CN118454711A - Heterojunction catalytic material rich in oxygen vacancies and preparation method and application thereof - Google Patents
Heterojunction catalytic material rich in oxygen vacancies and preparation method and application thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 56
- 239000001301 oxygen Substances 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 43
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 51
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 229940015043 glyoxal Drugs 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims abstract description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 8
- 239000012498 ultrapure water Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
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- 238000010521 absorption reaction Methods 0.000 description 9
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- 239000002086 nanomaterial Substances 0.000 description 7
- -1 cu 2S Substances 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
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- 229910001566 austenite Inorganic materials 0.000 description 1
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- 229910052976 metal sulfide Inorganic materials 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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- 238000001195 ultra high performance liquid chromatography 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
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Abstract
The invention discloses a heterojunction catalytic material rich in oxygen vacancies, a preparation method and application thereof, and belongs to the field of photocatalysts. The preparation method comprises the following steps: dissolving Bi (NO 3)3·5H2 O and sodium carbonate in ultrapure water respectively to prepare Bi (NO 3)3·5H2 O solution and Na 2CO3 solution), dripping Na 2CO3 solution into Bi (NO 3)3·5H2 O solution to obtain a mixture, adding glyoxal solution into the mixture, centrifugally collecting precipitate after stirring, washing and drying to obtain Bi 2O2CO3 rich in oxygen vacancies, dispersing Bi 2O2CO3 rich in oxygen vacancies, anhydrous copper acetate and thiourea into deionized water, carrying out hydrothermal reaction after stirring, cooling reactants, filtering, washing and drying to obtain a product Bi 2O2CO3/Cu9S5, namely the heterojunction catalytic material rich in oxygen vacancies.
Description
Technical Field
The invention belongs to the field of photocatalysts, and particularly relates to a heterojunction catalytic material rich in oxygen vacancies, and a preparation method and application thereof.
Background
In the photocatalytic reaction, the heterojunction aims at the problems of insufficient visible light absorption and low charge separation efficiency of a single material by compounding two semiconductor materials with proper energy levels, which can widen the light absorption area and strengthen the interfacial charge transfer.
Bi 2O2CO3 has a unique layered structure and inherent distortion as a member of the austenite phase oxide, which facilitates separation of photogenerated charges. However, a single Bi 2O2CO3 material absorbs only in the uv region, so it cannot absorb visible light in constructing a heterojunction strategy. In order to obtain higher photocatalytic activity, the formation of defects on the surface of Bi 2O2CO3 is a very promising modification method, which can provide rich active sites for the adsorption and activation of reactants. Among all forms of defects, surface oxygen vacancies (O V) are of great concern. The surface oxygen vacancies can modulate the bandgap of the semiconductor over a range extending the photoresponsive region from ultraviolet to visible light. Therefore, if oxygen vacancies can be formed on the surface of Bi 2O2CO3, the visible light absorption of the Bi 2O2CO3 is expanded, and meanwhile, the Bi 2O2CO3 is compounded with a semiconductor with proper energy level, so that the charge separation efficiency is improved, and the photocatalytic activity can be greatly improved.
The key to the photocatalytic oxidation technique is the selection of semiconductor nanomaterials with excellent catalytic activity. Among these semiconductor nanomaterials, bi 2O2CO3 is a suitable candidate because it has a characteristic layered structure consisting of alternating Bi 2O2]2+ layers orthogonal to the CO 3 2- groups, which is effective in promoting the separation of photogenerated electrons and holes. However, since Bi 2O2CO3 has a wide bandgap of 3.3 eV, only ultraviolet light can be absorbed (< 376, nm). To overcome this limitation, by a heterostructure building strategy, built-in electric fields are built in the heterojunction, and photogenerated electrons and holes can be efficiently transferred between the conduction and valence bands of the heterojunction by a synergistic effect. In addition, it is also necessary to further extend the optical absorption of Bi 2O2CO3 using defect strategies.
In recent years, binary metal sulfide heterostructure nanomaterials have been promising in terms of improving high-efficiency photocatalytic activity, because heterostructures can promote extensive absorption of visible light, transport of photogenerated charge carriers, and reduce recombination rates. Copper sulfide (Cu xSy) is a unique system because it contains multiple crystalline phases and stoichiometric compositions, such as CuS, cu 2S、Cu1.75S、Cu9S5, cu 1.4 S, etc., which contribute to its excellent optical and electrical properties. Also, the characteristics of Cu xSy nanoparticles depend to a large extent on the crystal structure and the Cu/S ratio. Therefore, it is very important to prepare a high-quality Bi 2O2CO3 -loaded Cu 9S5 heterostructure in one pot and systematically study its photodegradation performance on organic pollutants.
