CN111229262B - Fixed Z-type Ag | AgBr/Ag/TiO2Composite membrane photocatalyst and preparation method and application thereof - Google Patents
Fixed Z-type Ag | AgBr/Ag/TiO2Composite membrane photocatalyst and preparation method and application thereof Download PDFInfo
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- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 title claims abstract description 108
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 90
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 45
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- 239000001257 hydrogen Substances 0.000 claims abstract description 38
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- 150000002500 ions Chemical class 0.000 claims abstract description 5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
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- 238000003756 stirring Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
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- 238000001035 drying Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- 238000006479 redox reaction Methods 0.000 abstract description 2
- 229940107698 malachite green Drugs 0.000 description 23
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 23
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
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- GTRGJJDVSJFNTE-UHFFFAOYSA-N chembl2009633 Chemical compound OC1=CC=C2C=C(S(O)(=O)=O)C=CC2=C1N=NC1=CC=CC=C1 GTRGJJDVSJFNTE-UHFFFAOYSA-N 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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Images
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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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a fixed Z-type Ag | AgBr/Ag/TiO2Composite membrane photocatalyst and its preparation method and application. Firstly forming an AgBr film on a silver foil by adopting a continuous ion layer adsorption method, secondly irradiating the surface of the AgBr film by adopting a xenon lamp to generate silver nano particles on the surface of the AgBr film, and finally preparing TiO by using a sol-gel spin coating method2Film, forming fixed Z-type Ag | AgBr/Ag/TiO2A composite membrane photocatalyst. The fixed Z-shaped photocatalyst can efficiently degrade organic dye and simultaneously produce hydrogen under the action of sunlight. The preparation method is simple and convenient, and the catalyst yield is high. And because a fixed Z-shaped photocatalytic system is generated, the photocatalytic oxidation reduction reaction can be simultaneously carried out, the photocatalytic hydrogen production activity is obviously improved, and pure hydrogen can be prepared.
Description
Technical Field
The invention belongs to the field of photocatalysts, and particularly relates to a method for adsorbing and condensing sol by adopting a continuous ion layerSynthesizing fixed Z type Ag | AgBr/Ag/TiO by glue spin coating method2The composite membrane photocatalyst and the application thereof in hydrogen production by photolysis of water under sunlight and degradation of organic dyes in water.
Background
The rapid development of economy has led to a dramatic increase in the development of fossil energy, leading to a rapid decline in fossil energy reserves and the initiation of the global "energy crisis". The energy crisis not only restricts the economic development, but also brings unfair wars brought by energy plunder. Therefore, the development of new energy is an urgent task. Recent research shows that hydrogen production by decomposing water by using a photocatalytic technology can be an effective way to solve the energy crisis. However, the current photocatalytic technology cannot meet the requirement of large-scale industrial production due to the problems of high recombination rate of photogenerated carriers of a single semiconductor photocatalyst, low solar energy utilization rate of a high-activity broadband semiconductor photocatalyst and the like. Therefore, it is necessary to modify the existing photocatalytic system to improve the photocatalytic activity.
Photocatalytic hydrogen production has been widely reported, but photocatalysts used in previous studies are mostly in powder form. Incomplete dispersion of the photocatalyst powder in the reaction solution results in low participation in the photocatalytic reaction, resulting in low hydrogen production efficiency. In addition, when the photocatalyst powder is used for photocatalytic degradation for simultaneous hydrogen production, CO generated by oxidation reaction2The impurity gases react with H generated by reduction2Mixing to produce H2Is not pure and can not be directly utilized. In fact, if the immobilization technique is adopted, the oxidation reaction and the reduction reaction can be separately performed by adjusting the order of immobilization of different photocatalytic films. This will separate the hydrogen gas from the impurity gas, thereby increasing the purity of the hydrogen gas. In addition, the recovery and utilization of the photocatalyst are not negligible. The traditional powdery photocatalyst needs to be subjected to centrifugation, washing, drying and other steps to carry out the next reaction. The photocatalyst is fixed on the immobilized carrier, so that the recovery difficulty of the photocatalyst can be greatly reduced, and the cyclic utilization of the photocatalyst can be easily realized. In conclusion, the development prospect of the photocatalyst immobilization technology is very wide, but the research on the photocatalyst immobilization technology is still carried out at presentIs not enough.
