CN110354840B - Preparation of beta-Bi2O3/BiVO4Method for preparing composite photocatalytic material - Google Patents
Preparation of beta-Bi2O3/BiVO4Method for preparing composite photocatalytic material Download PDFInfo
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- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 58
- 239000002243 precursor Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 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 claims description 9
- 238000000643 oven drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 19
- 230000015556 catabolic process Effects 0.000 abstract description 18
- 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 abstract description 5
- 229940043267 rhodamine b Drugs 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 229910052724 xenon Inorganic materials 0.000 abstract description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- 229910000416 bismuth oxide Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
Preparation of beta-Bi2O3/BiVO4A method for preparing a composite photocatalytic material belongs to the field of inorganic catalytic materials. The invention firstly prepares BiVO by a hydrothermal method4Then preparing beta-Bi by hydrothermal-coprecipitation-roasting method2O3/BiVO4A composite photocatalytic material. The method has the advantages of simple preparation process, less used equipment cost and less energy consumption. Prepared beta-Bi2O3/BiVO4The specific surface area is large, the stability is strong, the photocatalytic activity is high, under the irradiation of a simulated sunlight xenon lamp, 0.1g of the prepared composite photocatalytic material degrades 50mL of 10mg/L rhodamine B solution, and the degradation rate reaches 98% after the irradiation of light for 130 min. The product prepared by the invention can be widely used in the field of photocatalytic degradation of organic pollutants.
Description
Technical Field
The invention relates to a method for preparing beta-Bi2O3/BiVO4A method for preparing a composite photocatalytic material belongs to the technical field of inorganic catalytic materials.
Background
The semiconductor photocatalysis technology is a technology for treating environmental problems and plays a promoting role in wastewater treatment and other pollution treatment technologies. Conventional photocatalysts (e.g. TiO)2And ZnO) has a large band gap and only occupies too muchUltraviolet light (3.0-3.2eV) with the solar energy of 3% -5% is utilized. Found that Bi2O3BiOBr, BiOI and BiVO4The bismuth-based visible light catalytic material has the advantages of low cost, environmental protection and high efficiency, and is widely applied to the degradation and photolysis of H in organic water pollutants2And CO2And (4) reduction. beta-Bi2O3The (beta-bismuth oxide) is a typical tetragonal semiconductor photocatalyst, the band gap of the (beta-bismuth oxide) is 2.58eV, and the (beta-bismuth oxide) can absorb visible light with the wavelength of more than 400 nm. BiVO4The material has various structures of monoclinic scheelite type, tetragonal zirconium silicate type and tetragonal scheelite (high-temperature phase) type, the forbidden band width interval is 2.3-2.4 eV, the response visible light region is wide, and the photocatalysis effect is good. The preparation method mainly comprises a chemical precipitation method, a roasting method, a hydrothermal method and the like.
