CN114367301B - Method for synthesizing bismuth subnitrate/bismuth oxide composite material - Google Patents
Method for synthesizing bismuth subnitrate/bismuth oxide composite material Download PDFInfo
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- 229960001482 bismuth subnitrate Drugs 0.000 title claims abstract description 76
- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 61
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- HWSISDHAHRVNMT-UHFFFAOYSA-N Bismuth subnitrate Chemical compound O[NH+]([O-])O[Bi](O[N+]([O-])=O)O[N+]([O-])=O HWSISDHAHRVNMT-UHFFFAOYSA-N 0.000 title claims abstract 15
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 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 39
- 239000007787 solid Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 17
- 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 description 16
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 description 63
- 239000000243 solution Substances 0.000 description 59
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000000843 powder Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- -1 vanadium amine Chemical class 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229940073609 bismuth oxychloride Drugs 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J35/39—
-
- 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
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a method for synthesizing bismuth subnitrate/bismuth oxide composite material, which comprises the steps of uniformly mixing solid and liquid phases of a precursor solution of bismuth subnitrate and bismuth oxide synthesized by hydrothermal, and then calcining at high temperature to obtain the bismuth subnitrate/bismuth oxide composite material. The method is simple to operate, consumes less time, and the obtained bismuth subnitrate/bismuth oxide composite material has high crystallinity, better uniformity, good interface contact and good photocatalysis performance.
Description
Technical Field
The invention relates to a method for synthesizing bismuth subnitrate/bismuth oxide composite material, in particular to a technology for synthesizing bismuth subnitrate/bismuth oxide composite material with effective interface contact by a simple physical calcination method.
Background
Bismuth subnitrate (Bi) 6 O 6 (OH) 3 (NO 3 ) 3 ·1.5H 2 O) is a class of semiconductor materials, hexagonal crystalline platelets or microcrystalline powders. In this structure, bismuth (Bi) has d 10 The p-block metal of the configuration, bi 6s orbitals can interact with O2 p orbitals to form [ Bi ] 2 O 2 ] 2+ Layer [ Bi ] 2 O 2 ] 2+ The upper layer being free as an intermediate layerNitrate ions, the lower layer is hydroxyl, and the lower layer is connected through Bi-O bonds to form a sandwich structure, and the structure is favorable for migration and transmission of photo-generated electron holes and enhancement of photocatalytic performance. Bismuth oxide (Bi) 2 O 3 ) It is considered to be a typical oxide because of its non-toxic, low cost, narrow bandgap, polymorphism, etc. But Bi is 2 O 3 Practical application of the visible light responsive photocatalyst with a direct band gap of 2.8 eV is also limited by the rapid recombination of photo-generated electron-hole pairs. The semiconductor composite material has more excellent photoelectric and photocatalytic properties than a single semiconductor, and in order to prepare the bismuth subnitrate/bismuth oxide composite material with excellent properties more efficiently, a more perfect synthesis method needs to be explored.
Fang Deng et al first prepared bismuth oxychloride by adjusting the pH of the potassium chloride and bismuth nitrate solution, and then reduced the bismuth oxychloride to some extent by iron and hydrochloric acid to obtain the bismuth oxychloride/bismuth oxide composite material. But the operation process is complex and the preparation time is long.
The bismuth nitrate/vanadium bismuth oxide composite material is prepared by respectively preparing an aqueous solution of bismuth nitrate and a sodium hydroxide solution of vanadium amine oxide, mixing the two solutions and performing microwave hydrothermal. But the prepared sample has lower crystallinity.
The bismuth nitrate/graphite-like carbon nitride composite material is obtained by mixing and grinding bismuth nitrate solid with graphite-like carbon nitride solid, and then calcining. But the prepared composite material has lower uniformity and lower crystallinity.
The bismuth subnitrate/bismuth oxybromide composite material is prepared by a one-pot hydrothermal method by Xumin Hu and the like. The preparation method is simple, however, the photocatalytic performance of the material is poor.
