CN115814830A - Bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material and preparation method thereof - Google Patents
Bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material and preparation method thereof Download PDFInfo
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material and a preparation method thereof, and belongs to the technical field of photocatalysts. The preparation method of the photocatalyst comprises the following steps: to Na 2 Adding DMF into the S solution to obtain a first mixed solution; slowly adding the first mixed solution into Bi (NO) 3 ) 3 ·5H 2 Obtaining a second mixed solution in an O glycol solution; stirring the second mixed solution, then carrying out closed reaction at 150-240 ℃ for 12-48h, naturally cooling to room temperature after the reaction is finished, centrifuging, washing with water, washing with alcohol, and drying at room temperature to obtain the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material. The invention adopts bismuth and bismuth sulfide to carry out doping modification on the bismuth oxycarbonate photocatalysis material, thereby solving the problem of bismuth oxycarbonateThe problem of insufficient response of the photocatalytic material to ultraviolet light; the preparation method of the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material is simple, is easy for large-scale production, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material and a preparation method thereof.
Background
In the research of the photocatalytic technology, semiconductor photocatalysts are always concerned, and the degradation of organic matters is effectively carried out by utilizing visible light which accounts for the maximum ratio in the solar spectrum, which is one of the extremely promising technologies for solving the energy problem. The photocatalytic degradation is an advanced oxidation process involving generation of free radicals by semiconductor photocatalysts and oxygen, has the characteristics of high degradation speed, wide application range and the like, and can reduce secondary pollution in the degradation process. Domestic and foreign researches show that the catalytic oxidation technology has a good effect of removing PAEs in water. In the process of photocatalysis, the photocatalytic activity of the catalyst plays an important role, so that the search for the photocatalytic activity with a broad spectrum effect becomes a research hotspot in the field at present.
Gradually, bismuth-based photocatalysts appear in the visual field of people, and due to the fact that the bismuth-based photocatalysts have a proper forbidden bandwidth and low toxicity, and raw materials for preparing the bismuth-based photocatalysts are wide in source, the bismuth-based photocatalysts become ideal visible light catalytic materials. However, since Bi 2 O 2 CO 3 The forbidden band width of the photocatalyst is wide, the light absorption range is small, the photocatalytic activity of the photocatalyst is greatly limited, and the photocatalytic efficiency of the photocatalyst is not high. In order to overcome the defect, people continuously explore various strategies, find that the photocatalytic activity of the wide-bandgap photocatalytic material can be effectively improved by methods such as morphology adjustment, metal deposition or heterojunction construction and the like, and then the photocatalytic activity is improvedBesides, another strategy attracts our attention, which is the doping of metal elements. As a semimetal, bismuth nanoparticles not only have an ultra-narrow band gap, but also have Surface Plasmon Resonance (SPR) behavior. Therefore, bi nanoparticles are commonly used to functionalize other bismuth-based photoactive nanomaterials to enhance their photocatalytic activity.
But now to Bi/Bi 2 O 2 CO 3 /Bi 2 S 3 No studies have been performed. In order to overcome the problem of insufficient response of bismuth subcarbonate to ultraviolet light, simultaneously further improve the catalytic effect of the heterojunction containing bismuth subcarbonate, simplify the preparation method of the heterojunction containing bismuth subcarbonate and enable the heterojunction to be widely applied.
Disclosure of Invention
Aiming at the prior art, the invention aims to provide a bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material and a preparation method thereof. The bismuth and the bismuth sulfide are adopted to carry out doping modification on the bismuth oxycarbonate photocatalytic material, so that the problem of insufficient response of the bismuth oxycarbonate photocatalytic material to ultraviolet light is solved; the preparation method of the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material is simple, is easy for large-scale production, and has good application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material, which comprises the following steps of:
(1) Adding sodium sulfide into deionized water to obtain a sodium sulfide solution; adding N, N-Dimethylformamide (DMF) into a sodium sulfide solution to obtain a first mixed solution;
(2) Adding Bi (NO) 3 ) 3 · 5 H 2 Adding O into ethylene glycol to obtain Bi (NO) 3 ) 3 ·5H 2 O ethylene glycol solution; slowly adding the first mixed solution into Bi (NO) 3 ) 3 ·5H 2 Obtaining a second mixed solution in an O glycol solution;
(3) Stirring the second mixed solution, then carrying out closed reaction at 150-240 ℃ for 12-48h, naturally cooling to room temperature after the reaction is finished, centrifuging, washing with water, washing with alcohol, and drying at room temperature to obtain the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material.