The application aims to develop a heterojunction composite material rich in oxygen vacancies, and the oxygen vacancies rich in the surface of the heterojunction composite material are beneficial to the material to utilize more visible light, and meanwhile, the transfer of photo-generated electrons across a heterojunction interface provides a thought for solving the problem of recombination of photo-generated charges so as to provide a reference for relieving the problems of environmental pollution and energy crisis.
Disclosure of Invention
The invention aims to provide a heterojunction catalytic material rich in oxygen vacancies, and a preparation method and application thereof, so as to develop the heterojunction catalytic material which is simple in preparation method, rich in oxygen vacancies, higher in visible light utilization rate and charge separation efficiency, better in stability, capable of being recycled and capable of realizing photocatalytic degradation of organic pollutants.
The technical scheme of the invention is as follows:
(one)
A method for preparing a heterojunction catalytic material rich in oxygen vacancies, comprising the following steps:
A. Dissolving Bi (NO 3)3·5H2 O and sodium carbonate in ultrapure water respectively to prepare Bi (NO 3)3·5H2 O solution and Na 2CO3 solution), dropwise adding Na 2CO3 solution into Bi (NO 3)3·5H2 O solution to obtain mixed solution after magnetic stirring, adding glyoxal solution with a certain volume into the mixed solution, magnetically stirring at room temperature for a certain time, centrifugally collecting precipitate, washing with deionized water and absolute ethyl alcohol for multiple times respectively, and drying to obtain Bi 2O2CO3 rich in oxygen vacancies;
B. dispersing Bi 2O2CO3, anhydrous copper acetate and thiourea which are rich in oxygen vacancies into deionized water, stirring, slowly transferring the solution into a polytetrafluoroethylene lining hydrothermal reaction kettle for hydrothermal reaction, cooling reactants, filtering, washing with deionized water, and drying to obtain a product Bi 2O2CO3/Cu9S5, namely the heterojunction catalytic material which is rich in oxygen vacancies.
As a further development of the invention, in step A, the molar ratio of Bi (NO 3)3·5H2 O to sodium carbonate) is 1:2-4.
As a further improvement of the invention, in the step A, the volume ratio of the mixed solution to the glyoxal solution is 40:1-4.
As a further improvement of the invention, in the step A, an oven is used for drying, the drying temperature is 60-80 ℃, and the drying time is 12-24 h.
As a further improvement of the invention, in the step B, the molar ratio of Bi 2O2CO3, anhydrous copper acetate and thiourea is 0.01-0.1:1:1.
As a further improvement of the invention, in step B, the temperature of the hydrothermal reaction is 140-180 ℃ and the time of the hydrothermal reaction is 8-12 h.
In the step B, drying is performed by adopting an oven, wherein the drying temperature is 60-80 ℃, and the drying time is 8-12h.
(II)
The heterojunction catalytic material rich in oxygen vacancies is prepared by the preparation method of the heterojunction catalytic material rich in oxygen vacancies.
(III)
The application of heterojunction catalytic material rich in oxygen vacancies in photocatalytic degradation of pollutants.
Further, the contaminants include bisphenol a.
The beneficial effects of the invention are as follows: the invention constructs Bi 2O2CO3 and Cu 9S5 by constructing S-shaped heterojunction to form a photocatalysis nano composite material which is rich in oxygen vacancy, has stronger interfacial carrier separation capability, has a light absorption range covering the full visible spectrum and higher catalytic activity, namely Bi 2O2CO3/Cu9S5.Bi2O2CO3 is a typical photocatalysis candidate material, but its band gap is wider (3.3 eV), so it can only absorb ultraviolet rays (< 376 nm), and the single material charge separation efficiency is low; cu 9S5 is a photocatalytic material that responds in the near infrared region. Bi 2O2CO3 and Cu 9S5 are compounded, the separation of the photo-generated electron-hole pair of the Bi 2O2CO3/Cu9S5 composite photocatalysis nano material at the heterogeneous interface is successfully realized, the problem of electron-hole recombination in the band gap of the single Bi 2O2CO3 catalysis nano material is avoided, Meanwhile, oxygen vacancies are formed on the surface of Bi 2O2CO3, and doping energy levels can be formed in the band gap of Bi 2O2CO3 due to the existence of the oxygen vacancies, so that the visible light absorption range of Bi 2O2CO3 is widened, and light absorption complementation is formed between Bi 2O2CO3 and the visible light region of Cu 9S5. The heterojunction is constructed to more effectively enhance the heterojunction interface charge separation and electron transfer, and greatly improve the photocatalytic activity. Finally, the Bi 2O2CO3/Cu9S5 photocatalytic system rich in oxygen vacancies realizes effective pollutant degradation and has the characteristics of good stability and reusability.