Disclosure of Invention
The invention aims to provide a fixed Z-type Ag | AgBr/Ag/TiO2The composite membrane photocatalyst can enhance the photocatalytic activity of the semiconductor photocatalyst, realizes the separation and simultaneous execution of the photocatalytic hydrogen production reaction and the organic dye degradation reaction by an immobilization technology, and obviously improves the recovery utilization rate of the photocatalyst.
The technical scheme adopted by the invention is as follows: fixed Z-type Ag | AgBr/Ag/TiO2A composite membrane photocatalyst is prepared through continuous ion layer adsorption to form AgBr film on silver foil, xenon lamp irradiation to generate Ag nanoparticles on the surface of AgBr film, and sol-gel spin coating to prepare TiO2Film, forming fixed Z-type Ag | AgBr/Ag/TiO2A composite membrane photocatalyst.
Fixed Z-type Ag | AgBr/Ag/TiO2The preparation method of the composite membrane photocatalyst comprises the following steps:
1) cleaning the silver foil;
2) carrying out corrosion treatment on the cleaned silver foil;
3) washing the silver foil subjected to corrosion treatment with deionized water; then transferring the mixture to KBr solution to be soaked for 5.0-10.0min, and then transferring the mixture to AgNO3Soaking in the solution for 5.0-10.0min to complete one-time soaking adsorption, repeating soaking adsorption for 6-10 times, and forming a layer of AgBr film on the silver foil to obtain Ag | AgBr;
4) placing the AgBr film surface on a silver foil with one side facing upwards, and irradiating under a 300W xenon lamp for 5.0-10.0min to form a layer of Ag on the AgBr film surface to obtain Ag | AgBr/Ag;
5) by spin coating of TiO2Spin coating the sol on the surface of Ag | AgBr/Ag to form a layer of TiO2Drying the film at 60 deg.C for 10min, transferring to muffle furnace, calcining at 450 deg.C for 3.0h, cooling to room temperature, and spin-coating TiO on silver foil2One surface of the Z-shaped silver/TiO silver paste is polished by sand paper to prepare a fixed Z-shaped Ag | AgBr/Ag/TiO2A composite membrane photocatalyst.
Further, in the above preparation method, in step 1), the step of cleaning the silver foil is: and (3) cleaning the silver foil with a detergent, acetone and absolute ethyl alcohol in sequence under an ultrasonic condition.
Further, in the above preparation method, in step 2), the etching treatment of the cleaned silver foil is: putting the cleaned silver foil into a nitric acid aqueous solution for corrosion for 2.0-3.0min, and then transferring the silver foil into a hydrogen peroxide aqueous solution for corrosion for 2.0-3.0 min.
Further, in the above preparation method, step 5), the TiO2The preparation method of the sol comprises the following steps: a mixture of Ti (OBu)4Dissolving in mixed solution of anhydrous ethanol and acetylacetone, and stirring at 90-100 deg.C until TiO is formed2And (3) sol.
Further, in the above preparation method, step 5), the spin coating method is: spin-coat at 3000rpm for 20 s.
The fixed Z-type Ag | AgBr/Ag/TiO2The composite membrane photocatalyst is applied to the degradation of organic dye under sunlight. The method comprises the following steps: adding fixed Z-type Ag | AgBr/Ag/TiO into solution containing organic dye2The composite membrane photocatalyst is irradiated under sunlight.
The fixed Z-type Ag | AgBr/Ag/TiO2The composite membrane photocatalyst is applied to photocatalytic hydrogen production. The method comprises the following steps: adding fixed Z-type Ag | AgBr/Ag/TiO into aqueous solution containing organic dye2The composite membrane photocatalyst is irradiated under sunlight.
