CN114011441B - Composite photocatalyst and preparation method thereof - Google Patents
Composite photocatalyst and preparation method thereof Download PDFInfo
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- CN114011441B CN114011441B CN202111488371.5A CN202111488371A CN114011441B CN 114011441 B CN114011441 B CN 114011441B CN 202111488371 A CN202111488371 A CN 202111488371A CN 114011441 B CN114011441 B CN 114011441B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 140
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 229910052946 acanthite Inorganic materials 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 22
- 238000009210 therapy by ultrasound Methods 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 3
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 3
- 229940096017 silver fluoride Drugs 0.000 claims description 3
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- 239000004065 semiconductor Substances 0.000 abstract description 11
- 239000002784 hot electron Substances 0.000 abstract description 8
- 238000005215 recombination Methods 0.000 abstract description 8
- 230000006798 recombination Effects 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- -1 alkyl hydrocarbons Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a composite photocatalyst and a preparation method thereof, belonging to the technical field of photocatalytic materials. The invention loads Ag-Ag on the surface of the BiOBr photocatalyst2S complex of Ag-Ag2Ag in S complexes2The smaller Ag nano particles deposited on the S surface can effectively capture electrons, and the larger Ag nano particles can absorb visible light to generate plasmaVibration (SPR) effect to excite hot electrons and inject them into Ag2In the conduction band of S, the structure makes up the defects of the traditional photocatalyst (the recombination of photogenerated charges is inhibited by respectively sacrificing electrons and holes in two different semiconductors), and the catalytic efficiency of the composite photocatalyst is improved. The results of the examples show that the invention provides Ag-Ag2The degradation rate of the S/BiOBr composite photocatalyst reaches 94.6 percent after being illuminated for 30 min.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a composite photocatalyst and a preparation method thereof.
Background
In recent years, the photocatalytic technology has been widely used due to its characteristics of degrading organic substances, decomposing water to produce hydrogen, reducing carbon dioxide to produce alkyl hydrocarbons, and reducing heavy metal ions under the drive of solar energy. The catalysis principle is as follows: under the drive of solar energy, electrons in a valence band can jump into a conduction band to form photo-generated electrons in the conduction band and photo-generated holes in the valence band. The photo-generated electrons and the holes can migrate to the surface of the catalyst and generate oxidation-reduction reaction with the organic matters attached to the surface of the catalyst, so that the aim of degrading the organic matters is fulfilled. Currently, Bi-based photocatalysts are widely studied for their good visible light catalytic properties. However, the catalytic efficiency of the Bi-based photocatalyst is low due to the large amount of photogenerated charge recombination. In order to suppress the recombination of photo-generated charges, the photocatalytic efficiency is improved. The Bi-based photocatalyst has been modified by methods such as the construction of a Z-type heterojunction.
The Z-type heterogeneous method is constructed by compounding two semiconductors with matched electric potentials, so that a photo-generated electron in a semiconductor conduction band is compounded with a hole in another semiconductor valence band, and the separation efficiency of photo-generated charges is improved. Although this structure can effectively suppress the separation of photo-generated charges, the recombination of photo-generated charges is suppressed by sacrificing electrons and holes in two different semiconductors, which results in a significant decrease in the number of photo-generated charges participating in the photocatalytic reaction, and a consequent decrease in the photocatalytic efficiency. Therefore, it is desirable to provide a composite photocatalyst with high photocatalytic efficiency.
Disclosure of Invention
The invention aims to provide a composite photocatalyst and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a composite photocatalyst, which comprises a BiOBr photocatalyst and Ag-Ag loaded on the surface of the BiOBr photocatalyst2S complex; the Ag-Ag2The S complex comprises Ag2S and Ag deposited on the surface of the Ag2Ag on the surface of S; the BiOBr photocatalyst and Ag-Ag2The mass ratio of S is 1: (0.05-0.24).
Preferably, the Ag-Ag2Ag in S complexes2The mass ratio of S to Ag is (0.14-10): 1.
preferably, the Ag-Ag2Ag in S complexes2S is cubic nanoparticles, and Ag is spherical nanoparticles.
