CN115893487B - Bismuth sulfide nano material with controllable morphology and preparation method and application thereof - Google Patents
Bismuth sulfide nano material with controllable morphology and preparation method and application thereof Download PDFInfo
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- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 title claims abstract description 137
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 6
- 229950004394 ditiocarb Drugs 0.000 claims description 6
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 claims description 3
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002073 nanorod Substances 0.000 abstract description 20
- 239000002135 nanosheet Substances 0.000 abstract description 19
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 7
- 230000033228 biological regulation Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 5
- 238000004729 solvothermal method Methods 0.000 abstract description 4
- 239000002071 nanotube Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 8
- 239000002064 nanoplatelet Substances 0.000 description 8
- 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 8
- 229940043267 rhodamine b Drugs 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 5
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 4
- BWKIBIZZLRPKFY-UHFFFAOYSA-N 1,2,3-benzothiadiazole-5-carbaldehyde Chemical compound O=CC1=CC=C2SN=NC2=C1 BWKIBIZZLRPKFY-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- WWGXHTXOZKVJDN-UHFFFAOYSA-M sodium;n,n-diethylcarbamodithioate;trihydrate Chemical compound O.O.O.[Na+].CCN(CC)C([S-])=S WWGXHTXOZKVJDN-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 125000003916 ethylene diamine group Chemical group 0.000 description 1
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- 239000002057 nanoflower Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a bismuth sulfide nano material with controllable morphology, and a preparation method and application thereof, wherein the preparation method comprises the following steps: providing Bi (S) 2 CNEt 2 ) 3 Powder and fatty amine solvent; the Bi (S) 2 CNEt 2 ) 3 The powder is dispersed in the fatty amine solvent, and then reacts for a preset time at a preset reaction temperature to obtain the bismuth sulfide nano material with the required morphology. The invention adopts solvothermal reaction and uses a single precursor Bi (S 2 CNEt 2 ) 3 The powder takes aliphatic amine solvent as solvent,the bismuth sulfide nano-materials (nano-sheet bismuth sulfide nano-materials, nano-tubular bismuth sulfide nano-materials and nano-rod bismuth sulfide nano-materials) with different shapes can be prepared by simply controlling the reaction time and the reaction temperature under the same reaction system without any substance regulation and control, and the method is simple, safe and pollution-free.
Description
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to a bismuth sulfide nano material with controllable morphology, a preparation method and application thereof.
Background
Bismuth sulfide is a direct bandgap semiconductor material, has good light absorption and excellent optoelectronic properties, attracts much attention in recent years, and has been used in various fields such as photocatalysis, photovoltaics, medicine, and energy storage. In order to be widely researched and applied, the simple and controllable synthesis of bismuth sulfide materials is required to be higher. At present, bismuth sulfide has been prepared into various morphologies, and bismuth sulfide with different morphologies has unique properties, in particular, bismuth sulfide nano-materials, the catalytic properties of which are closely related to the morphologies. Up to now, bismuth sulfide with different morphologies is prepared by solvothermal, hydrothermal or ionothermal reactions under different reaction systems and by utilizing different reactants and combining with pH regulation of a surfactant or a solution, and the preparation cost is increased, the preparation complexity is increased and the research and application of bismuth sulfide are limited to a certain extent while morphology regulation is realized.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide the bismuth sulfide nano material with controllable morphology, and the preparation method and application thereof, and aims to solve the problem that the bismuth sulfide material with different morphology is obtained by different preparation methods under different reaction systems and cannot be prepared by the same preparation method under the same system.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, a method for preparing a bismuth sulfide nanomaterial with controllable morphology is provided, wherein the method comprises the following steps:
providing Bi (S) 2 CNEt 2 ) 3 Powder and fatty amine solvent;
the Bi (S) 2 CNEt 2 ) 3 The powder is dispersed in the fatty amine solvent, and then reacts for a preset time at a preset reaction temperature to obtain the bismuth sulfide nano material with the required morphology.
Optionally, the carbon number of the carbon chain of the fatty amine solvent is less than or equal to 3.