At present, research on composite photocatalysts mainly focuses on improving the catalytic activity of the composite photocatalysts. For example, four-pointed star BiVO in 2016, 4 months, 32 th vol4/Bi2O3Preparation and Performance of the catalyst "(reference 1) the following text, bismuth vanadate in the form of a quadrangle star was synthesized by hydrothermal method, and then the bismuth vanadate was immersed in an alkali solution for a second hydrothermal treatment to prepare BiVO4/Bi2O3A catalyst. The method has the following defects: (1) the composite catalyst has low photocatalytic activity and BiVO (BiVO) under simulated sunlight4/Bi2O3The degradation rate of the catalyst 2h to rhodamine B is only 89.2%; (2) BiVO4In the preparation process, a mixed solution of nitric acid and ethylene glycol is used for preparing a bismuth nitrate solution, sodium dodecyl benzene sulfonate is added in the preparation of an ammonium metavanadate solution, high-concentration organic wastewater is generated, and a large amount of volatile substances are discharged in the subsequent drying and heat treatment processes, so that the atmospheric environment is polluted; the hydrothermal reaction time is long (24h), and the energy consumption is high; (3) the preparation condition of the compound is strict, the proportion of the two is difficult to control, and Bi in the compound is2O3In fact the destruction of BiVO by alkaline (sodium hydroxide) etching4BiVO coated by hydrothermal method after crystal surface4The outer layer of the crystal causes serious agglomeration phenomenon, and influences the composite adsorption performance and photocatalytic activity. And for example, "Applied Catalysis B" Environmental "2017, 12-month 2019, volume 259-268" Construction of p-n-heterojunction beta-Bi2O3/BiVO4In the context of nanocomposite with improved phosphor property and enhanced activity in degradation of ortho-dichlorobenzene "(reference 2), beta-Bi is synthesized by a one-step hydrothermal method using sodium oleate as a dispersant, bismuth nitrate and sodium metavanadate as raw materials2O3/BiVO4. The method has the following defects: (1) the beta-Bi prepared by the method2O3/BiVO4The catalyst has lower photocatalytic activity, and the degradation rate of o-dichlorobenzene in 6 hours under simulated sunlight is less than 80 percent; (2) prepared beta-Bi2O3/BiVO4The specific surface area is small, which is not beneficial to improving the photocatalytic activity; (3) sodium oleate is used as a dispersing agent in the preparation process, n-hexane and absolute ethyl alcohol are required to be used for washing for multiple times, high-concentration organic wastewater (or waste liquid) is generated, and a large amount of volatile organic matters are discharged in the subsequent drying and heat treatment processes, so that the atmospheric environment is polluted.
Disclosure of Invention
The object of the present invention is directed to the preparation of beta-Bi2O3、BiVO4In the process, the problems of high organic matter consumption, poor compound photocatalytic activity and the like are solved by adopting a hydrothermal-roasting method to prepare beta-Bi2O3/BiVO4The method of the composite photocatalytic material improves the activity and the stability of the composite photocatalytic material, the preparation process is simple, the period is short, the catalytic activity is high, and the beta-Bi of the invention2O3/BiVO4The preparation method of the composite photocatalytic material comprises the following steps:
(1)BiVO4hydrothermal preparation of
2.45g of Bi (NO) were weighed out separately3)3·5H2O and 0.58g NH4VO3Simultaneously dissolved in 20.0mL of HNO with the concentration of 4.0mol/L3Forming a yellow transparent solution in the solution; adjusting the pH value of the solution with saturated sodium bicarbonate solution, and magnetically stirringObtaining a precursor after half an hour; transferring the obtained precursor into a 100mL high-pressure reaction kettle, sealing completely, placing into an oven, reacting at 180 ℃ for 2H, taking out, naturally cooling to room temperature, filtering, and using H to obtain a filter cake2Washing with O and anhydrous alcohol for 3 times, oven drying at 80 deg.C for 12 hr, taking out, grinding with quartz mortar into powder to obtain BiVO4。
(2)β-Bi2O3/BiVO4Hydrothermal-roasting preparation of
A proper amount of bismuth nitrate solution is weighed and slowly poured into 20mL of 2.0mol/L HNO3Carrying out ultrasonic treatment on the solution and mechanically shaking for half an hour until the solution is clear; the clarified solution was added to 40mL of 0.6mol/L Na at a constant rate2CO3Mechanically stirring for 2h, and aging for 1h to obtain beta-Bi2O3The precursor solution of (1); according to the precursor BiVO4BiVO was weighed at a ratio of 1.5:1, 1:0.5, 1:1.5 and 0.5:1, respectively4Adding into the precursor solution, stirring for 30min, filtering the mixed solution, oven drying, placing in a muffle furnace, roasting at 380 deg.C for 10min, rapidly taking out, naturally cooling to room temperature to obtain bright yellow powder as compound beta-Bi2O3/BiVO4。
By adopting the technical scheme, the invention mainly has the following effects:
(1) beta-Bi prepared by the method of the invention2O3/BiVO4The composite photocatalytic material has high photocatalytic activity, and 0.1g of prepared beta-Bi is irradiated by a xenon lamp (340-800 nm) simulating sunlight2O3/BiVO4The composite photocatalytic material is dispersed in 50mL of rhodamine B solution with the concentration of 10mg/L, the illumination is carried out for 130min, and the degradation rate reaches 98%.