The invention also provides a preparation method of the composite photocatalyst in the technical scheme, which comprises the following steps:
(1) mixing soluble silver salt solution and soluble sulfide solution for double decomposition reaction to obtain Ag2S, suspending liquid;
(2) ag obtained in the step (1)2Performing ultrasonic treatment on the S suspension to obtain Ag-Ag2S complex;
(3) the Ag-Ag obtained in the step (2)2And mixing the S compound with the BiOBr photocatalyst for hydrothermal reaction to obtain the composite photocatalyst.
Preferably, the soluble silver salt in the soluble silver salt solution in the step (1) comprises silver nitrate, silver fluoride or silver chlorate.
Preferably, Ag in the soluble silver salt solution in the step (1)+The concentration of (b) is 0.01-0.04 mol/L.
Preferably, the soluble sulfide in the soluble sulfide solution in step (1) comprises sodium sulfide, lithium sulfide or potassium sulfide.
Preferably, S in the soluble sulfide solution in the step (1)2 -The concentration of (b) is 0.01-0.04 mol/L.
Preferably, the power of the ultrasonic treatment in the step (2) is 20-60 kHz, and the time of the ultrasonic treatment is 20-60 min.
Preferably, the temperature of the hydrothermal reaction in the step (3) is 80-120 ℃, and the time of the hydrothermal reaction is 0.5-2 h.
The technical scheme of the invention provides a composite photocatalyst, which comprises a BiOBr photocatalyst and Ag-Ag loaded on the surface of the BiOBr photocatalyst2S complex; the Ag-Ag2The S complex comprises Ag2S and Ag deposited on the surface of the Ag2Ag on the surface of S; the BiOBr photocatalyst and Ag-Ag2The mass ratio of S is 1: (0.05-0.24). The invention loads Ag-Ag on the surface of the BiOBr photocatalyst2The S compound can enable the BiOBr photocatalyst to obtain more excellent photocatalytic performance; wherein Ag-Ag2S complex is in Ag2Ag nano particles are deposited on the surface of S, the smaller Ag nano particles can effectively capture electrons, meanwhile, the larger Ag nano particles can absorb visible light to generate a plasma resonance (SPR) effect, the SPR effect can excite hot electrons, and the hot electrons can be injected into Ag2In a conduction band of the S (namely the semiconductor with the Z-shaped heterojunction sacrificing holes), photo-generated charges are supplemented for the Z-shaped heterojunction, so that the catalytic efficiency of the Z-shaped BiOBr composite photocatalyst is further improved, and the problem that the photo-catalytic effect is reduced due to the fact that recombination of the photo-generated charges is inhibited by sacrificing electrons and holes in two different semiconductors is solved.
The results of the examples show that the Ag-Ag provided by the invention is compared with the traditional BiOBr photocatalyst as can be seen from the fluorescence spectrogram2The fluorescence intensity of the S/BiOBr composite photocatalyst shows a tendency of gradually reducing, and the demonstration shows thatThe photoproduction charge separation efficiency of the composite photocatalyst provided by the invention is obviously improved; the Ag-Ag provided by the invention2The degradation rate of the S/BiOBr composite photocatalyst after being irradiated for 30min reaches 94.6%, which is obviously higher than that of the photocatalysts in comparative examples 1-3. Therefore, the composite photocatalyst provided by the invention has a better photocatalytic effect.
Drawings
FIG. 1 shows a composite photocatalyst Ag-Ag provided by the invention2A schematic diagram of the catalytic mechanism of S/BiOBr;
FIG. 2 is a schematic flow chart of a method for preparing the composite photocatalyst according to example 1 of the present invention;
FIG. 3 shows the general BiOBr photocatalyst of comparative example 1 and Ag-Ag of example 1 according to the present invention2XRD spectrum of the S/BiOBr photocatalyst;
figure 4 is an SEM image of a conventional BiOBr photocatalyst according to comparative example 1 of the present invention;
FIG. 5 shows Ag-Ag in example 1 of the present invention2SEM picture of S/BiOBr photocatalyst;
FIG. 6 shows a conventional BiOBr photocatalyst according to comparative example 1 and Ag-Ag according to example 1 of the present invention2EDS spectra of the S/BiOBr photocatalyst;
FIG. 7 shows a conventional BiOBr photocatalyst according to comparative example 1 and Ag-Ag according to example 1 of the present invention2A fluorescence spectrum of the S/BiOBr photocatalyst;
FIG. 8 shows the photocatalysts provided in comparative examples 1 to 3 and Ag-Ag in example 1 of the present invention2Histogram of catalytic degradation of the organic dye acid orange seven (AO7) by S/BiOBr photocatalyst.