The invention has the beneficial effects that: the invention fixes Z-type Ag | AgBr/Ag/TiO2The composite membrane photocatalyst is prepared by a continuous ion layer adsorption method and a sol-gel spin coating method, the preparation method is simple and convenient, and the catalyst yield is high. And because a fixed Z-shaped photocatalytic system is generated, the photocatalytic oxidation reduction reaction can be simultaneously carried out, the photocatalytic hydrogen production activity is obviously improved, and pure hydrogen can be prepared. The novel fixed Z-shaped Ag | AgBr/Ag/TiO2Compared with the traditional Z-shaped photocatalyst, the composite membrane photocatalyst has more electron flow direction, ensures the sufficient separation of electrons and holes, and increases the photocatalytic hydrogen production activity. Fixed Z-type Ag | AgBr/Ag/TiO prepared by the invention2The composite membrane photocatalyst not only reduces the recombination rate of photoproduction electrons and photoproduction holes, improves the photocatalytic activity, but also greatly improves the recycling rate of the photocatalyst.
Drawings
FIG. 1 is Ag | AgBr/Ag/TiO2X-ray diffraction pattern of (a).
FIG. 2 is Ag | AgBr/Ag/TiO2Scanning electron microscopy of (a).
FIG. 3 is Ag | AgBr/Ag/TiO2Ag | AgBr and Ag | TiO2Hydrogen production effect diagram of photocatalyst
FIG. 4 shows Ag | AgBr/Ag/TiO concentrations for different sacrificial agent concentrations2The hydrogen production effect of the composite membrane photocatalyst is shown.
FIG. 5 is Ag | AgBr/Ag/TiO2Five times of hydrogen production cycle experiment diagrams of the composite membrane photocatalyst.
Detailed Description
Example 1
Fixing Z type Ag | AgBr/Ag/TiO2Composite membrane photocatalyst
The preparation method comprises the following steps:
1) cleaning: silver foil (2.50X 5.00 cm) to be purchased2) Washing with detergent, acetone and absolute ethyl alcohol in turn under ultrasonic condition.
2) And (3) corrosion treatment: putting the cleaned silver foil into dilute nitric acid (volume ratio, HNO)3:H2O1: 5) for 2.0min, then transferred to hydrogen peroxide (volume ratio, H)2O2:H2O ═ 1:2) for 2.0 min. Repeatedly cleaning the corroded silver foil by using deionized water and drying;
3) preparation of Ag | AgBr: the silver foil after corrosion treatment is firstly transferred into 0.50mol/L KBr solution to be soaked for 5.0min and then transferred into 0.50mol/L AgNO3Soaking in the solution for 5.0min to complete one-time soaking adsorption. I.e. the soaking adsorption step in the two solutions is an adsorption cycle. Repeatedly soaking and adsorbing, circulating for 8 times, and forming a layer of AgBr film on the silver foil to obtain Ag | AgBr;
4) preparation of Ag | AgBr/Ag: placing the AgBr film surface on the silver foil under a 300W xenon lamp to irradiate for 5.0min, reducing a part of AgBr to Ag after irradiation, and forming a layer of Ag on the AgBr film surface to obtain Ag AgBr/Ag;
5)TiO2preparation of sol: 13.890g (0.04mol) Ti (OBu)4Dissolved in a mixed solution of 40mL of absolute ethanol and 2.044g of acetylacetone (0.02mol) to prepare TiO2And (3) precursor. Adding TiO into the mixture2Stirring the precursor at 90-100 ℃ until TiO is formed2And (3) sol.
