CN112108161B - Method for rapidly preparing bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst, product and application thereof - Google Patents
Method for rapidly preparing bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst, product and application thereof Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 49
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 49
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 43
- 239000002135 nanosheet Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 129
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 41
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 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 abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000005303 weighing Methods 0.000 claims abstract description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 hydroxyl free radical Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention relates to a method for rapidly preparing a bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst and a product and application thereof.A method for rapidly preparing a bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst comprises the steps of accurately weighing ammonium metavanadate, hexadecyl ammonium bromide, sodium hydroxide and deionized water, dissolving the sodium hydroxide in the deionized water to prepare a sodium hydroxide solution, and then adding the ammonium metavanadate and the hexadecyl ammonium bromide into the sodium hydroxide solution; after the solution is stirred uniformly, bismuth nitrate is added into the solution, and then the solution is reacted in a hydrothermal reaction kettle for a period of time at a certain temperature. And after natural cooling, centrifuging, washing and drying to obtain the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst. The bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst obtained by the preparation method provided by the invention has the advantages of high separation efficiency of photo-generated electrons and holes, good effect of photocatalytic degradation of formaldehyde, simple operation, few steps, easily available raw materials, low cost and suitability for large-scale production.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a method for rapidly preparing a bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst, and a product and application thereof.
Background
Energy is the material basis on which humans live and on which human civilization exists. Since the 21 st century, with the rapid development of industry, the demand of human beings for energy has been greatly increased, which causes the exhaustion of non-renewable fossil energy on the one hand and also brings about very serious environmental problems on the other hand. Because solar energy has the characteristics of cleanness, large energy, abundant reserves and the like, the technology for utilizing the solar energy becomes a key for solving the energy and environmental crisis in the new century. The photocatalytic technology can utilize solar energy to purify the environment and convert energy, and becomes a research hotspot. On one hand, the solar energy with low density can be converted into chemical energy with high density to solve the energy crisis, and on the other hand, the environmental crisis can be solved by decomposing various pollutants, killing bacteria and viruses and the like. However, the existing photocatalytic materials still have various problems.
Bismuth vanadate is a bright yellow inorganic chemical, does not contain heavy metal elements harmful to human bodies, and is an environment-friendly low-carbon metal oxide substance. Besides, it also has a certain photocatalytic property. Under the irradiation of sunlight, electrons on the valence band of bismuth vanadate can generate transition to generate photoproduction electron and hole pair, and the photoproduction electron reacts with the hole, oxygen in the air and water to generate hydroxyl free radical, superoxide free radical and the like, so that bacteria, viruses and the like such as escherichia coli and staphylococcus aureus can be killed. In addition, the bismuth vanadate is also applied to office or home environments to decompose organic compounds and toxic substances in the air, such as benzene, formaldehyde, ammonia, TVOC and the like, so as to play a role in purifying the air. However, bismuth vanadate has some problems at present, for example, the recombination of photo-generated electrons and holes is easy to occur, so that a certain amount of photo-generated electron/hole pairs are consumed, and the exertion of the photocatalytic performance is greatly influenced.
Due to the difference of valence band and conduction band positions of the two semiconductors, when light is irradiated by sunlight to separate electrons and holes, the photogenerated electrons and the holes can migrate, so that the electrons and the holes are respectively positioned on the surfaces of different semiconductors, and the recombination of the photogenerated electrons and the holes is further inhibited. However, the current method for constructing the heterojunction is too cumbersome, and it is necessary to synthesize a semiconductor photocatalyst first, and then synthesize another photocatalyst on the surface of the semiconductor, so as to construct the heterojunction.
Disclosure of Invention
Aiming at the defect that the existing bismuth vanadate photo-generated electron and hole separation efficiency is low, the invention aims to provide a method for quickly preparing a bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst.
Yet another object of the present invention is to: provides a bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst product prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a method for rapidly preparing a bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst comprises the following steps:
1) Weighing ammonium metavanadate, hexadecyl ammonium bromide, sodium hydroxide and deionized water, firstly dissolving sodium hydroxide in the deionized water to prepare a sodium hydroxide solution with the concentration of 0.1-10 mol/L, and then adding the ammonium metavanadate and the hexadecyl ammonium bromide into the sodium hydroxide solution to obtain a mixed solution, wherein the mass ratio of the ammonium metavanadate to the hexadecyl ammonium bromide is 1;
2) Adding bismuth nitrate into the mixed solution according to the mass ratio of the ammonium metavanadate to the bismuth nitrate of 1:1-10, then adding the bismuth nitrate into a hydrothermal reaction kettle, heating the mixture to 100-200 ℃ in an oven, reacting for 1-48 h, naturally cooling, centrifuging, washing and drying to obtain the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst.
