CN112973728A - Pt-Cu/ZnO plasma photocatalyst and preparation method and application thereof - Google Patents
Pt-Cu/ZnO plasma photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 53
- 229910018883 Pt—Cu Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 57
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 24
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 229960003638 dopamine Drugs 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims abstract description 8
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- 239000000243 solution Substances 0.000 claims description 50
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- 239000007787 solid Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 7
- 239000002211 L-ascorbic acid Substances 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 11
- 238000007146 photocatalysis Methods 0.000 abstract description 6
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- 229910052751 metal Inorganic materials 0.000 description 8
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- 230000001105 regulatory effect Effects 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 5
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- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 229940120638 avastin Drugs 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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Abstract
The invention discloses a Pt-Cu/ZnO plasma photocatalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding Pt/C catalyst into ethanol, dispersing, adding dopamine, polyvinyl pyrrolidone, acetonitrile and ascorbic acid, and dripping CuCl2Obtaining Cu-Pt/C @ PDA after reaction; adding zinc acetate into ethanol, adding ethyl acetate, heating and stirring, adding Cu/Pt/C @ PDA, and stirring at constant temperature to a sol state; and calcining the sol-gel to obtain the Pt-Cu/ZnO plasma photocatalyst. The invention provides a preparation method of a Pt-Cu/ZnO plasma photocatalyst, which has the advantages of simple process, low cost, wide raw material, easy control of the preparation process, high yield and the like. The product prepared by the invention is nano-scale particles with uniform size, can exert size effect in the photocatalysis process, improves the photocatalysis activity,has good catalytic degradation efficiency for degrading methylene blue.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to a Pt-Cu/ZnO plasma photocatalyst as well as a preparation method and application thereof.
Background
With the progress of society and the acceleration of industrialization, environmental issues become a problem to be solved, and it is well known that photocatalysis is proved to be a promising environmental cleaning technology for purifying organic pollutants and reducing inorganic oxides. Since TiO is generally used2The light utilization rate is low, the recombination rate of photo-generated electrons and holes is high, and the catalytic activity of the photocatalyst is low. 2008, Awazu modified noble metal Ag into TiO2On the surface of, thereby in TiO2The surface generates a plasma resonance effect, and surface plasma photocatalysis is proposed for the first time (J.Am, chem.Soc,2008,130(5): 1676-1680). the plasma resonance effect is that when metal nanoparticles are excited by light with a certain wavelength range, internal electrons generate oscillation, and plasma resonance absorption in the region shows stronger absorption in a visible light region. In addition, a Schottky junction is formed between the metal and the semiconductor, and when photo-generated electrons are transferred from the inside of the semiconductor to the surface of the metal, the photo-generated electrons can directly drift into current, so that the separation of the photo-generated electrons and holes is facilitated, and the catalytic efficiency is improved. Li Aichang et al in TiO2/SnO2A layer of Ag cluster is deposited on the surface of the film, and the catalytic activity is equivalent to that of TiO2/SnO 22 times before modification (Chinese Journal of Noferrous Metal.2009,19(3): 511-516). Because the noble metal modification has two characteristics of plasma resonance effect and Schottky junction, the light response is improved, the electron-hole separation is promoted, and the method becomes a hotspot research direction for developing novel photocatalysts.
In the existing plasma photocatalysts, elementary substance noble metals are used as units to modify the photocatalysts, but when the elementary substance noble metals are used to modify the photocatalysts, the photocatalysts are limited by the photoresponse range and the light utilization rate of the elementary substance noble metals. There is no report on metal alloy modified photocatalyst.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a preparation method of a Pt-Cu/ZnO plasma photocatalyst, and the prepared plasma photocatalyst is a ZnO photocatalyst modified by Pt-Cu alloy particles with a plasma resonance effect, and compared with a single metal, the prepared plasma photocatalyst can widen the photoresponse range and has light utilization rate.
The invention also provides the prepared Pt-Cu/ZnO plasma photocatalyst and application thereof.
