CN116273097A - Bi/BiPMo 12 O 40 Composite photocatalyst and preparation method and application thereof - Google Patents
Bi/BiPMo 12 O 40 Composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN116273097A CN116273097A CN202211386288.1A CN202211386288A CN116273097A CN 116273097 A CN116273097 A CN 116273097A CN 202211386288 A CN202211386288 A CN 202211386288A CN 116273097 A CN116273097 A CN 116273097A
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 150000001621 bismuth Chemical class 0.000 claims abstract description 15
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002077 nanosphere Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 16
- 239000003242 anti bacterial agent Substances 0.000 claims description 7
- 229940088710 antibiotic agent Drugs 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 10
- 229940012189 methyl orange Drugs 0.000 abstract description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 8
- 239000004098 Tetracycline Substances 0.000 abstract description 7
- 235000019364 tetracycline Nutrition 0.000 abstract description 7
- 150000003522 tetracyclines Chemical class 0.000 abstract description 7
- 229960002180 tetracycline Drugs 0.000 abstract description 6
- 229930101283 tetracycline Natural products 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000004005 microsphere Substances 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 229910001430 chromium ion Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- PDDXOPNEMCREGN-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum;hydrate Chemical compound O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O PDDXOPNEMCREGN-UHFFFAOYSA-N 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
- B01J27/192—Molybdenum with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention belongs to the technical field of photocatalysis, and discloses a metal simple substance Bi nanosphere modified BiPMo 12 O 40 Microsphere formation of Bi/BiPMo 12 O 40 Adding soluble bismuth salt and phosphomolybdic acid into deionized water, mixing and stirring uniformly, and cooling to room temperature after heating for reaction to obtain the bismuth phosphomolybdate; then adding the prepared bismuth phosphomolybdate and soluble bismuth salt into glycol solution, stirring by ultrasonic, and performing hydrothermal reaction to obtain Bi/BiPMo with high-efficiency photocatalytic performance 12 O 40 A composite photocatalyst. The photocatalyst obtained by the method can degrade methyl orange to 97.5%, degrade tetracycline to 77.5%, reduce hexavalent chromium to 89.33%, and maintain good degradation performance and stability after eight times of degradation cycle.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a metal simple substance Bi nanosphere modified BiPMo 12 O 40 Microsphere formation of Bi/BiPMo 12 O 40 A method for compounding a photocatalyst.
Background
Antibiotics and textile printing and dyeing wastewater are serious water pollution, and seriously threaten the health of people. Thus, degradation of organic contaminants such as antibiotics, dyes, and hexavalent chromium ions in wastewater is a very important issue. The photocatalysis technology has the advantages of green and low energy consumption, has potential value in the aspect of environmental purification, and is an important technology for degrading organic pollutants in wastewater.
Bismuth-based photocatalysts have unique electronic structures and excellent visible light absorption capacity, and are of great interest to researchers because of their good catalytic degradation performance on refractory organic compounds under irradiation of visible light. Phosphomolybdic acid has good catalytic effect and huge application potential, and is a hotspot for sewage treatment, and research interests of scientists are aroused. However, the photo-generated carrier has low light absorption capability and high complexity, so that the dissolution rate of phosphomolybdic acid in water is limited, the recovery rate of the phosphomolybdic acid as a catalyst is low, the photocatalytic activity and the like are required to be further improved. In this respect, it is important to develop a new strategy to increase the photoreaction efficiency and to suppress the photoelectron-hole pair complexation.
Disclosure of Invention
In view of the above, the invention provides a catalyst capable of efficiently catalyzing and oxidizing methylene dichloride at a lower temperature and a preparation method thereof, aiming at the defects of complex preparation process, low catalytic efficiency, easy deactivation caused by chlorine poisoning, excessive decomposition temperature of chlorinated alkane, excessive byproducts and the like of the existing gas-phase catalytic chlorocarbon catalyst.
It should be noted that bismuth is a non-noble metal, is an ideal substitute for noble metals, and the bismuth-based photocatalyst has a unique electronic structure and good visible light absorption performance, provides good catalytic action on organic compounds which are difficult to degrade under irradiation of visible light, is relatively inexpensive and nontoxic, and has unique photoelectric properties, and when compounded with other semiconductors, the photocatalytic performance is remarkably improved by synergistic action after compounding with other semiconductors.
