained in the above method and stirred for 10-60 min.
In the preparation method, the mixture obtained after codeposition is subjected to supernatant removal and then the residual solid is washed to remove the interference of impurity ions. The washing is ultrapure water washing, then solid-liquid separation is carried out by centrifugation (the rotating speed is 5000 r/min), the centrifugation time is 15 min, and the washing is continuously carried out for a plurality of times.
In the preparation method, the obtained solid is subjected to photoreduction in water for 1-5 h, and then dried to obtain the solid.
In the preparation method, the drying temperature is 50-100 ℃.
The dried sample was used after grinding in an agate mortar.
The material prepared by the method has a mesoporous structure, the average size of the material is 2-20 nm, and the specific surface area of the material is 50-150 m2In the nano photocatalytic material, the mass ratio of BiOBr is 5-20%, and the mass ratio of Ag/AgBr is 0.15-0.75%.
The invention has the following beneficial effects:
1. the material has excellent photocatalytic performance, is beneficial to the rapid movement of electrons and holes generated by the excitation of sunlight in the material, reduces the internal recombination rate, and further improves the photocatalytic activity of the material.
2. The invention uses TiO2The material is a substrate, has better stability, optimizes the energy band structure of the material by introducing BiOBr, forms a p-n heterojunction with the BiOBr and improves the recombination of photogenerated electron holesAnd the material can efficiently absorb visible light, so that the utilization rate of sunlight is improved, and the photocatalytic degradation efficiency of pollutants is improved.
3. According to the invention, by loading Ag/AgBr, the plasma resonance effect of the Ag/AgBr supported photocatalyst enables the photo-generated electron-hole recombination rate of the material to be reduced, and the photocatalytic activity of the material is greatly improved.
4. The raw materials involved in the preparation process of the material are easy to obtain, the synthesis operation is simple, the catalytic activity of the material is high, the performance is stable, and the material is beneficial to large-scale industrial production and water pollution prevention and control application.
Description of the drawings:
fig. 1 is an HRTEM photograph of the photocatalytic material obtained in example 5 and an energy spectrum corresponding to the material.
FIG. 2 is an XPS spectrum of the photocatalytic material obtained in example 5.
FIG. 3 is a BET specific surface area and a pore size measurement chart of the photocatalytic material obtained in example 5.
Fig. 4 is a degradation kinetic curve of the photocatalytic materials obtained in examples 1, 3 and 5 under sunlight for anthracene.
Fig. 5 is a degradation kinetic curve of the photocatalytic materials obtained in examples 1 and 5 under sunlight and visible light for anthracene.
FIG. 6 is an Electron Paramagnetic Resonance (EPR) spectrum of the photocatalytic material obtained in example 5 for generating free radicals under sunlight.
FIG. 7 is a schematic view of the principle that the photocatalytic material obtained in example 5 degrades anthracene, which is an organic pollutant, under sunlight.
The specific implementation mode is as follows:
the present invention will be described in more detail below with reference to specific examples, but the scope of the present invention is not limited to these examples.
Example 1 (comparative): blank TiO2Preparation of
Uniformly mixing titanyl sulfate and urea (the mass ratio is 3: 2) in a water solvent, and continuously stirring for 10-30 min. Transferring the obtained mixed solution into a stainless steel autoclave with a Teflon lining, and carrying out hydrothermal treatment at 140 ℃ and 180 ℃ for 8-24 h. And standing the hydrothermal suspension to remove supernatant, washing the obtained precipitate for several times, drying at 50-100 ℃ for 5-10 hours to obtain a solid, and grinding the solid for an experiment of degrading anthracene through photocatalysis.
Example 2: BiOBr/TiO2Preparation of
TiO2The procedure of preparation (a) was in accordance with example 1. Uniformly mixing a certain amount of bismuth nitrate pentahydrate, acetic acid and water, continuously stirring for 10-60 min, pouring into a certain amount of mixed solution of potassium bromide and water, continuously stirring for 10-60 min, and aging for 1-5 h. Pouring a certain amount of TiO into the obtained suspension under the condition of vigorous stirring2And stirring the suspension with water for 30 min, standing to remove supernatant, washing the obtained precipitate for several times, drying at 50-100 ℃ for 8-16 h to obtain a solid, and grinding the solid for an experiment for degrading anthracene by photocatalysis.