The technical scheme is as follows: in order to achieve the purpose, the preparation method of the Pt-Cu/ZnO plasma photocatalyst comprises the following steps:
(1) preparing a Pt-Cu alloy: adding Pt/C catalyst into ethanol solution, ultrasonically stirring at room temperature until the Pt/C catalyst is uniformly dispersed, adding dopamine (PDA), stirring at room temperature, adding polyvinyl pyrrolidone, acetonitrile and ascorbic acid, and dropwise adding CuCl while stirring2Reacting the solution, filtering to obtain a solid, and centrifugally washing to obtain Cu-Pt/C @ PDA;
(2) preparing sol-gel: adding zinc acetate into an ethanol solution, adding an ethyl acetate solution, heating and stirring, adding the Cu/Pt/C @ PDA obtained in the step (1), stirring at a constant temperature to a sol state, and drying to obtain sol gel;
(3) and (3) calcining the sol gel obtained in the step (2) in an air atmosphere, and washing a product to obtain the Pt-Cu/ZnO plasma photocatalyst.
Wherein, in the step (1), 10-100 mg of Pt/C catalyst is added into ethanol solution, ultrasonic stirring is carried out at room temperature for 1-2h until the catalyst is uniformly dispersed, 10-40 mg of dopamine (PDA) is added, stirring is carried out at room temperature for 5-6h, 10-20 ml of 3-8 wt% polyvinyl pyrrolidone aqueous solution, 6-15 ml of acetonitrile and 1-5 ml of 0.1mol/L ascorbic acid aqueous solution are added, and 0.5-5 ml of 0.01mol/LCuCl aqueous solution is dropwise added while stirring2The solution is reacted and then filtered to obtain a solid which is washed by centrifugation to obtain Cu-Pt/C @ PDA.
Adding 1.8-2.0g of zinc acetate into 50-60ml of ethanol solution in the step (2), adding 30-50 ml of ethyl acetate solution, heating and stirring to raise the temperature to 70-80 ℃, stirring for 0.5-2 h, adding the Cu/Pt/C @ PDA obtained in the step (1) and the constant-temperature solution at 70-80 ℃ to 10-20 ml of sol state for generally 5-10h, and drying in a drying oven at 80-100 ℃ for 8-12 h.
And (3) calcining the sol-gel obtained in the step (2) in an air atmosphere at the calcining temperature of 700-800 ℃, preserving the temperature for 8-12 hours, and washing with deionized water to obtain the Pt-Cu/ZnO plasma photocatalyst.
Preferably, in the step (1), 20 to 93mg Pt/C catalyst is added into the ethanol solution, and 0.5 to 2.5ml of 0.01mol/LCuCl is dripped under stirring2And (3) solution.
Preferably, in the step (1), 88mg Pt/C catalyst containing 10 wt% Pt is added to the ethanol solution, the mixture is ultrasonically stirred at room temperature for 2h until the mixture is uniformly dispersed, 40mg dopamine (PDA) is added, the mixture is stirred at room temperature for 5h, 10ml of 8 wt% aqueous solution of polyvinyl pyrrolidone, 10ml acetonitrile and 1ml of 0.1mol/L aqueous solution of ascorbic acid are added, and 0.5ml of 0.01mol/LCuCl is dropwise added while stirring2And (3) reacting the solution for 2 hours, filtering to obtain a solid, and centrifuging and washing three times by a centrifugal machine to obtain Cu0.1-Pt0.9/C @ PDA.
The Pt-Cu/ZnO plasma photocatalyst prepared by the preparation method of the Pt-Cu/ZnO plasma photocatalyst is provided by the invention.
The Pt-Cu/ZnO plasma photocatalyst prepared by the preparation method of the Pt-Cu/ZnO plasma photocatalyst is applied to catalytic degradation of organic pollutant methylene blue.