Detailed Description
The invention provides a composite photocatalyst, which comprises a BiOBr photocatalyst and Ag-Ag loaded on the surface of the BiOBr photocatalyst2S complex; the Ag-Ag2The S complex comprises Ag2S and Ag deposited on the surface of the Ag2Ag on the surface of S; the BiOBr photocatalyst and Ag-Ag2The mass ratio of S is 1: (0.05-0.24).
The composite photocatalyst provided by the invention comprises a BiOBr photocatalyst. According to the invention, the traditional BiOBr photocatalyst is modified, so that the photocatalytic efficiency of the BiOBr photocatalyst can be effectively improved.
In the present invention, the morphology of the BiOBr photocatalyst is preferably a sheet. The invention is more beneficial to uniformly loading Ag-Ag on the surface of the sheet BiOBr photocatalyst by selecting the sheet BiOBr photocatalyst2And the compound S is used for better modifying the BiOBr photocatalyst.
The composite photocatalyst provided by the invention also comprises Ag-Ag loaded on the surface of the BiOBr photocatalyst2And (3) an S complex. The invention loads Ag-Ag on the surface of the BiOBr photocatalyst2The S compound can enable the BiOBr photocatalyst to obtain more excellent photocatalytic performance.
In the invention, the BiOBr photocatalyst and Ag-Ag2The mass ratio of S is 1: (0.05-0.24), preferably 1: (0.08 to 0.22), more preferably 1: (0.1 to 0.2), most preferably 1: (0.12-0.15).
In the present invention, the Ag-Ag2The S complex comprises Ag2S and Ag deposited on the surface of the Ag2Ag on the surface of S. The invention is prepared by adding Ag-Ag2Ag in S complexes2The Ag nano particles are deposited on the surface of S, so that the smaller Ag nano particles can effectively capture electrons, the larger Ag nano particles can absorb visible light to generate a plasma resonance (SPR) effect, the effect can excite hot electrons, the hot electrons can be injected into a conduction band of a Z-type heterojunction (namely a semiconductor which specifically sacrifices a hole) of the BiOBr photocatalyst to supplement photo-generated charges for the Z-type heterojunction, the catalytic efficiency of the Z-type composite photocatalyst is further improved, and the problem that the photo-catalytic effect is reduced due to the fact that recombination of the photo-generated charges is inhibited by sacrificing electrons and holes in two different semiconductors is solved.
In the present invention, the Ag-Ag2Ag in S complexes2The mass ratio of S to Ag is preferably (0.14-10): 1, more preferably (1 to 8): 1, most preferably (2-6): 1. the invention controls Ag-Ag2Ag in S complexes2The mass ratio of S to Ag is in the range, which is more favorable for Ag nano particles to capture electrons, so that Ag-Ag can capture the electrons2Better absorption of visible light production by S-complexesGenerating plasma resonance (SPR) effect, and further effectively improving the photocatalysis effect of the composite photocatalyst.
In the present invention, the Ag-Ag2Ag in S complexes2S is preferably a cubic nanoparticle; the Ag-Ag2The Ag in the S composite is preferably spherical nanoparticles. The Ag-Ag of the invention2Ag in the S compound is spherical nano-particles and is in-situ deposited on the cubic nano-particles2On the S surface, smaller Ag nano particles can better capture electrons, larger Ag nano particles can absorb visible light to generate plasma resonance (SPR) effect, and heat electrons are excited to be injected into Ag2And in the S conduction band (namely in the semiconductor sacrificing the hole), the Z-type heterojunction is supplemented with photo-generated charges, and the catalytic efficiency of the Z-type composite photocatalyst is further improved.
The composite photocatalyst provided by the invention overcomes the defect that the traditional Z-shaped composite photocatalyst inhibits the recombination of photo-generated charges by respectively sacrificing electrons and holes in two different semiconductors, and can effectively improve the catalytic efficiency of the photocatalyst.
