CN111018365A - Method for in-situ preparation of silver nanoparticle loaded ZnO nano-foam - Google Patents
Method for in-situ preparation of silver nanoparticle loaded ZnO nano-foam Download PDFInfo
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- 239000008208 nanofoam Substances 0.000 title claims abstract description 52
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 15
- 239000004332 silver Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- XKKVXDJVQGBBFQ-UHFFFAOYSA-L zinc ethanol diacetate Chemical compound C(C)O.C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-] XKKVXDJVQGBBFQ-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 27
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 9
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- 239000011787 zinc oxide Substances 0.000 description 82
- 238000001354 calcination Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
-
- 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
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- B01J35/39—
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- B01J35/40—
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
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Abstract
A method for in-situ preparation of ZnO nano-foam loaded with silver nanoparticles relates to the field of photocatalytic materials, in particular to a method for preparing ZnO nano-foam loaded with silver nanoparticles. The method aims to solve the problems that the conventional method for loading ZnO on silver nanoparticles needs complicated secondary deposition steps and the loading capacity and catalytic activity of the silver nanoparticles are poor. The method comprises the following steps: firstly, preparing a zinc acetate-ethanol solution, namely a seed solution; uniformly coating the seed liquid on the cleaned FTO glass, drying and sintering to obtain the FTO glass with the ZnO seed layer; thirdly, placing the FTO glass with the ZnO seed layer in a reaction solution for reaction, washing and drying; and fourthly, sintering the dried sample to finish the process. The preparation method is simple to operate, low in cost, convenient for recycling of the photocatalytic material and excellent in catalytic degradation performance. The method is used for preparing the silver nanoparticle loaded ZnO nano foam material.
Description
Technical Field
The invention relates to the field of photocatalytic materials, in particular to a preparation method of ZnO nano foam loaded with silver nanoparticles.
Background
With the growth of population and the development of industrialization, the pollution of organic pollutants to the environment has become a worldwide problem. The use of sustainable energy, solar energy, to degrade organic pollutants is considered an effective method to relieve environmental stress. Under the irradiation of sunlight, the photocatalyst can degrade organic pollutants into H2O and CO2Without generating additional contaminants.
Zinc oxide is an important II-VI type semiconductor material, has received wide attention due to its application in photocatalysis, and ZnO has high photosensitivity, low manufacturing cost, low toxicity, and good electron transfer ability as compared with other metal oxide semiconductors, and thus is widely used as a photocatalyst to degrade pollutants in water. The photocatalytic activity of ZnO is currently limited in two ways: (1) ZnO is a wide-band-gap semiconductor, so that the ZnO can only absorb in an ultraviolet region, and is not beneficial to the efficient utilization of sunlight; (2) the quantum efficiency of ZnO is very low due to the rapid recombination of photo-generated electron-hole pairs, which greatly limits the photocatalytic activity of ZnO. Therefore, continuous improvement of ZnO photocatalysts has been the direction of researchers, and efforts have been made to prepare ZnO-based photocatalysts under visible light by means of metal or nonmetal doping, noble metal loading, and the like. The surface structure of the zinc oxide modified by the noble metal is the most effective way for accelerating the separation of carriers and improving the catalytic activity.
Silver nanoparticles are a precious metal nanomaterial that is readily available and, due to their specific Localized Surface Plasmon Resonance (LSPR) properties in the visible region, have proven promising in collecting the photon energy required for chemical reactions. In the existing Ag loading technology, a secondary light deposition method is common. However, the method needs secondary deposition, and the steps are complicated; in addition, the method can only load Ag nano particles on the surface of the material, but can not enter the photocatalyst, so that the improvement of the loading and the catalytic activity is limited.
Disclosure of Invention
The invention provides a method for in-situ preparation of silver nanoparticle loaded ZnO nano-foam, aiming at solving the problems that the existing method for loading ZnO on silver nanoparticles needs complicated secondary deposition steps and has poor silver nanoparticle loading capacity and catalytic activity.