The invention also provides a bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst prepared according to the method.
The invention provides an application of a bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst as a catalyst in photocatalytic degradation of formaldehyde.
The method for rapidly preparing the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst provided by the invention comprises the following steps: accurately weighing ammonium metavanadate, hexadecyl ammonium bromide, sodium hydroxide and deionized water, dissolving the sodium hydroxide in the deionized water to prepare a sodium hydroxide solution, then adding the ammonium metavanadate and the hexadecyl ammonium bromide into the sodium hydroxide solution, stirring the solution uniformly, then adding bismuth nitrate into the solution, and then reacting the solution in a hydrothermal reaction kettle at a certain temperature for a period of time. And after natural cooling, centrifuging, washing and drying to obtain the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst.
According to the invention, a one-step reaction method is adopted, and the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst is prepared through hydrothermal reaction, so that on one hand, the photoproduction electron/hole separation efficiency of bismuth vanadate is improved through the construction of a heterojunction; on the other hand, the preparation method is rapid through a one-step method, and the defect that the steps are complicated in the preparation process of the common heterojunction is overcome. The bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst prepared by the preparation method provided by the invention has the advantages of high separation efficiency of photo-generated electrons and holes, good formaldehyde photocatalytic degradation effect, excellent formaldehyde degradation performance under visible light, no less than 90% of degradation rate, simple operation, few steps, easily obtained raw materials, low cost and suitability for expanded production.
Drawings
Fig. 1, TEM photograph of bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst prepared in example 1;
fig. 2 TEM diffractogram of bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst prepared in example 1, with the dots being due to bismuth vanadate crystal lattice and the rings being due to bismuth oxybromide.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
A bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst is rapidly prepared according to the following steps:
1) Accurately weighing ammonium metavanadate, hexadecyl ammonium bromide, sodium hydroxide and deionized water according to the mass ratio of the ammonium metavanadate to the hexadecyl ammonium bromide being 1.4, firstly, dissolving the sodium hydroxide in the deionized water to prepare a sodium hydroxide solution with the concentration of 1 mol/L, and then, adding the ammonium metavanadate and the hexadecyl ammonium bromide into the sodium hydroxide solution according to the mass ratio of the ammonium metavanadate to the sodium hydroxide solution being 1;
2) Adding bismuth nitrate into the mixed solution according to the mass ratio of ammonium metavanadate to bismuth nitrate 1:2, then adding the mixed solution into a hydrothermal reaction kettle, heating the mixed solution to 150 ℃ in an oven, reacting for 24 hours, naturally cooling, centrifuging, washing and drying to obtain the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst.
Fig. 1, TEM photograph of bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst prepared in example 1;
fig. 2 TEM diffraction photographs of the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst prepared in example 1, the dots in the figures being due to the bismuth vanadate crystal lattice and the rings being due to bismuth oxybromide.
The performance degradation rate of the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst prepared by the method in the embodiment for degrading formaldehyde under visible light reaches 92.6%, and is detailed in table 1.
Example 2
A bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst is similar to that in example 1, and is rapidly prepared according to the following steps:
1) Accurately weighing ammonium metavanadate, hexadecyl ammonium bromide, sodium hydroxide and deionized water according to the mass ratio of the ammonium metavanadate to the hexadecyl ammonium bromide being 1.6, firstly, dissolving the sodium hydroxide in the deionized water to prepare a sodium hydroxide solution with the concentration of 1.5 mol/L, and then, adding the ammonium metavanadate and the hexadecyl ammonium bromide into the sodium hydroxide solution according to the mass ratio of the ammonium metavanadate to the sodium hydroxide solution being 1;
2) Adding bismuth nitrate into the mixed solution according to the mass ratio of ammonium metavanadate to bismuth nitrate of 1:3, then adding the mixed solution into a hydrothermal reaction kettle, heating the mixed solution to 180 ℃ in an oven, reacting for 12 hours, naturally cooling, centrifuging, washing and drying to obtain the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst.
The degradation rate of the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst prepared by the method in the embodiment for degrading formaldehyde under visible light reaches 95.7%, and is detailed in table 1.
Example 3
A bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst is similar to that in example 1, and is prepared rapidly according to the following steps:
1) Accurately weighing ammonium metavanadate, hexadecyl ammonium bromide, sodium hydroxide and deionized water according to the mass ratio of the ammonium metavanadate to the hexadecyl ammonium bromide being 1;
2) Adding bismuth nitrate into the mixed solution according to the mass ratio of ammonium metavanadate to bismuth nitrate of 1: 2.5, then adding the mixed solution into a hydrothermal reaction kettle, heating the mixed solution to 160 ℃ in an oven, reacting for 36 hours, naturally cooling, centrifuging, washing and drying to obtain the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst.