The invention also provides a preparation method of the composite photocatalyst in the technical scheme, which comprises the following steps:
(1) mixing soluble silver salt solution and soluble sulfide solution for double decomposition reaction to obtain Ag2S, suspending liquid;
(2) ag obtained in the step (1)2Performing ultrasonic treatment on the S suspension to obtain Ag-Ag2S complex;
(3) the Ag-Ag obtained in the step (2)2And mixing the S compound with the BiOBr photocatalyst for hydrothermal reaction to obtain the composite photocatalyst.
The invention mixes soluble silver salt solution and soluble sulfide solution to carry out double decomposition reaction to obtain Ag2And (4) suspending the S.
In the present invention, the soluble silver salt in the soluble silver salt solution preferably includes silver nitrate, silver fluoride or silver chlorate, more preferably silver nitrate. In the present invention, the solvent of the soluble silver salt solution is preferably one or both of deionized water and absolute ethyl alcohol.
In the present invention, Ag in the soluble silver salt solution+The concentration of (b) is preferably 0.01 to 0.04mol/L, more preferably 0.02 to 0.03mol/L, and most preferably 0.024 to 0.028 mol/L.
In the present invention, the soluble sulfide in the soluble sulfide solution preferably includes sodium sulfide, lithium sulfide, or potassium sulfide, and more preferably sodium sulfide. In the present invention, the solvent of the soluble sulfide solution is preferably one or both of deionized water and ethanol.
In the present invention, S in the soluble sulfide solution2-The concentration of (b) is preferably 0.01 to 0.04mol/L, more preferably 0.02 to 0.03mol/L, and most preferably 0.024 to 0.028 mol/L.
In the present invention, the mixing is preferably performed under stirring conditions; the stirring is preferably magnetic stirring; the time of the magnetic stirring is preferably 8-15 min, and more preferably 10-12 min.
In the present invention, the reaction equation of the metathesis reaction is preferably as shown in formula I;
2AgNO3+Na2S＝2NaNO3+Ag2s (precipitation) formula I;
the present invention has no particular requirement on the temperature of the metathesis reaction. In the present invention, the temperature of the metathesis reaction is preferably room temperature.
To obtain Ag2After the S suspension, the invention uses the Ag2Performing ultrasonic treatment on the S suspension to obtain Ag-Ag2And (3) an S complex. The invention is through the pair of Ag2The S suspension is subjected to ultrasonic treatment, and Ag can be obtained by sonochemical reaction of ultrasonic2Ag remaining in the S suspension+Sufficiently reduced to be in Ag2And depositing silver elementary substance on the surface of the S in situ.
In the invention, the ion reaction equation of the sonochemical reaction in the ultrasonic treatment process is preferably as shown in formula II;
Ag++e-+Ag2S＝Ag-Ag2s (reaction conditions, ultrasonic treatment) formula II;
in the invention, the power of ultrasonic treatment is preferably 20-60 kHz, and more preferably 40 kHz; the time of ultrasonic treatment is preferably 20-60 min, more preferably 25-55 min, and most preferably 30-40 min. The invention is more beneficial to the residual Ag by controlling the power and the time of the ultrasonic treatment within the range+Fully reduced and uniformly deposited on Ag2S surface, thereby obtaining Ag-Ag with good structure2And (3) an S complex.
In the present invention, the temperature of the ultrasonic treatment is preferably room temperature.
After the ultrasonic treatment is finished, the invention preferably carries out centrifugal separation, deionized water washing and vacuum drying on the ultrasonic treated product in sequence to obtain Ag-Ag2And (3) an S complex. In the invention, the number of times of washing with deionized water is preferably 1-5 times, and more preferably 2-3 times; the temperature of the vacuum drying is preferably 50-80 ℃, and more preferably 60-70 ℃; the vacuum drying time is preferably 2-5 hours, and more preferably 3-4 hours.
To obtain Ag-Ag2After S compounding, the invention uses the Ag-Ag2And mixing the S compound with the BiOBr photocatalyst for hydrothermal reaction to obtain the composite photocatalyst. The invention can lead Ag to Ag by carrying out hydrothermal reaction2The S compound is uniformly loaded on the surface of the BiOBr photocatalyst, so that the BiOBr photocatalyst is modified.