Preferably, bi (NO) 3 ) 3 ·5H 2 The molar ratio of O to sodium sulfide is (1-5) to (1-5).
Preferably, the stirring is magnetic stirring, and the stirring time is 15-60min.
Preferably, the temperature of the centrifugation is 4-25 ℃, the rotation speed of the centrifugation is 4000-12000rpm, and the time of the centrifugation is 5-15min.
In a second aspect of the invention, the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material prepared by the preparation method is provided.
In a third aspect of the invention, the application of the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material in photocatalytic degradation of plasticizers is provided.
In the above application, preferably, the plasticizer is BBP.
The invention has the beneficial effects that:
(1) At present to Bi/Bi 2 O 2 CO 3 /Bi 2 S 3 The research does not appear yet, and the invention adopts a one-step method to synthesize the ternary composite material, has simple process flow and the characteristics of low cost and easy large-scale production.
(2) Bi/Bi prepared by the invention 2 O 2 CO 3 /Bi 2 S 3 The heterojunction is tested and found to have the following advantages: the optical property of the prepared sample is verified through the UV-Vis diffuse reflection spectrum, the light absorption capacity of the bismuth oxycarbonate is greatly enhanced after Bi and bismuth sulfide are doped, the absorption band is widened to the visible light range, and the photocatalytic performance of the product is obviously improved. The bismuth sulfide heterojunction can accelerate the separation of electron-hole, and prolong the service life of photo-generated electron or hole; the bismuth nanoparticles have an ultra-narrow band gap and Surface Plasmon Resonance (SPR) behavior, and can effectively improve the photocatalytic activity of the photocatalyst. Thus, bismuth oxycarbonate and bismuth sulfide may act synergistically, furtherThe photocatalysis capability of the material is improved, and pollutants such as plasticizer and the like are effectively degraded.
Drawings
FIG. 1 shows Bi/Bi prepared in example 2 2 O 2 CO 3 /Bi 2 S 3 XRD patterns of the heterostructure photocatalytic materials.
FIG. 2 shows the preparation of Bi/Bi prepared in example 2 2 O 2 CO 3 /Bi 2 S 3 SEM photographs of the heterostructure photocatalytic material.
Fig. 3 shows the results of the solid fluorescence characterization test of the photocatalytic materials prepared in example 2, comparative example 1 to comparative example 2.
Fig. 4 is a graph comparing the degradation of the photocatalytic materials prepared in example 2 and comparative examples 1 to 4 to the plasticizer BBP.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. 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 application belongs.
Description of terms:
room temperature: the temperature is 15-25 ℃.
As mentioned above, due to Bi 2 O 2 CO 3 The forbidden band width of the photocatalyst is wide, the light absorption range is small, the photocatalytic activity of the photocatalyst is greatly limited, and the photocatalytic efficiency of the photocatalyst is not high. In order to solve the problem, the inventor prepares a bismuth oxycarbonate-bismuth sulfide heterostructure photocatalyst in earlier research, and solves the problem that bismuth oxycarbonate as a photocatalytic material has insufficient response to ultraviolet light.
For the doping of metal elements, patent CN 108745393A discloses a bismuth-bismuth oxycarbonate heterostructure photocatalyst, which adopts Bi (NO) 3 ) 3 · 5 H 2 O is used as a raw material, methanol is used as a solvent and a reducing agent, and the produced bismuth-bismuth oxycarbonate heterostructure photocatalyst is a simple substance bismuth nano particle deposited on the surface of the flaky bismuth oxycarbonate, so that the problem that the bismuth oxycarbonate as a photocatalytic material has insufficient response to ultraviolet light is solvedAnd (5) problems are solved.