6) Preparation of Ag | AgBr/Ag/TiO2: coating TiO on the surface of Ag | AgBr/Ag by adopting a spin coating method (spin coating for 20s at 3000 rpm)2Sol to form a layer of TiO2The film was then dried at 60 ℃ for 10min and transferred to a muffle furnace, calcined at 450 ℃ for 3.0h, cooled to room temperature, and the other side of the silver foil (without spin-coating TiO) was applied2Surface) is polished by sand paper to obtain the fixed Z-shaped Ag | AgBr/Ag/TiO2A composite membrane photocatalyst.
(II) comparative example
Comparative example 1: preparation of Ag | AgBr
Washing the silver foil subjected to corrosion treatment with deionized water; then transferring the mixture to KBr solution of 0.50mol/L for soaking for 5.0min, and transferring the mixture to AgNO of 0.50mol/L3Soaking in the solution for 5.0min to complete one-time soaking adsorption. And repeating the soaking and adsorption, circulating for 8 times, forming a layer of AgBr film on the silver foil, and washing the surface of the silver foil with deionized water for three times. And finally, polishing one surface of the silver foil by using sand paper, and reserving the other surface to obtain Ag | AgBr.
Comparative example 2: preparation of Ag | TiO2
13.890g (0.04mol) Ti (OBu)4Dissolved in a mixed solution of 40mL of absolute ethanol and 2.044g of acetylacetone (0.02mol) to prepare TiO2And (3) precursor. Mixing TiO with2Stirring the precursor at 90-100 ℃ until TiO is formed2And (3) sol. Then, the surface of the silver foil after the etching treatment was coated with TiO by spin coating (spin coating at 3000rpm for 20 seconds)2And (3) sol. Form a layer of TiO2The film was then dried at 60 ℃ for 10min and transferred to a muffle furnace, calcined at 450 ℃ for 3.0h, cooled to room temperature, and the other side of the silver foil (uncoated)Coated with TiO2Surface) is polished by sand paper to obtain Ag | TiO2。
(III) characterization of the catalyst
FIG. 1 shows a fixed Z-type Ag | AgBr/Ag/TiO2The XRD pattern of the composite membrane photocatalyst can obviously find AgBr, Ag and TiO from figure 12And the positions of the characteristic peaks are not obviously moved, indicating that the fixed Z-type Ag | AgBr/Ag/TiO is successfully prepared2A composite membrane photocatalyst.
FIG. 2 is a fixed Z-type Ag | AgBr/Ag/TiO2Scanning electron microscopy of composite membrane photocatalysts. The silver foil, AgBr film and TiO of the immobilized support are clearly visible in FIG. 22The existence of the film can be inferred that the silver nano particles are positioned on the AgBr film and the TiO2Between the films. The test result shows that the Z-shaped Ag is fixed2Composite membrane photocatalysts were successfully prepared.
EXAMPLE 2 immobilization of Z-form Ag | AgBr/Ag/TiO2Application of composite membrane photocatalyst in photocatalytic hydrogen production
Comparison of hydrogen production effects of different catalysts
The experimental method comprises the following steps: A300W xenon lamp is used as a simulated solar light source. Photocatalytic hydrogen production experiments were performed in a 500mL Pyrex reactor system at a temperature of 25 ℃ and a pressure of 101325 Pa. 500mL of 50mg/L aqueous solution of malachite green were added to 3 500mL Pyrex reactors, and the Ag | AgBr/Ag/TiO solutions prepared in example 1 were added under constant stirring2Ag | AgBr and Ag | TiO2A photocatalyst. Before irradiation, the reaction system was purged with argon for 30min to remove dissolved air. The system was then irradiated with a 300W xenon lamp for 5.0 h. The generated gas was periodically analyzed by gas chromatography.
Compare Ag | AgBr/Ag/TiO2Composite membrane photocatalyst and other two photocatalysts (Ag | AgBr and Ag | TiO)2) The effect of photocatalytic hydrogen production under the irradiation of simulated sunlight. The results are shown in FIG. 3.