The source of the BiOBr photocatalyst is not particularly limited in the invention, and the BiOBr photocatalyst known to those skilled in the art can be adopted.
The mixing operation described in the present invention is not particularly critical, and the mixing operation known to those skilled in the art is used to mix Ag-Ag2And (3) uniformly mixing the S compound with the BiOBr photocatalyst.
In the invention, the temperature of the hydrothermal reaction is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 100 ℃; the time of the hydrothermal reaction is preferably 0.5-2 h, more preferably 1-1.8 h, and most preferably 1.2-1.5 h. The invention is more beneficial to Ag-Ag by controlling the temperature and the time of the hydrothermal reaction within the range2S compound is uniformly loaded on BiOBr photocatalysisThe surface is coated, so that the BiOBr photocatalyst obtains better modification effect.
After the hydrothermal reaction is finished, the invention preferably carries out centrifugal separation, deionized water washing and vacuum drying on the product of the hydrothermal reaction in sequence to obtain the composite photocatalyst. In the invention, the number of times of washing with deionized water is preferably 1-5 times, and more preferably 2-3 times; the temperature of the vacuum drying is preferably 50-80 ℃, and more preferably 60-70 ℃; the vacuum drying time is preferably 2-5 hours, and more preferably 3-4 hours.
The method based on ultrasonic treatment provided by the invention can enable Ag to be deposited on Ag more uniformly in situ2S surface, so that the larger Ag nano particles can absorb visible light to generate plasma resonance (SPR) effect and excite hot electrons to be injected into Ag2In the S conduction band, photo-generated charges are supplemented for the Z-shaped heterojunction, so that the catalytic efficiency of the Z-shaped composite photocatalyst is effectively improved; meanwhile, the invention is more beneficial to Ag-Ag through hydrothermal reaction2The S compound is uniformly loaded on the surface of the BiOBr photocatalyst, so that the modification of the BiOBr photocatalyst is realized. The preparation method of the composite photocatalyst provided by the invention is simple in process, easy in parameter control, green, environment-friendly and low in cost.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the 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
The composite photocatalyst of the embodiment comprises a BiOBr photocatalyst and Ag-Ag loaded on the surface of the BiOBr photocatalyst2S composite composition; the Ag-Ag2S complex is composed of Ag2S and Ag deposited on the surface of the Ag2Ag on the surface of S; the BiOBr photocatalyst and Ag-Ag2The mass ratio of S is 1: 0.12; the Ag-Ag2Ag in S complexes2The mass ratio of S to Ag was 2.297: 1.
Wherein, the Ag-Ag2Ag in S complexes2S is cubic nanoparticles, and Ag is spherical nanoparticles.
The preparation method of the composite photocatalyst comprises the following steps:
(1) mixing 7.5mL of soluble silver salt solution and 2.5mL of soluble sulfide solution, and carrying out double decomposition reaction to obtain Ag2S, suspending liquid;
wherein the soluble silver salt solution is Ag+Silver nitrate solution (solvent is deionized water and ethanol) with concentration of 0.024mol/L, and soluble sulfide solution uses S2-Sodium sulfide solution (solvent is deionized water and ethanol) with concentration of 0.024mol/L, and mixing mode is magnetic stirring at room temperature for 10 min.
(2) Ag obtained in the step (1)2Performing ultrasonic treatment on the S suspension to obtain Ag-Ag2S complex;
wherein the power of ultrasonic treatment is 40kHz, the time is 30min, and the temperature is room temperature; after the ultrasonic treatment is finished, centrifugally separating the product, washing the product for 3 times by using deionized water, and then drying the product for 4 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain Ag-Ag2And (3) an S complex.
(3) The Ag-Ag obtained in the step (2)2Mixing the S compound with a BiOBr photocatalyst and then carrying out hydrothermal reaction to obtain a composite photocatalyst;
wherein the mixing operation is room-temperature stirring, the temperature of the hydrothermal reaction is 100 ℃, and the time is 1 h; and after the hydrothermal reaction is finished, centrifugally separating the product, washing the product for 3 times by using deionized water, and drying the product for 4 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the composite photocatalyst.