However, there is no report on simultaneous doping modification with bismuth sulfide and bismuth. Based on the above, the invention carries out deep research on the simultaneous doping modification of bismuth sulfide and bismuth of bismuth oxycarbonate, develops and designs a one-step method for synthesizing Bi/Bi 2 O 2 CO 3 /Bi 2 S 3 A method of ternary composites.
In one embodiment of the invention, a one-step method for synthesizing Bi/Bi is provided 2 O 2 CO 3 /Bi 2 S 3 A method of ternary composite material comprising the steps of:
to Na 2 Adding DMF into the S solution to obtain a first mixed solution; slowly adding the first mixed solution into Bi (NO) 3 ) 3 ·5H 2 Obtaining a second mixed solution in an O ethylene glycol solution; stirring the second mixed solution, then carrying out closed reaction at 150-240 ℃ for 12-48h, naturally cooling to room temperature after the reaction is finished, centrifuging, washing with water, washing with alcohol, and drying at room temperature to obtain the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material.
In the synthesis method of the invention, bi (NO) is used 3 ) 3 ·5H 2 O is used as a bismuth source, sodium sulfide is used as a sulfur source, and DMF and ethylene glycol are used as a carbon source and a reducing agent while being used as solvents. By the method, simultaneous doping of bismuth sulfide and bismuth in bismuth subcarbonate can be realized in one step. Moreover, tests prove that: compared with single bismuth sulfide doping and single bismuth doping, the bismuth sulfide and the bismuth are simultaneously doped, so that the catalytic efficiency of the photocatalytic material can be obviously improved, and the synergistic effect is achieved.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples and comparative examples of the present invention are conventional in the art and are commercially available. The experimental procedures, for which no detailed conditions are indicated, were carried out according to the usual experimental procedures or according to the instructions recommended by the supplier.
Example 1:
adding 5mmol of Bi (NO) 3 ) 3 ·5H 2 Adding O into 15mL of ethylene glycol, stirring and dissolving to obtain Bi (NO) 3 ) 3 ·5H 2 And (4) O ethylene glycol solution. Adding 3mmol of Na 2 S is added into 35mL of water and stirred to be dissolved to obtain Na 2 And (5) preparing an S solution.
To Na 2 Adding 10mL of DMF into the S solution to obtain a first mixed solution, and slowly adding the first mixed solution to Bi (NO) 3 ) 3 ·5H 2 And (4) adding the mixture into an O-glycol solution to obtain a second mixed solution. And placing the second mixed solution on a magnetic stirrer for mechanical stirring for 30min. Transferring the second mixed solution into a lining made of polytetrafluoroethylene, and placing the lining in a reaction kettle for reaction at 180 ℃ for 24 hours; and after the reaction is finished, naturally cooling to room temperature, centrifuging, washing with water, washing with alcohol, and drying at room temperature to obtain the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material.
Example 2:
4mmol of Bi (NO) 3 ) 3 ·5H 2 Adding O into 15mL of ethylene glycol, stirring and dissolving to obtain Bi (NO) 3 ) 3 ·5H 2 And (4) O ethylene glycol solution. Adding 3mmol of Na 2 S is added into 35mL of water and stirred to be dissolved to obtain Na 2 And (5) preparing an S solution.
To Na 2 Adding 10mL of DMF into the S solution to obtain a first mixed solution, and slowly adding the first mixed solution to Bi (NO) 3 ) 3 ·5H 2 And (4) adding the mixture into an O-glycol solution to obtain a second mixed solution. And placing the second mixed solution on a magnetic stirrer for mechanical stirring for 30min. Transferring the second mixed solution into a lining made of polytetrafluoroethylene, and placing the lining in a reaction kettle for reaction at 180 ℃ for 24 hours; and after the reaction is finished, naturally cooling to room temperature, centrifuging, washing with water, washing with alcohol, and drying at room temperature to obtain the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material.
The XRD pattern of the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material is shown in fig. 1, and it can be seen from fig. 1 that this example indeed prepared a bismuth-bismuth oxycarbonate-bismuth sulfide heterojunction. Fig. 2 shows an SEM photograph of the bismuth-bismuth oxycarbonate-bismuth sulfide prepared in this example, and the structural state of the composite material can be clearly seen.