(2) The invention is prepared by a hydrothermal-roasting method, and the specific surface area of the composite photocatalytic material reaches 16.45m2The preparation method has the advantages of strong stability, simple preparation operation, less required equipment and low energy consumption.
Drawings
FIG. 1 is BiVO4、β-Bi2O3And beta-Bi2O3X-ray diffraction pattern of (a).
FIG. 2 shows beta-Bi2O3、BiVO4、β-Bi2O3/BiVO4FT-IR diagram of (1).
FIG. 3 is a view of beta-Bi2O3、BiVO4And beta-Bi2O3/BiVO4SEM image of (d).
FIG. 4 shows β -Bi2O3、BiVO4And different mass ratios of beta-Bi2O3/BiVO4Degradation rate of (c) is compared with the graph.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
Preparation of beta-Bi2O3/BiVO4The method for preparing the composite photocatalytic material comprises the following specific steps:
(1)BiVO4hydrothermal preparation of
2.45g of Bi (NO) were weighed out separately3)3·5H2O and 0.58g NH4VO3Simultaneously dissolved in 20.0mL of HNO with the concentration of 4.0mol/L3Forming a yellow transparent solution in the solution; regulating the pH value of the solution by using a saturated sodium bicarbonate solution, and magnetically stirring for half an hour to obtain a precursor; transferring the obtained precursor into a 100mL high-pressure reaction kettle, sealing completely, placing into an oven, reacting at 180 ℃ for 2H, taking out, naturally cooling to room temperature, filtering, and using H to obtain a filter cake2Washing with O and anhydrous alcohol for 3 times, oven drying at 80 deg.C for 12 hr, taking out, grinding with quartz mortar into powder to obtain BiVO4。
(2)β-Bi2O3/BiVO4Hydrothermal-roasting preparation of
A proper amount of bismuth nitrate solution is weighed and slowly poured into 20mL of 2.0mol/L HNO3Carrying out ultrasonic treatment on the solution and mechanically shaking for half an hour until the solution is clear; the clarified solution was added to 40mL of 0.6mol/L Na at a constant rate2CO3Mechanically stirring for 2h, and aging for 1h to obtain beta-Bi2O3The precursor solution of (1); according to the precursor BiVO4BiVO is weighed according to the proportion of 1:14Adding a precursor solutionStirring for 30min, filtering the mixed solution, drying, roasting in a muffle furnace at 380 deg.C for 10min, taking out, and naturally cooling to room temperature to obtain bright yellow powder as compound beta-Bi2O3/BiVO4。
Example 2
Preparation of beta-Bi2O3/BiVO4The method for preparing the composite photocatalytic material comprises the following specific steps:
(1) the same as in (1) in example 1.
(2)β-Bi2O3/BiVO43Hydrothermal-roasting preparation of
A proper amount of bismuth nitrate solution is weighed and slowly poured into 20mL of 2.0mol/L HNO3Carrying out ultrasonic treatment on the solution and mechanically shaking for half an hour until the solution is clear; the clarified solution was added to 40mL of 0.6mol/L Na at a constant rate2CO3Mechanically stirring for 2h, and aging for 1h to obtain beta-Bi2O3The precursor solution of (1); according to the precursor BiVO4BiVO is weighed in a ratio of 0.5:14Adding into the precursor solution, stirring for 30min, filtering the mixed solution, oven drying, placing in a muffle furnace, roasting at 380 deg.C for 10min, rapidly taking out, naturally cooling to room temperature to obtain bright yellow powder as compound beta-Bi2O3/BiVO4。
Example 3
Preparation of beta-Bi2O3/BiVO4The method for preparing the composite photocatalytic material comprises the following specific steps:
(1) the same as in (1) in example 1.