Disclosure of Invention
The invention aims to provide a simple and efficient method for synthesizing bismuth subnitrate/bismuth oxide composite material, which is simple and easy to operate, and has short preparation period, and the obtained composite material has high crystallinity, better uniformity and excellent interface contact performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for synthesizing bismuth subnitrate/bismuth oxide composite material, comprising the steps of:
1) Adding bismuth nitrate pentahydrate into water, and stirring to prepare bismuth nitrate solution A;
2) Transferring the prepared bismuth nitrate solution A into a hydrothermal kettle for hydrothermal reaction;
3) After the hydrothermal reaction is finished, collecting precipitate, washing and drying to obtain bismuth subnitrate solid;
4) Adding bismuth nitrate pentahydrate into water, and stirring to prepare bismuth nitrate solution B with a certain concentration;
5) Slowly dropwise adding 25vol% ammonia water solution into the continuously stirred bismuth nitrate solution B, and adjusting the pH of the solution;
6) Adding a certain mass of bismuth subnitrate solid prepared in the step 3) into the solution obtained in the step 5), and uniformly stirring;
7) Transferring the mixture obtained in the step 6) into a crucible, and calcining to obtain the bismuth subnitrate/bismuth oxide composite material.
The stirring time in the step 1) is 10 min, and the concentration of the obtained bismuth nitrate solution A is 12.12 g/L.
The hydrothermal reaction in the step 2) is to heat up to 180 ℃ at a speed of 5 ℃/min, and heat preservation is carried out for 12 h.
The washing and drying in the step 3) is to control the centrifugal speed to 4000 revolutions per minute, firstly wash 3 times with deionized water, then wash 2 times with absolute ethyl alcohol, and then dry 2 h at 60 ℃.
The stirring time in the step 4) is 10 min, and the concentration of the obtained bismuth nitrate solution B is 50 g/L.
The pH value of the solution after the adjustment in the step 5) is 10.
The solid bismuth subnitrate added in step 6) is 2.945-14.725mg/mL and the stirring time is 15 min.
Step 7) the calcination is to heat up to 240 ℃ at a rate of 5 ℃/min and treat for 120min.
The beneficial effects of the invention are as follows:
1. the invention has simple operation, easy control and short time consumption.
2. According to the invention, the bismuth subnitrate/bismuth oxide composite material synthesized by preparing the bismuth oxide precursor solution and uniformly mixing the bismuth subnitrate solution with the bismuth subnitrate powder obtained by the hydrothermal reaction and calcining the bismuth subnitrate powder has a good photocatalysis effect.
3. The bismuth subnitrate/bismuth oxide composite material is prepared by a simple calcination method, and the method is also applicable to the preparation of other bismuth-based composite materials.
Drawings
FIG. 1 is an X-ray diffraction pattern of bismuth subnitrate/bismuth oxide composite materials (BBN-BO-X%) prepared in examples 1-4.
FIG. 2 is a scanning electron microscope image of bismuth subnitrate (BBN), bismuth Oxide (BO) and bismuth subnitrate/bismuth oxide composite material (BBN-BO) prepared in example 2.
FIG. 3 is a graph comparing photocatalytic capacities of bismuth subnitrate/bismuth oxide composite material (BBN-BO) prepared in example 2 with those of composite materials BBN-BO-HT and BBN-BO-MI prepared in comparative example.
Detailed Description
A method for synthesizing bismuth subnitrate/bismuth oxide composite material, comprising the steps of:
1) Adding bismuth nitrate pentahydrate into water, and stirring for 10 min to prepare bismuth nitrate solution A with the concentration of 12.12 g/L;
2) Transferring the prepared bismuth nitrate solution A into a hydrothermal kettle, heating to 180 ℃ at a speed of 5 ℃/min, and carrying out hydrothermal reaction for 12 h;
3) After the hydrothermal reaction is finished, collecting precipitate, controlling the centrifugal speed to 4000 rpm, washing with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and drying at 60 ℃ for 2 h to obtain bismuth subnitrate solid;
4) Adding bismuth nitrate pentahydrate into water, and stirring for 10 min to prepare bismuth nitrate solution B with the concentration of 50 g/L;
5) Slowly dropwise adding 25vol% ammonia water solution into the continuously stirred bismuth nitrate solution B to adjust the pH value of the solution to 10;
6) Adding the bismuth subnitrate solid prepared in the step 3) into the solution obtained in the step 5) according to the amount of 2.945-14.725mg/mL, and stirring for 15min to be uniform;
7) Transferring the mixture obtained in the step 6) into a crucible, heating to 240 ℃ at a speed of 5 ℃/min, and calcining for 120min to obtain the bismuth subnitrate/bismuth oxide composite material.
