CN113087016A - Preparation method of rod-shaped bismuth sulfide/reduced graphene oxide composite material - Google Patents
Preparation method of rod-shaped bismuth sulfide/reduced graphene oxide composite material Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 77
- 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 54
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- 238000000034 method Methods 0.000 claims description 20
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- 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 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
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- 239000000376 reactant Substances 0.000 abstract description 2
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 9
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The invention relates to a preparation method of a shape-controllable rod-shaped bismuth sulfide/reduced graphene oxide composite material, which comprises the following steps: the preparation method comprises the steps of ultrasonically dispersing graphene oxide in deionized water to obtain a graphene mixed solution; mixing and uniformly mixing a bismuth-containing inorganic substance serving as a bismuth source, a sulfur-containing compound serving as a sulfur source and deionized water serving as a solvent, and carrying out hydrothermal reaction on the mixed solution and the graphene solution obtained in the step; thirdly, repeatedly washing the precipitate obtained after the hydrothermal reaction by using deionized water and ethanol, and performing centrifugal treatment; and fourthly, drying the precipitate in vacuum to finally obtain the composite material. The preparation method is simple to operate, the size of the bismuth sulfide rod in the prepared composite material can be regulated and controlled by the proportion of the reactant bismuth source to the graphene, and the graphene has good electron mobility and unique surface property, so that the performance of the composite material is improved by utilizing the synergistic effect of the bismuth sulfide and the graphene.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a preparation method of a rod-shaped bismuth sulfide/reduced graphene oxide composite material.
Background
Bismuth sulfide is an n-type semiconductor with a direct band gap (1.3-1.7 eV), and is widely applied to the fields of gas sensors, photoresponsive devices, solar cells and the like due to unique electronic characteristics, excellent optical properties, excellent energy conversion efficiency and high absorption coefficient. To date, different morphologies of bismuth sulfide have been synthesized by different methods, including sonochemistry, microwave irradiation, chemical deposition, hydrothermal or solvothermal and epitaxial growth, to explore their different applications. Compared with the hydrothermal method, some methods have the limitations of low yield, complex process, high cost and poor controllability. Furthermore, simple bismuth sulfide nanostructures are generally prone to aggregation, resulting in a reduction in their surface area, limiting their catalytic performance. Therefore, in order to improve the catalytic performance of the composite material, a carbon material is designed to serve as an ideal supporting substrate, and the bismuth sulfide graphene composite material with uniform dispersion and controllable morphology and size is obtained by utilizing the good electron mobility and the unique surface property of graphene.
Graphene is subjected to ultrasonic dispersion in a document of Sensors and activators B, Chemical 2018,257,936-943, a bismuth source is added and stirred for 10 hours, then a sulfur source (thioacetamide) is added after centrifugation, and hydrothermal reaction is carried out for 12 hours to generate the bismuth sulfide/reduced graphene oxide composite material. Due to the synergistic effect of the reduced graphene oxide thin sheet and the bismuth sulfide nanorod, excellent sensing performance is shown when electrochemical detection is carried out on dopamine.
Chinese patent publication No. CN102910617A discloses a method for preparing graphene-bismuth sulfide composite material by water bath, which comprises adding bismuth-containing inorganic substance and sulfur-containing compound into deionized water, adding strong acid and graphite oxide, dissolving completely, stirring to obtain mixed sol, reacting at constant temperature, reducing the intermediate product, washing, centrifuging, and vacuum drying to obtain graphene-bismuth sulfide nano composite powder.
The Chinese patent with publication number CN106378158A discloses a bismuth sulfide/titanium dioxide/graphene composite material prepared by adding bismuth nitrate, a sulfur source and graphene into absolute ethyl alcohol and tetrabutyl titanate serving as solvents by adopting a solvothermal method to prepare a composite material and calcining the composite material, wherein the bismuth sulfide/titanium dioxide/graphene composite material is used for catalytic degradation of organic pollutants.
The preparation method is simple to operate, the reduction of the graphene oxide and the preparation of the bismuth sulfide/reduced graphene oxide composite material are realized through one-step hydrothermal process, the bismuth sulfide in the prepared composite material is rod-shaped, the size of the bismuth sulfide can be regulated and controlled through the proportion of a reactant bismuth source and the graphene, and the graphene has good electron mobility and unique surface property, so that the performance of the composite material is improved by utilizing the synergistic effect of the bismuth sulfide and the graphene, and the obtained composite material is widely applied to the fields of solar batteries, supercapacitors, thermoelectric devices, electrochemical sensors, photocatalysis and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a rodlike bismuth sulfide/reduced graphene oxide composite material which is low in cost, simple in process and controllable in shape.