The method for in-situ preparation of the silver nanoparticle loaded ZnO nano-foam comprises the following steps:
firstly, preparing a seed solution:
preparing a zinc acetate-ethanol solution with the concentration of 0.1-0.2 mol/L, namely a seed solution;
secondly, preparing a ZnO seed layer on the FTO conductive substrate:
uniformly coating the seed solution obtained in the step one on cleaned FTO glass, drying at 80-85 ℃, and then sintering for 30-40 minutes at 400-450 ℃ in a muffle furnace in an air atmosphere to obtain FTO glass with a ZnO seed layer;
thirdly, preparing Ag nano particles loaded on the Zn (OH) F nano foam structure:
placing the FTO glass with the ZnO seed layer in a reaction solution at 91-93 ℃, reacting for 4-6 hours, taking out the FTO glass with the ZnO seed layer, repeatedly washing with deionized water, and naturally drying to obtain a dried sample;
fourthly, calcining:
and sintering the dried sample for 30-60 min at 400-450 ℃ by using a tubular furnace at the heating rate of 1-10 ℃/min to complete the method.
Further, the specific method for preparing the seed liquid in the step one comprises the following steps: stirring for 3-4 h at 80-85 ℃ by a reflux method to prepare a zinc acetate-ethanol solution with the concentration of 0.1-0.2 mol/L.
Further, the coating method in the second step comprises the following specific steps: and coating the cleaned FTO glass on the cleaned FTO glass by a film drawing machine at the speed of 200-220 mm/min for 3-5 times.
Further, the reaction solution in the third step is composed of 0.02-0.05 mol/L of zinc acetate, 0.02-0.05 mol/L of hexamethylenetetramine, 0.03-0.0475 mol/L of ammonium fluoride, 0.001-0.005 mol/L of sodium citrate and 0.0001-0.0015 mol/L of silver nitrate water solution.
Further, gas N is introduced into the sintering process in the fourth step2Or Ar2。
The invention has the beneficial effects that:
according to the invention, the Ag/ZnO nano foam structure is grown on the glass substrate through a simple in-situ one-step method, and Ag nano particles can be uniformly loaded in and on the surface of the ZnO nano structure while the growth of the original ZnO structure is not hindered.
The composite material prepared by the method can fully utilize visible light, expand the light absorption range of ZnO, ensure that the operation of photocatalytic degradation of organic pollutants is simple, the cost is low, the recycling of the photocatalytic material is convenient, and the composite material has excellent catalytic degradation performance.
The catalytic activity of the silver nanoparticle loaded ZnO nano-foam prepared by the method is far higher than that of the unloaded ZnO nano-foam, the catalytic efficiency is improved to 38 percent from the original 15 percent, and the activity is improved by about 2.5 times.
After 3 times of repeated photodegradation catalysis, the prepared silver nanoparticle loaded ZnO nano-foam is reduced from 38% to 34%, and the catalytic efficiency is reduced by 4%. The result shows that the Ag nano particles loaded on the ZnO nano foam structure still have higher catalytic activity after being recycled, the cyclicity is good, and the performance of the catalyst is stable.
In addition, the Ag/ZnO nano foam structure grows on the glass substrate, so that the catalytic material is more favorably recycled.
