CN112973687A - Silver/bismuth tungstate composite photocatalytic material and preparation method thereof - Google Patents
Silver/bismuth tungstate composite photocatalytic material and preparation method thereof Download PDFInfo
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- CN112973687A CN112973687A CN202110255115.5A CN202110255115A CN112973687A CN 112973687 A CN112973687 A CN 112973687A CN 202110255115 A CN202110255115 A CN 202110255115A CN 112973687 A CN112973687 A CN 112973687A
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 93
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 91
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 55
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 51
- 239000004332 silver Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 239000008367 deionised water Substances 0.000 claims abstract description 38
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 38
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims abstract description 35
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 28
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 19
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims abstract description 15
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 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 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
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Abstract
The invention provides a silver/bismuth tungstate composite photocatalytic material and a preparation method thereof, wherein the preparation method comprises the following steps: respectively adding bismuth nitrate pentahydrate and sodium tungstate dihydrate into deionized water, stirring and carrying out ultrasonic treatment to obtain solution A and solution B; dripping the B liquid into the A liquid, stirring and carrying out ultrasonic treatment to obtain a C liquid, and carrying out heat preservation, washing and drying to obtain a bismuth tungstate photocatalyst; adding polyethylene glycol 4000 and polyvinylpyrrolidone into deionized water, performing ultrasonic treatment, adding bismuth tungstate, performing ultrasonic treatment and stirring, adding a silver nitrate solution, stirring under the condition of ultraviolet irradiation, washing, and drying to obtain the silver/bismuth tungstate composite photocatalytic material. The invention also comprises the composite photocatalytic material prepared by the method. The silver/bismuth tungstate composite photocatalytic material is prepared by a simple photoreduction method, and the problems of narrow photoresponse range, high photo-generated charge recombination rate, relatively poor stability and the like in the prior art are effectively solved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a silver/bismuth tungstate composite photocatalytic material and a preparation method thereof.
Background
With the rapid development of the human society, the environmental pollution problem is increasingly aggravated, and great challenges are brought to the global sustainable development. The semiconductor photocatalysis technology has the outstanding characteristics of low cost, simple operation, high-efficiency degradation of organic pollutants, less secondary pollution and the like, becomes a new environmental management means in recent years, and has attracted extensive attention of people for searching high-efficiency photocatalysts.
Bismuth tungstate (Bi)2WO6) Is a novel photocatalytic material with narrow band gap, high visible light catalytic activity, stable chemical property, flaky crystal and easy self-assembly into various shapes, and is different from common photocatalysts, such as TiO2、ZnO、Cu2O and Fe3O4Etc. bismuth tungstate has a structure of Bi2O2 2+Fluorite layer and WO4 2-According to related reports, the perovskite layered structure formed by the octahedral layers alternately has more excellent semiconductor performance in the aspects of application efficiency of photocatalytic degradation of organic matters and light quanta. However, bismuth tungstate still has two problems of narrow photoresponse range and high photo-generated charge recombination rate, the photocatalytic activity of the photocatalyst is seriously influenced, and the practical application of the bismuth tungstate photocatalytic material is greatly limited.