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1
Bismuth nitrate pentahydrate solid of 0.485 and g is taken, added into a beaker filled with 40 ml deionized water, and stirred at a constant temperature of 25 ℃ for 10 min to obtain bismuth nitrate solution with the concentration of 12.12 g/L. Transferring the stirred bismuth nitrate solution into a hydrothermal kettle with a 50 ml polytetrafluoroethylene lining, controlling the heating rate to be 5 ℃/min, raising the temperature to 180 ℃, carrying out heat preservation reaction for 12 h, controlling the centrifugation rate to be 4000 rpm after the hydrothermal kettle is cooled to room temperature, washing the obtained precipitate with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and then drying at 60 ℃ for 2 h to obtain the bismuth subnitrate solid powder. The bismuth nitrate pentahydrate solid of 5 g is added into a beaker filled with 100 ml deionized water, and stirred at constant temperature of 25 ℃ for 10 min to obtain bismuth nitrate solution with the concentration of 50 g/L. Then, 25vol% ammonia water solution is added dropwise into the bismuth nitrate solution under the condition of continuous stirring until the pH value of the solution is 10, so as to obtain a precursor solution of bismuth oxide. Adding 0.0589 g bismuth subnitrate powder into 20ml bismuth oxide precursor solution, stirring for 15min to make the bismuth subnitrate powder uniform, transferring the mixture into a crucible with the volume of 50 ml, controlling the heating rate of a muffle furnace to be 5 ℃/min, and preserving heat at 240 ℃ for 120min, and cooling the muffle furnace to room temperature to obtain the bismuth subnitrate/bismuth oxide composite material with the bismuth subnitrate mass ratio of 10%.
Example 2
Bismuth nitrate pentahydrate solid of 0.485 and g is taken, added into a beaker filled with 40 ml deionized water, and stirred at a constant temperature of 25 ℃ for 10 min to obtain bismuth nitrate solution with the concentration of 12.12 g/L. Transferring the stirred bismuth nitrate solution into a hydrothermal kettle with a 50 ml polytetrafluoroethylene lining, controlling the heating rate to be 5 ℃/min, raising the temperature to 180 ℃, carrying out heat preservation reaction for 12 h, controlling the centrifugation rate to be 4000 rpm after the hydrothermal kettle is cooled to room temperature, washing the obtained precipitate with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and then drying at 60 ℃ for 2 h to obtain the bismuth subnitrate solid powder. The bismuth nitrate pentahydrate solid of 5 g is added into a beaker filled with 100 ml deionized water, and stirred at constant temperature of 25 ℃ for 10 min to obtain bismuth nitrate solution with the concentration of 50 g/L. Then, 25vol% ammonia water solution is added dropwise into the bismuth nitrate solution under the condition of continuous stirring until the pH value of the solution is 10, so as to obtain a precursor solution of bismuth oxide. Adding 0.1178 g bismuth subnitrate powder into 20ml bismuth oxide precursor solution, stirring for 15min to make the bismuth subnitrate powder uniform, transferring the mixture into a crucible with the volume of 50 ml, controlling the heating rate of a muffle furnace to be 5 ℃/min, and preserving heat at 240 ℃ for 120min, and cooling the muffle furnace to room temperature to obtain the bismuth subnitrate/bismuth oxide composite material with the bismuth subnitrate mass ratio of 20%.
Example 3
Bismuth nitrate pentahydrate solid of 0.485 and g is taken, added into a beaker filled with 40 ml deionized water, and stirred at a constant temperature of 25 ℃ for 10 min to obtain bismuth nitrate solution with the concentration of 12.12 g/L. Transferring the stirred bismuth nitrate solution into a hydrothermal kettle with a 50 ml polytetrafluoroethylene lining, controlling the heating rate to be 5 ℃/min, raising the temperature to 180 ℃, carrying out heat preservation reaction for 12 h, controlling the centrifugation rate to be 4000 rpm after the hydrothermal kettle is cooled to room temperature, washing the obtained precipitate with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and then drying at 60 ℃ for 2 h to obtain the bismuth subnitrate solid powder. The bismuth nitrate pentahydrate solid of 5 g is added into a beaker filled with 100 ml deionized water, and stirred at constant temperature of 25 ℃ for 10 min to obtain bismuth nitrate solution with the concentration of 50 g/L. Then, 25vol% ammonia water solution is added dropwise into the bismuth nitrate solution under the condition of continuous stirring until the pH value of the solution is 10, so as to obtain a precursor solution of bismuth oxide. Adding 0.1767 g bismuth subnitrate powder into 20ml bismuth oxide precursor solution, stirring for 15min to make the bismuth subnitrate powder uniform, transferring the mixture into a crucible with the volume of 50 ml, controlling the heating rate of a muffle furnace to be 5 ℃/min, and preserving heat at 240 ℃ for 120min, and obtaining the bismuth subnitrate/bismuth oxide composite material with the bismuth subnitrate mass ratio of 30% after the muffle furnace is cooled to room temperature.