Drawings
FIG. 1 is a scanning electron microscope image of Bi 2O2CO3/Cu9S5 prepared in example 1 of the present invention;
FIG. 2 is a graph showing the diffuse ultraviolet reflectance spectrum of Bi2O2CO3/Cu9S5、Bi2O2CO、Cu9S5 prepared in example 1 and comparative examples 1 and 2 of the present invention;
FIG. 3 is a Fourier diffuse reflection infrared spectrum of Bi2O2CO3/Cu9S5、Bi2O2CO、Cu9S5 prepared in example 1 and comparative examples 1 and 2 of the present invention;
FIG. 4 is an EPR spectrum of Bi 2O2CO3/Cu9S5、Bi2O2CO3 prepared in example 1 and comparative example 1 of the present invention;
FIG. 5 is a graph showing the comparison of the performance of Bi2O2CO3/Cu9S5、Bi2O2CO、Cu9S5 of the present invention in terms of the degradation of bisphenol A by visible light catalysis prepared in example 1 and comparative examples 1 and 2;
FIG. 6 is a graph showing the degradation of Bi 2O2CO3/Cu9S5 prepared in example 1 according to the present invention by the repeated use of bisphenol A by the visible light catalytic degradation.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
Example 1,
A method for preparing a heterojunction catalytic material rich in oxygen vacancies, comprising the following steps:
A. 2mmol Bi (NO 3)3·5H2 O and 6mmol sodium carbonate are respectively dissolved in 20mL ultrapure water to prepare Bi (NO 3)3·5H2 O solution and Na 2CO3 solution, after magnetic stirring for 10 min at 600 r/min, the whole Na 2CO3 solution is dropwise added to Bi (NO 3)3·5H2 O solution to obtain mixed solution; 2ml glyoxal solution (volume concentration is 40%) is added to the mixed solution; 600 r/min magnetic stirring for 24h at room temperature is carried out, and then the precipitate is centrifugally collected, washed with deionized water and absolute ethyl alcohol for multiple times respectively, and the product is dried for 12h at 80 ℃ in an oven to obtain Bi 2O2CO3 rich in oxygen vacancies.
B. Sequentially dispersing Bi 2O2CO3, anhydrous copper acetate and thiourea into 50ml deionized water to obtain mixed suspension, wherein the concentrations of the Bi 2O2CO3, the anhydrous copper acetate and the thiourea in the mixed suspension are respectively 0.005 mol/L, 0.1 mol/L and 0.1 mol/L; slowly transferring the solution into a polytetrafluoroethylene lining hydrothermal reaction kettle after stirring to carry out hydrothermal reaction, wherein the hydrothermal reaction is carried out for 10 hours at 160 ℃; and cooling the reactant, filtering, washing with deionized water for 3-6 times, and drying in an oven at 80 ℃ for 8h times to obtain a product Bi 2O2CO3/Cu9S5, namely the heterojunction catalytic material rich in oxygen vacancies.
Fig. 1 is a scanning electron microscope image of Bi 2O2CO3/Cu9S5 prepared in this example, and as shown in fig. 1, the Bi 2O2CO3/Cu9S5 composite photocatalytic nanomaterial is a heterogeneous nanoparticle and nanoplatelet composite structure.
EXAMPLE 2,
A method for preparing a heterojunction catalytic material rich in oxygen vacancies, comprising the following steps:
A. 2 mmol Bi (NO 3)3·5H2 O and 8mmol sodium carbonate are respectively dissolved in 40mL ultrapure water to prepare Bi (NO 3)3·5H2 O solution and Na 2CO3 solution, after magnetic stirring is carried out for 15 min at 600 r/min, na 2CO3 solution is dropwise added to Bi (NO 3)3·5H2 O solution to obtain mixed solution, 1ml glyoxal solution (volume concentration is 40%) is added to the mixed solution, after magnetic stirring is carried out for 24 h at room temperature at 600 r/min, centrifugal collection is carried out, precipitation is respectively washed by deionized water and absolute ethyl alcohol for multiple times, and the product is dried for 12 h at 80 ℃ in an oven to obtain Bi 2O2CO3 rich in oxygen vacancies.
