CN112774679A - Immobilized forced Z-shaped composite membrane photocatalyst and preparation method and application thereof - Google Patents
Immobilized forced Z-shaped composite membrane photocatalyst and preparation method and application thereof Download PDFInfo
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- CN112774679A CN112774679A CN202110137115.5A CN202110137115A CN112774679A CN 112774679 A CN112774679 A CN 112774679A CN 202110137115 A CN202110137115 A CN 202110137115A CN 112774679 A CN112774679 A CN 112774679A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 101
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000012528 membrane Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000010408 film Substances 0.000 claims abstract description 83
- 239000001257 hydrogen Substances 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 47
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 claims abstract description 33
- 238000004528 spin coating Methods 0.000 claims abstract description 28
- 239000010409 thin film Substances 0.000 claims abstract description 11
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- 238000006731 degradation reaction Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005260 corrosion Methods 0.000 claims description 14
- 230000007797 corrosion Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000975 dye Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 244000137852 Petrea volubilis Species 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910019804 NbCl5 Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000006479 redox reaction Methods 0.000 abstract description 2
- KSCQDDRPFHTIRL-UHFFFAOYSA-N auramine O Chemical compound [H+].[Cl-].C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 KSCQDDRPFHTIRL-UHFFFAOYSA-N 0.000 description 23
- 230000015556 catabolic process Effects 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 13
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 239000005297 pyrex Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003622 immobilized catalyst Substances 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 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
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
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- 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
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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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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- 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
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Abstract
The invention relates to an immobilized forced Z-shaped composite membrane photocatalyst and a preparation method and application thereof. Firstly, forming AgNbO on silver foil by adopting sol-gel spin coating method3Thin film, then using photoreduction method on AgNbO3Depositing silver nano particles on the surface of the film, and finally preparing Er on the outermost side by using a sol-gel spin coating method3+:YAlO3@Nb2O5Forming a thin film of immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5A composite membrane photocatalyst. The immobilized forced Z-shaped composite membrane photocatalyst can efficiently degrade organic dye and simultaneously produce hydrogen under the action of sunlight. The preparation method of the inventionSimple and convenient, and high catalyst yield. And because the immobilized forced 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 and obtained.
Description
Technical Field
The invention belongs to lightThe field of catalysts, in particular to an immobilized forced Z-shaped Ag | AgNbO synthesized by a sol-gel spin coating method and a photoreduction method3/Ag/Er3+:YAlO3@Nb2O5The 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 hydrogen is used as secondary energy, and has the advantages of high energy density, high combustion heat value, safety, stability and the like. The vigorous development of hydrogen energy to replace traditional fossil energy is an important strategy to alleviate the energy crisis. The solar photocatalytic hydrogen production by water decomposition is one of the most attractive methods in the prior art. Since the first report in 1972 that water molecules on the surface of a titanium dioxide electrode can be cracked into hydrogen under ultraviolet light irradiation, the acquisition of a high-activity semiconductor photocatalyst becomes a research hotspot. However, single semiconductor photocatalysts are relatively poor in activity due to high recombination rates of photo-induced carriers and insufficient oxidation-reduction potentials. The construction of a Z-type photocatalytic system by combining two monomeric photocatalysts having matched band structures is considered to be an effective means for improving photocatalytic activity. In addition, after proper modification, the Z-type photocatalyst not only has stronger oxidizing capability, but also has stronger reducing capability, so that organic pollutants (which can be regarded as a sacrificial agent for promoting the photocatalytic hydrogen production reaction) can be effectively removed, and hydrogen is generated at the same time. The method has profound significance for restraining environmental pollution and obtaining clean energy.