Drawings
FIG. 1 is an XRD diffractogram of Ag nanoparticles loaded on the ZnO nano-foam structure in example 1;
FIG. 2 is a surface electron microscope image of Ag nanoparticles loaded on the ZnO nano-foam structure in example 1;
FIG. 3 is a side view corresponding to the SEM of FIG. 2;
FIG. 4 is an electron microscope cross-sectional view of the ZnO nano-foam structure loaded with Ag nanoparticles in example 1;
FIG. 5 is an XPS total spectrum of Ag nanoparticles loaded on a ZnO nano-foam structure in example 1;
FIG. 6 is an XPS plot of Ag nanoparticles loading the ZnO nanofoam structure of example 1;
FIG. 7 is a graph of UV-VIS spectrum of Ag loaded nanofoam structure of ZnO example 1;
FIG. 8 is a steady-state photo-voltage spectrum of the ZnO nano-foam structure loaded with Ag nano-particles in example 1;
FIG. 9 shows the degradation efficiency of the ZnO nano-foam structure loaded with Ag nanoparticles in example 1 in the degradation of rhodamine B under simulated sunlight;
FIG. 10 is a result of a repeated degradation experiment of Ag nanoparticles loaded on a ZnO nano-foam structure in example 1 to degrade rhodamine B under simulated sunlight;
fig. 11 is a photograph of the ZnO nanofoam structure loaded Ag nanoparticles of example 1 after 3 repetitions of degrading rhodamine B under simulated sunlight.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the method for in-situ preparation of the silver nanoparticle-loaded ZnO nanofoam according to the embodiment comprises the following steps:
firstly, preparing a seed solution:
preparing a zinc acetate-ethanol solution with the concentration of 0.1-0.2 mol/L, namely a seed solution;
secondly, preparing a ZnO seed layer on the FTO conductive substrate:
uniformly coating the seed solution obtained in the step one on cleaned FTO glass, drying at 80-85 ℃, and then sintering for 30-40 minutes at 400-450 ℃ in a muffle furnace in an air atmosphere to obtain FTO glass with a ZnO seed layer;
thirdly, preparing Ag nano particles loaded on the Zn (OH) F nano foam structure:
placing the FTO glass with the ZnO seed layer in a reaction solution at 91-93 ℃, reacting for 4-6 hours, taking out the FTO glass with the ZnO seed layer, repeatedly washing with deionized water, and naturally drying to obtain a dried sample;
fourthly, calcining:
and sintering the dried sample for 30-60 min at 400-450 ℃ by using a tubular furnace to obtain the finished product.
The second step of the present embodiment is to perform sintering to prepare a ZnO seed layer, which can be prepared in an air atmosphere and is performed in a muffle furnace from the viewpoint of reducing energy consumption, so that the seed layer does not need to be calcined in a tube furnace. And the fourth calcination step is to prepare the Ag/ZnO nano-foam structure, and considering that the sample contains Ag particles, in order to avoid side reaction of Ag with other gases mainly containing oxygen in the air at high temperature, the calcination atmosphere here adopts N2Or Ar2. The tubular furnace is convenient for introducing N2Or Ar2。
Too short a calcination time does not allow the Zn (OH) F intermediate to be completely converted to ZnO, and a long calcination time may cause structural collapse of ZnO. The calcination time of this embodiment enables the foam structure to be free from collapse while maintaining the ZnO transition to completion.
According to the embodiment, the Ag/ZnO nano foam structure grows on the glass substrate through a simple in-situ one-step method, and Ag nano particles can be uniformly loaded in and on the surface of the ZnO nano structure while the growth of the original ZnO structure is not hindered.
The composite material prepared by the method can fully utilize visible light, expand the light absorption range of ZnO, and ensure that the operation of photocatalytic degradation of organic pollutants is simple, the cost is low, the photocatalytic material is convenient to recycle, and the composite material has excellent catalytic degradation performance.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the specific method for preparing the seed liquid in the first step comprises the following steps: stirring for 3-4 h at 80-85 ℃ by a reflux method to prepare a zinc acetate-ethanol solution with the concentration of 0.1-0.2 mol/L. The rest is the same as the first embodiment.
The method adopts a reflux method to prepare the seed liquid, the reflux method is simple and easy to operate, and the zinc acetate can be uniformly dispersed in the ethanol solution in a short time.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the coating method in the second step comprises the following specific steps: and coating the cleaned FTO glass on the cleaned FTO glass by a film drawing machine at the speed of 200-220 mm/min for 3-5 times. The other is the same as in the first or second embodiment.
Because the liquid itself has surface tension, the improper speed can destroy the uniformity of the seed layer on the FTO glass. Therefore, a uniform seed layer can be produced on the FTO using the coating speed of the present embodiment. In order to facilitate the later growth of Zn (OH) F intermediate, the seed layer is kept to have certain thickness and surface smoothness and uniformity by adopting the fractional coating.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: and step three, the reaction solution consists of 0.02-0.05 mol/L of zinc acetate, 0.02-0.05 mol/L of hexamethylenetetramine, 0.03-0.0475 mol/L of ammonium fluoride, 0.001-0.005 mol/L of sodium citrate and 0.0001-0.0015 mol/L of silver nitrate aqueous solution. The others are the same as in one of the first to third embodiments.