In recent years, people mainly solve the problems by regulating morphology of the bismuth tungstate photocatalytic material, compounding semiconductors and the like. However, the prior reported preparation methods of mesoporous bismuth tungstate microspheres and bismuth tungstate nanofiber cloth have relatively complex controllable synthesis process of morphological structures; a preparation method for forming a heterojunction by compounding bismuth tungstate with different semiconductors is also reported, but the stability of the composite material is relatively poor.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the silver/bismuth tungstate composite photocatalytic material and the preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the silver/bismuth tungstate composite photocatalytic material comprises the following steps:
(1) respectively adding bismuth nitrate pentahydrate and sodium tungstate dihydrate into deionized water, stirring at room temperature for 10-20min, and performing ultrasonic treatment for 10-20min to obtain solution A and solution B; dripping the solution B into the solution A, continuously stirring for 50-70min, and performing ultrasonic treatment for 20-40min to obtain solution C; adding the solution C into a reaction kettle, preserving the heat for 10-14h at the temperature of 190 ℃ below zero and 170 ℃, washing the solution C for 2-4 times by using distilled water and absolute ethyl alcohol in sequence, and finally drying the solution C for 22-26h at the temperature of 50-70 ℃ to obtain a bismuth tungstate photocatalyst;
(2) adding polyethylene glycol 4000 and polyvinylpyrrolidone into deionized water, performing ultrasonic treatment until the polyethylene glycol 4000 and the polyvinylpyrrolidone are completely dissolved, stirring for 10-20min, then adding bismuth tungstate, performing ultrasonic treatment and stirring uniformly, then adding a silver nitrate solution with the concentration of 1-8g/L under a dark condition, stirring for 20-40min in a water bath kettle at the temperature of 40-60 ℃, stirring for 50-70min under the irradiation condition of 30-34W of ultraviolet light, washing for 2-4 times by using distilled water and absolute ethyl alcohol in sequence, and finally drying for 22-26h at the temperature of 50-70 ℃ to obtain the silver/bismuth tungstate composite photocatalytic material.
Further, in the step (1), the mass volume ratio of the pentahydrate bismuth nitrate to the deionized water is 1.8-2:60g/ml, and the mass volume ratio of the sodium tungstate dihydrate to the deionized water is 0.6-0.7:20 g/ml.
Further, the mass volume ratio of the bismuth nitrate pentahydrate to the deionized water is 1.942:60g/ml, and the mass volume ratio of the sodium tungstate dihydrate to the deionized water is 0.658:20 g/ml.
Further, in the step (2), the mass ratio of the polyethylene glycol 4000 to the polyvinylpyrrolidone is 1: 1; the mass-volume ratio of the polyethylene glycol 4000 to the deionized water is 0.1-0.2:50 g/ml.
Further, the mass-volume ratio of the polyethylene glycol 4000 to the deionized water is 0.15:50 g/ml.
Further, in the step (2), the mass ratio of the polyethylene glycol 4000 to the bismuth tungstate is 0.15: 0.5-0.6.
Further, the mass ratio of the polyethylene glycol 4000 to the bismuth tungstate is 0.15: 0.58.
Further, in the step (1) and the step (2), drying is carried out at a temperature of 60 ℃ for 24 hours.
The silver/bismuth tungstate composite photocatalytic material is prepared by the preparation method of the silver/bismuth tungstate composite photocatalytic material.
The silver/bismuth tungstate composite photocatalytic material is applied to photocatalysis.
In summary, the invention has the following advantages:
1. the invention prepares silver/bismuth tungstate (Ag/Bi) by a simple photoreduction method2WO6) The composite photocatalytic material has simple and controllable preparation process, widens the response range of bismuth tungstate visible light, enhances the separation efficiency of bismuth tungstate photon-generated carriers, improves the photocatalytic efficiency, and effectively solves the problems of narrow photoresponse range, high photon-generated charge recombination rate, relatively poor stability and the like in the prior art. The prepared silver/bismuth tungstate composite photocatalytic material has the degradation rate of over 99 percent to rhodamine B within 120min by taking the rhodamine B as a target pollutant, and has important application in environmental pollution such as sewage treatment and the like.
2. The invention carries out noble metal doping modification on the bismuth tungstate photocatalytic material, prepares the silver/bismuth tungstate composite photocatalytic material by a simple photoreduction method, widens the response range of bismuth tungstate visible light, enhances the separation efficiency of bismuth tungstate photon-generated carriers, and greatly improves the photocatalytic efficiency. The silver can be used as an electron acceptor to promote the separation of photogenerated electron-hole pairs and the transfer of interface electrons, and the plasma donor on the surface of the silver can improve the catalytic activity of the bismuth tungstate under the irradiation of visible light. The method takes rhodamine B as a target pollutant, the degradation rate of the prepared silver/bismuth tungstate composite photocatalytic material to the rhodamine B can reach more than 96% within 100min, and the method has important application in environmental pollution such as sewage treatment and the like, while the degradation rate of the bismuth tungstate photocatalytic material synthesized by adopting a conventional hydrothermal method can only reach 89%. Meanwhile, the preparation method is simple, short in time, low in cost, high in safety and capable of being widely popularized and used.