Research on photocatalytic hydrogen production has been widely reported, but most of the photocatalysts used at present exist in the form of powder. The uneven dispersion of the photocatalyst powder in the reaction solution results in a limited number of photocatalyst particles actually participating in the photocatalytic reaction, thereby failing to exhibit the entire photocatalytic activity. And because single photocatalyst particles are easy to agglomerate, the ideal Z-shaped composite photocatalyst is difficult to prepare by using the traditional method. Meanwhile, the regeneration and utilization of the photocatalyst powder are difficult, and the loss is inevitable in the processes of centrifuging and washing. Fortunately, the above problems can be well solved by the photocatalyst immobilization technique, i.e., by immobilizing one or more layers of photocatalyst thin films on an immobilization support. The immobilization technology of the photocatalyst can 'force' different photocatalyst films to be compounded, and the tight combination of different photocatalyst particles is realized. Meanwhile, the fixed photocatalyst particles can fully participate in the photocatalytic reaction, and the photocatalytic activity of the photocatalyst is exerted to the maximum extent. Moreover, the immobilization of the photocatalyst obviously reduces the difficulty of recycling, and brings a high recycling rate which is obviously improved. In addition, in the current photocatalytic hydrogen production process, gases such as (carbon dioxide and oxygen) produced by the oxidation reaction of organic contaminants occurring at the valence band of the photocatalyst are mixed with hydrogen produced by the reduction reaction of water splitting to produce hydrogen occurring at the conduction band. This requires further separation and purification to obtain pure hydrogen, which greatly increases the production cost. If a photocatalyst thin film is fixed in a specific order using a photocatalyst fixing technique, it is possible to simultaneously perform photocatalytic oxidation and reduction reactions on both sides of an immobilized carrier, respectively, to obtain pure hydrogen and carbon dioxide or oxygen, by utilizing the conductivity of the immobilized carrier. Thus, large-scale industrialized solar photocatalytic hydrogen production is expected to be realized, and the prepared hydrogen can really reach the practical degree. In summary, the development prospect of the photocatalyst immobilization technology is very broad, but the research on the photocatalyst immobilization technology is not enough at present.
Disclosure of Invention
The invention aims to provide an immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5The 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: an immobilized Z-shaped forced composite membrane photocatalyst is prepared by forming AgNbO on silver foil by sol-gel spin coating method3Thin film, then using photoreduction method on AgNbO3Depositing silver nano particles on the surface of the film, and finally using sol-gelEr prepared at outermost side by spin coating method3+:YAlO3@Nb2O5Forming a thin film of immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5A composite membrane photocatalyst.
The preparation method of the immobilized forced Z-shaped 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 AgNbO is added3The sol is spin-coated on the surface of the silver foil by adopting a spin coating method to form a layer of AgNbO3Drying the film at 60 ℃ for 10min, transferring the film to a muffle furnace, calcining the film for 2.0h at 300 ℃, then heating the film to 650 ℃ and calcining the film for 2.0h, and cooling the film to room temperature to obtain Ag | AgNbO3A film.
4) Mixing Ag | AgNbO3Soaking the film in AgNO3In the solution, the whole system is irradiated by a 64W low-pressure mercury lamp with lambda less than or equal to 254nm in Ag | AgNbO3Forming a layer of Ag nano particles on the surface of the film to obtain Ag | AgNbO3a/Ag film;
5) er is prepared by spin coating3+:YAlO3@Nb2O5The sol is coated on Ag | AgNbO in a spinning mode3Forming a layer of Er on the surface of the/Ag film3+:YAlO3@Nb2O5Drying the film at 60 ℃ for 10min, transferring the film to a muffle furnace, calcining the film for 2.0h at 300 ℃, heating the film to 650 ℃ again, calcining the film for 2.0h, cooling the film to room temperature, and spin-coating Er on the silver foil3+:YAlO3@Nb2O5One side of the sol is polished by sand paper to prepare the immobilized forced Z-shaped Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5A 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 solution for corrosion for 2.0-3.0min, and then transferring the silver foil into a hydrogen peroxide solution for corrosion for 2.0-3.0 min.
Further, in the above preparation method, step 3), the AgNbO3The preparation method of the sol comprises the following steps: reacting NH4H2[NbO(C2O4)3]·3H2O、AgNO3And C6H8O7Mixing, dissolving in hydrogen peroxide solution, adding nitric acid, heat treating at 65 deg.C for 1.0 hr, cooling to room temperature, adding ammonia water solution, adjusting pH to 6.5, and heat treating at 120 deg.C to obtain AgNbO3And (3) sol.