FIG. 3 shows Ag | AgBr/Ag/TiO2Ag | AgBr and Ag | TiO2The effect of the photocatalyst on photocatalytic hydrogen production, as can be seen from FIG. 3It is seen that the photocatalytic hydrogen production by the three photocatalysts almost increases with the increase of the irradiation time. But three photocatalysts (Ag | AgBr/Ag/TiO)2Ag | AgBr and Ag | TiO2) There is a significant difference in the amount of hydrogen produced. The results show that the Ag | AgBr/Ag/TiO prepared by the invention can be used for any time2The hydrogen production of the composite membrane photocatalyst is obviously higher than that of other two photocatalysts. In particular, at 5.0h, Ag | AgBr/Ag/TiO2The hydrogen production of the composite membrane photocatalyst can reach 588.4 mu mol.
Effect of (II) sacrificial agent concentration on photocatalytic hydrogen production
The experimental method comprises the following steps: A300W xenon lamp is used as a simulated solar light source. Photocatalytic hydrogen production experiments were performed in a 500mL Pyrex reactor system at a temperature of 25 ℃ and a pressure of 101325 Pa. Respectively adding 500mL of malachite green aqueous solution with the concentration of 10mg/L, 30mg/L and 50mg/L into 3 Pyrex reactors with the concentration of 500mL, and respectively adding Ag | AgBr/Ag/TiO under the condition of constant stirring2A photocatalyst. Before irradiation, the reaction system was purged with argon for 30min to remove dissolved air. The system was then irradiated with a 300W xenon lamp for 5.0 h. The generated gas was periodically analyzed by gas chromatography.
Ag | AgBr/Ag/TiO at different concentrations of sacrificial agent (malachite Green)2The photocatalytic hydrogen production activity of the composite membrane photocatalyst is shown in fig. 4.
FIG. 4 shows three different concentrations (10mg/L, 30mg/L and 50mg/L) versus Ag | AgBr/Ag/TiO2The influence of the composite membrane photocatalyst on photocatalytic hydrogen production can be seen from fig. 4, and the catalytic hydrogen production increases with the increase of the irradiation time under all concentration conditions. However, the hydrogen production of the three different concentrations (10mg/L, 30mg/L and 50mg/L) is significantly different. The results show that the concentration of the sacrificial agent is most favorable for Ag | AgBr/Ag/TiO when the concentration of the sacrificial agent is 50mg/L2The composite membrane photocatalyst can be used for photocatalytic hydrogen production. Especially when the simulated sunlight irradiates for 5.0h, Ag | AgBr/Ag/TiO2The hydrogen production of the composite membrane photocatalyst can reach 588.4 mu mol.
(III) changing the influence of the using times of the catalyst on photocatalytic hydrogen production
The experimental method comprises the following steps: using a 300W xenon lamp asSimulating a solar light source. Photocatalytic hydrogen production experiments were performed in a 500mL Pyrex reactor system at a temperature of 25 ℃ and a pressure of 101325 Pa. Adding 500mL of 10mg/L malachite green solution into a 500mL Pyrex reactor, and adding Ag | AgBr/Ag/TiO under constant stirring2A composite membrane photocatalyst. Before irradiation, the reaction system was purged with argon for 30min to remove dissolved air. The system was then irradiated with a 300W xenon lamp for 3.0 h. The generated gas was periodically analyzed by gas chromatography.
After every 3.0h, the photocatalyst in the solution was taken out and dried, and the obtained immobilized photocatalyst was subjected to four hydrogen production experiments again, with the results shown in fig. 5.
As shown in FIG. 5, Ag | AgBr/Ag/TiO prepared by the invention2The hydrogen yield of the composite membrane photocatalyst is not obviously reduced after five times of cycle tests, which shows that the prepared immobilized photocatalyst has good stability.