B. Sequentially dispersing Bi 2O2CO3, anhydrous copper acetate and thiourea into 50ml deionized water to obtain mixed suspension, wherein the concentrations of the Bi 2O2CO3, the anhydrous copper acetate and the thiourea in the mixed suspension are respectively 0.001 mol/L, 0.1 mol/L and 0.1 mol/L; slowly transferring the solution into a polytetrafluoroethylene lining hydrothermal reaction kettle after stirring to carry out hydrothermal reaction, wherein the hydrothermal reaction is carried out for 12 hours at 140 ℃; and cooling the reactant, filtering, washing with deionized water for 3-6 times, and drying in an oven at 80 ℃ for 8h times to obtain a product Bi 2O2CO3/Cu9S5, namely the heterojunction catalytic material rich in oxygen vacancies.
EXAMPLE 3,
A method for preparing a heterojunction catalytic material rich in oxygen vacancies, comprising the following steps:
A. 2 mmol Bi (NO 3)3·5H2 O and 4mmol sodium carbonate are respectively dissolved in 30 mL ultrapure water to prepare Bi (NO 3)3·5H2 O solution and Na 2CO3 solution, after magnetic stirring is carried out for 20 min at 600 r/min, na 2CO3 solution is dropwise added to Bi (NO 3)3·5H2 O solution to obtain mixed solution, 4ml glyoxal solution (volume concentration is 40%) is added to the mixed solution, magnetic stirring is carried out for 24 h at room temperature for 600 r/min, centrifugal collection is carried out, precipitation is collected, deionized water and absolute ethyl alcohol are respectively used for washing for multiple times, and the product is dried for 24 h at 60 ℃ in an oven to obtain Bi 2O2CO3 rich in oxygen vacancies.
B. Sequentially dispersing Bi 2O2CO3, anhydrous copper acetate and thiourea into 50 ml deionized water to obtain mixed suspension, wherein the concentrations of the Bi 2O2CO3, the anhydrous copper acetate and the thiourea in the mixed suspension are respectively 0.01 mol/L, 0.1 mol/L and 0.1 mol/L; slowly transferring the solution into a polytetrafluoroethylene lining hydrothermal reaction kettle after stirring to carry out hydrothermal reaction, wherein the hydrothermal reaction is carried out for 8 hours at 180 ℃; and cooling the reactant, filtering, washing with deionized water for 3-6 times, and drying in an oven at 60 ℃ for 12h times to obtain the product Bi 2O2CO3/Cu9S5, namely the heterojunction catalytic material rich in oxygen vacancies.
Comparative example 1,
Preparation of Bi 2O2CO3 only: 2mmol Bi (NO 3)3·5H2 O and 8 mmol sodium carbonate are respectively dissolved in 20mL ultrapure water to prepare Bi (NO 3)3·5H2 O solution and Na 2CO3 solution, after 600 r/min magnetic stirring is carried out on the solution for 20 min), na 2CO3 solution is dropwise added to Bi (NO 3)3·5H2 O solution to obtain mixed solution, 1 ml glyoxal solution (volume concentration is 40%) is added to the mixed solution, after 24 h is magnetically stirred at room temperature for 600 r/min, the precipitate is collected by centrifugation, the precipitate is respectively washed with deionized water and absolute ethyl alcohol for multiple times, and the product is dried in an oven at 60 ℃ for 24 h to obtain Bi 2O2CO3 rich in oxygen vacancies.
Comparative example 2,
Preparation of Cu 9S5 alone: sequentially dispersing anhydrous copper acetate and thiourea into 50 ml deionized water to obtain a mixed suspension, wherein the concentration of the anhydrous copper acetate and thiourea in the mixed suspension is 0.1 mol/L; slowly transferring the solution into a polytetrafluoroethylene lining hydrothermal reaction kettle after stirring to carry out hydrothermal reaction, wherein the hydrothermal reaction is carried out for 12 hours at 140 ℃; and cooling the reactant, filtering, washing with deionized water for 3-6 times, and drying in an oven at 80 ℃ for 8 h to obtain the product Cu 9S5.