(2)β-Bi2O3/BiVO4Hydrothermal-roasting preparation of
A proper amount of bismuth nitrate solution is weighed and slowly poured into 20mL of 2.0mol/L HNO3Carrying out ultrasonic treatment on the solution and mechanically shaking for half an hour until the solution is clear; the clarified solution was added to 40mL of 0.6mol/L Na at a constant rate2CO3Mechanically stirring for 2h, and aging for 1h to obtain the beta-Bi2O3The precursor solution of (1); according to the precursor BiVO4BiVO is weighed according to the proportion of 1.5:14Adding into the precursor solution, stirring for 30min, filtering the mixed solution, oven drying, placing in a muffle furnace, roasting at 380 deg.C for 10min, rapidly taking out, naturally cooling to room temperature to obtain bright yellow powder as compound beta-Bi2O3/BiVO4。
Example 4
Preparation of beta-Bi2O3/BiVO4The method for preparing the composite photocatalytic material comprises the following specific steps:
(1) the same as in (1) in example 1.
(2)β-Bi2O3/BiVO4Hydrothermal-roasting preparation of
A proper amount of bismuth nitrate solution is weighed and slowly poured into 20mL of 2.0mol/L HNO3Carrying out ultrasonic treatment on the solution and mechanically shaking for half an hour until the solution is clear; the clarified solution was added to 40mL of 0.6mol/L Na at a constant rate2CO3Mechanically stirring for 2h, and aging for 1h to obtain the beta-Bi2O3The precursor solution of (1); according to the precursor BiVO4BiVO is weighed according to the proportion of 1:1.54Adding into the precursor solution, stirring for 30min, filtering the mixed solution, oven drying, placing in a muffle furnace, roasting at 380 deg.C for 10min, rapidly taking out, naturally cooling to room temperature to obtain bright yellow powder as compound beta-Bi2O3/BiVO4。
Example 5
Preparation of beta-Bi2O3/BiVO4The method for preparing the composite photocatalytic material comprises the following specific steps:
(1) the same as in (1) in example 1.
(2)β-Bi2O3/BiVO4Hydrothermal-roasting preparation of
A proper amount of bismuth nitrate solution is weighed and slowly poured into 20mL of 2.0mol/L HNO3Carrying out ultrasonic treatment on the solution and mechanically shaking for half an hour until the solution is clear; the clarified solution was added to 40mL of 0.6mol/L Na at a constant rate2CO3Mechanically stirring for 2h, and aging for 1h to obtain the beta-Bi2O3The precursor solution of (1); according to the precursor BiVO4Is 1:0Weighing BiVO according to the proportion of 54Adding into the precursor solution, stirring for 30min, filtering the mixed solution, oven drying, placing in a muffle furnace, roasting at 380 deg.C for 10min, rapidly taking out, naturally cooling to room temperature to obtain bright yellow powder as compound beta-Bi2O3/BiVO4。
Results of the experiment
Composite photocatalytic material prepared in example 1 beta-Bi2O3/BiVO4The catalytic degradation activity is optimal. For convenience of comparison, beta-Bi was prepared2O3And (3) sampling. beta-Bi2O3The preparation method is that BiVO is not added in the step (2) of the example 14。
β-Bi2O3As shown in FIG. 1(b), each diffraction peak corresponds to pure β -Bi2O3The characteristic peak (JCPDS #27-0050) with characteristic reflection peaks including (210), (201), (220), (222), (200) and (400) etc. proves that the sample is the pure square crystal structure of beta-Bi2O3。β-Bi2O3The infrared absorption spectrum of (2) is 1383cm-1、846.3cm-1、 585.6cm-1The peak at is beta-Bi2O3Typical Bi — O bond absorption peak.