The technical scheme adopted by the invention is as follows:
a rod-shaped bismuth sulfide/reduced graphene oxide composite material is prepared by the following steps:
the preparation method comprises the steps of ultrasonically dispersing graphene oxide in deionized water to obtain a graphene mixed solution;
mixing and uniformly mixing a bismuth-containing inorganic substance serving as a bismuth source, a sulfur-containing compound serving as a sulfur source and deionized water serving as a solvent, and carrying out hydrothermal reaction on the mixed solution and the graphene solution obtained in the step;
thirdly, repeatedly washing the precipitate obtained after the hydrothermal reaction by using deionized water and ethanol, and performing centrifugal treatment;
and fourthly, drying the precipitate in vacuum to finally obtain the composite material.
In the step, the mass concentration of the graphene mixed solution is 1 mg/mL; the ultrasonic treatment time is 2-4 h, and the power is 55 kHz.
And in the step II, the mass ratio of the bismuth source to the sulfur source is 1: 6-1: 12.
And in the step II, the inorganic salt containing bismuth is selected from any combination of bismuth nitrate, bismuth chloride and bismuth acetate, and the concentration of the mixed bismuth source solution is 0.002 mol/L-0.005 mol/L.
And in the step II, the sulfur source is selected from thiourea, thioacetamide, sodium sulfide nonahydrate and sodium thiosulfate, and the concentration of the mixed sulfur source solution is 0.015-0.05 mol/L.
And in the step II, the hydrothermal reaction temperature is 120-180 ℃, and the hydrothermal reaction time is 8-12 h.
And in the step three, the centrifugal rotating speed is 5000-8000 rpm, and the centrifugation is performed for 3-7 min each time.
And in the step four, the vacuum drying temperature is 60 ℃, the vacuum drying time is 6-12 hours, and finally the bismuth sulfide/reduced graphene oxide composite material with controllable appearance and size is prepared.
The invention has the advantages and positive effects that:
the invention adopts a one-step hydrothermal method to prepare the composite material, has low cost and simple and easy process, and is easy to realize large-scale production. The synthesized bismuth sulfide reduced graphene oxide composite material has uniform two-phase dispersion, can be widely used for solar cells, supercapacitors, thermoelectric devices, electrochemical sensors, photocatalysis and the like, and has wide application prospect.
Compared with the prior art, the invention has the following advantages: (1) the preparation process is simple and convenient, the process cost is low (2) the addition of graphene is effective, the product bismuth sulfide is agglomerated, the size of bismuth sulfide can be adjusted by regulating and controlling the proportion of reaction materials, and (3) the special structure of the obtained bismuth sulfide/reduced graphene oxide composite material utilizes the synergistic effect between the graphene oxide and the bismuth sulfide, so that the catalytic performance of the composite material is enhanced.
Drawings
Fig. 1 is an XRD chart of the bismuth sulfide/reduced graphene oxide composite material prepared in example 1 of the present invention.
Fig. 2 is an SEM image of bismuth sulfide/reduced graphene oxide prepared by example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
Example 1
1. Preparing a 1mg/mL graphene solution:
weighing 250mg of graphene, placing the graphene in a small beaker, adding deionized water, performing ultrasonic dispersion, conducting drainage to a 250mL volumetric flask by using a glass rod, then performing constant volume by using deionized water to obtain a graphene solution of 1mg/mL, and performing ultrasonic dispersion for 2 hours to obtain a uniform graphene aqueous solution.