Further, in the above preparation method, step 5), the Er is3+:YAlO3@Nb2O5The preparation method of the sol comprises the following steps: reacting NbCl5Dispersing in anhydrous ethanol, stirring for 30min, and adding C5H8O2And deionized water, continuously stirring the obtained solution for 1.0h, and finally adding Er3+:YAlO3Aging the mixed solution at room temperature to obtain Er3+:YAlO3@Nb2O5And (3) sol.
Further, in the above preparation method, step 3 and step 5), the spin coating method is: spin-coat at 3000rpm for 20 s.
The invention provides an immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5The composite membrane photocatalyst is applied to the degradation of organic dye under sunlight.
Further, the method is as follows: adding the immobilized forced Z-type Ag | AgNbO into a solution containing an organic dye3/Ag/Er3+:YAlO3@Nb2O5The composite membrane photocatalyst is irradiated under sunlight.
The invention provides an immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Photocatalytic preparation of composite membrane photocatalystUse in hydrogen.
Further, the method is as follows: adding the immobilized forced Z-type Ag | AgNbO into a solution containing an organic dye3/Ag/Er3+:YAlO3@Nb2O5The composite membrane photocatalyst is irradiated under sunlight.
The invention has the beneficial effects that: the invention relates to immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5The composite membrane photocatalyst is prepared by a sol-gel spin coating method and a photoreduction method, the preparation method is simple and convenient, and the catalyst yield is high. And because an immobilized forced Z-shaped system is generated, the photocatalytic oxidation reduction reaction can be carried out separately and simultaneously, so that the photocatalytic hydrogen production activity is obviously improved, and pure hydrogen can be prepared and obtained. The novel immobilized forced Z-shaped Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Compared 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. The immobilized forced Z-type Ag | AgNbO prepared by the invention3/Ag/Er3+:YAlO3@Nb2O5The 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
In the attached drawings of the specification, Er is expressed by Er: YAP3+:YAlO3。
FIG. 1 is Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5X-ray diffraction pattern of (a).
FIG. 2 is Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Cross-sectional scanning electron microscopy images of (a).
FIG. 3 is Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Ag/Nb2O5、Ag|AgNbO3/Er3+:YAlO3@Nb2O5、Ag|AgNbO3And Ag | Nb2O5The hydrogen production effect of the photocatalyst is shown.
FIG. 4 shows Ag | AgNbO at different concentrations of sacrificial agent3/Ag/Er3+:YAlO3@Nb2O5The hydrogen production effect of the composite membrane photocatalyst is shown.
FIG. 5 is Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Five times of hydrogen production cycle experiment diagrams of the composite membrane photocatalyst.
Detailed Description
Example 1
Immobilization forced Z type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Composite 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 | AgNbO3Film formation:
2.24g of NH4H2[NbO(C2O4)3]·3H2O，0.85g AgNO3And 4.20g C6H8O7Mixing and dissolving in 15mL of 30% hydrogen peroxide solution, and adding 1mL of HNO3Then heating the obtained mixed solution at 65 ℃ for 1.0h, cooling to room temperature, dropwise adding ammonia water to adjust the pH value of the solution to about 6.5, and finally carrying out heat treatment on the obtained yellow solution at 120 ℃ until a dark brown sol with strong viscosity is formed, namely AgNbO3And (3) sol.
By spin coatingCovering method, AgNbO3The sol is coated on the surface of the silver foil after the corrosion treatment for 20s at 3000rpm, and a layer of AgNbO is formed on the surface of the silver foil3Drying the film at 60 deg.C for 10min, transferring to muffle furnace, calcining at 300 deg.C for 2.0h, heating to 650 deg.C, calcining for 2.0h, cooling to room temperature to obtain Ag | AgNbO3A film;
4) preparation of Ag | AgNbO3Ag film:
mixing Ag | AgNbO3Soaking the film in 0.10mol/L AgNO3In the solution, the whole system is irradiated by a 64W low-pressure mercury lamp (lambda is less than or equal to 254nm) in Ag | AgNbO3AgNbO of thin film3Forming a layer of Ag nano particles on the surface to obtain Ag | AgNbO3a/Ag film;
5) preparation of Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Film formation:
reacting NbCl5、C5H8O2The molar ratio of the absolute ethyl alcohol to the deionized water was adjusted to 1:4:45: 0.6. First NbCl5Dispersing in anhydrous ethanol, stirring for 30min, and adding C5H8O2And deionized water, continuously stirring the obtained solution for 1.0h, and finally adding Er3+:YAlO3Aging the mixed solution at room temperature until forming resin-like Er3+:YAlO3@Nb2O5And (3) sol.