Example 3:
3mmol of Bi (NO) 3 ) 3 ·5H 2 Adding O into 15mL of ethylene glycol, stirring and dissolving to obtain Bi (NO) 3 ) 3 ·5H 2 And (4) O ethylene glycol solution. Adding 3mmol of Na 2 S is added into 35mL of water and stirred to be dissolved to obtain Na 2 And (5) preparing an S solution.
To Na 2 Adding 10mL of DMF into the S solution to obtain a first mixed solution, and slowly adding the first mixed solution to Bi (NO) 3 ) 3 ·5H 2 And (4) adding O-glycol solution to obtain a second mixed solution. And placing the second mixed solution on a magnetic stirrer for mechanical stirring for 30min. Transferring the second mixed solution into a lining made of polytetrafluoroethylene, and placing the lining in a reaction kettle for reaction at 160 ℃ for 24 hours; and after the reaction is finished, naturally cooling to room temperature, centrifuging, washing with water, washing with alcohol, and drying at room temperature to obtain the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material.
Comparative example 1: preparation of bismuth oxycarbonate photocatalyst
Adding 0.5g of urea into deionized water, stirring to dissolve, adding 2.75mmol of Bi (NO) into the solution 3 ) 3 ·5H 2 And O, mechanically stirring. After completion of stirring, a mixed solution was obtained. The mixed solution was placed on a magnetic stirrer and mechanically stirred for 30min. Transferring the mixed solution into a lining made of polytetrafluoroethylene, and placing the lining in a reaction kettle for reaction at 200 ℃ for 24 hours; and after the reaction is finished, naturally cooling to room temperature, centrifuging, washing with water and alcohol, and drying at room temperature to obtain the bismuthyl carbonate photocatalytic material.
Comparative example 2: preparation of bismuth sulfide photocatalyst
4mmol of Bi (NO) 3 ) 3 ·5H 2 Adding O into 15mL of water, stirring and dissolving to obtain Bi (NO) 3 ) 3 ·5H 2 And (4) O solution. Adding 3mmol of Na 2 S is added into 35mL of water and stirred to be dissolved to obtain Na 2 And (5) preparing an S solution.
Mixing Na 2 The S solution was slowly added to Bi (NO) 3 ) 3 ·5H 2 In O solution. And finally, mechanically stirring the mixed solution on a magnetic stirrer for 30min. Transferring the mixed solution into a lining made of polytetrafluoroethylene, and placing the lining in a reaction kettle for reaction at 180 ℃ for 24 hours; and after the reaction is finished, naturally cooling to room temperature, centrifuging, washing with water and alcohol, and drying at room temperature to obtain the bismuth sulfide heterostructure photocatalytic material.
Comparative example 3: preparation of bismuth-bismuthyl carbonate photocatalyst
2.425 g of Bi (NO) 3 ) 3 ·5H 2 O was added to a mixed solution of 15mL of methanol and 15mL of deionized water. Transferring the mixed solution into a lining made of polytetrafluoroethylene, and placing the lining in a reaction kettle for reaction at 180 ℃ for 12 hours; and after the reaction is finished, naturally cooling to room temperature, centrifuging, washing with water and alcohol, and drying at room temperature to obtain the bismuth-bismuthyl carbonate heterostructure photocatalytic material.
Comparative example 4: preparation of bismuth oxycarbonate-bismuth sulfide photocatalyst
Adding 0.5g of urea into deionized water, stirring to dissolve, adding 2.75mmol of Bi (NO) into the solution 3 ) 3 ·5H 2 And O, mechanically stirring. After the stirring, 3mmol of sodium sulfide was added to obtain a mixed solution. The mixed solution was placed on a magnetic stirrer and mechanically stirred for 30min. Transferring the mixed solution into a lining made of polytetrafluoroethylene, and placing the lining in a reaction kettle for reaction at 200 ℃ for 24 hours; and after the reaction is finished, naturally cooling to room temperature, centrifuging, washing with water, washing with alcohol, and drying at room temperature to obtain the bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material.