2. Preparing a bismuth sulfide/reduced graphene oxide composite material:
in a 50mL beaker, 0.14mmol (67.9mg) of Bi (NO) was added separately3)3·5H2O, 1.12mmol (85.25mg) of thiourea (molar ratio thiourea/Bi (NO)3)3·5H2O ═ 8: 1) and 10ml of deionized water, and the system was stirred for 30min to form a uniform white suspension. Adding 36ml of graphene solution under the stirring condition, continuously stirring for 30min, transferring the solution to a lining of a reaction kettle made of polytetrafluoroethylene, placing the lining in a steel reaction kettle, screwing the reaction kettle tightly, placing the reaction kettle in an oven, setting the temperature to be 180 ℃, and reacting for 12h to realize the compounding of bismuth sulfide and graphene and the reduction of graphene under the reaction condition. After the reaction is finished, the reaction product is placed in a centrifugal tube after the reaction kettle is naturally cooled, the reaction product is repeatedly washed by deionized water and absolute ethyl alcohol, and then dried in a vacuum drying oven at 60 ℃ to obtain a black powder product, and the drying at the temperature does not influence the structure of the bismuth sulfide/reduced graphene oxide composite material. And then carrying out X-ray diffraction spectrum and scanning electron microscope characterization on the obtained sample.
The mass ratio of bismuth nitrate to graphene in this example was 1: at the ratio of the amount of the substance, the morphology of the synthesized bismuth sulfide is a uniform rod-like structure and successfully supported on the graphene sheet.
Example 2
The same procedure as in example 1 was followed, except that in this example the ratio of the amounts of bismuth nitrate and graphene charge material was 6:1, the hydrothermal temperature was 180 ℃ and the hydrothermal time was 12 h.
Example 3
The same procedure as in example 1 was followed, except that in this example the ratio of the amounts of bismuth nitrate and graphene charge material was 4:1, the hydrothermal temperature was 180 ℃ and the hydrothermal time was 12 h.
Example 4
The same procedure as in example 1 was followed, except that in this example the ratio of the amounts of bismuth nitrate and graphene charge material was 2:1, the hydrothermal temperature was 180 ℃ and the hydrothermal time was 12 h.
Example 5
The operation procedure is the same as that in example 1, but the ratio of the bismuth nitrate to the graphene charge material in this example is 1:2, the hydrothermal temperature is 180 ℃, and the hydrothermal time is 12 h.
Example 6
Example 1 is repeated, but the synthesis temperature and time of the steps are changed, and the bismuth sulfide graphene composite material is synthesized by hydrothermal reaction for 8 hours at 120 ℃. The structure was confirmed by X-ray diffraction pattern and scanning electron microscopy.
Example 7
The example 1 is repeated, the synthesis temperature and time of the steps are changed, and the bismuth sulfide graphene composite material is synthesized by hydrothermal reaction for 12 hours at the temperature of 120 ℃. The structure was confirmed by X-ray diffraction pattern and scanning electron microscopy.
Example 8
Example 1 was repeated, but with the modification of step Bi (NO)3)3·5H2The molar ratio of O to thiourea is 1:6, and the bismuth sulfide/reduced graphene oxide composite material is synthesized by hydrothermal reaction for 12 hours at 180 ℃. The structure was confirmed by X-ray diffraction pattern and scanning electron microscopy.
Example 9
Example 1 was repeated, but with the modification of step Bi (NO)3)3·5H2The molar ratio of O to thiourea is 1:12, and the hydrothermal reaction is carried out at 180 DEGAnd reacting for 12 hours under the condition to synthesize the bismuth sulfide/reduced graphene oxide composite material. The structure was confirmed by X-ray diffraction pattern and scanning electron microscopy.
Example 10
Example 1 was repeated, but thiourea was changed to thioacetamide, and the structure of the bismuth sulfide/reduced graphene oxide composite was confirmed by X-ray diffraction pattern and scanning electron microscope.
Example 11
Example 1 was repeated, but the thiourea was changed to sodium sulfide nonahydrate, and the structure of the bismuth sulfide/reduced graphene oxide composite material was confirmed by X-ray diffraction pattern and scanning electron microscope.
Example 12
Example 1 was repeated, but thiourea was changed to sodium thiosulfate to obtain a bismuth sulfide/reduced graphene oxide composite material, and the structure thereof was confirmed by X-ray diffraction pattern and scanning electron microscope.
Example 13
Example 1 was repeated, but bismuth nitrate was changed to bismuth chloride, and the structure of the bismuth sulfide/reduced graphene oxide composite material was confirmed by X-ray diffraction pattern and scanning electron microscope.
Example 14
Example 1 was repeated, but bismuth nitrate was changed to bismuth acetate, and the structure of the bismuth sulfide/reduced graphene oxide composite material was confirmed by X-ray diffraction pattern and scanning electron microscope.