Er is prepared by spin coating3+:YAlO3@Nb2O5The sol was spin coated on Ag | AgNbO at 3000rpm for 20s3Forming a layer of Er on the surface of the/Ag film3+:YAlO3@Nb2O5Drying the film at 60 ℃ for 10min, transferring the film to a muffle furnace, calcining the film at 300 ℃ for 2.0h, heating the film to 650 ℃ again, calcining the film for 2.0h, cooling the film to room temperature, and spin-coating Er on the silver foil3+:YAlO3@Nb2O5One side of the sol is polished by sand paper to prepare the immobilized forced Z-shaped Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5A composite membrane photocatalyst.
(II) comparative example
Comparative example 1: preparation of Ag | AgNbO3Film(s)
AgNbO is prepared by spin coating3The sol is coated on the surface of the silver foil after the corrosion treatment for 20s at 3000rpm, and a layer of AgNbO is formed on the surface of the silver foil3Drying the film at 60 deg.C for 10min, transferring to muffle furnace, calcining at 300 deg.C for 2.0h, heating to 650 deg.C, calcining for 2.0h, cooling to room temperature, and spin-coating AgNbO on silver foil3One side of the sol is polished by sand paper to prepare Ag | AgNbO3A film.
Comparative example 2: preparation of Ag | Nb2O5Film(s)
Reacting NbCl5、C5H8O2The molar ratio of the absolute ethyl alcohol to the deionized water was adjusted to 1:4:45: 0.6. First NbCl5Dispersing in anhydrous ethanol, stirring for 30min, and adding C5H8O2And deionized water, stirring the obtained solution for 1.0h, and aging the mixed solution at room temperature until resin-like Nb is formed2O5And (3) sol.
Applying a spin coating method to Nb2O5The sol is coated on the surface of the silver foil after corrosion treatment for 20s at 3000rpm, and a layer of Nb is formed on the surface of the silver foil2O5Drying the film at 60 deg.C for 10min, transferring to muffle furnace, calcining at 300 deg.C for 2.0 hr, heating to 650 deg.C, calcining for 2.0 hr, cooling to room temperature, and spin-coating Nb on silver foil2O5One side of the sol is polished by sand paper to prepare Ag | Nb2O5A film.
Comparative example 3: preparation of Ag | AgNbO3/Ag/Nb2O5Film(s)
AgNbO is prepared by spin coating3The sol is coated on the surface of the silver foil after the corrosion treatment for 20s at 3000rpm, and a layer of AgNbO is formed on the surface of the silver foil3Drying the film at 60 deg.C for 10min, transferring to muffle furnace, calcining at 300 deg.C for 2.0h, heating to 650 deg.C, calcining for 2.0h, cooling to room temperature to obtain Ag | AgNbO3A film.
Mixing Ag | AgNbO3Soaking the film in 0.10mol/L AgNO3Solutions ofThen irradiating the whole system with a 64W low-pressure mercury lamp (lambda is less than or equal to 254nm) to obtain the Ag | AgNbO3AgNbO of thin film3Forming a layer of Ag nano particles on the surface to obtain Ag | AgNbO3a/Ag film.
Applying a spin coating method to Nb2O5The sol was spin coated on Ag | AgNbO at 3000rpm for 20s3A layer of Nb is formed on the surface of the/Ag film2O5Drying the film at 60 deg.C for 10min, transferring to muffle furnace, calcining at 300 deg.C for 2.0 hr, heating to 650 deg.C, calcining for 2.0 hr, cooling to room temperature, and spin-coating Nb on silver foil2O5One side of the sol is polished by sand paper to prepare Ag | AgNbO3/Ag/Nb2O5A film.
Comparative example 4: preparation of Ag | AgNbO3/Er3+:YAlO3@Nb2O5Film(s)
AgNbO is prepared by spin coating3The sol is coated on the surface of the silver foil after the corrosion treatment for 20s at 3000rpm, and a layer of AgNbO is formed on the surface of the silver foil3Drying the film at 60 deg.C for 10min, transferring to muffle furnace, calcining at 300 deg.C for 2.0h, heating to 650 deg.C, calcining for 2.0h, cooling to room temperature to obtain Ag | AgNbO3A film.