Drawings
FIG. 1 is a photocatalytic degradation curve of a silver/bismuth tungstate composite photocatalytic material;
FIG. 2 is an EDS spectrogram of the silver/bismuth tungstate composite photocatalytic material;
FIG. 3 is a TEM spectrogram and an HRTRM image of the silver/bismuth tungstate composite photocatalytic material;
FIG. 4 shows PL spectrum, UV-Vis DRS spectrum and forbidden band width of bismuth tungstate and silver/bismuth tungstate composite photocatalytic material.
Detailed Description
Example 1
A silver/bismuth tungstate composite photocatalytic material is prepared by the following steps:
(1) respectively adding bismuth nitrate pentahydrate and sodium tungstate dihydrate into deionized water, stirring at room temperature for 10min, and performing ultrasonic treatment for 10min to obtain solution A and solution B; dripping the solution B into the solution A, continuously stirring for 50min, and performing ultrasonic treatment for 20min to obtain solution C; adding the solution C into a reaction kettle, preserving the heat for 10 hours at the temperature of 170 ℃, washing the solution C with distilled water and absolute ethyl alcohol for 2 times, and finally drying the solution C for 22 hours at the temperature of 50 ℃ to obtain a bismuth tungstate photocatalyst; the mass volume ratio of the bismuth nitrate pentahydrate to the deionized water is 1.8:60g/ml, and the mass volume ratio of the sodium tungstate dihydrate to the deionized water is 0.6:20 g/ml;
(2) adding polyethylene glycol 4000 and polyvinylpyrrolidone into deionized water, performing ultrasonic treatment until the polyethylene glycol 4000 and the polyvinylpyrrolidone are completely dissolved, stirring for 10min, then adding bismuth tungstate, performing ultrasonic treatment and stirring uniformly, adding a silver nitrate solution with the concentration of 1g/L under a dark condition, stirring for 20min in a water bath kettle at the temperature of 40 ℃, stirring for 50min under the irradiation condition of 30W ultraviolet light, washing for 2 times by using distilled water and absolute ethyl alcohol in sequence, and finally drying for 22h at the temperature of 50 ℃ to obtain the silver/bismuth tungstate composite photocatalytic material. The mass ratio of the polyethylene glycol 4000 to the polyvinylpyrrolidone is 1: 1; the mass-volume ratio of the polyethylene glycol 4000 to the deionized water is 0.1:50 g/ml; the mass ratio of the polyethylene glycol 4000 to the bismuth tungstate is 0.15: 0.5.
Example 2
A silver/bismuth tungstate composite photocatalytic material is prepared by the following steps:
(1) respectively adding bismuth nitrate pentahydrate and sodium tungstate dihydrate into deionized water, stirring at room temperature for 15min, and performing ultrasonic treatment for 15min to obtain solution A and solution B; dripping the solution B into the solution A, continuously stirring for 60min, and performing ultrasonic treatment for 25min to obtain solution C; adding the solution C into a reaction kettle, preserving the heat for 11 hours at the temperature of 175 ℃, washing for 3 times by using distilled water and absolute ethyl alcohol in sequence, and finally drying for 24 hours at the temperature of 55 ℃ to obtain a bismuth tungstate photocatalyst; the mass volume ratio of the bismuth nitrate pentahydrate to the deionized water is 1.92:60g/ml, and the mass volume ratio of the sodium tungstate dihydrate to the deionized water is 0.65:20 g/ml;
(2) adding polyethylene glycol 4000 and polyvinylpyrrolidone into deionized water, performing ultrasonic treatment until the polyethylene glycol 4000 and the polyvinylpyrrolidone are completely dissolved, stirring for 15min, then adding bismuth tungstate, performing ultrasonic treatment and stirring uniformly, adding a silver nitrate solution with a concentration of 3g/L under a dark condition, stirring for 25min in a water bath kettle at a temperature of 50 ℃, stirring for 55min under the irradiation condition of 314W ultraviolet light, washing for 3 times by using distilled water and absolute ethyl alcohol in sequence, and finally drying for 24h at a temperature of 55 ℃ to obtain the silver/bismuth tungstate composite photocatalytic material. The mass ratio of the polyethylene glycol 4000 to the polyvinylpyrrolidone is 1: 1; the mass-volume ratio of the polyethylene glycol 4000 to the deionized water is 0.13:50 g/ml; the mass ratio of the polyethylene glycol 4000 to the bismuth tungstate is 0.15: 0.55.