Compared with single metal, the Pt-Cu alloy particle modified ZnO photocatalyst with the plasma resonance effect can widen the photoresponse range and improve the light utilization rate. In addition, for the alloy particles, the alloy components can be regulated and controlled, and the component effect is exerted, so that the energy band structure of photocatalysis is regulated and controlled, the energy band regulation and control of the photocatalyst are realized, and the photocatalysis efficiency is improved. In addition, the Pt-Cu/ZnO photocatalyst is prepared by a sol-gel method, and the obtained samples are all nano-scale particles which are uniformly distributed.
In the invention, Pt is modified (regulated) ZnO, and the addition of Cu is mainly used for regulating the work function of Pt and modifying Pt, so that the formed PtCu alloy has more advantages than single Pt in removing the modification of the Pt, and the regulation is more reasonable.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the invention provides a preparation method of a Pt-Cu/ZnO plasma photocatalyst, which has the advantages of simple process, low cost, wide raw material range, easy control of the preparation process, high yield and the like.
(2) The invention can realize the energy band regulation of the photocatalyst by regulating and controlling the alloy components, and broadens the photoresponse range in samples of the same grade. The Pt-Cu/ZnO photocatalyst is prepared by a sol-gel method, and the obtained sample is nano-scale particles with uniform size, so that the size effect can be exerted in the photocatalytic process, and the photocatalytic activity is improved. In addition, the catalyst has good catalytic degradation efficiency for degrading methylene blue (organic pollutants).
(3) Because ZnO has a larger forbidden band width (3.2eV) and only responds to ultraviolet light, the ZnO modified by simple substance Pt can expand the photoresponse range and improve the photocatalytic performance, but can not regulate and control the loaded Pt. The Pt-Cu metal alloy is used for modifying the semiconductor, components among metals are changed through component effects among the metals, and the regulation and control of the work function of the metal alloy are realized, so that the photocatalytic energy band structure is regulated and controlled more reasonably, and the photocatalytic performance is improved.
Drawings
FIG. 1 is a flow chart of the preparation of the present invention.
Detailed Description
The present invention is further illustrated by the following examples.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The experimental procedures, in which specific conditions are not indicated in the examples, are generally carried out under conventional conditions or conditions recommended by the manufacturer.
Example 1
1. Preparing a Pt-Cu alloy: adding 49mg of Pt/C (10 wt% Pt) catalyst (alatin) into 75% ethanol aqueous solution by volume fraction, ultrasonically stirring at room temperature for 1h until the catalyst is uniformly dispersed, adding 40mg of dopamine (PDA), stirring at room temperature for 4h, adding 10ml of 5 wt% polyvinyl pyrrolidone aqueous solution (PVP-K30), 6ml of acetonitrile and 4ml of 0.1mol/L ascorbic acid aqueous solution, and dropwise adding 2.5ml of 0.01mol/LCuCl while stirring2Reacting the aqueous solution for 1h, filtering to obtain a solid, and centrifugally washing with deionized water for three times to obtain Cu0.5-Pt0.5/C@PDA。
2. Preparing sol-gel: adding 1.8g of zinc acetate into 50mL of ethanol water solution with volume fraction of 75%, adding 30mL of ethyl acetate solution, heating and stirring to raise the temperature to 70 ℃, stirring for 0.5h, adding all Cu/Pt/C @ PDA obtained in the step (1), stirring to 20mL of sol state at constant temperature of 70 ℃, and drying in a drying oven at 80 ℃ for 10 h.
3. Calcining the sol obtained in the step (2) in an air atmosphere, wherein the temperature rise rate of the calcination is 5 ℃/min, the calcination temperature is 750 ℃, the heat preservation time is 10h, and finally washing the product with deionized water for three times to obtain Pt0.5-Cu0.5/ZnO plasma photocatalyst.
The flow of the preparation process of this example is shown in fig. 1.