Er is prepared by spin coating3+:YAlO3@Nb2O5The sol was spin coated on Ag | AgNbO at 3000rpm for 20s3Forming a layer of Er on the surface of the film3+:YAlO3@Nb2O5Drying the film at 60 ℃ for 10min, transferring the film to a muffle furnace, calcining the film at 300 ℃ for 2.0h, heating the film to 650 ℃ again, calcining the film for 2.0h, cooling the film to room temperature, and spin-coating Er on the silver foil3+:YAlO3@Nb2O5One side of the sol is polished by sand paper to prepare Ag | AgNbO3/Er3+:YAlO3@Nb2O5A film.
(III) characterization of the catalyst
FIG. 1 shows immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5The XRD pattern of the composite membrane photocatalyst can obviously find AgNbO from figure 13、Ag、Er3+:YAlO3And Nb2O5And the positions of the characteristic peaks are not obviously moved, indicating that the immobilized forced Z-type Ag | AgNbO is successfully prepared3/Ag/Er3+:YAlO3@Nb2O5A composite membrane photocatalyst.
FIG. 2 shows immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Cross-sectional scanning electron microscopy of composite membrane photocatalysts. The silver foil of the immobilization support, AgNbO, is clearly visible in FIG. 23Film and Nb2O5The existence of the thin film can be inferred that the silver nano particles are positioned in AgNbO3Film and Nb2O5Between films and Er3+:YAlO3Has been coated with Nb2O5In the film. The test result shows that the immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Composite membrane photocatalysts were successfully prepared.
Example 2
Immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Application of composite membrane photocatalyst in photocatalytic hydrogen production (I) 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. Into 3 500mL Pyrex reactors, 500mL of a 50mg/L aqueous solution of auramine O were added, and the Ag | AgNbO prepared in example 1 was added under constant stirring3/Ag/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Ag/Nb2O5、Ag|AgNbO3And Ag | Nb2O5A 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. Using a gas chromatographThe gas generated is analyzed.
Compare Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Composite membrane photocatalyst and other four kinds of photocatalyst (Ag | AgNbO)3/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Ag/Nb2O5、Ag|AgNbO3And Ag | Nb2O5) The effect of photocatalytic hydrogen production under the irradiation of simulated sunlight. The results are shown in FIG. 3.
FIG. 3 shows Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Ag/Nb2O5、Ag|AgNbO3And Ag | Nb2O5The influence of the photocatalysts on photocatalytic hydrogen production can be seen from fig. 3, and the photocatalytic hydrogen production of the five photocatalysts almost increases with the increase of the irradiation time. But five photocatalysts (Ag | AgNbO)3/Ag/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Ag/Nb2O5、Ag|AgNbO3And Ag | Nb2O5) There is a significant difference in the amount of hydrogen produced. The result shows that the Ag | AgNbO prepared by the invention can be used for any time3/Ag/Er3+:YAlO3@Nb2O5The hydrogen production of the composite membrane photocatalyst is obviously higher than that of other two photocatalysts. Especially 3.0h, Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5The hydrogen production of the composite membrane photocatalyst can reach 318.4 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 auramine O aqueous solution with the concentration of 10mg/L, 30mg/L and 50mg/L into 3 Pyrex reactors with the concentration of 500mL, and stirring constantlyUnder the condition, respectively adding Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5A 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.
Ag | AgNbO at different concentrations of sacrificial agent (auramine O)3/Ag/Er3+:YAlO3@Nb2O5The 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 | AgNbO3/Ag/Er3+:YAlO3@Nb2O5The 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 irradiation time under all concentration conditions. However, the hydrogen production amounts under three different concentration conditions (10mg/L, 30mg/L and 50mg/L) are significantly different. The results show that Ag | AgNbO is most favored when the concentration of the sacrificial agent is 50mg/L3/Ag/Er3+:YAlO3@Nb2O5The composite membrane photocatalyst can be used for photocatalytic hydrogen production. Especially when the simulated sunlight irradiates for 3.0h, the Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5The hydrogen production of the composite membrane photocatalyst can reach 318.4 mu mol.