Example 3
A silver/bismuth tungstate composite photocatalytic material is prepared by the following steps:
(1) respectively adding bismuth nitrate pentahydrate and sodium tungstate dihydrate into deionized water, stirring at room temperature for 15min, and performing ultrasonic treatment for 15min to obtain solution A and solution B; dripping the solution B into the solution A, continuously stirring for 60min, and performing ultrasonic treatment for 30min to obtain solution C; adding the solution C into a reaction kettle, preserving the heat for 12 hours at the temperature of 180 ℃, washing the solution C with distilled water and absolute ethyl alcohol for 3 times, and finally drying the solution C for 24 hours at the temperature of 60 ℃ to obtain a bismuth tungstate photocatalyst; the mass volume ratio of the bismuth nitrate pentahydrate to the deionized water is 1.942:60g/ml, and the mass volume ratio of the sodium tungstate dihydrate to the deionized water is 0.658:20 g/ml;
(2) adding polyethylene glycol 4000 and polyvinylpyrrolidone into deionized water, performing ultrasonic treatment until the polyethylene glycol 4000 and the polyvinylpyrrolidone are completely dissolved, stirring for 15min, then adding bismuth tungstate, performing ultrasonic treatment and stirring uniformly, adding a silver nitrate solution with a concentration of 4g/L under a dark condition, stirring for 30min in a water bath kettle at a temperature of 50 ℃, stirring for 60min under a 32W ultraviolet irradiation condition, washing for 3 times by using distilled water and absolute ethyl alcohol in sequence, and finally drying for 24h at a temperature of 60 ℃ to obtain the silver/bismuth tungstate composite photocatalytic material. The mass ratio of the polyethylene glycol 4000 to the polyvinylpyrrolidone is 1: 1; the mass-volume ratio of the polyethylene glycol 4000 to the deionized water is 0.15:50 g/ml; the mass ratio of the polyethylene glycol 4000 to the bismuth tungstate is 0.15: 0.58.
Example 4
A silver/bismuth tungstate composite photocatalytic material is prepared by the following steps:
(1) respectively adding bismuth nitrate pentahydrate and sodium tungstate dihydrate into deionized water, stirring at room temperature for 20min, and performing ultrasonic treatment for 20min to obtain solution A and solution B; dripping the solution B into the solution A, continuously stirring for 70min, and performing ultrasonic treatment for 40min to obtain solution C; adding the solution C into a reaction kettle, preserving the heat for 14 hours at the temperature of 190 ℃, washing the solution C with distilled water and absolute ethyl alcohol for 4 times in sequence, and finally drying the solution C for 26 hours at the temperature of 70 ℃ to obtain a bismuth tungstate photocatalyst; the mass volume ratio of the bismuth nitrate pentahydrate to the deionized water is 2:60g/ml, and the mass volume ratio of the sodium tungstate dihydrate to the deionized water is 0.7:20 g/ml;
(2) adding polyethylene glycol 4000 and polyvinylpyrrolidone into deionized water, performing ultrasonic treatment until the polyethylene glycol 4000 and the polyvinylpyrrolidone are completely dissolved, stirring for 20min, then adding bismuth tungstate, performing ultrasonic treatment and stirring uniformly, adding a silver nitrate solution with a concentration of 8g/L under a dark condition, stirring for 40min in a water bath kettle at a temperature of 60 ℃, stirring for 70min under the irradiation condition of 34W ultraviolet light, washing for 4 times by using distilled water and absolute ethyl alcohol in sequence, and finally drying for 26h at a temperature of 70 ℃ to obtain the silver/bismuth tungstate composite photocatalytic material. The mass ratio of the polyethylene glycol 4000 to the polyvinylpyrrolidone is 1: 1; the mass-volume ratio of the polyethylene glycol 4000 to the deionized water is 0.2:50 g/ml; the mass ratio of the polyethylene glycol 4000 to the bismuth tungstate is 0.15: 0.5.