Example 2
1. Preparing a Pt-Cu alloy: adding 69mg of Pt/C (10 wt% Pt) catalyst (alatin) into 75% volume fraction ethanol aqueous solution, ultrasonically stirring at room temperature for 1h until the catalyst is uniformly dispersed, adding 40mg of dopamine (PDA), stirring at room temperature for 5h, adding 12ml of 3 wt% polyvinyl pyrrolidone aqueous solution (PVP-K30), 8ml of acetonitrile and 1ml of 0.1mol/L ascorbic acid aqueous solution, and dropwise adding 1.5ml of 0.01mol/LCuCl while stirring2Reacting the aqueous solution for 2 hours, filtering to obtain a solid, and centrifugally washing with deionized water for three times to obtain Cu0.3-Pt0.7/C@PDA。
2. Preparing sol-gel: adding 1.8g of zinc acetate into 50ml of ethanol water solution with volume fraction of 75%, adding 30ml of ethyl acetate solution, heating and stirring to raise the temperature to 75 ℃, stirring for 0.5h, adding all the Cu/Pt/C @ PDA obtained in the step (1), stirring at constant temperature of 70 ℃ to 20ml of sol state, and drying in a drying oven at 80 ℃ for 10 h.
3. Calcining the sol obtained in the step (2) in an air atmosphere, wherein the temperature rise rate of the calcination is 10 ℃/min, the calcination temperature is 800 ℃, the heat preservation time is 8h, and finally washing the product with deionized water for three times to obtain Pt0.7-Cu0.3/ZnO plasma photocatalyst.
Example 3
1. Preparing a Pt-Cu alloy: adding 88mg Pt/C (10 wt% Pt) catalyst (avastin) into 75% ethanol water solution by volume fraction, and ultrasonically stirring at room temperatureStirring for 2 hr until uniformly dispersed, adding 40mg dopamine (PDA), stirring at room temperature for 5 hr, adding 10ml 8 wt% polyvinylpyrrolidone water solution (PVP-K30), 10ml acetonitrile, 1ml 0.1mol/L ascorbic acid water solution, and dropwise adding 0.5ml 0.01mol/LCuCl while stirring2Reacting the solution for 2 hours, filtering to obtain a solid, and centrifugally washing with deionized water for three times to obtain Cu0.1-Pt0.9/C@PDA。
2. Preparing sol-gel: adding 1.8g of zinc acetate into 50ml of ethanol water solution with volume fraction of 75%, adding 30ml of ethyl acetate solution, heating and stirring to raise the temperature to 80 ℃, stirring for 0.5h, adding all the Cu/Pt/C @ PDA obtained in the step (1), stirring to 20ml of sol state at constant temperature of 80 ℃, and drying in a drying oven at 100 ℃ for 12 h.
3. Calcining the sol obtained in the step (2) in an air atmosphere, wherein the temperature rise rate of the calcination is 10 ℃/min, the calcination temperature is 800 ℃, the heat preservation time is 8h, and finally washing the product with deionized water for three times to obtain Pt0.9-Cu0.1/ZnO plasma photocatalyst.
Example 4
1. Preparing a Pt-Cu alloy: adding 20mg of Pt/C (10 wt% Pt) catalyst (alatin) into 75% ethanol aqueous solution by volume fraction, ultrasonically stirring at room temperature for 1h until the solution is uniformly dispersed, adding 40mg of dopamine (PDA), stirring at room temperature for 2h, adding 20ml of 5 wt% polyvinyl pyrrolidone aqueous solution (PVP-K30), 15ml of acetonitrile and 5ml of 0.1mol/L ascorbic acid aqueous solution, and dropwise adding 2.3ml of 0.01mol/L water CuCl while stirring2Reacting the solution for 1h, filtering to obtain a solid, and centrifugally washing with deionized water for three times to obtain Cu0.7-Pt0.3/C@PDA。
2. Preparing sol-gel: adding 1.8g of zinc acetate into 50ml of ethanol water solution with volume fraction of 75%, adding 30ml of ethyl acetate solution, heating and stirring to raise the temperature to 75 ℃, stirring for 0.5h, adding all the Cu/Pt/C @ PDA obtained in the step (1), stirring for 5h at the constant temperature of 75 ℃, allowing the solution to be in a 10ml sol state, drying in a drying oven at 80 ℃ for 10h
3. Calcining the sol obtained in the step (2) in an air atmosphere, wherein the temperature rise speed of the calcination is 5 ℃/min, the calcination temperature is 700 ℃,the heat preservation time is 12h, and the final product is washed three times by deionized water to obtain Pt0.3-Cu0.7/ZnO plasma photocatalyst.