EXAMPLE 3 immobilization of Z-form Ag | AgBr/Ag/TiO2Application of composite membrane photocatalyst in photocatalytic degradation of organic pollutants
Influence of (I) different catalysts on degradation rate of malachite green
The experimental method comprises the following steps: 100mL of 10mg/L malachite green aqueous solution were weighed and placed in 3 specially-made quartz tubes, and the Ag | AgBr/Ag/TiO solutions prepared in example 1 were added2Ag | AgBr and Ag | TiO2The photocatalyst is irradiated for 3.0h under simulated sunlight, 10mL of the photocatalyst is taken out every half hour and centrifuged, and the ultraviolet spectrum of the supernatant is measured at 200-800nm after the supernatant is taken out. The absorbance at 617nm was taken to calculate the degradation rate of malachite green. The results are shown in Table 1.
TABLE 1 Ag | AgBr/Ag/TiO2Ag | AgBr and Ag | TiO2Degradation rate of photocatalyst for degrading malachite green
Compare Ag | AgBr/Ag/TiO2Composite membrane photocatalyst and other two photocatalysts (Ag | AgBr and Ag | TiO)2) In the simulation of solar illuminationThe effect of degrading malachite green by irradiation of light. Table 1 shows Ag | AgBr/Ag/TiO2Ag | AgBr and Ag | TiO2The photocatalyst has different effects of photocatalytic degradation of malachite green. As can be seen from Table 1, the Ag | AgBr/Ag/TiO prepared by the invention under the condition of the irradiation time of 3.0h2The composite membrane photocatalyst has the highest degradation rate, and the degradation rate reaches 93.04 percent.
(II) influence of substrate concentration on degradation rate of malachite green
The experimental method comprises the following steps: 100mL of malachite green aqueous solution with the concentration of 10mg/L, 15mg/L, 20mg/L, 25mg/L and 30mg/L are measured and respectively placed in 5 special quartz tubes, and Ag | AgBr/Ag/TiO is respectively added2The composite membrane photocatalyst is irradiated for 3.0h under simulated sunlight, 10mL of the composite membrane photocatalyst is taken out every half hour and centrifuged, and the ultraviolet spectrum of the supernatant is measured at 200-800nm after the supernatant is taken out. The absorbance at 617nm was taken to calculate the degradation rate of malachite green. The results are shown in Table 2.
TABLE 2 Ag | AgBr/Ag/TiO at different substrate concentrations2Degradation rate of composite membrane photocatalyst for degrading malachite green
Comparing Ag | AgBr/Ag/TiO at different substrate concentrations2The composite membrane photocatalyst has the effect of photocatalytic degradation of malachite green under the irradiation of simulated sunlight. Table 2 shows Ag | AgBr/Ag/TiO at five different concentrations (10mg/L, 15mg/L, 20mg/L, 25mg/L and 30mg/L)2The composite membrane photocatalyst has different effects of photocatalytic degradation of malachite green. As can be seen from Table 2, when the concentration of malachite green is 10mg/L and the simulated solar irradiation time is 3.0h, the Ag | AgBr/Ag/TiO prepared by the invention2The degradation rate of the composite membrane photocatalyst is highest and reaches 93.04 percent.
(III) influence of changing using times of catalyst on degradation rate of malachite green
The experimental method comprises the following steps: weighing 100mL of 10mg/L malachite green water solution in a special quartz tube, and adding Ag | AgBr/Ag/TiO2Composite membrane photocatalystIrradiating for 3.0h under simulated sunlight, taking out 10mL of solution every 0.5h, centrifuging, taking the supernatant, and measuring the ultraviolet spectrum of the supernatant at 200-800 nm. The absorbance at 617nm was taken to calculate the degradation rate of malachite green, the photocatalyst in the solution was taken out and dried after every 3.0h, and the obtained immobilized catalyst was subjected to four photocatalytic degradation experiments again, with the results shown in table 3.
TABLE 3 Ag | AgBr/Ag/TiO2Degradation rate of five-time degradation malachite green cycle experiment of composite membrane photocatalyst
As shown in Table 3, Ag | AgBr/Ag/TiO2The composite membrane photocatalyst has good stability, and the degradation rate is basically not reduced through five times of repeated experiments, which shows that the prepared immobilized photocatalyst has good stability.