FIG. 1 (upper diagram is Bi)2S3 isXRD pattern, lower part is Bi2S3XRD pattern of/rGO-1) is Bi prepared by the method of the invention in example 12S3XRD pattern of/rGO-1, as can be seen in FIG. 1: FIG. 1 shows Bi obtained2S3XRD pattern of/rGO-1. From the spectrum of bismuth sulfide, we clearly see that strong diffraction peaks appear at 23.72 °, 24.93 °, 28.61 ° and 31.80 °, which correspond to the (101), (130), (211) and (221) crystal planes respectively, and compared with the standard card, all the diffraction peaks can be respectively indexed to orthorhombic phase bismuth sulfide (JCPDS No.17-0320), and the diffraction peaks of examples 2-14 are basically the same as those of example 1. Because of the large number of maps, it is used in this applicationThe X-ray diffraction patterns and scanning electron micrographs of examples 2-14 were not shown.
In addition, no other impurity diffraction peaks were found, indicating that the product we prepared is a very pure sample of bismuth sulfide. From Bi2S3The map comparison of/rGO-1 shows that Bi is involved2S3The main peak is not obviously changed after the graphene is modified, which shows that the in-situ modification method is used for Bi2S3Has no influence on the formation of (2).
FIG. 2 is an SEM image of a bismuth sulfide/reduced graphene oxide composite material prepared in example 1 of the present invention, and it can be seen from FIG. 2 that rod-like Bi fixed on reduced graphene oxide flakes2S3。
Although the embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the embodiments disclosed.
Claims (8)
1. A preparation method of a rod-shaped bismuth sulfide/reduced graphene oxide composite material is characterized by comprising the following steps: the method comprises the following steps:
the preparation method comprises the steps of ultrasonically dispersing graphene oxide in deionized water to obtain a graphene mixed solution;
mixing and uniformly mixing bismuth-containing inorganic substances serving as a bismuth source, a sulfur-containing compound serving as a sulfur source and deionized water serving as a solvent, and carrying out hydrothermal reaction on the mixed solution and the graphene solution obtained in the step;
thirdly, repeatedly washing the precipitate obtained after the hydrothermal reaction by using deionized water and ethanol, and performing centrifugal treatment;
and fourthly, drying the precipitate in vacuum to finally obtain the bismuth sulfide/reduced graphene oxide composite material with controllable appearance and size.
2. The method for preparing a rod-shaped bismuth sulfide/reduced graphene oxide composite material according to claim 1, wherein: in the step, the mass concentration of the graphene mixed solution is 1 mg/mL; the ultrasonic treatment time is 2-4 h, and the power is 55 kHz.
3. The method for preparing a rod-shaped bismuth sulfide/reduced graphene oxide composite material according to claim 1, wherein: in the step II, the mass ratio of the bismuth source to the sulfur source is 1: 6-1: 12.
4. The method for preparing a rod-shaped bismuth sulfide/reduced graphene oxide composite material according to claim 1, wherein: in the step II, the hydrothermal reaction temperature is 120-180 ℃, and the hydrothermal reaction time is 8-12 h.
5. The method for preparing a rod-shaped bismuth sulfide/reduced graphene oxide composite material according to claim 1, wherein: in the step three, the centrifugal rotating speed is 5000-8000 rpm, and each time of centrifugation is 3-7 min.
6. The method for preparing a rod-shaped bismuth sulfide/reduced graphene oxide composite material according to claim 1, wherein: and step four, the vacuum drying temperature is 60 ℃, and the vacuum drying time is 6-12 h.
7. The method for preparing a rod-like bismuth sulfide/reduced graphene oxide composite material according to claim 3, wherein: in the step II, the inorganic salt containing bismuth is selected from any combination of bismuth nitrate, bismuth chloride and bismuth acetate, and the concentration of the mixed bismuth source solution is 0.002 mol/L-0.005 mol/L.
8. The method for preparing a rod-like bismuth sulfide/reduced graphene oxide composite material according to claim 3, wherein: in the step II, the sulfur source is selected from thiourea, thioacetamide, sodium sulfide nonahydrate and sodium thiosulfate, and the concentration of the mixed sulfur source solution is 0.015-0.05 mol/L.
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