BiVO4The XRD pattern of the crystal is shown in figure 1(a), the characteristic diffraction peak of the crystal is matched with that of JCPDS PDF document No.14-0688, and stronger diffraction peaks exist in the crystal faces of (110), (011), (121), (040), (200), (002), (211), (150), (240), (042), (220), (161), (321) and (123), which indicates that m-BiVO is prepared4。BiVO4The infrared absorption spectrum of (c) is shown in FIG. 2(b), at 615cm-1Is attributed to VO4V3, at 430cm-1The peak of (A) is VO4Is caused by the inconsistent contractile motion of v1, further demonstrating the presence of BiVO in the sample4The complete crystal form of (a).
XRD diffraction of the composite photocatalytic material is shown in figure 1(c), and beta-Bi2O3/BiVO4The diffraction peak of the sample not only contains BiVO4And (110), (011), (040), (161) characteristic diffraction peaks, and β-Bi2O3The characteristic diffraction peaks of (201), (210), (002), (220), (400) and (421) are simultaneously present, the diffraction peaks are sharp and no hetero-peak appears, which shows that BiVO4/β-Bi2O3The sample preparation was successful. beta-Bi2O3/BiVO4The infrared absorption spectrum of (2) is shown in FIG. 2(c), which is 1386cm-1And 845cm-1Having beta-Bi present therein2O3Has a characteristic absorption peak at 630cm for Bi-O bonds of (A)-1Where an absorption peak of V-O is found, again, beta-Bi is illustrated2O3/BiVO4Successful synthesis of the catalyst, BiVO in the entire preparation4And beta-Bi2O3The self structure of the BiVO is not changed, and the BiVO is proved4And beta-Bi2O3Is present.
BiVO4/β-Bi2O3Is shown in fig. 3. BiVO can be seen from FIG. 3(a)4Irregular dumbbell shape, FIG. 3 (b). beta. -Bi2O3Then, the shape is irregular like a plate/rod, and FIG. 3(c) shows β -Bi2O3/BiVO4The appearance of the beta-Bi similar to a sheet can be seen2O3Around which a dumbbell-shaped BiVO is loaded4Prove that beta-Bi2O3/BiVO4The preparation is successful. BiVO can also be seen from FIG. 3(c)4/β-Bi2O3After compounding, the size is reduced, and BiVO is also reduced4Due to BiVO4And beta-Bi2O3A heterojunction is formed between the two layers, and BiVO is prevented4The agglomeration phenomenon of the compound is avoided, the specific surface area of the compound is increased, more surface active positions are provided, and the BiVO is improved4And beta-Bi2O3The photocatalytic degradation effect of (2).
A photocatalysis experiment shows that under the irradiation of a xenon lamp simulating sunlight, 50mL of rhodamine B solution with the concentration of 10mg/L is degraded by using 0.1g of the prepared composite photocatalytic material, and the degradation rate of rhodamine B reaches 98% after illumination for 130 min. And beta-Bi2O3、 BiVO4And the degradation rates of the samples prepared in examples 1-5 are shown in FIG. 4, BiVO4/β-Bi2O3The mass ratio of 1: the degradation effect is optimal at 1 hour, and at 130min, the RhB is completely degraded basically; when BiVO4Mass is constant, beta-Bi2O3/BiVO4The degradation rate firstly shows a trend of firstly rising and then falling along with the increase of the proportion of the bismuth oxide; when beta-Bi2O3Constant mass of beta-Bi2O3/BiVO4The degradation rate of the bismuth oxide is firstly increased along with the increase of the proportion of the bismuth oxide, and then the degradation rate of the bismuth oxide is in a descending trend; and when BiVO4/β- Bi2O3The final degradation effect is substantially consistent when the mass ratio of (1.5: 1) to (1: 1.5) is provided. Therefore, when BiVO4/β-Bi2O3The mass ratio of (1): the specific surface area is maximum at 1 (16.45 m)2/g) is provided with the most surface active sites, so the degradation effect is optimal, the degradation rate reaches 98% in 130min, and the degradation rate of the compound is higher than that of single-phase BiVO4And beta-Bi2O3The degradation rate is high, and the photocatalytic activity is improved.