Example 3: BiOBr/TiO of optimal BiOBr proportion2Preparation of
The reaction and procedure were as in example 2. In the operation process, the synthetic BiOBr/TiO is obtained by controlling the added amounts of pentahydrate bismuth nitrate and potassium bromide2The mass proportion of BiOBr in the material is 0%, 5%, 10%, 15% and 20%. And the photocatalytic activity test of the material is carried out under simulated solar light to determine the optimal BiOBr ratio.
Example 4: Ag/AgBr/BiOBr/TiO2Preparation of
TiO2The procedure of preparation (a) was in accordance with example 1. Uniformly mixing a certain amount of bismuth nitrate pentahydrate, silver nitrate, acetic acid and water, continuously stirring for 10-60 min, pouring into a certain amount of mixed solution of potassium bromide and water, continuously stirring for 10-60 min, and aging for 1-5 h. Pouring a certain amount of TiO into the obtained suspension under the condition of vigorous stirring2Stirring with water for 10-60 min, standing to remove supernatant, washing the obtained precipitate for several times, and drying at 50-100 deg.C for 8-16 h to obtain solid. And mixing a certain amount of solid with water, carrying out photoreduction for 1-5 h under simulated solar light, drying for 4-8 h at 50-100 ℃, and grinding for an experiment for degrading anthracene through photocatalysis.
Example 5 Ag/A for optimal Ag/AgBr ratiogBr/BiOBr/TiO2Preparation of
The reaction and procedure were as in example 4. Under the optimal proportion of BiOBr, the synthetic Ag/AgBr/BiOBr/TiO is obtained by controlling the amount of silver nitrate added in the reaction2The mass ratio of Ag to AgBr in the material is 0.15%, 0.3% and 0.75%. And the photocatalytic activity test of the material is carried out under simulated solar light to determine the optimal Ag/AgBr ratio.
And (3) testing and results: the method for investigating the photocatalytic activity of the material provided by the invention comprises the following steps:
0.02 g of catalyst is added into 200 mL of anthracene solution with the concentration of 30 ug/L, and the simulated sunlight degradation reaction is carried out under the conditions that the temperature is 20-30 ℃ and the pH value is 7. Setting dark adsorption time of the material for 1-2 h before reaction, then placing the material under illumination for catalytic degradation, sampling according to preset time, and measuring the concentration of anthracene in the solution after filtering.
FIG. 1 shows the optimum Ag/AgBr/BiOBr/TiO obtained in example 52HRTEM of photocatalytic material and corresponding material energy spectrum (EDS). From the HRTEM image, TiO can be seen2Having a flower-like structure with an average particle size of about 45 nm and a lattice spacing (0.35 nm) which corresponds to the spacing of the anatase crystal form, indicates that the material is predominantly in the form of the highly catalytically active anatase phase. The BiOBr is present as nanoplatelets having a size of about 700 nm. The lattice spacing of BiOBr is 0.28 nm. Ag and AgBr nanoparticles were not observed in HRTEM images due to the low mass of Ag/AgBr. The EDS spectra show the major elements Ti, O, Bi and Br in the material, from which it can be seen that BiOBr was successfully supported on the material.
FIG. 2 shows the optimum Ag/AgBr/BiOBr/TiO ratio obtained in example 52XPS spectra of photocatalytic materials. The Bi 4f peak in the material moves to a lower energy level, which indicates that the BiOBr and TiO in the system2The crystal structure has the effect of mutual combination, and the material is also shown to form a heterojunction structure. The Ag 3d peak can be divided into two peaks, which indicates that the Ag element is Ag+And Ag0These two forms exist, also indicating that Ag/AgBr was successfully supported on the material.
FIG. 3 shows the optimum Ag/AgBr/BiOBr/TiO from example 52Photocatalytic materialThe result of the BET adsorption-desorption curve of (1) shows that the specific surface area of the material is 95.65 m2The average pore diameter is 13.04 nm, so the material has larger specific surface area and can provide a large amount of surface adsorption sites and photocatalytic active sites.
Fig. 4 compares the photocatalytic activity of the synthesized materials of examples 1, 3, and 5. The result shows that the synthesized new material has much higher photocatalytic activity than other similar materials, even reaches TiO29.32 times the rate of photocatalytic degradation of anthracene.
FIG. 5 compares Ag/AgBr, BiOBr-loaded TiO2(example 5) and unsupported TiO2Photocatalytic activity of the photocatalytic material of (example 1) under sunlight and visible light. The results show that the loading of Ag/AgBr and BiOBr can effectively improve the photocatalytic activity of the material, wherein one important reason is that the Ag/AgBr as a photosensitizer and the BiOBr can improve the visible light activity of the material.