Optionally, the fatty amine solvent is at least one selected from trimethylamine, monoethylamine, ethylenediamine and propylamine.
Alternatively, the Bi (S 2 CNEt 2 ) 3 The preparation method of the powder comprises the following steps:
providing an aqueous bismuth nitrate solution and an aqueous sodium diethyldithiocarbamate solution;
dropwise adding the bismuth nitrate aqueous solution into the diethyl sodium dithiocarbamate aqueous solution, and reacting to obtain the Bi (S) 2 CNEt 2 ) 3 And (3) powder.
Alternatively, the Bi (S 2 CNEt 2 ) 3 The ratio of the powder to the fatty amine solvent is (0.15-0.3) g: (10-20) mL.
Optionally, reacting for 1-12 h at the reaction temperature of 80-200 ℃ to obtain the bismuth sulfide nano material with the required morphology.
Optionally, reacting for 0.5-2 hours at the reaction temperature of 80-130 ℃ to obtain nano flaky bismuth sulfide nano material;
reacting for 3-6 h at the reaction temperature of 130-150 ℃ to obtain nano-tubular bismuth sulfide nano-material;
reacting for 8-12 h at the reaction temperature of 130-150 ℃ to obtain the nano rod-shaped bismuth sulfide nano material.
In a second aspect of the invention, a bismuth sulfide nanomaterial with controllable morphology is provided, wherein the bismuth sulfide nanomaterial is prepared by the preparation method disclosed by the invention.
In a third aspect, the invention provides an application of the morphology-controllable bismuth sulfide nanomaterial in the field of photocatalysis.
Optionally, the morphology-controllable bismuth sulfide nanomaterial is applied to photocatalytic decomposition of organic pollutants as a photocatalyst.
The beneficial effects are that: the invention provides a preparation method of a bismuth sulfide nano material with controllable morphology, which specifically adopts solvothermal reaction and uses a single precursor Bi (S 2 CNEt 2 ) 3 The powder takes the aliphatic amine solvent as the solvent, does not need any substance regulation and control, and can prepare the required bismuth sulfide nano-materials (nano-sheet bismuth sulfide nano-materials, nano-tubular bismuth sulfide nano-materials and nano-rod bismuth sulfide nano-materials) with different shapes and uniformity by simply controlling the reaction time and the reaction temperature, and the method is simple, safe and pollution-free. The bismuth sulfide nano material with controllable morphology is prepared by a simple same preparation method under the same reaction system, and the blank of preparing bismuth sulfide nano materials with different morphologies by the same preparation method under the same reaction system is overcome.
Drawings
FIG. 1 is an XRD pattern of bismuth sulfide nanosheets, bismuth sulfide nanotubes, and bismuth sulfide nanorods prepared in examples 1 to 3 of the present invention.
FIG. 2 is a FESEM image of bismuth sulfide nanoplatelets, bismuth sulfide nanotubes, and bismuth sulfide nanorods prepared in examples 1-3 of the present invention, wherein (a) is a FESEM image of bismuth sulfide nanoplatelets prepared in example 1, and (d) is an enlarged image of (a); (b) An FESEM image of bismuth sulfide nanotubes prepared in example 2, and (e) an enlarged image of (b); (c) The FESEM image of the bismuth sulfide nanorods prepared in example 3, and (f) is an enlarged image of (c).
Fig. 3 is an EDS diagram of the bismuth sulfide nanosheets prepared in example 1 of the present invention.
FIG. 4 is a graph showing the results of decomposing rhodamine B with the bismuth sulfide nanosheets, bismuth sulfide nanotubes, and bismuth sulfide nanorods prepared in examples 1 to 3 of the present invention, wherein (a) is C t /C 0 A time-dependent graph, (b) is ln (C) 0 /C t ) Time-dependent graph.
In fig. 5, (a) is a FESEM view of bismuth sulfide prepared at 130 ℃ for 0.5h, (b) is a FESEM view of bismuth sulfide prepared at 130 ℃ for 2h, (c) is a FESEM view of bismuth sulfide prepared at 130 ℃ for 4h, and (d) is a FESEM view of bismuth sulfide prepared at 130 ℃ for 8 h.