The reaction solution in the concentration ratio of the embodiment controls the morphology of ZnO foam and the optimal size range of Ag nanoparticles.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: introducing gas N in the sintering process in the fourth step2Or Ar2. The other is the same as one of the first to fourth embodiments.
The fourth sintering step is to prepare Ag/ZnO nano foam structure, and considering that the sample contains Ag particles, in order to avoid side reaction of Ag with other gases mainly containing oxygen in the air at high temperature, the calcination atmosphere here adopts N2Or Ar2。
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and the temperature rise rate of the sintering in the fourth step is 1-10 ℃/min. The other is the same as one of the first to fifth embodiments.
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Example 1:
the method for preparing the silver nanoparticle-loaded ZnO nanofoam in situ comprises the following steps:
firstly, the size is 1.5 multiplied by 2.5cm2The FTO glass is sequentially ultrasonically cleaned for 10 minutes by deionized water, acetone, ethanol, acetone and ethanol, and then N is used2Drying for later use;
secondly, stirring for 3 hours at 80 ℃ by a reflux method to prepare zinc acetate-ethanol seed liquid with the concentration of 0.1 mol/L;
thirdly, uniformly coating the seed liquid on cleaned FTO glass for 3 times at the speed of 200mm/min by using a film drawing machine, drying at the temperature of 80 ℃, and then burning for 30 minutes at the temperature of 450 ℃ in an air atmosphere by using a muffle furnace;
fourthly, placing the sintered FTO glass attached with the ZnO seed layer in a reaction solution at the temperature of 92 ℃, reacting for 4 hours, then taking out the FTO glass provided with the ZnO seed layer, repeatedly washing with deionized water, and naturally drying to obtain a dried sample;
the reaction solution consists of 0.03mol/L of zinc acetate, 0.03mol/L of hexamethylenetetramine, 0.0475mol/L of ammonium fluoride, 0.005mol/L of sodium citrate and 0.0008mol/L of silver nitrate aqueous solution.
Fifthly, sintering the dried sample at 450 ℃ for 30min by using a tubular furnace at the heating rate of 5 ℃/min, and introducing nitrogen in the sintering process to finish the process.
The XRD diffraction pattern of the Ag nano particles loaded on the ZnO nano foam structure in the embodiment is shown in FIG. 1 (◆ in FIG. 1 represents FTO, ● represents Ag), the sample conforms to the ZnO wurtzite structure and the simple substance Ag structure, and the diffraction peaks completely correspond to ZNO card PDF-36-1451 and Ag card PDF-04-0783.
The surface electron microscope image of the ZnO nano foam structure loaded with Ag nano particles is shown in figure 2, and after doping, the Ag nano particles can be clearly seen loaded on the surface of ZnO while the original ordered structure is maintained.
A surface scan corresponding to the SEM image of FIG. 2 is shown in FIG. 3. Thus showing that the Ag nano particles are successfully loaded on the ZnO nano sheet.
The electron microscope cross-sectional view of the ZnO nano-foam structure loaded with Ag nano-particles is shown in FIG. 4, which illustrates that the in-situ synthesis method enables the Ag nano-particles to be successfully loaded in the ZnO foam.
An XPS total spectrum of the ZnO nano-foam structure loaded with Ag nano-particles is shown in FIG. 5. An XPS diagram of Ag element loaded Ag nanoparticles in a ZnO nano foam structure is shown in FIG. 6. The Ag is successfully loaded on the foamy ZnO in the form of simple substance Ag particles.
An ultraviolet-visible absorption spectrogram of the ZnO nano foam structure loaded with the Ag nano particles is shown in FIG. 7, wherein a solid line in FIG. 7 represents Ag/ZnO, and a dotted line represents ZnO. The addition of Ag nano particles expands the light absorption capacity of ZnO.