FIG. 6 shows that the species of free radicals generated by the material obtained in example 5 under light irradiation are measured by ESR, and it can be seen that the material forms superoxide radical under light irradiation, which can effectively degrade organic pollutants in aqueous solution.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.
Claims (6)
1. Ag/AgBr/BiOBr/TiO with plasma resonance effect2The preparation of the ternary nano photocatalytic material is characterized in that the nano material has a mesoporous structure, the average pore diameter of the nano material is 2-20 nm, and the specific surface area of the nano material is 50-150 m2In the nano photocatalytic material, the mass ratio of BiOBr is 5-20%, and the mass ratio of Ag/AgBr is 0.15-0.75%.
2. A process for preparing a photocatalytic material as defined in claim 1, which comprises subjecting a predetermined amount of titanyl sulfate and urea to hydrothermal treatment in an aqueous solvent to obtain titanium dioxide, mixing a predetermined amount of the obtained titanium dioxide with bismuth nitrate pentahydrate, silver nitrate, acetic acid and potassium bromide in an aqueous solvent, synthesizing the material by codeposition, washing, drying and photoreduction.
3. The method according to claim 2, wherein the mass ratio of titanyl sulfate/urea is 3:2, the mass ratio of bismuth nitrate pentahydrate/titanyl sulfate is 0.04-0.2, and the mass ratio of silver nitrate/titanyl sulfate is (6.8-34) 10-3。
4. The method of claim 2, wherein the washing is ultra-pure water washing for several times to remove interference of impurity ions.
5. The method of claim 4, wherein the water washing is centrifugal washing, the centrifugal rotation speed is 5000 r/min, and the centrifugal time is 15 min.
6. The method of claim 2, wherein the photoreduction is performed by using a xenon lamp light source with the intensity of 95 mW/cm2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010594057.4A CN113842929A (en) | 2020-06-28 | 2020-06-28 | Preparation method of plasma resonance effect ternary nano sunlight catalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837285A (en) * | 2010-05-10 | 2010-09-22 | 西华师范大学 | Preparation method of high-activity segregative TiO2 photocatalyst |
| CN102211030A (en) * | 2011-04-11 | 2011-10-12 | 山东大学 | Nano silver/silver bromide/bismuth oxybromide heterogeneous visible light photo-catalytic material and preparation method thereof |
| CN103143389A (en) * | 2013-01-31 | 2013-06-12 | 华东师范大学 | Visible-light-induced photocatalyst and preparation method thereof |
| CN106732688A (en) * | 2016-12-30 | 2017-05-31 | 河南理工大学 | Composite magnetic visible light catalyst silver silver halide BiOX cobalt ferrite and preparation method thereof |
| CN106807413A (en) * | 2017-02-17 | 2017-06-09 | 盐城工学院 | A kind of Ag@AgBr/CaTiO with Plasmon Surface Resonance effect3Photochemical catalyst and preparation method thereof |
-
2020
- 2020-06-28 CN CN202010594057.4A patent/CN113842929A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837285A (en) * | 2010-05-10 | 2010-09-22 | 西华师范大学 | Preparation method of high-activity segregative TiO2 photocatalyst |
| CN102211030A (en) * | 2011-04-11 | 2011-10-12 | 山东大学 | Nano silver/silver bromide/bismuth oxybromide heterogeneous visible light photo-catalytic material and preparation method thereof |
| CN103143389A (en) * | 2013-01-31 | 2013-06-12 | 华东师范大学 | Visible-light-induced photocatalyst and preparation method thereof |
| CN106732688A (en) * | 2016-12-30 | 2017-05-31 | 河南理工大学 | Composite magnetic visible light catalyst silver silver halide BiOX cobalt ferrite and preparation method thereof |
| CN106807413A (en) * | 2017-02-17 | 2017-06-09 | 盐城工学院 | A kind of Ag@AgBr/CaTiO with Plasmon Surface Resonance effect3Photochemical catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHANSHAN LIU，ET AL.: "One-pot synthesis of TiO2–WO3 composite nanocrystallites with improved photocatalytic properties under natural sunlight irradiation" * |
| ZHIYUAN LIU，ET AL.: "Constructing AgBr/BiOBr microspheres assembled by nanosheets on TiO2 nanotube arrays for the enhanced photoelectrochemical performance" * |
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