FIG. 6 is an SEM image of the product obtained in comparative example 1 using water as a solvent at various reaction temperatures and reaction times, where (a) is 150℃for 6h; (b) 150 ℃ for 24 hours; (c) 180℃for 6h; (d) 180 ℃ for 24 hours; (e) 200 ℃ for 24h.
FIG. 7 is an SEM image of the product obtained in comparative example 2 using ethanol as a solvent at various reaction temperatures and reaction times, where (a) is 120℃for 6h; (b) 120 ℃ for 12 hours; (c) 150 ℃ for 6h; (d) 150 ℃ for 24 hours; (e) 180 ℃ for 6h; (f) 180℃for 12h.
FIG. 8 is an SEM image of the product obtained in comparative example 3 using ethylene glycol as a solvent at various reaction temperatures and reaction times, where (a) is 150℃for 6h; (b) 150 ℃ for 24 hours; (c) 200 ℃ for 12 hours; (d) 200 ℃ for 24 hours.
Detailed Description
The invention provides a bismuth sulfide nano material with controllable morphology, a preparation method and application thereof, and aims to make the purposes, the technical scheme and the effects of the bismuth sulfide nano material clearer and more definite, and the bismuth sulfide nano material is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The embodiment of the invention provides a preparation method of a bismuth sulfide nano material with controllable morphology, which comprises the following steps:
s1, bi (S) 2 CNEt 2 ) 3 Powder and fatty amine solvent;
s2, the Bi (S 2 CNEt 2 ) 3 Powder bodyDispersing the bismuth sulfide nano material in the aliphatic amine solvent, and then reacting for a preset time at a preset reaction temperature to obtain the bismuth sulfide nano material with the required micro morphology.
The embodiment of the invention provides a preparation method of a bismuth sulfide nano material with controllable morphology, which specifically adopts solvothermal reaction and uses a single precursor Bi (S 2 CNEt 2 ) 3 The powder takes the aliphatic amine solvent as the solvent, does not need any substance regulation (such as morphology control agent or pH value regulator), can prepare the required bismuth sulfide nano-materials (nano-sheet bismuth sulfide nano-materials, nano-tubular bismuth sulfide nano-materials and nano-rod bismuth sulfide nano-materials) with different morphologies and uniformity only by simply controlling the reaction time and the reaction temperature, and has the advantages of simple method, safety and no pollution. The bismuth sulfide nano material with controllable morphology is prepared by a simple same preparation method under the same reaction system, and the blank of preparing bismuth sulfide nano materials with different morphologies by the same preparation method under the same reaction system is overcome.
It is understood that the topography in this embodiment refers to a microscopic topography, i.e. a topography that is observed by magnifying the material (e.g. by scanning electron microscopy).
In one embodiment, the aliphatic amine solvent has 3 or less carbon atoms in the carbon chain.
In one embodiment, the aliphatic amine solvent is at least one selected from trimethylamine, monoethylamine, ethylenediamine, and propylamine, but is not limited thereto. Wherein trimethylamine and monoethylamine are gases, and when the gas is specifically used, it was dissolved in water to prepare an aqueous solution having a mass fraction of 30 wt%.
In one embodiment, the Bi (S 2 CNEt 2 ) 3 The preparation method of the powder comprises the following steps:
s11, providing a bismuth nitrate aqueous solution and a sodium diethyl dithiocarbamate aqueous solution;
s12, dropwise adding the bismuth nitrate aqueous solution into the diethyl sodium dithiocarbamate aqueous solution, and reacting to obtain the Bi (S) 2 CNEt 2 ) 3 And (3) powder.
In the present embodiment, bi (S 2 CNEt 2 ) 3 The powder can be prepared by directly mixing bismuth nitrate and an aqueous solution of diethyl sodium dithiocarbamate, and the preparation method is simple and easy to operate.