Experimental example 1
By adopting the preparation method shown in example 3, silver nitrate solutions with concentrations of 1g/L, 2g/L, 4g/L and 8g/L are respectively adopted to prepare different silver/bismuth tungstate composite photocatalytic materials which are respectively marked as S1, S2, S3 and S4, and then a photocatalytic degradation experiment is carried out, and the result is shown in figure 1.
Photocatalytic degradation experiment:
selecting a RhB solution as a target degradation product, wherein the reaction temperature is room temperature, and the light source is a 400W xenon lamp. Adding 50mg of silver/bismuth tungstate composite photocatalytic material into 50ml of RhB solution with the concentration of 10mg/L, and stirring for 30min under the dark condition to ensure that the photocatalyst and the RhB are uniformly mixed and achieve adsorption-desorption balance. Placing the solution with adsorption-desorption balance under xenon lamp for photocatalytic degradation experiment, wherein the distance from the bottom of the lamp to the liquid surface is 10cm, placing 4ml of supernatant into a centrifuge tube every 20min, centrifuging with high speed desk centrifuge (rotation speed of 4000r/min for 5min) to remove catalyst powder, collecting supernatant, and measuring its absorbance (lambda) with ultraviolet-visible spectrophotometerMax553nm) according to Lambert-Beer's law, the concentrations of RhB solutions at different times were obtained and the degradation rates were calculated.
As can be seen from figure 1, the degradation rate of the silver/bismuth tungstate composite photocatalytic material to rhodamine B can reach more than 99% within 120min, and the photocatalytic performance of bismuth tungstate is greatly improved. The degradation rate of the bismuth tungstate photocatalytic material synthesized by the conventional hydrothermal method can only reach 89.9%.
Experimental example 2
And respectively obtaining an EDS spectrogram, a TEM spectrogram and an HRTRM image of the silver/bismuth tungstate composite photocatalytic material (S2), wherein the EDS spectrogram, the TEM spectrogram and the HRTRM image are respectively 2-3. In the 4 th diagram of FIG. 2, the peaks are Ag, W, O-kal, W, Bi, Ag, W and Bi in the order from top to bottom and from left to right; in FIG. 3, a-c are TEM spectra, d is HRTRM image, and in FIG. d, the upper part is Bi2WO6(002)0.271nm and 0.234nm for Ag (111) in the lower part.
As can be seen from FIG. 2, the silver/bismuth tungstate composite photocatalytic material obtained by the method has silver and is uniformly distributed. As can be seen from FIG. 3, 5-10nm Ag nanoparticles were uniformly distributed on the bismuth tungstate nanosheets, with a interplanar spacing of 0.271nm corresponding to Bi2WO6And the interplanar spacing of 0.234nm corresponds to the (111) crystal plane of the Ag nano-particles。
Then, PL spectrum, UV-Vis DRS spectrum and forbidden bandwidth of the bismuth tungstate and silver/bismuth tungstate composite photocatalytic material are respectively obtained, as shown in FIG. 4. Wherein a is PL spectrum, b is UV-VisDRS spectrum, c is forbidden bandwidth.