(III) changing the influence of the using times of the catalyst on photocatalytic hydrogen production
The experimental method comprises the following steps: 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. Adding 500mL of auramine O solution with the concentration of 10mg/L into a 500mL Pyrex reactor, and adding Ag | AgNbO under the constant stirring condition3/Ag/Er3+:YAlO3@Nb2O5A 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 each 3.0h, the photocatalyst in the solution was taken out and dried, and the obtained immobilized photocatalyst was subjected to five photocatalytic hydrogen production cycle experiments, with the results shown in fig. 5.
As shown in FIG. 5, Ag | AgNbO prepared by the invention3/Ag/Er3+:YAlO3@Nb2O5The 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
Immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Application of composite membrane photocatalyst in photocatalytic degradation of organic pollutants
Influence of (I) different catalysts on degradation rate of auramine O
The experimental method comprises the following steps: 100mL of 10mg/L auramine O aqueous solution is measured and respectively put into 3 specially-made quartz tubes, and the Ag | AgNbO prepared in the example 1 is respectively added3/Ag/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Ag/Nb2O5、Ag|AgNbO3And Ag | Nb2O5The 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 degradation rate of auramine O was calculated by taking the absorbance at 428 nm. The results are shown in Table 1.
TABLE 1 degradation rates of different photocatalysts for degrading auramine O
Compare Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5Composite membrane photocatalyst and other four kinds of photocatalyst (Ag | AgNbO)3/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Ag/Nb2O5、Ag|AgNbO3And Ag | Nb2O5) In thatThe effect of photocatalytic degradation of auramine O under sunlight irradiation is simulated. Table 1 shows Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Er3+:YAlO3@Nb2O5、Ag|AgNbO3/Ag/Nb2O5、Ag|AgNbO3And Ag | Nb2O5The photocatalyst has different effects on photocatalytic degradation of auramine O. As can be seen from Table 1, the Ag | AgNbO prepared by the invention is irradiated for 3.0h3/Ag/Er3+:YAlO3@Nb2O5The degradation rate of the composite membrane photocatalyst is the highest, and the degradation rate reaches 92.72%.
(II) influence of substrate concentration on degradation rate of auramine O
The experimental method comprises the following steps: 100mL of auramine O aqueous solution with the concentration of 10mg/L, 20mg/L and 30mg/L are measured and respectively put into 5 special quartz tubes, and Ag | AgNbO is respectively added3/Ag/Er3+:YAlO3@Nb2O5The 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 degradation rate of auramine O was calculated by taking the absorbance at 428 nm. The results are shown in Table 2.
TABLE 2 degradation rate of composite membrane photocatalyst for degrading auramine O under different substrate concentration conditions
Comparing Ag | AgNbO at different substrate concentrations3/Ag/Er3+:YAlO3@Nb2O5The composite film photocatalyst has the effect of photocatalytic degradation of auramine O under simulated sunlight irradiation. Table 2 shows Ag | AgNbO at three different concentrations (10mg/L, 20mg/L and 30mg/L)3/Ag/Er3+:YAlO3@Nb2O5The composite film photocatalyst has different effects of photocatalytic degradation of auramine O. As can be seen from Table 2, when the concentration of auramine O is 10mg/L and the simulated sunlight irradiation time is 3.0h, the Ag | AgNb prepared by the inventionO3/Ag/Er3+:YAlO3@Nb2O5The degradation rate of the composite membrane photocatalyst is the highest, and the degradation rate reaches 92.72%.
(III) influence of changing using times of catalyst on degradation rate of auramine O
The experimental method comprises the following steps: 100mL of 10mg/L auramine O aqueous solution is measured and put into a special quartz tube, and Ag | AgNbO is added3/Ag/Er3+:YAlO3@Nb2O5The 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 degradation rate of auramine O was calculated by taking the absorbance at 428nm, the photocatalyst in the solution was taken out and dried after each 3.0h, and the obtained immobilized catalyst was subjected to five photocatalytic degradation cycles, with the results shown in Table 3.