Example 2
Ag-Ag from example 12Ag in S complexes2The mass ratio of S to Ag was replaced with 4.594:1, and the volumes of the soluble silver salt solution and the soluble sulfide solution in step (1) of the preparation method were replaced with 25mL and 10mL, respectively, and the remaining technical characteristics were the same as those in example 1.
Example 3
The BiOBr photocatalyst and Ag-Ag of example 12Replacing the mass ratio of S by 1: 0.24, and the rest technical characteristics are the same as those of the embodiment 1.
Comparative example 1
A common BiOBr photocatalyst.
Comparative example 2
Provides Ag2S/BiOBr photocatalyst, BiOBr photocatalyst and Ag2The mass ratio of S is 1:0.12, the ultrasonic treatment step of the preparation method of the embodiment 1 is omitted, and the other technical characteristics are the same as those of the embodiment 1.
Comparative example 3
The Ag/BiOBr photocatalyst is provided, the mass ratio of the BiOBr photocatalyst to Ag is 1:0.12, the step of adding soluble sulfide in the preparation method of example 1 is omitted, and the rest technical characteristics are the same as those of example 1.
FIG. 1 shows a composite photocatalyst Ag-Ag provided by the invention2A schematic diagram of the catalytic mechanism of S/BiOBr. As can be seen from FIG. 1, Ag2S and BiOBr form a Z-type heterojunction by sacrificing Ag2Holes in the S valence band and electrons in the BiOBr conduction band inhibit the recombination of photo-generated charges. And Ag-Ag provided by the application2The S/BiOBr photocatalyst is loaded with Ag-Ag2S complex, and Ag-Ag2S complex in Ag2The noble metal Ag nano particles deposited on the surface of S play a role in capturing electrons on one hand, and generate hot electrons due to the plasma resonance effect on the other hand, and the hot electrons can be injected into Ag2In the S conduction band, with Ag2Original photo-generated electrons in an S conduction band jointly participate in a photocatalytic reaction, so that the sacrificial photo-generated charges in the Z-type heterojunction are compensated, and the purpose of obtaining the efficient three-way composite photocatalyst is achieved.
Fig. 2 is a schematic flow chart of a preparation method of the composite photocatalyst provided in embodiment 1 of the present invention. Inventive example 1 AgNO3Solution and Na2Mixing the S solution, magnetically stirring for 10min to perform full double decomposition reaction, and performing ultrasonic treatment on the reaction solution for 30min to obtain Ag-Ag product2S complex; as can be seen from FIG. 2, Ag-Ag2Ag in the S compound is spherical nano-particles and is deposited in cubic Ag2S surface; then the BiOBr photocatalyst is dissolved in 80mL of deionized water, and then the solution is mixed with Ag-Ag2The S compound is jointly placed in a hydrothermal reaction kettle for hydrothermal reaction to obtain Ag-Ag2An S/BiOBr composite photocatalyst; as can be seen from FIG. 2, Ag-Ag2The S compound is loaded on the surface of the sheet BiOBr photocatalyst.
FIG. 3 shows the general BiOBr photocatalyst of comparative example 1 and Ag-Ag of example 1 according to the present invention2XRD pattern of S/BiOBr photocatalyst. As can be seen from FIG. 3, the Ag-Ag of example 1 compared to the BiOBr monomer2Weak Ag appears in S/BiOBr photocatalyst2S diffraction peak, which proves that the composite photocatalyst Ag-Ag provided by the invention2Ag in S/BiOBr2S, but lower content of S leads to Ag2The diffraction peak of S is not significant. However, the composite photocatalyst Ag-Ag of example 12The diffraction peak of Ag does not appear in S/BiOBr, which is mainly caused by the low content of Ag, and the phase of BiOBr is not obviously changed.
FIG. 4 is an SEM photograph of a conventional BiOBr photocatalyst of comparative example 1 of the present invention, and FIG. 5 is Ag-Ag of example 1 of the present invention2SEM image of S/BiOBr photocatalyst. As can be seen from FIGS. 4 to 5, the surface of the ordinary BiOBr photocatalyst is smooth and flaky; and example 1 provides Ag-Ag2S/BiOBr photocatalyst Ag2Ag nano particles are deposited on the surface of the S cube, and Ag-Ag2The S compound is uniformly loaded on the surface of the BiOBr, and on one hand, the Ag-Ag provided by the invention is clearly shown2The actual structure of the S/BiOBr photocatalyst is shown, and the preparation method provided by the invention can successfully prepare Ag-Ag2An S/BiOBr photocatalyst.