As can be seen from FIG. 4, at the excitation wavelength of 325, the bismuth tungstate has a wider emission band of 350-600nm, and the strongest emission peak appears at 467 nm; after bismuth tungstate is compounded with Ag, the intensity of an S2 peak is obviously reduced, and the recombination rate of photo-generated electrons and holes is reduced; meanwhile, the absorption capacity of S2 to light is improved, the light response range is enlarged, and the forbidden bandwidth is reduced.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (10)
1. A preparation method of a silver/bismuth tungstate composite photocatalytic material is characterized by comprising the following steps:
(1) respectively adding bismuth nitrate pentahydrate and sodium tungstate dihydrate into deionized water, stirring at room temperature for 10-20min, and performing ultrasonic treatment for 10-20min to obtain solution A and solution B; dripping the solution B into the solution A, continuously stirring for 50-70min, and performing ultrasonic treatment for 20-40min to obtain solution C; adding the solution C into a reaction kettle, preserving the heat for 10-14h at the temperature of 190 ℃ below zero and 170 ℃, washing the solution C for 2-4 times by using distilled water and absolute ethyl alcohol in sequence, and finally drying the solution C for 22-26h at the temperature of 50-70 ℃ to obtain a bismuth tungstate photocatalyst;
(2) adding polyethylene glycol 4000 and polyvinylpyrrolidone into deionized water, performing ultrasonic treatment until the polyethylene glycol 4000 and the polyvinylpyrrolidone are completely dissolved, stirring for 10-20min, then adding bismuth tungstate, performing ultrasonic treatment and stirring uniformly, then adding a silver nitrate solution with the concentration of 1-8g/L under a dark condition, stirring for 20-40min in a water bath kettle at the temperature of 40-60 ℃, stirring for 50-70min under the irradiation condition of 30-34W of ultraviolet light, washing for 2-4 times by using distilled water and absolute ethyl alcohol in sequence, and finally drying for 22-26h at the temperature of 50-70 ℃ to obtain the silver/bismuth tungstate composite photocatalytic material.
2. The preparation method of the silver/bismuth tungstate composite photocatalytic material as claimed in claim 1, wherein in the step (1), the mass-to-volume ratio of the bismuth nitrate pentahydrate to the deionized water is 1.8-2:60g/ml, and the mass-to-volume ratio of the sodium tungstate dihydrate to the deionized water is 0.6-0.7:20 g/ml.
3. The preparation method of the silver/bismuth tungstate composite photocatalytic material as claimed in claim 2, wherein the mass-to-volume ratio of the bismuth nitrate pentahydrate to the deionized water is 1.942:60g/ml, and the mass-to-volume ratio of the sodium tungstate dihydrate to the deionized water is 0.658:20 g/ml.
4. The preparation method of the silver/bismuth tungstate composite photocatalytic material as claimed in claim 1, wherein in the step (2), the mass ratio of the polyethylene glycol 4000 to the polyvinylpyrrolidone is 1: 1; the mass-volume ratio of the polyethylene glycol 4000 to the deionized water is 0.1-0.2:50 g/ml.
5. The preparation method of the silver/bismuth tungstate composite photocatalytic material as claimed in claim 1, wherein the mass-to-volume ratio of the polyethylene glycol 4000 to the deionized water is 0.15:50 g/ml.
6. The preparation method of the silver/bismuth tungstate composite photocatalytic material as claimed in claim 1, wherein in the step (2), the mass ratio of the polyethylene glycol 4000 to the bismuth tungstate is 0.15: 0.5-0.6.
7. The preparation method of the silver/bismuth tungstate composite photocatalytic material as claimed in claim 1, wherein the mass ratio of the polyethylene glycol 4000 to the bismuth tungstate is 0.15: 0.58.
8. The method for preparing the silver/bismuth tungstate composite photocatalytic material as claimed in claim 1, wherein in the step (1) and the step (2), the silver/bismuth tungstate composite photocatalytic material is dried at a temperature of 60 ℃ for 24 hours.
9. The silver/bismuth tungstate composite photocatalytic material prepared by the preparation method of the silver/bismuth tungstate composite photocatalytic material as claimed in any one of claims 1 to 8.