The invention takes phosphomolybdic acid and soluble bismuth salt (bismuth nitrate) as raw materials and synthesizes Bi/BiPMo by adopting a hydrothermal one-step method 12 O 40 Nanosphere composite materials. Under the irradiation of ultraviolet and visible light, biPMo 12 O 40 Some Bi in nanospheres 3+ Is reduced to Bi-NPs by in-situ light to form Bi/BiPMo 12 O 40 Composite material, enhanced Bi/BiPMo 12 O 40 Is a visible light absorption of (a).
In addition, SPR generates strong local electromagnetic field to accelerate Bi/BiPMo 12 O 40 Intermediate photoproduction e and h + Is a charge separation of (a). Therefore, bi/BiPMo synthesized by the present invention 12 O 40 The composite photocatalyst is prepared by using visible light (lambda)>420 nm) shows high-efficiency and durable photocatalytic performance under irradiation.
In order to achieve the above object, the present invention provides the following technical solutions:
Bi/BiPMo 12 O 40 The preparation method of the composite photocatalyst specifically comprises the following steps:
1) Adding soluble bismuth salt and phosphomolybdic acid into deionized water, mixing and stirring uniformly, cooling to room temperature after heating for reaction, and drying to obtain the phosphomolybdic acid bismuth;
2) Adding the bismuth phosphomolybdate and the soluble bismuth salt prepared in the step 1) into glycol solution, carrying out ultrasonic stirring and hydrothermal reaction, filtering and drying to obtain Bi/BiPMo with high-efficiency photocatalytic performance 12 O 40 A composite photocatalyst.
Optionally, in step 1), the molar ratio of the soluble bismuth salt to the phosphomolybdic acid is 1:1, and the volume of deionized water is 10mL; the heating reaction temperature is 50-80 ℃, and the heating reaction time is 2-4h.
Further, the drying temperature in the step 1) is 60-120 ℃ and the drying time is 4-8h.
Optionally, in the step 2), the molar ratio of the bismuth phosphomolybdate to the soluble bismuth salt is 10:1, the hydrothermal reaction temperature is 160-200 ℃, and the hydrothermal reaction time is 8-12h.
Further, the drying temperature in the step 2) is 60-120 ℃ and the drying time is 4-8h.
Further, the bismuth phosphomolybdate BiPMo 12 O 40 Adding reducer glycol, ultrasonic treating for 30min, and stirring for 6 hr.
And the soluble bismuth salt is bismuth nitrate, bismuth chloride, bismuth acetate and other soluble bismuth salts, the phosphomolybdic acid is phosphomolybdic acid hydrate, and the ethylene glycol is analytically pure 98%.
The invention also claims a Bi/BiPMo prepared by the method 12 O 40 Composite photocatalyst, the Bi/BiPMo 12 O 40 The diameter size of the composite photocatalyst is 50-100nm, and the composite photocatalyst is a nano spherical composite material with stable structure and good dispersion performance, and has good performance of degrading antibiotics and dyes under the irradiation of visible light.
And, the invention claims the Bi/BiPMo 12 O 40 The application of the composite photocatalyst in photocatalytic degradation of antibiotics and dyes.
Compared with the prior art, the Bi/BiPMo provided by the invention can be seen from the technical scheme 12 O 40 The composite photocatalyst, the preparation method and the application thereof have the following excellent effects:
1) Bi/BiPMo according to the invention 12 O 40 The composite photocatalyst has the characteristics of stable structure, good dispersibility and adsorptivity and the like, is favorable for electron transmission, and has optimal performance in the aspects of degrading antibiotics, dyes and reducing hexavalent chromium ions.
2) The preparation method of the invention is simple and low in cost, and the prepared Bi/BiPMo 12 O 40 Composite photocatalyst can be usedUnder the irradiation of visible light, the photocatalyst has excellent performances of photocatalytic degradation of antibiotics and dyes, the degradation of methyl orange is 97.5% in 50min, the degradation of tetracycline is 77.5% in 180min, and the reduction of hexavalent chromium ions is 89.33% in 30 min;
3) Bi/BiPMo according to the invention 12 O 40 The composite photocatalyst has high stability and can still maintain good catalytic effect after eight times of circulation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram of Bi/BiPMo 12 O 40 XRD spectra of composite photocatalyst.
FIG. 2 is a Bi/BiPMo 12 O 40 Degradation methyl orange performance diagram of composite photocatalyst.