Claims (2)
1. Preparation of beta-Bi2O3/BiVO4A method of compounding a photocatalytic material, the method comprising the steps of:
(1)BiVO4the hydrothermal method comprises the following steps: 2.45g of Bi (NO) were weighed out separately3)3·5H2O and 0.58g NH4VO3Simultaneously dissolved in 20.0mL of HNO with the concentration of 4.0mol/L3Forming a yellow transparent solution in the solution; regulating the pH value of the solution by using a saturated sodium bicarbonate solution, and magnetically stirring for half an hour to obtain a precursor; transferring the obtained precursor into a 100mL high-pressure reaction kettle, sealing completely, placing into an oven, reacting at 180 ℃ for 2H, taking out, naturally cooling to room temperature, filtering, and using H to obtain a filter cake2Washing with O and anhydrous alcohol for 3 times, oven drying at 80 deg.C for 12 hr, taking out, grinding with quartz mortar into powder to obtain BiVO4；
(2)β-Bi2O3/BiVO4The hydrothermal-roasting preparation: a proper amount of bismuth nitrate solution is weighed and slowly poured into 20mL of 2.0mol/L HNO3Carrying out ultrasonic treatment on the solution and mechanically shaking for half an hour until the solution is clear; will be at the topThe clarified solution was added to 40mL of 0.6mol/L Na at a constant rate2CO3Mechanically stirring for 2h, and aging for 1h to obtain beta-Bi2O3The precursor solution of (1); according to the precursor BiVO4BiVO was weighed at a ratio of 1.5:1, 1:0.5, 1:1.5 and 0.5:1, respectively4Adding into the precursor solution, stirring for 30min, filtering the mixed solution, oven drying, placing in a muffle furnace, roasting at 380 deg.C for 10min, rapidly taking out, naturally cooling to room temperature to obtain bright yellow powder as compound beta-Bi2O3/BiVO4。
2. The method of claim 1 for preparing beta-Bi2O3/BiVO4The method of preparing composite photocatalytic material features that hydrothermal roasting process is used to prepare the composite photocatalytic material with catalytic active component beta-Bi2O3And BiVO4The firm combination between them.
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| CN111293321B (en) * | 2020-02-22 | 2022-02-08 | 青岛科技大学 | Pt/BiVO4/Bi2O3Photoelectric auxiliary preparation method of catalyst and photoelectric catalysis application thereof |
| CN111266101B (en) * | 2020-02-22 | 2021-08-24 | 青岛科技大学 | In-situ generation BiVO4/Bi2O3Method for heterojunction and photocatalytic application thereof |
| CN111215066B (en) * | 2020-02-22 | 2021-08-24 | 青岛科技大学 | Pt/BiVO4/Bi2O3Photo-assisted preparation method of catalyst and application of photo-assisted preparation method to photoelectrocatalysis |
| CN111841584B (en) * | 2020-08-28 | 2023-03-21 | 台州学院 | Preparation method of BiVO4/NiSe2/Bi compound |
| CN112973741B (en) * | 2020-11-27 | 2022-07-05 | 北京理工大学 | Preparation method of Z-form bismuth-based photocatalyst |
| CN112516992B (en) * | 2020-12-14 | 2022-04-22 | 三峡大学 | Preparation method and application of bismuth vanadate-based composite material |
| CN113769729B (en) * | 2021-09-17 | 2024-03-29 | 西安近代化学研究所 | BiVO with different appearances 4 Shape controllable preparation method of photocatalysis material |
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