The solid fluorescence characterization test results of the photocatalytic materials prepared in example 2 and comparative examples 1-2 are shown in fig. 2, and it can be seen from fig. 2 that the composite photocatalytic material has lower fluorescence intensity compared with a single material, which indicates that the formation of bismuth-bismuth oxycarbonate-bismuth sulfide heterojunction effectively improves the separation efficiency of electron holes.
Application example: application of composite photocatalyst in degradation of organic pollutant Butyl Benzyl Phthalate (BBP) under visible light
50mg of the photocatalyst prepared in example 2 and comparative examples 1 to 4 was placed in 100mL beakers, 25mL of ultrapure water was added thereto, the mixture was dispersed uniformly by sonication for 20min, and 25mL of a 20mg/L BBP solution was added to the homogenized solution after sonication, thereby obtaining a 10mg/L BBP solution as a photocatalytic system and 0.5g/L of the catalyst. Stirring with a magnetic stirrer. And (3) placing the beaker on a magnetic stirrer, and carrying out dark reaction under the stirring condition to uniformly disperse the catalyst in the system and achieve adsorption balance.
After the dark reaction (sampling 2 mL), a xenon lamp light source is started, and a visible light catalytic degradation experiment is carried out. In the process of photocatalytic reaction, 2mL samples are taken every 30min, and the reaction time is 2h in total.
Centrifuging for 5min at 10000 deg.C, separating solid and liquid, recovering catalyst, filtering the liquid with 0.45 μm filter head (organic system), placing into a chromatographic bottle, and storing at 4 deg.C.
And (3) measuring the pollutant concentration of the prepared sample by using high performance liquid chromatography to judge the degradation efficiency of the composite material. As can be seen from fig. 4, the catalyst prepared in example 2 can effectively degrade BBP, and the residual rate of the degraded BBP is about 12%; the residual rates of the bismuth oxycarbonate prepared in the comparative example 1 and the bismuth sulfide prepared in the comparative example 2 after BBP degradation are respectively about 80% and 58%; the residual rates of the bismuth-bismuthyl carbonate prepared in the comparative example 3 and the bismuth sulfide-bismuthyl carbonate prepared in the comparative example 4 for degrading BBP are respectively about 55% and 43%, and compared with the degradation effect of the bismuthyl carbonate prepared in the comparative example 1, the degradation effect is respectively improved by 25% and 37%. The degradation effect of bismuth-bismuth oxycarbonate-bismuth sulfide relative to bismuth oxycarbonate is improved by about 68%, and the improvement effect is higher than that of bismuth-bismuth oxycarbonate and bismuth sulfide-bismuth oxycarbonate, so that the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material prepared by the invention can realize effective degradation of plasticizers such as BBP (barium boron phosphate).
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. A preparation method of a bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material is characterized by comprising the following steps:
to Na 2 Adding DMF into the S solution to obtain a first mixed solution; slowly adding the first mixed solution into Bi (NO) 3 ) 3 ·5H 2 Obtaining a second mixed solution in an O ethylene glycol solution;
stirring the second mixed solution, then carrying out closed reaction at 150-240 ℃ for 12-48h, naturally cooling to room temperature after the reaction is finished, centrifuging, washing with water, washing with alcohol, and drying at room temperature to obtain the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material.
2. The method according to claim 1, wherein Na is 2 The volume ratio of the S solution to the DMF is (30-40): 10.
3. the method according to claim 1, wherein Bi (NO) 3 ) 3 ·5H 2 O and Na 2 The molar ratio of S is (1-5) to (1-5).
4. The method according to claim 1, wherein the stirring is magnetic stirring, and the stirring time is 15-60min.
5. The method according to claim 1, wherein the temperature of centrifugation is 4-25 ℃, the rotation speed of centrifugation is 4000-12000rpm, and the time of centrifugation is 5-15min.
6. A bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material prepared by the preparation method of any one of claims 1 to 5.
7. Use of the bismuth-bismuth oxycarbonate-bismuth sulfide heterostructure photocatalytic material of claim 6 in the photocatalytic degradation of plasticizers.
8. Use according to claim 7, wherein the plasticizer is BBP.
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