The performance degradation rate of the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst prepared by the method in the embodiment for degrading formaldehyde under visible light reaches 90.2%, and is detailed in table 1.
Table 1 performance of the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst prepared by the method of the present invention in degrading formaldehyde under visible light:
Claims (6)
1. a method for rapidly preparing a bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst is characterized by comprising the following specific steps:
1) Weighing ammonium metavanadate, hexadecyl ammonium bromide, sodium hydroxide and deionized water, firstly dissolving sodium hydroxide in the deionized water to prepare a sodium hydroxide solution with the concentration of 0.1-10 mol/L, and then adding the ammonium metavanadate and the hexadecyl ammonium bromide into the sodium hydroxide solution to obtain a mixed solution, wherein the mass ratio of the ammonium metavanadate to the hexadecyl ammonium bromide is 1 (0.01-10), and the mass ratio of the ammonium metavanadate to the sodium hydroxide solution is 1 (20-1000);
2) Adding bismuth nitrate into the mixed solution according to the mass ratio of the ammonium metavanadate to the bismuth nitrate of 1:1-10, adding the mixed solution into a hydrothermal reaction kettle, heating the mixed solution to 100-200 ℃ in an oven, reacting for 1-48 h, naturally cooling, centrifuging, washing and drying to obtain the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst.
2. The method for rapidly preparing the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst according to claim 1, which is characterized by comprising the following steps:
1) Accurately weighing ammonium metavanadate, hexadecyl ammonium bromide, sodium hydroxide and deionized water according to the mass ratio of the ammonium metavanadate to the hexadecyl ammonium bromide being 1.4, firstly, dissolving the sodium hydroxide in the deionized water to prepare a sodium hydroxide solution with the concentration of 1 mol/L, and then, adding the ammonium metavanadate and the hexadecyl ammonium bromide into the sodium hydroxide solution according to the mass ratio of the ammonium metavanadate to the sodium hydroxide solution being 1;
2) Adding bismuth nitrate into the mixed solution according to the mass ratio of ammonium metavanadate to bismuth nitrate 1:2, then adding the mixed solution into a hydrothermal reaction kettle, heating the mixed solution to 150 ℃ in an oven, reacting for 24 hours, naturally cooling, centrifuging, washing and drying to obtain the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst.
3. The method for rapidly preparing the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst according to claim 1, which is characterized by comprising the following steps:
1) Accurately weighing ammonium metavanadate, hexadecyl ammonium bromide, sodium hydroxide and deionized water according to the mass ratio of the ammonium metavanadate to the hexadecyl ammonium bromide being 1.6, firstly, dissolving the sodium hydroxide in the deionized water to prepare a sodium hydroxide solution with the concentration of 1.5 mol/L, and then, adding the ammonium metavanadate and the hexadecyl ammonium bromide into the sodium hydroxide solution according to the mass ratio of the ammonium metavanadate to the sodium hydroxide solution being 1;
2) Adding bismuth nitrate into the mixed solution according to the mass ratio of ammonium metavanadate to bismuth nitrate of 1:3, then adding the mixed solution into a hydrothermal reaction kettle, heating the mixed solution to 180 ℃ in an oven, reacting for 12 hours, naturally cooling, centrifuging, washing and drying to obtain the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst.
4. The method for rapidly preparing the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst according to claim 1, which is characterized by comprising the following steps:
1) Accurately weighing ammonium metavanadate, hexadecyl ammonium bromide, sodium hydroxide and deionized water according to the mass ratio of the ammonium metavanadate to the hexadecyl ammonium bromide being 1.5, firstly, dissolving the sodium hydroxide in the deionized water to prepare a sodium hydroxide solution with the concentration of 2 mol/L, and then, adding the ammonium metavanadate and the hexadecyl ammonium bromide into the sodium hydroxide solution according to the mass ratio of the ammonium metavanadate to the sodium hydroxide solution being 1;
2) Adding bismuth nitrate into the mixed solution according to the mass ratio of ammonium metavanadate to bismuth nitrate of 1: 2.5, then adding the mixed solution into a hydrothermal reaction kettle, heating the mixed solution to 160 ℃ in an oven, reacting for 36 hours, naturally cooling, centrifuging, washing and drying to obtain the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst.
5. A bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst, characterized by being prepared according to the method of any one of claims 1 to 4.
6. The application of the bismuth vanadate/bismuth oxybromide nanosheet heterojunction photocatalyst according to claim 2 as a catalyst in photocatalytic degradation of formaldehyde.
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