Example 4
Bismuth nitrate pentahydrate solid of 0.485 and g is taken, added into a beaker filled with 40 ml deionized water, and stirred at a constant temperature of 25 ℃ for 10 min to obtain bismuth nitrate solution with the concentration of 12.12 g/L. Transferring the stirred bismuth nitrate solution into a hydrothermal kettle with a 50 ml polytetrafluoroethylene lining, controlling the heating rate to be 5 ℃/min, raising the temperature to 180 ℃, carrying out heat preservation reaction for 12 h, controlling the centrifugation rate to be 4000 rpm after the hydrothermal kettle is cooled to room temperature, washing the obtained precipitate with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and then drying at 60 ℃ for 2 h to obtain the bismuth subnitrate solid powder. The bismuth nitrate pentahydrate solid of 5 g is added into a beaker filled with 100 ml deionized water, and stirred at constant temperature of 25 ℃ for 10 min to obtain bismuth nitrate solution with the concentration of 50 g/L. Then, 25vol% ammonia water solution is added dropwise into the bismuth nitrate solution under the condition of continuous stirring until the pH value of the solution is 10, so as to obtain a precursor solution of bismuth oxide. Adding 0.2945 g bismuth subnitrate powder into 20ml bismuth oxide precursor solution, stirring for 15min to make the bismuth subnitrate powder uniform, transferring the mixture into a crucible with the volume of 50 ml, controlling the heating rate of a muffle furnace to be 5 ℃/min, and preserving heat at 240 ℃ for 120min, and obtaining the bismuth subnitrate/bismuth oxide composite material with the bismuth subnitrate mass ratio of 50% after the muffle furnace is cooled to room temperature.
FIG. 1 is an X-ray diffraction pattern of bismuth subnitrate/bismuth oxide composite materials (BBN-BO-X%) prepared in examples 1-4. As can be seen from the graph, the bismuth subnitrate/bismuth oxide composite materials prepared by the invention have higher crystallinity, and the X-ray diffraction peak of the bismuth subnitrate/bismuth oxide composite materials completely accords with the standard card.
FIG. 2 is a scanning electron microscope image of bismuth subnitrate (BBN), bismuth Oxide (BO) and bismuth subnitrate/bismuth oxide composite material (BBN-BO) prepared in example 2. From the figure, the synthesized bismuth subnitrate is flaky, the bismuth oxide is in a flower-shaped morphology, and the bismuth subnitrate/bismuth oxide composite material presents a lamellar stacked morphology, which indicates that the bismuth subnitrate nano-sheets are uniformly combined with the 3D flower-shaped bismuth oxide.
The bismuth subnitrate/bismuth oxide composite materials prepared in examples 1 to 4 were each 25. 25mg and were used to degrade 50 ml and 20 mg/L rhodamine B dye solutions under simulated sunlight, and the dye removal was measured after 60 minutes, and the results are shown in Table 1.
Comparative photocatalytic Effect of bismuth subnitrate/bismuth oxide composite Material obtained in example 1
Comparative example 1
(1) Preparation of bismuth subnitrate: bismuth nitrate pentahydrate solid of 0.485 and g is taken, added into a beaker filled with 40 ml deionized water, and stirred at a constant temperature of 25 ℃ for 10 min to obtain bismuth nitrate solution with the concentration of 12.12 g/L. Transferring the stirred bismuth nitrate solution into a hydrothermal kettle with a 50 ml polytetrafluoroethylene lining, controlling the heating rate to be 5 ℃/min, raising the temperature to 180 ℃, carrying out heat preservation reaction for 12 h, controlling the centrifugation rate to be 4000 rpm after the hydrothermal kettle is cooled to room temperature, washing the obtained precipitate with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and then drying at 60 ℃ for 2 h to obtain the bismuth subnitrate solid powder.
(2) Preparation of bismuth oxide: another 0.485 and g pentahydrate bismuth nitrate solid and 0.213 and g sodium sulfate are dissolved in 20mL distilled water and stirred at room temperature for 45min to obtain a mixed solution. Then 0.36 g of NaOH is dissolved in 20mL deionized water and stirred for 15min, then the obtained NaOH solution is slowly dripped into the prepared mixed solution, stirred for 45min, then the mixed solution is transferred into a hydrothermal kettle with a 50 ml polytetrafluoroethylene lining, the heating rate is controlled to be 5 ℃/min, the temperature is increased to 120 ℃, the reaction is kept at 12 h, after the hydrothermal kettle is cooled to room temperature, the centrifugation rate is controlled to be 4000 rpm, the obtained precipitate is firstly washed 3 times with deionized water and then washed 2 times with absolute ethyl alcohol, and then dried at 60 ℃ for 2 h, thus obtaining bismuth oxide solid powder.