Example 5
Example 5 was prepared identically to example 3, except that: adjusting Pt/C and CuCl2Taking 86mgPt/C (10 wt% Pt) catalyst, and dropping 0.6ml 0.01mol/LCuCl2Solution, making to a molar ratio Pt0.88-Cu0.12/ZnO plasma photocatalyst.
Example 6
Example 6 was prepared identically to example 3, except that: adjusting Pt/C and CuCl2Taking 90mg Pt/C (10 wt% Pt) catalyst, and dropwise adding 0.4ml of 0.01mol/LCuCl2Solution, making to a molar ratio Pt0.92-Cu0.08/ZnO plasma photocatalyst.
Example 7
Example 7 was prepared identically to example 3, except that: adjusting Pt/C and CuCl2In proportion, 93mgPt/C (10 wt% Pt) catalyst was added dropwise to 0.25ml of 0.01mol/LCuCl2Solution, making to a molar ratio Pt0.95-Cu0.05/ZnO plasma photocatalyst.
Example 8
Example 8 was prepared identically to example 3, except that: adjusting Pt/C and CuCl2In proportion, 77.5mg of Pt/C (10 wt% Pt) catalyst was added dropwise to 0.7ml of 0.01mol/LCuCl2Solution, making to a molar ratio Pt0.85-Cu0.15/ZnO plasma photocatalyst.
Comparative example 1
1. Adding 40mg dopamine (PDA) into 50ml ethanol water solution with volume fraction of 75%, stirring for 5h, adding 10ml 8 wt% polyvinyl pyrrolidone water solution (PVP-K30), 10ml acetonitrile, 1ml 0.1mol/L ascorbic acid water solution, and dropwise adding 0.5ml 0.01mol/LCuCl while stirring2And (3) reacting the aqueous solution for 2 hours, filtering to obtain a solid, and centrifugally washing with deionized water for three times to obtain the Cu @ PDA.
2. Preparing sol-gel: adding 1.8g of zinc acetate into 50ml of ethanol water solution with volume fraction of 75%, adding 30ml of ethyl acetate solution, heating and stirring to raise the temperature to 80 ℃, stirring for 0.5h, adding the Cu @ PDA obtained in the step (1), stirring for 5h at constant temperature of 80 ℃, allowing the solution to be in a sol state of 20ml, and drying in a drying oven at 100 ℃ for 12 h.
3. And (3) calcining the sol obtained in the step (2) in an air atmosphere, wherein the calcining temperature rise speed is 10 ℃/min, the calcining temperature is 800 ℃, the heat preservation time is 8h, and finally, washing the product with deionized water for three times to obtain the Cu/ZnO photocatalyst.
Comparative example 2
Comparative example 2 was prepared in the same manner as in example 3, except that CuCl was not added in step (1)2And obtaining the Pt/ZnO photocatalyst.
Test example 1
Methylene blue decomposition test: 100ml of 10mg/L methylene blue was taken, 1g of the sample prepared in the above examples and comparative examples was put in the solution, and after 1 hour of xenon lamp irradiation, the reaction solution was taken and the concentration thereof was measured. The degradation rate of methylene blue can be obtained by the ratio of the concentration of methylene blue after the reaction to the initial concentration, as shown in tables 1 and 2.