FIG. 3 is a Bi/BiPMo 12 O 40 And (3) a tetracycline degradation performance graph of the composite photocatalyst.
FIG. 4 is a Bi/BiPMo 12 O 40 And the performance diagram of the composite photocatalyst for reducing hexavalent chromium ions.
FIG. 5 is a Bi/BiPMo 12 O 40 And (3) performance cycle diagram of degrading methyl orange, tetracycline and reducing hexavalent chromium ions of the composite photocatalyst.
FIG. 6 is a Bi/BiPMo 12 O 40 SEM image of the composite photocatalyst.
Detailed Description
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention discloses a metal simple substance Bi nanosphere modified BiPMo 12 O 40 Microsphere formation of Bi/BiPMo 12 O 40 Adding soluble bismuth salt and phosphomolybdic acid into deionized water, mixing and stirring uniformly, and cooling to room temperature after heating for reaction to obtain the bismuth phosphomolybdate; then adding the prepared bismuth phosphomolybdate and soluble bismuth salt into glycol solution, stirring by ultrasonic, and performing hydrothermal reaction to obtain Bi/BiPMo with high-efficiency photocatalytic performance 12 O 40 A composite photocatalyst.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
The technical scheme of the invention will be further described below with reference to specific embodiments.
Example 1
This example provides a Bi/BiPMo with efficient photocatalytic performance 12 O 40 The preparation method of the composite photocatalyst comprises the following steps:
3mmol Bi (NO) 3 ) 3 ·5H 2 O、3mmol H 3 PMo 12 O 40 ·xH 2 O was dissolved in 10mL of deionized water and stirred at a constant temperature of 60℃for 2h to form a homogeneous solution. After the solution was cooled to room temperature, a pale yellow precipitate was collected by centrifugation, washed with deionized water and absolute ethanol, and dried at 110℃for 6 hours to give 3mmol of BiPMo 12 O 40 。
3mmol of BiPMo which has been prepared 12 O 40 To 35ml of ethylene glycol solution, and 0.015mmol of Bi (NO 3 ) 3 ·5H 2 O, the mixed solution is treated by ultrasonic for 30min, and then stirred for 6h, so as to obtain a uniform suspension.
Transferring the suspension to a polytetrafluoroethylene-lined materialIn a stainless steel autoclave of (2), the stainless steel autoclave was placed in an oven and heated at 180℃for 10 hours. Thus obtaining brown gray precipitate, collecting the brown gray precipitate by centrifugation, washing with deionized water and absolute ethyl alcohol, drying at 80 ℃ for 4 hours, finally obtaining 0.5% Bi/BiPMo with high-efficiency photocatalytic performance 12 O 40 。
Example 2
This example provides a Bi/BiPMo with efficient photocatalytic performance 12 O 40 The preparation method of the composite photocatalyst comprises the following steps:
3mmol Bi (NO) 3 ) 3 ·5H 2 O、3mmol H 3 PMo 12 O 40 ·xH 2 O was dissolved in 10mL of deionized water and stirred at a constant temperature of 60℃for 2h to form a homogeneous solution. After the solution was cooled to room temperature, a pale yellow precipitate was collected by centrifugation, washed with deionized water and absolute ethanol, and dried at 110℃for 6 hours to give 3mmol of BiPMo 12 O 40 。
3mmol of BiPMo which has been prepared 12 O 40 To 35ml of ethylene glycol solution, and 0.03mmol of Bi (NO 3 ) 3 ·5H 2 O, the mixed solution is treated by ultrasonic for 30min, and then stirred for 6h, so as to obtain a uniform suspension.
The suspension was transferred to a stainless steel autoclave lined with polytetrafluoroethylene, which was placed in an oven and heated at 180 ℃ for 10h. Thus obtaining brown gray precipitate, collecting the brown gray precipitate by centrifugation, washing with deionized water and absolute ethyl alcohol, drying at 80 ℃ for 4 hours, finally obtaining 1.0% Bi/BiPMo with high-efficiency photocatalytic performance 12 O 40 。
Example 3
This example provides a Bi/BiPMo with efficient photocatalytic performance 12 O 40 The preparation method of the composite photocatalyst comprises the following steps:
3mmol Bi (NO) 3 ) 3 ·5H 2 O、3mmol H 3 PMo 12 O 40 ·xH 2 O was dissolved in 10mL of deionized water and stirred at a constant temperature of 60℃for 2h to form a homogeneous solution. After the solution was cooled to room temperature, a pale yellow precipitate was collected by centrifugation, washed with deionized water and absolute ethanol, and dried at 110℃for 6 hours to give 3mmol of BiPMo 12 O 40 。
3mmol of BiPMo which has been prepared 12 O 40 To 35ml of ethylene glycol solution, and 0.06mmol of Bi (NO 3 ) 3 ·5H 2 O, the mixed solution is treated by ultrasonic for 30min, and then stirred for 6h, so as to obtain a uniform suspension.