In step S11, the bismuth nitrate aqueous solution can be prepared by dissolving bismuth nitrate pentahydrate in water. The aqueous solution of sodium diethyldithiocarbamate can be prepared by dissolving sodium diethyldithiocarbamate trihydrate in water.
In S12, the bismuth nitrate aqueous solution is dropwise added into the diethyl sodium dithiocarbamate aqueous solution at normal temperature, and the Bi (S) is obtained after the reaction 2 CNEt 2 ) 3 And (3) powder. Wherein the molar ratio of bismuth nitrate in the bismuth nitrate aqueous solution to sodium diethyl dithiocarbamate in the sodium diethyl dithiocarbamate aqueous solution is 1:3.
in one embodiment, the Bi (S 2 CNEt 2 ) 3 The ratio of the powder to the fatty amine solvent is (0.15-0.3) g: (10-20) mL.
When the aliphatic amine solvent is selected from trimethylamine and monoethylamine, bi (S 2 CNEt 2 ) 3 The ratio of the powder to the trimethylamine water solution with the mass fraction of 30 percent is (0.15-0.3) g: (10-20) mL; bi (S) 2 CNEt 2 ) 3 The ratio of the powder to the monoethylamine aqueous solution with the mass fraction of 30 percent is (0.15-0.3) g: (10-20) mL.
When the aliphatic amine solvent is selected from ethylenediamine and propylamine, bi (S 2 CNEt 2 ) 3 The ratio of the powder to the ethylenediamine is 0.15-0.3) g: (10-20) mL, bi (S) 2 CNEt 2 ) 3 The ratio of the powder to the propylamine is (0.15-0.3) g: (10-20) mL.
In one embodiment, the bismuth sulfide nano material with the required morphology is obtained by reacting for 1 to 12 hours at the reaction temperature of 80 to 200 ℃.
In some specific embodiments, reacting for 0.5-2 hours at a reaction temperature of 80-130 ℃ to obtain nano-sheet bismuth sulfide nano-material (i.e. bismuth sulfide nano-sheet);
reacting for 3-6 h at the reaction temperature of 130-150 ℃ to obtain a nano-tubular bismuth sulfide nano-material (namely a bismuth sulfide nano-tube);
reacting for 8-12 h at the reaction temperature of 130-150 ℃ to obtain the nano rod-shaped bismuth sulfide nano material (namely the bismuth sulfide nano rod).
The invention provides a preparation method of bismuth sulfide nanosheets (80-130 ℃ and 0.5-2 h), bismuth sulfide nanotubes (130-150 ℃ and 3-6 h) and bismuth sulfide nanorods (130-150 ℃ and 8-12 h) under a single precursor without any matter regulation and control, wherein morphology of bismuth sulfide is increased along with the increase of the time, the bismuth sulfide is crushed and regrown into the nanotubes from the nanosheets, the nanotube walls are gradually thickened and grown into the nanorods, specifically, the growth process of the bismuth sulfide can be shown in a graph (a) which is a FESEM graph (obtained nanosheets) of the bismuth sulfide prepared under the conditions of 130 ℃ and 0.5h, b) which is a FESEM graph (obtained nanosheets) of the bismuth sulfide prepared under the conditions of 130 ℃ and 2h, c) which is a FESEM graph (obtained nanotubes) of the bismuth sulfide prepared under the conditions of 130 ℃ and 4h, and d) which is a FESEM graph (obtained under the conditions of 130 ℃ and 8 h.
The embodiment of the invention also provides the bismuth sulfide nano material with controllable morphology, wherein the bismuth sulfide nano material is prepared by adopting the preparation method disclosed by the embodiment of the invention.
The bismuth sulfide nano material with controllable morphology provided by the embodiment of the invention can be bismuth sulfide nano sheets, bismuth sulfide nano tubes and bismuth sulfide nano rods. The bismuth sulfide nanosheets, bismuth sulfide nanotubes and bismuth sulfide nanorods have proper band gaps (1.3-1.7 eV) and energy bands, and are good visible light catalysts.