TABLE 1
TABLE 2
As can be seen from tables 1 and 2, Pt was prepared in which the molar ratio of Pt to Cu was different between Cu/ZnO in comparative example 1 and examples 1 to 40.5-Cu0.5/ZnO、Pt0.7-Cu0.3/ZnO、Pt0.9-Cu0.1/ZnO、Pt0.3-Cu0.7The degradation rate of the ZnO to the methylene blue is 58.1 percent, 74.3 percent, 78.5 percent, 88.4 percent and 71.6 percent respectively. It can be seen that the catalytic activity of the photocatalytic sample modified with noble metal Pt is significantly enhanced compared to the Cu/ZnO of comparative example 1, andtheoretically, with the increase of the Pt content, the catalytic activity is also enhanced, and compared with the Pt/ZnO of the comparative example 2, the degradation rate is 67.3%, and the catalytic activity is enhanced compared with the Pt/ZnO modified by Pt alone, however, compared with other examples, the catalytic activity is greatly inferior, which shows that the work function of metal Pt can be regulated and controlled by introducing Cu into Pt/ZnO, and the catalytic activity of the photocatalytic sample is improved. In addition, in the experiment of the invention, the activity of the photocatalytic catalyst modified by the noble metal Pt is obviously enhanced, but the photocatalytic catalyst modified by the noble metal Pt has very good degradation effect on methylene blue when the molar ratio of Pt to Cu is 0.9:0.1, and examples 5-8 can change slightly when the ratio is still better than that of a comparative example, but the degradation rate is still better than that of the comparative example, but the effect is obviously reduced and cannot reach more than 80%, while example 3 can reach more than 88% of degradation rate and is improved by more than 10% compared with other examples, so that the synergy is obvious, and the synergistic effect of Pt and Cu is obvious under the specific molar ratio.
Claims (7)
1. A preparation method of a Pt-Cu/ZnO plasma photocatalyst is characterized by comprising the following steps:
(1) preparing a Pt-Cu alloy: adding Pt/C catalyst into ethanol solution, ultrasonically stirring at room temperature until the Pt/C catalyst is uniformly dispersed, adding dopamine (PDA), stirring at room temperature, adding polyvinyl pyrrolidone, acetonitrile and ascorbic acid, and dropwise adding CuCl while stirring2Reacting the solution, filtering to obtain a solid, and centrifugally washing to obtain Cu-Pt/C @ PDA;
(2) preparing sol-gel: adding zinc acetate into an ethanol solution, adding an ethyl acetate solution, heating and stirring, adding the Cu/Pt/C @ PDA obtained in the step (1), stirring at a constant temperature to a sol state, and drying to obtain sol gel;
(3) and (3) calcining the sol gel obtained in the step (2) in an air atmosphere, and washing a product to obtain the Pt-Cu/ZnO plasma photocatalyst.
2. The method for preparing a Pt-Cu/ZnO plasma photocatalyst as claimed in claim 1, wherein the step (1) comprises adding 10-100 mg Pt/C catalyst into ethanol solution, and ultrasonically stirring at room temperatureAfter 1-2h until the dispersion is uniform, adding 10-40 mg of dopamine (PDA), stirring at room temperature for 5-6h, adding 10-20 ml of 3-8 wt% polyvinylpyrrolidone aqueous solution, 6-15 ml of acetonitrile and 1-5 ml of 0.1mol/L ascorbic acid aqueous solution, and dropwise adding 0.5-5 ml of 0.01mol/LCuCl while stirring2The solution is reacted and then filtered to obtain a solid which is washed by centrifugation to obtain Cu-Pt/C @ PDA.
3. The preparation method of the Pt-Cu/ZnO plasma photocatalyst according to claim 1, wherein in the step (2), 1.8-2.0g of zinc acetate is added into 50-60ml of ethanol solution, 30-50 ml of ethyl acetate solution is added, the temperature is raised to 70-80 ℃ by heating and stirring, the stirring is carried out for 0.5-2 h, the Cu/Pt/C @ PDA obtained in the step (1) is added, the stirring is carried out at a constant temperature of 70-80 ℃ to 10-20 ml of sol state, and the obtained product is dried in a drying oven at 80-100 ℃ for 8-12 h.
4. The preparation method of the Pt-Cu/ZnO plasma photocatalyst according to claim 1, wherein in the step (3), the sol-gel obtained in the step (2) is calcined in an air atmosphere at 700-800 ℃, and is kept warm for 8-12 h, and is washed with deionized water to obtain the Pt-Cu/ZnO plasma photocatalyst.