The steady-state photovoltage spectrogram of the ZnO nano foam structure loaded with the Ag nano particles is shown in FIG. 8, wherein a curve 1 in the graph 8 represents Ag/ZnO, and a curve 2 represents ZnO. The addition of the Ag nano particles inhibits the recombination of photo-generated charge carriers, which is beneficial to the photo-generated charge carriers to participate in a photocatalytic reaction before the recombination.
The degradation efficiency of Ag nano particles loaded on a ZnO nano foam structure in the degradation of rhodamine B under simulated sunlight is shown in figure 9, ■ in the figure 9 represents a blank, ● represents ZnO,
represents Ag/ZnO. It can be seen that the catalytic activity of the ZnO nano-foam structure loaded with Ag nano-particles far exceeds that of the unsupported ZnO nano-foam structure, the catalytic efficiency is improved to 38% from the original 15%, and the activity is improved by about 2.5 times.
The repetitive degradation experiment result of the ZnO nano foam structure loaded Ag nano particles for degrading rhodamine B under simulated sunlight is shown in figure 10. It can be seen that the Ag nano particles loaded on the ZnO nano foam structure are reduced from 38% to 34% after 3 times of repeated photodegradation catalysis, and the catalytic efficiency is only reduced by 4%. The result shows that the Ag nano particles loaded on the ZnO nano foam structure still have higher catalytic activity after being recycled, the cyclicity is good, and the performance of the catalyst is stable.
The photo of the ZnO nano foam structure loaded Ag nano particles after 3 times of repeatability of degrading rhodamine B under simulated sunlight is shown in figure 11, and the catalyst film growing on the glass substrate is fine and uniform, which shows that the ZnO nano foam structure loaded Ag nano particle catalyst has stable performance and simple recovery.
Claims (6)
1. A method for preparing silver nanoparticle-loaded ZnO nano-foam in situ is characterized by comprising the following steps:
firstly, preparing a zinc acetate-ethanol solution with the concentration of 0.1-0.2 mol/L, namely a seed solution;
uniformly coating the seed liquid obtained in the step one on cleaned FTO glass, drying at 80-85 ℃, and sintering at 400-450 ℃ for 30-40 minutes in a muffle furnace in an air atmosphere to obtain FTO glass with a ZnO seed layer;
placing the FTO glass with the ZnO seed layer in a reaction solution at 91-93 ℃, reacting for 4-6 hours, taking out the FTO glass with the ZnO seed layer, repeatedly washing with deionized water, and naturally drying to obtain a dried sample;
and fourthly, sintering the dried sample for 30-60 min at 400-450 ℃ by using a tubular furnace, thus completing the preparation.
2. The method for preparing the silver nanoparticle-loaded ZnO nanofoam in situ as claimed in claim 1, wherein the specific method for preparing the seed solution in the first step is as follows: stirring for 3-4 h at 80-85 ℃ by a reflux method to prepare a zinc acetate-ethanol solution with the concentration of 0.1-0.2 mol/L.
3. The method for preparing the silver nanoparticle-loaded ZnO nanofoam in situ as claimed in claim 1 or 2, wherein the specific method of coating in step two is: and coating the cleaned FTO glass on the cleaned FTO glass by a film drawing machine at the speed of 200-220 mm/min for 3-5 times.
4. The method for preparing ZnO nano-foam loaded with silver nanoparticles in situ according to claim 3, wherein the reaction solution in the third step is composed of 0.02-0.05 mol/L of zinc acetate, 0.02-0.05 mol/L of hexamethylenetetramine, 0.03-0.0475 mol/L of ammonium fluoride, 0.001-0.005 mol/L of sodium citrate and 0.0001-0.0015 mol/L of silver nitrate aqueous solution.
5. The method for in-situ preparation of silver nanoparticle-loaded ZnO nanofoam according to claim 4, wherein N is introduced during the sintering process in the fourth step2Or Ar2。
6. The method for in-situ preparation of the silver nanoparticle-loaded ZnO nanofoam according to claim 5, wherein the temperature rise rate of the sintering in the fourth step is 1-10 ℃/min.
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