10. The use of the silver/bismuth tungstate composite photocatalytic material of claim 9 in photocatalysis.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114345380A (en) * | 2022-01-18 | 2022-04-15 | 西南交通大学 | Bismuth oxychloride/bismuth tungstate nano-catalyst and preparation method and application thereof |
| CN115445616A (en) * | 2022-10-21 | 2022-12-09 | 厦门理工学院 | Preparation method and application of silver-doped bismuth tungstate heterojunction photocatalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040198625A1 (en) * | 2001-06-28 | 2004-10-07 | Mckechnie Malcolm Tom | Photocatalytic composition |
| CN102294246A (en) * | 2011-06-11 | 2011-12-28 | 西南交通大学 | Preparation method for Cu2O/ZnO heterojunction |
| CN102764653A (en) * | 2011-05-06 | 2012-11-07 | 中国科学院合肥物质科学研究院 | Silver-modified bismuth tungstate composite photocatalyst, its preparation method and application thereof |
| CN104190449A (en) * | 2014-08-20 | 2014-12-10 | 江苏大学 | Preparation method for hollow Ag/AgCl nano-structure photocatalysis material |
| CN106362742A (en) * | 2016-08-31 | 2017-02-01 | 暨南大学 | Ag/ZnO nano-composite, preparation method thereof and application of composite |
| CN109847771A (en) * | 2019-03-05 | 2019-06-07 | 桂林理工大学 | A kind of bismuth tungstate-carbonitride-silver orthophosphate ternary efficient visible light catalyst and preparation method thereof |
| WO2021034268A1 (en) * | 2019-08-19 | 2021-02-25 | Singapore University Of Technology And Design | Visible-light-driven design of bismuth-based photocatalytic degrading material |
-
2021
- 2021-03-09 CN CN202110255115.5A patent/CN112973687A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040198625A1 (en) * | 2001-06-28 | 2004-10-07 | Mckechnie Malcolm Tom | Photocatalytic composition |
| CN102764653A (en) * | 2011-05-06 | 2012-11-07 | 中国科学院合肥物质科学研究院 | Silver-modified bismuth tungstate composite photocatalyst, its preparation method and application thereof |
| CN102294246A (en) * | 2011-06-11 | 2011-12-28 | 西南交通大学 | Preparation method for Cu2O/ZnO heterojunction |
| CN104190449A (en) * | 2014-08-20 | 2014-12-10 | 江苏大学 | Preparation method for hollow Ag/AgCl nano-structure photocatalysis material |
| CN106362742A (en) * | 2016-08-31 | 2017-02-01 | 暨南大学 | Ag/ZnO nano-composite, preparation method thereof and application of composite |
| CN109847771A (en) * | 2019-03-05 | 2019-06-07 | 桂林理工大学 | A kind of bismuth tungstate-carbonitride-silver orthophosphate ternary efficient visible light catalyst and preparation method thereof |
| WO2021034268A1 (en) * | 2019-08-19 | 2021-02-25 | Singapore University Of Technology And Design | Visible-light-driven design of bismuth-based photocatalytic degrading material |
Non-Patent Citations (3)
| Title |
|---|
| SHUISHENG WU等: ""Photoinduced Synthesis of Hierarchical Flower-Like Ag/Bi2WO6 Microspheres as an Efficient Visible Light Photocatalyst"", 《INTERNATIONAL JOURNAL OF PHOTOENERGY》 * |
| 李远勋等: "《功能材料的制备与性能表征》", 30 September 2018, 西南交通大学出版社 * |
| 王婕: ""四针状氧化锌晶须的表面改性及其光催化性能研究"", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114345380A (en) * | 2022-01-18 | 2022-04-15 | 西南交通大学 | Bismuth oxychloride/bismuth tungstate nano-catalyst and preparation method and application thereof |
| CN115445616A (en) * | 2022-10-21 | 2022-12-09 | 厦门理工学院 | Preparation method and application of silver-doped bismuth tungstate heterojunction photocatalyst |
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