5. The method for preparing Pt-Cu/ZnO plasma photocatalyst as claimed in claim 1, wherein in step (1), 88mg Pt/C catalyst containing 10 wt% Pt is preferably added to the ethanol solution, and after ultrasonic stirring at room temperature for 2h until the catalyst is uniformly dispersed, 40mg dopamine (PDA) is added, stirring is performed at room temperature for 5h, 10ml of 8 wt% aqueous solution of polyvinylpyrrolidone, 10ml of acetonitrile, 1ml of 0.1mol/L aqueous solution of ascorbic acid is added, and 0.5ml of 0.01mol/LCuCl is added dropwise while stirring2And (3) reacting the solution for 2 hours, filtering to obtain a solid, and centrifuging and washing three times by a centrifugal machine to obtain Cu0.1-Pt0.9/C @ PDA.
6. A Pt-Cu/ZnO plasma photocatalyst prepared by the method of preparing a Pt-Cu/ZnO plasma photocatalyst of claim 1.
7. An application of the Pt-Cu/ZnO plasma photocatalyst prepared by the preparation method of the Pt-Cu/ZnO plasma photocatalyst disclosed by claim 1 in catalytic degradation of organic pollutant methylene blue.
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| CN114505102A (en) * | 2022-03-08 | 2022-05-17 | 河北科技师范学院 | ZnO @ PDA/Ag-Ag2O nano composite material and preparation method and application thereof |
| CN115591559A (en) * | 2022-09-16 | 2023-01-13 | 武汉榆汐科技有限公司（Cn） | Preparation method of PtCu alloy ternary heterojunction photocatalyst, product and application thereof |
| CN116328778A (en) * | 2023-04-06 | 2023-06-27 | 吉林大学 | Plasmon metallic copper-metal oxide composite structure catalyst and method for catalyzing gas phase formic acid to prepare hydrogen under room temperature visible light |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391008A (en) * | 2016-09-21 | 2017-02-15 | 苏州大学 | Method for loading three-dimensional zinc oxide surface with metal nanoparticles |
| CN107790127A (en) * | 2017-11-13 | 2018-03-13 | 盐城工学院 | A kind of Pt Ag/WO3Plasma photocatalysis agent and its preparation method and application |
-
2021
- 2021-02-01 CN CN202110140057.1A patent/CN112973728B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391008A (en) * | 2016-09-21 | 2017-02-15 | 苏州大学 | Method for loading three-dimensional zinc oxide surface with metal nanoparticles |
| CN107790127A (en) * | 2017-11-13 | 2018-03-13 | 盐城工学院 | A kind of Pt Ag/WO3Plasma photocatalysis agent and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| PARAMASIVAN GOMATHISANKAR ET AL.: ""Enhanced photocatalytic hydrogen production from aqueous methanol solution using ZnO with simultaneous photodeposition of Cu"", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| PENGYU DONG ET AL.: ""Highly enhanced photocatalytic activity of WO3 thin films loaded with Pt–Ag bimetallic alloy nanoparticles"", 《RSC ADVANCES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114505102A (en) * | 2022-03-08 | 2022-05-17 | 河北科技师范学院 | ZnO @ PDA/Ag-Ag2O nano composite material and preparation method and application thereof |
| CN114505102B (en) * | 2022-03-08 | 2023-08-22 | 河北科技师范学院 | ZnO@PDA/Ag-Ag 2 O nanocomposite and preparation method and application thereof |
| CN115591559A (en) * | 2022-09-16 | 2023-01-13 | 武汉榆汐科技有限公司（Cn） | Preparation method of PtCu alloy ternary heterojunction photocatalyst, product and application thereof |
| CN116328778A (en) * | 2023-04-06 | 2023-06-27 | 吉林大学 | Plasmon metallic copper-metal oxide composite structure catalyst and method for catalyzing gas phase formic acid to prepare hydrogen under room temperature visible light |
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