The embodiment of the invention also provides application of the bismuth sulfide nanomaterial with controllable morphology in the photocatalysis field. The bismuth sulfide nano material has proper band gap (1.3-1.7 eV) and energy band, is a good visible light catalyst, and has catalytic performance closely related to morphology.
In one embodiment, the morphology-controllable bismuth sulfide nanomaterial is used as a photocatalyst for photocatalytic decomposition of organic pollutants.
The following is a detailed description of specific examples.
Example 1
Bismuth nitrate pentahydrate is added into deionized water, and magnetically stirred for two hours at room temperature to obtain a solution A;
sodium diethyldithiocarbamate trihydrate (the molar ratio of the sodium diethyldithiocarbamate trihydrate to bismuth nitrate pentahydrate is 3:1) is added into deionized water, and magnetically stirred at room temperature for two hours to obtain a solution B;
under the condition of magnetic stirring, the solution A is dropwise added into the solution B, yellow solid is generated from the solution by transparency, and the yellow solid is continuously increased along with the dropping process. After 2h of magnetic stirring, the mixture was suction filtered to give a yellow solid, which was then dried in a dry oven at 60℃for 12h to give Bi (S) 2 CNEt 2 ) 3 Powder;
0.15g Bi (S) 2 CNEt 2 ) 3 The powder is added into a 50mL polytetrafluoroethylene kettle, 10mL of ethylenediamine monohydrate is added, and the mixture is magnetically stirred for 1h and then dispersed for 1h by ultrasonic. And (3) placing the dispersed solution into a homogeneous reaction furnace, carrying out suction filtration after reacting for 2 hours at the temperature of 100 ℃ under the condition of rotary stirring (30 rpm), alternately washing the obtained black solid substance with alcohol and deionized water for three times, and then placing the solution into a drying box and drying for 12 hours at the temperature of 60 ℃ to obtain the bismuth sulfide nano-sheet.
Example 2
Bi(S 2 CNEt 2 ) 3 The preparation method of the powder is the same as in example 1.
0.15g Bi (S) 2 CNEt 2 ) 3 The powder is added into a 50mL polytetrafluoroethylene kettle, 10mL of ethylenediamine monohydrate is added, and the mixture is magnetically stirred for 1h and then dispersed for 1h by ultrasonic. Placing the dispersed solution in a homogeneous reaction furnace, reacting at 150deg.C for 3 hr under rotary stirring (30 rpm), and vacuum filtering to obtain black solid materialAnd (3) alternately washing the bismuth sulfide nano-tubes with alcohol and deionized water for three times, and then drying the bismuth sulfide nano-tubes in a drying oven at 60 ℃ for 12 hours to obtain the bismuth sulfide nano-tubes.
Example 3
Bi(S 2 CNEt 2 ) 3 The preparation method of the powder is the same as in example 1.
0.15g Bi (S) 2 CNEt 2 ) 3 The powder is added into a 50mL polytetrafluoroethylene kettle, 10mL of ethylenediamine monohydrate is added, and the mixture is magnetically stirred for 1h and then dispersed for 1h by ultrasonic. And (3) placing the dispersed solution into a homogeneous reaction furnace, carrying out suction filtration after reacting for 12 hours at the temperature of 150 ℃ under the condition of rotary stirring (30 rpm), alternately washing the obtained black solid substance with alcohol and deionized water for three times, and then placing the solution into a drying box and drying for 12 hours at the temperature of 60 ℃ to obtain the bismuth sulfide nanorod.
And (3) testing:
(1) XRD tests were performed on bismuth sulfide nanoplatelets, bismuth sulfide nanotubes and bismuth sulfide nanorods prepared in examples 1 to 3, and the results are shown in FIG. 1.
The results show that: the XRD of bismuth sulfide obtained under the reaction conditions of 100deg.C for 2h in example 1 is significantly different from those of bismuth sulfide obtained under the reaction conditions of 150deg.C for 3h in example 2 and 150deg.C for 12h in example 3, because bismuth sulfide nanoplatelets are amorphous obtained under the reaction conditions of 100deg.C for 2h in example 1. XRD peaks of bismuth sulfide obtained under the reaction conditions of 150 ℃ in example 2, 3h and 150 ℃ in example 3, 12h correspond to the peak positions of standard PDF cards one by one, indicating that pure-phase bismuth sulfide is obtained and shows good crystallinity.