FIG. 6 shows a conventional BiOBr photocatalyst according to comparative example 1 and Ag-Ag according to example 1 of the present invention2EDS spectra of S/BiOBr photocatalysts. As can be seen from FIG. 6, five elements of Bi, O, Br, Ag and S exist in the composite photocatalyst provided by the invention.
FIG. 7 shows a conventional BiOBr photocatalyst according to comparative example 1 and Ag-Ag according to example 1 of the present invention2Fluorescence spectrum of the S/BiOBr photocatalyst. As can be seen from FIG. 7, compare to the generalIntroducing BiOBr photocatalyst, the composite photocatalyst Ag-Ag provided by the invention2The fluorescence intensity of the S/BiOBr shows a gradually-decreasing trend, and the Ag-Ag method provided by the invention is proved2The photoproduction charge separation efficiency of the S/BiOBr composite photocatalyst is obviously improved.
FIG. 8 shows a conventional BiOBr photocatalyst according to comparative example 1, Ag according to comparative example 22S/BiOBr photocatalyst, Ag/BiOBr photocatalyst of comparative example 3 and Ag-Ag of example 12Histogram of catalytic degradation of S/BiOBr photocatalyst AO 7. As can be seen from FIG. 8, BiOBr, Ag/BiOBr, Ag2S/BiOBr and Ag-Ag2The degradation rates of the S/BiOBr photocatalyst after being illuminated for 30min respectively reach 55.8%, 65%, 80.2% and 94.6%. Therefore, the composite photocatalyst provided by the invention has the best catalytic degradation effect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The composite photocatalyst comprises a BiOBr photocatalyst and Ag-Ag loaded on the surface of the BiOBr photocatalyst2S complex; the Ag-Ag2The S complex comprises Ag2S and Ag deposited on the surface of the Ag2Ag on the surface of S; the BiOBr photocatalyst and Ag-Ag2The mass ratio of S is 1: (0.05-0.24).
2. The composite photocatalyst of claim 1, wherein the Ag-Ag is2Ag in S complexes2The mass ratio of S to Ag is (0.14-10): 1.
3. the composite photocatalyst of claim 1 or 2, wherein the Ag-Ag is2Ag in S complexes2S is cubic nanoparticles, and Ag is spherical nanoparticles.
4. A method for preparing a composite photocatalyst as claimed in any one of claims 1 to 3, comprising the steps of:
(1) mixing soluble silver salt solution and soluble sulfide solution for double decomposition reaction to obtain Ag2S, suspending liquid;
(2) ag obtained in the step (1)2Performing ultrasonic treatment on the S suspension to obtain Ag-Ag2S complex;
(3) the Ag-Ag obtained in the step (2)2And mixing the S compound with the BiOBr photocatalyst for hydrothermal reaction to obtain the composite photocatalyst.
5. The method according to claim 4, wherein the soluble silver salt in the soluble silver salt solution in the step (1) comprises silver nitrate, silver fluoride or silver chlorate.
6. The production method according to claim 4 or 5, wherein Ag in the soluble silver salt solution in the step (1)+The concentration of (b) is 0.01-0.04 mol/L.
7. The method according to claim 4, wherein the soluble sulfide in the soluble sulfide solution in the step (1) comprises sodium sulfide, lithium sulfide or potassium sulfide.
8. The production method according to claim 4 or 7, wherein S in the soluble sulfide solution in the step (1)2-The concentration of (b) is 0.01-0.04 mol/L.
9. The preparation method according to claim 4, wherein the power of the ultrasonic treatment in the step (2) is 20-60 kHz, and the time of the ultrasonic treatment is 20-60 min.
10. The preparation method according to claim 4, wherein the temperature of the hydrothermal reaction in the step (3) is 80 to 120 ℃, and the time of the hydrothermal reaction is 0.5 to 2 hours.
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