(3) Preparation of the composite material: and (3) uniformly mixing 0.1178 g basic bismuth nitrate powder and 0.4712 g bismuth oxide, transferring the mixture into a hydrothermal kettle with a 50 ml polytetrafluoroethylene lining, controlling the heating rate to be 5 ℃/min, raising the temperature to 240 ℃, carrying out heat preservation reaction for 2 h, controlling the centrifugation rate to be 4000 rpm after the hydrothermal kettle is cooled to room temperature, washing the obtained precipitate with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and then drying the precipitate at 60 ℃ for 2 h to obtain the composite BBN-BO-HT.
Comparative example 2
Steps (1), (2) refer to comparative example 1;
(3) Preparation of the composite material: and (3) uniformly mixing 0.1178 g basic bismuth nitrate powder and 0.4712 g bismuth oxide, and grinding to obtain the composite material BBN-BO-MI.
The bismuth subnitrate/bismuth oxide composite material prepared in example 2 and the composite materials BBN-BO-HT and BBN-BO-MI prepared in comparative examples 1 and 2 were taken and each 25 and mg was used to degrade 50 ml and 20 mg/L rhodamine B dye solutions under simulated sunlight irradiation, and the dye removal was measured at regular intervals, and the results are shown in FIG. 3.
As can be seen from FIG. 3, the bismuth subnitrate/bismuth oxide composite material prepared by the calcination method of the present invention has better photocatalytic performance.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. A method of synthesizing bismuth subnitrate/bismuth oxide composite material, the method comprising the steps of:
1) Adding bismuth nitrate pentahydrate into water, and stirring to prepare bismuth nitrate solution A;
2) Transferring the prepared bismuth nitrate solution A into a hydrothermal kettle for hydrothermal reaction;
3) After the hydrothermal reaction is finished, collecting precipitate, washing and drying to obtain bismuth subnitrate solid;
4) Adding bismuth nitrate pentahydrate into water, and stirring to prepare bismuth nitrate solution B with a certain concentration;
5) Slowly dripping ammonia water solution into the continuously stirred bismuth nitrate solution B, and regulating the pH value of the solution;
6) Adding a certain mass of bismuth subnitrate solid prepared in the step 3) into the solution obtained in the step 5), and uniformly stirring;
7) Transferring the mixture obtained in the step 6) into a crucible, and calcining to obtain a bismuth subnitrate/bismuth oxide composite material;
the concentration of the bismuth nitrate solution B obtained in the step 4) is 50 g/L;
step 5), regulating the pH value of the solution to be 10;
the amount of bismuth subnitrate solid added in step 6) is 2.945-14.725mg/mL.
2. A method of synthesizing bismuth subnitrate/bismuth oxide composite material according to claim 1, wherein: the concentration of bismuth nitrate solution A obtained in the step 1) was 12.12. 12.12 g/L.
3. A method of synthesizing bismuth subnitrate/bismuth oxide composite material according to claim 1, wherein: the hydrothermal reaction in the step 2) is to heat up to 180 ℃ at a speed of 5 ℃/min, and heat preservation is carried out for 12 h.
4. A method of synthesizing bismuth subnitrate/bismuth oxide composite material according to claim 1, wherein: the aqueous ammonia solution used in step 5) has a volume concentration of 25%.
5. A method of synthesizing bismuth subnitrate/bismuth oxide composite material according to claim 1, wherein: the stirring time in step 6) was 15 min.
6. A method of synthesizing bismuth subnitrate/bismuth oxide composite material according to claim 1, wherein: step 7) the calcination is to heat up to 240 ℃ at a rate of 5 ℃/min and treat for 120min.
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| CN104437536A (en) * | 2014-11-13 | 2015-03-25 | 重庆大学 | Preparation method of manganese zinc ferrite/bismuth oxide magnetic photocatalyst |
| CN106824213A (en) * | 2017-02-20 | 2017-06-13 | 上海大学 | A kind of basic bismuth carbonate/bismuth oxychloride photocatalyst of cobalt/cobalt oxide doping and preparation method thereof |
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