The suspension was transferred to a stainless steel autoclave lined with polytetrafluoroethylene, which was placed in an oven and heated at 180 ℃ for 10h. Thus obtaining brown gray precipitate, collecting the brown gray precipitate by centrifugation, washing with deionized water and absolute ethyl alcohol, drying at 80 ℃ for 4 hours, finally obtaining 2.0% Bi/BiPMo with high-efficiency photocatalytic performance 12 O 40 。
Example 4
This example provides a Bi/BiPMo with efficient photocatalytic performance 12 O 40 The preparation method of the composite photocatalyst comprises the following steps:
3mmol Bi (NO) 3 ) 3 ·5H 2 O、3mmol H 3 PMo 12 O 40 ·xH 2 O was dissolved in 10mL of deionized water and stirred at a constant temperature of 60℃for 2h to form a homogeneous solution. After the solution was cooled to room temperature, a pale yellow precipitate was collected by centrifugation, washed with deionized water and absolute ethanol, and dried at 110℃for 6 hours to give 3mmol of BiPMo 12 O 40 。
3mmol of BiPMo which has been prepared 12 O 40 To 35ml of ethylene glycol solution, and 0.09mmol of Bi (NO 3 ) 3 ·5H 2 O, the mixed solution is treated by ultrasonic for 30min, and then stirred for 6h, so as to obtain a uniform suspension.
Transferring the suspension into a stainless steel autoclave lined with polytetrafluoroethylene, and placing the stainless steel autoclave into an ovenHeating at 180deg.C for 10h. Thus obtaining brown gray precipitate, collecting the brown gray precipitate by centrifugation, washing with deionized water and absolute ethyl alcohol, drying at 80 ℃ for 4 hours, finally obtaining 3.0% Bi/BiPMo with high-efficiency photocatalytic performance 12 O 40 。
As can be seen from FIG. 1, the prepared BiPMo 12 O 40 And Bi/BiPMo in different proportions 12 O 40 XRD spectrum of material, and pure H 3 Mo 12 O 40 Is different from the XRD spectrum of (C) because of H 3 Mo 12 O 40 H in (1) + The cation has been completely formed into BiPMo 12 O 40 Bi of (2) 3+ The cation is substituted. The crystal face indexes are (212), (220), (115), (312), (305), (335), (630), (529) and (619), but after roasting at 400 ℃, diffraction peaks become smaller, the crystal surface index changes, and the crystal structure of the material changes remarkably.
Further, the composite catalysts of different proportions did not observe a characteristic peak of reduced bismuth element. The main reasons are that the characteristic peak of bismuth and Bi/BiPMo 12 O 40 Is very close to the characteristic peak of (a); secondly, the characteristic peak of the reduced material is hardly observed due to the excessively low content of the reduced bismuth.
As can be seen from FIG. 2, the Bi/BiPMo prepared 12 O 40 Under the irradiation of visible light, the composite photocatalyst has excellent performance of photocatalytic degradation of methyl orange. The automatic degradation of methyl orange in solution under visible light is negligible in the absence of catalyst. Under the same conditions, biPMo 12 O 40 The nanospheres degrade about 31.25% of the MO within 50 minutes. And when part of Bi 3+ Bi/BiPMo when photo-reduced 12 O 40 The photocatalytic degradation of the methyl orange reaches 97.5 percent.
As can be seen from FIG. 3, the Bi/BiPMo prepared 12 O 40 The composite photocatalyst has excellent photocatalytic degradation performance on tetracycline under irradiation of visible light. In the absence of catalyst, the degradation efficiency of TC was 8.52%. Bi/BiPMo under the same conditions 12 O 40 The degradation rate of the composite catalyst reaches 77.5 percent and is higher than that of pure catalystBiPMo 12 O 40 (58%) and other materials.