In the above examples, malachite green is used as the organic dye, but the organic dye degraded by the present invention is not limited to malachite green, and the method of the present invention is suitable for degrading any organic dye, such as rhodamine B, acid brilliant orange, etc.
Claims (10)
1. Fixed Z-type Ag | AgBr/Ag/TiO2The composite membrane photocatalyst is characterized in that an AgBr film is formed on a silver foil by adopting a continuous ion layer adsorption method, a xenon lamp is adopted to irradiate the surface of the AgBr film, silver nano particles are generated on the surface of the AgBr film, and finally a sol-gel spin coating method is used for preparing TiO2Film, forming fixed Z-type Ag | AgBr/Ag/TiO2A composite membrane photocatalyst.
2. The fixed Z-form Ag | AgBr/Ag/TiO of claim 12The preparation method of the composite membrane photocatalyst is characterized by comprising the following steps:
1) cleaning the silver foil;
2) carrying out corrosion treatment on the cleaned silver foil;
3) cleaning the silver foil subjected to corrosion treatment by using deionized water;then transferring the mixture to KBr solution to be soaked for 5.0-10.0min, and then transferring the mixture to AgNO3Soaking in the solution for 5.0-10.0min to complete one-time soaking adsorption, repeating soaking adsorption for 6-10 times, and forming a layer of AgBr film on the silver foil to obtain Ag | AgBr;
4) placing the AgBr film surface on a silver foil with one side facing upwards, and irradiating under a 300W xenon lamp for 5.0-10.0min to form a layer of Ag on the AgBr film surface to obtain Ag | AgBr/Ag;
5) by spin coating of TiO2Spin coating the sol on the surface of Ag | AgBr/Ag to form a layer of TiO2Drying the film at 60 deg.C for 10min, transferring to muffle furnace, calcining at 450 deg.C for 3.0h, cooling to room temperature, and spin-coating TiO on silver foil2One surface of the Z-shaped silver/TiO silver paste is polished by sand paper to prepare a fixed Z-shaped Ag | AgBr/Ag/TiO2A composite membrane photocatalyst.
3. The method according to claim 2, wherein the step 1) of cleaning the silver foil comprises: and (3) cleaning the silver foil with a detergent, acetone and absolute ethyl alcohol in sequence under an ultrasonic condition.
4. The method according to claim 2, wherein the step 2) of etching the cleaned silver foil comprises: putting the cleaned silver foil into a nitric acid aqueous solution for corrosion for 2.0-3.0min, and then transferring the silver foil into a hydrogen peroxide aqueous solution for corrosion for 2.0-3.0 min.
5. The method according to claim 2, wherein in step 5), the TiO is2The preparation method of the sol comprises the following steps: a mixture of Ti (OBu)4Dissolving in mixed solution of anhydrous ethanol and acetylacetone, and stirring at 90-100 deg.C until TiO is formed2And (3) sol.
6. The method according to claim 2, wherein in step 5), the spin coating method is: spin-coat at 3000rpm for 20 s.
7. The fixed Z-form Ag | AgBr/Ag/TiO of claim 12The composite membrane photocatalyst is applied to the degradation of organic dye under sunlight.
8. Use according to claim 7, characterized in that: the method comprises the following steps: adding the fixed Z-form Ag | AgBr/Ag/TiO of claim 1 to a solution containing an organic dye2The composite membrane photocatalyst is irradiated under sunlight.
9. The fixed Z-form Ag | AgBr/Ag/TiO of claim 12The composite membrane photocatalyst is applied to photocatalytic hydrogen production.
10. Use according to claim 9, characterized in that the method is as follows: adding the fixed Z-form Ag | AgBr/Ag/TiO of claim 1 to an aqueous solution containing an organic dye2The composite membrane photocatalyst is irradiated under sunlight.
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