TABLE 3 degradation rate of five degradation auramine O cycle experiment of composite membrane photocatalyst
As shown in Table 3, Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5The 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, the organic dye is auramine O, but the degraded organic dye of the present invention is not limited to auramine O, and the method of the present invention is suitable for degrading any organic dye, such as rhodamine B, brilliant acid orange, etc.
Claims (10)
1. The immobilized Z-type composite membrane photocatalyst is characterized in that the immobilized Z-type composite membrane photocatalyst is prepared by forming AgNbO on silver foil by adopting a sol-gel spin coating method3Thin film, then using photoreduction method on AgNbO3Depositing silver nano particles on the surface of the film, and finally preparing E on the outermost side by using a sol-gel spin coating methodr3+:YAlO3@Nb2O5Forming a thin film of immobilized forced Z-type Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5A composite membrane photocatalyst.
2. The method for preparing the immobilized Z-type composite membrane photocatalyst according to claim 1, comprising the steps of:
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 AgNbO is added3The sol is spin-coated on the surface of the silver foil by adopting a spin coating method to form a layer of AgNbO3Drying the film at 60 ℃ for 10min, transferring the film to a muffle furnace, calcining the film for 2.0h at 300 ℃, then heating the film to 650 ℃ and calcining the film for 2.0h, and cooling the film to room temperature to obtain Ag | AgNbO3A film;
4) mixing Ag | AgNbO3Soaking the film in AgNO3In the solution, the whole system is irradiated by a 64W low-pressure mercury lamp with lambda less than or equal to 254nm in Ag | AgNbO3Forming a layer of Ag nano particles on the surface of the film to obtain Ag | AgNbO3a/Ag film;
5) er is prepared by spin coating3+:YAlO3@Nb2O5The sol is coated on Ag | AgNbO in a spinning mode3Forming a layer of Er on the surface of the/Ag film3+:YAlO3@Nb2O5Drying the film at 60 ℃ for 10min, transferring the film to a muffle furnace, calcining the film for 2.0h at 300 ℃, heating the film to 650 ℃ again, calcining the film for 2.0h, cooling the film to room temperature, and spin-coating Er on the silver foil3+:YAlO3@Nb2O5One side of the sol is polished by sand paper to prepare the immobilized forced Z-shaped Ag | AgNbO3/Ag/Er3+:YAlO3@Nb2O5A 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 solution for corrosion for 2.0-3.0min, and then transferring the silver foil into a hydrogen peroxide solution for corrosion for 2.0-3.0 min.
5. The method according to claim 2, wherein in step 3), the AgNbO is3The preparation method of the sol comprises the following steps: reacting NH4H2[NbO(C2O4)3]·3H2O、AgNO3And C6H8O7Mixing, dissolving in hydrogen peroxide solution, adding nitric acid, heat treating at 65 deg.C for 1.0h, cooling to room temperature, adding ammonia water solution, adjusting pH to 6.5, and heat treating at 120 deg.C to obtain AgNbO3And (3) sol.
6. The method according to claim 2, wherein in step 5), said Er3+:YAlO3@Nb2O5The preparation method of the sol comprises the following steps: reacting NbCl5Dispersing in anhydrous ethanol, stirring for 30min, and adding C5H8O2And deionized water, continuously stirring the obtained solution for 1.0h, and finally adding Er3+:YAlO3Aging the mixed solution at room temperature to obtain Er3+:YAlO3@Nb2O5And (3) sol.
7. The method of claim 2, wherein in step 3 and step 5), the spin coating method is: spin-coat at 3000rpm for 20 s.
8. The immobilized forced Z-type Ag | AgNbO of claim 13/Ag/Er3+:YAlO3@Nb2O5Degradation of composite membrane photocatalyst under sunlightApplication in organic dyes.
9. Use according to claim 8, characterized in that: the method comprises the following steps: adding the immobilized forced Z-type Ag | AgNbO of claim 1 to a solution containing an organic dye3/Ag/Er3+:YAlO3@Nb2O5The composite membrane photocatalyst is irradiated under sunlight.
10. The immobilized forced Z-type Ag | AgNbO of claim 13/Ag/Er3+:YAlO3@Nb2O5The composite membrane photocatalyst is applied to photocatalytic hydrogen production.
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