As can be seen from FIG. 4, the Bi/BiPMo prepared 12 O 40 The composite photocatalyst has excellent performance of photocatalytic reduction of hexavalent chromium ions under irradiation of visible light. In the absence of a catalyst, only 9.79% of the hexavalent chromium ions were photo-reduced. Bi/BiPMo after photo-deposition of Bi-NPs 12 O 40 The photocatalytic activity of (C) is obviously enhanced, 1.0 percent of Bi/BiPMo 12 O 40 Under the irradiation of visible light, hexavalent chromium ions can be degraded by 89.33% within 30 min.
As can be seen from FIG. 5, the Bi/BiPMo prepared 12 O 40 The composite photocatalyst can slightly reduce the reduction efficiency of Cr (VI) and the degradation efficiency of MO and tetracycline when the composite photocatalyst is recycled for eight times, which is possibly related to the loss of the catalyst in the recycling process and can be attributed to necessary experimental errors, but still has good performances of degrading methyl orange, tetracyclines and reducing hexavalent chromium ions, which indicates that the composite catalyst has good stability.
FIG. 6 shows that the prepared Bi/BiPMo 12 O 40 The morphology feature of the composite photocatalyst under a scanning electron microscope can be observed under the scanning electron microscope 12 O 40 The sample consists of nanospheres with nonuniform shapes and sizes, and a large number of Bi nano-particles are uniformly anchored in the BiPMo 12 O 40 A nanosphere.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. Bi/BiPMo 12 O 40 Preparation method of composite photocatalyst, its special purposeCharacterized in that the method specifically comprises the following steps:
1) Adding soluble bismuth salt and phosphomolybdic acid into deionized water, mixing and stirring uniformly, cooling to room temperature after heating for reaction, and drying to obtain the phosphomolybdic acid bismuth;
2) Adding the bismuth phosphomolybdate and the soluble bismuth salt prepared in the step 1) into glycol solution, carrying out hydrothermal reaction after ultrasonic stirring, filtering and drying to obtain Bi/BiPMo with high-efficiency photocatalytic performance 12 O 40 A composite photocatalyst.
2. A Bi/BiPMo according to claim 1 12 O 40 The preparation method of the composite photocatalyst is characterized in that in the step 1), the mole ratio of the soluble bismuth salt to the phosphomolybdic acid is 1:1, the heating reaction temperature is 50-80 ℃, and the heating reaction time is 2-4h.
3. A Bi/BiPMo according to claim 1 or 2 12 O 40 The preparation method of the composite photocatalyst is characterized in that the drying temperature in the step 1) is 60-120 ℃ and the drying time is 4-8h.
4. A Bi/BiPMo according to claim 1 12 O 40 The preparation method of the composite photocatalyst is characterized in that in the step 2), the molar ratio of the bismuth phosphomolybdate to the soluble bismuth salt is 10:1, the hydrothermal reaction temperature is 160-200 ℃, and the hydrothermal reaction time is 8-12h.
5. A Bi/BiPMo according to claim 1 or 4 12 O 40 The preparation method of the composite photocatalyst is characterized in that the drying temperature in the step 2) is 60-120 ℃ and the drying time is 4-8h.
6. A Bi/BiPMo prepared by the method of claim 1 12 O 40 The composite photocatalyst is characterized in that the Bi/BiPMo 12 O 40 The composite photocatalyst is in a nano sphere shape, and the Bi/BiPMo 12 O 40 The diameter size of the composite photocatalyst is 50-100nm.
7. A Bi/BiPMo prepared by the method of claim 1 12 O 40 Composite photocatalyst or Bi/BiPMo according to claim 6 12 O 40 The application of the composite photocatalyst in photocatalytic degradation of antibiotics and dyes.
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| CN106732527A (en) * | 2016-12-29 | 2017-05-31 | 中南大学 | A kind of bismuth/composite bismuth vanadium photocatalyst and preparation method thereof and the application in photocatalytic degradation organic matter |
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| CN106732527A (en) * | 2016-12-29 | 2017-05-31 | 中南大学 | A kind of bismuth/composite bismuth vanadium photocatalyst and preparation method thereof and the application in photocatalytic degradation organic matter |
| CN107262085A (en) * | 2017-07-21 | 2017-10-20 | 江苏大学 | A kind of preparation method of bismuth/calcium niobate potassium plasma nano composite |
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