(2) SEM test was conducted on bismuth sulfide nanoplatelets, bismuth sulfide nanotubes, and bismuth sulfide nanorods prepared in examples 1-3, and the results are shown in FIG. 2. As shown in FIGS. 2 (a) and (d), bismuth sulfide nanoplatelets having a diameter of about 400nm and a thickness of about several nanometers were obtained in example 1 under a reaction condition of 100℃for 2 hours. As shown in FIGS. 2 (b) and (e), bismuth sulfide nanotubes were obtained in example 2 under the reaction conditions of 150℃and 3 hours, and the diameter of the nanotubes was 0.3 to 1. Mu.m, and the length was about 2 to 3. Mu.m. As shown in FIGS. 2 (c) and (f), bismuth sulfide nanorods with diameters of about 100 to 200 nm and lengths of about 2 to 4 μm were obtained in example 3 under the reaction conditions of 150℃and 12 hours.
(3) The EDS diagram of the bismuth sulfide nanosheets in example 1 is shown in FIG. 3, and the result shows that the Bi: S of the bismuth sulfide nanosheets is 39.6:60.4, and the error from the theoretical content is less than 1%.
(4) Bismuth sulfide has proper band gap (1.3-1.7 eV) and energy band, is a good visible light catalyst, and has specific surface areas of 12.7, 14.2 and 3.4m respectively of the bismuth sulfide nano-sheet, the bismuth sulfide nano-tube and the bismuth sulfide nano-rod in the measurement and implementation examples 1-3 2 ·g -1 。
(5) The bismuth sulfide nanoplatelets, bismuth sulfide nanotubes, and bismuth sulfide nanorods of examples 1-3 were subjected to a photocatalytic decomposition rhodamine B experiment in which a 500W xenon lamp (with 400nm cut-off filter added, retaining visible light) was used as a light source, and the results were shown in FIGS. 4 (a) and (B), C t The concentration of rhodamine B at t is expressed as the concentration of the bismuth sulfide nano material decomposed rhodamine B at t minutes, C 0 Is the initial rhodamine B concentration. In the graph (a), the highest decomposition efficiency of rhodamine B at 140min reached 41%. In FIG. (B), the bismuth sulfide nanoplatelets have a rate constant of 4.1X10 for rhodamine B decomposition under visible light -3 min -1 . The specific surface area, the decomposition rate of rhodamine B, the surface catalytic activity, and the reaction rate constant are summarized in table 1 below.
TABLE 1 Properties of the products prepared in examples 1-3
Comparative example 1 Water was used as the solvent
1mmol of BiCl 3 、4mmol CH 4 N 2 S, adding 20mL of hydrochloric acid solution (wherein the concentration of HCL is 1 mol/L) into a polytetrafluoroethylene kettle, uniformly stirring, and repeating for 5 times to obtain 5 parts of the same reaction solution;
then placing the mixture in a homogeneous reaction furnace, respectively reacting for 6h at 150 ℃, 24h at 150 ℃, 6h at 180 ℃, 24h at 180 ℃ and 24h at 200 ℃, carrying out suction filtration, alternately washing the obtained product with alcohol and deionized water for three times, and then placing the product in a drying box and drying for 12h at 60 ℃ to obtain 5 parts of product, wherein corresponding SEM images are respectively shown in (a) - (e) in fig. 6, and the results show that the obtained product has similar appearance and is a nanowire at different reaction temperatures and times.
Comparative example 2 ethanol was used as solvent
1mmol of BiCl 3 、4mmol CH 4 N 2 S, adding 10mL of ethanol into a polytetrafluoroethylene kettle, uniformly stirring, and repeating for 6 times to obtain 6 parts of the same reaction liquid;
then placing the mixture in a homogeneous reaction furnace, respectively reacting for 6h at 120 ℃, 12h at 120 ℃, 6h at 150 ℃, 24h at 150 ℃, 6h at 180 ℃ and 12h at 180 ℃, carrying out suction filtration, alternately washing the obtained product with alcohol and deionized water for three times, and then placing the product in a drying oven and drying for 12h at 60 ℃ to obtain 6 parts of the product, wherein the corresponding SEM images are respectively shown in (a) - (f) in FIG. 7, and the results show that the obtained product has similar appearance and is a nano rod due to different reaction temperatures and times.
Comparative example 3 ethylene glycol was used as solvent
1mmol of BiCl 3 、6mmol CH 4 N 2 S, adding 10mL of ethylene glycol into a polytetrafluoroethylene kettle, uniformly stirring, and repeating for 4 times to obtain 4 parts of the same reaction liquid;
then placing the mixture in a homogeneous reaction furnace, respectively reacting for 6h at 150 ℃, reacting for 24h at 150 ℃, reacting for 12h at 200 ℃ and reacting for 24h at 200 ℃, carrying out suction filtration, alternately washing the obtained product with alcohol and deionized water for three times, then placing the product in a drying box and drying for 12h at 60 ℃ to obtain 4 parts of products, wherein corresponding SEM images are respectively shown in (a) - (d) in fig. 8, and the results show that the obtained products are similar in appearance and are nanoflower in different reaction temperatures and times.
In summary, the invention provides the bismuth sulfide nano material with controllable morphologyA material, a preparation method and application thereof. The invention adopts solvothermal reaction and uses a single precursor Bi (S 2 CNEt 2 ) 3 The powder takes the aliphatic amine solvent as the solvent, does not need any substance regulation (such as morphology control agent or pH value regulator), can prepare the required bismuth sulfide nano-materials (nano-sheet bismuth sulfide nano-materials, nano-tubular bismuth sulfide nano-materials and nano-rod bismuth sulfide nano-materials) with different morphologies and uniformity only by simply controlling the reaction time and the reaction temperature, and has the advantages of simple method, safety and no pollution. The bismuth sulfide nano material with controllable morphology is prepared by a simple same preparation method under the same reaction system, so that the blank of preparing bismuth sulfide nano materials with different morphologies is made up by the same preparation method under the same reaction system.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (5)
1. The preparation method of the bismuth sulfide nano material with controllable morphology is characterized by comprising the following steps:
providing Bi (S) 2 CNEt 2 ) 3 Powder and fatty amine solvent;
the Bi (S) 2 CNEt 2 ) 3 Dispersing the powder in the fatty amine solvent, and then
Reacting for 3-6 hours at the reaction temperature of 130-150 ℃ to obtain a nano-tubular bismuth sulfide nano-material;
the fatty amine solvent is at least one selected from trimethylamine water solution with the mass fraction of 30%, monoethylamine water solution with the mass fraction of 30%, ethylenediamine and propylamine;
the Bi (S) 2 CNEt 2 ) 3 The ratio of the powder to the fatty amine solvent is (0.15-0.3) g: (10-20) mL.
2. According to claim 1The preparation method of the bismuth sulfide nano material with controllable morphology is characterized in that the Bi (S 2 CNEt 2 ) 3 The preparation method of the powder comprises the following steps:
providing an aqueous bismuth nitrate solution and an aqueous sodium diethyldithiocarbamate solution;
dropwise adding the bismuth nitrate aqueous solution into the diethyl sodium dithiocarbamate aqueous solution, and reacting to obtain the Bi (S) 2 CNEt 2 ) 3 And (3) powder.
3. The bismuth sulfide nano material with controllable morphology is characterized in that the bismuth sulfide nano material is prepared by the preparation method of any one of claims 1-2.
4. The use of the morphology-controllable bismuth sulfide nanomaterial of claim 3 in the field of photocatalysis.
5. The use according to claim 4, characterized in that the morphology-controllable bismuth sulfide nanomaterial is used as a photocatalyst in photocatalytic decomposition of organic pollutants.
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