Evaluation of photocatalytic degradation Property
The photocatalytic degradation performance was evaluated for example 1 and comparative examples 1 and 2 as follows:
The photodegradation process was performed in a 250 ml custom double-walled quartz beaker with a cooling water circulation system to keep the reaction temperature constant. A300W xenon lamp (lambda >420 nm) was used as a visible light source with an average light intensity of 200 mW/cm 2. Before the reaction starts, 50mg photocatalyst is dispersed in bisphenol A solution (10 mg/L), pH is controlled to be about 7 by 0.1M hydrochloric acid or sodium hydroxide solution, and the suspension is continuously stirred during the whole reaction. The dark adsorption experiments were performed 30 minutes before light irradiation to reach adsorption-desorption equilibrium between bisphenol a and photocatalyst. Then, PMS of 1 mM was added. In the photodegradation process, 1 mL reaction liquid is taken out at regular intervals, then the reaction liquid passes through a 0.22 mu m filter, ultra-high performance liquid chromatography analysis is prepared, the mobile phase is acetonitrile and ultrapure water, the ratio is 50:50, and the detection wavelength is 278 nm. The relative concentration (C/C 0) was used to calculate the degradation efficiency.
FIG. 2 is a graph showing the diffuse ultraviolet reflectance spectrum of Bi2O2CO3/Cu9S5、Bi2O2CO、Cu9S5 prepared in example 1 and comparative examples 1 and 2 of the present invention. As shown in fig. 2, it can be found that the light absorption cut-off edge of Bi 2O2CO3 alone is about 370-nm, while having a slightly weaker absorption tail at > 400-nm, indicating that it can use a certain visible light. Whereas the light absorption of Cu 9S5 covers the whole full visible absorption spectrum. After the two materials are compounded, the light absorption of the Bi 2O2CO3/Cu9S5 material covers the whole full visible spectrum, especially the enhancement of the absorption tail peak, which shows the improvement of the light trapping efficiency.
FIG. 3 is a Fourier diffuse reflection infrared spectrum of Bi2O2CO3/Cu9S5、Bi2O2CO、Cu9S5 prepared in example 1 and comparative examples 1 and 2 of the present invention. as shown in the figure 3 of the drawings, for the telescopic vibrational modes of Bi 2O2CO3,1333 cm-1 and 1526 cm -1 with peaks from CO 3 2-, The absorption bands at 878 cm -1 and 525 cm -1 are caused by Bi-O bonds, and the weak absorption band near 690 cm -1 is attributable to the in-plane deformation of CO 3 2-. The result of the Fourier transform infrared spectrum shows that the functional group and the internal structure of Bi 2O2CO3 are not changed basically after the surface oxygen vacancies are introduced. In addition, no other signal was present on the Bi 2O2CO3 sample, indicating that no other surface complex was formed during the synthesis. For the peak at Cu 9S5,593 cm-1 to represent the stretching vibration of the Cu-S bond, the peak at 1118 cm -1 coincides with the C-O stretching vibration, the weak peak at 1082 cm -1 is related to the absorption peak of SO 4 2-, The absorption peaks at 1386 cm -1、1544 cm-1 and 2909cm -1 are respectively assigned to the deformation vibrations of the-C-H bond and to the asymmetric and symmetric stretching vibrations of the-C-H 3, and the absorption peaks at 3436 cm -1 are respectively assigned to the deformation vibrations of the hydroxyl (O-H) bond. the major typical absorption peaks of original Bi 2O2CO3 and Cu 9S5 remained in the Bi 2O2CO3/Cu9S5 samples, further indicating successful synthesis of Bi 2O2CO3/Cu9S5 composite heterojunction photocatalysts.
FIG. 4 is an EPR spectrum of Bi 2O2CO3/Cu9S5、Bi2O2CO3 prepared in example 1 and comparative example 1 of the present invention. As shown in fig. 4, a distinct signal appears in the Bi 2O2CO3/Cu9S5、Bi2O2CO3 sample, as expected, with all peaks at g=2.003, which is derived from unpaired electrons trapped on the oxygen vacancies. The introduction of surface oxygen vacancies may be the addition of glyoxal solution during the synthesis, indicating successful preparation of the oxygen vacancy-enriched Bi 2O2CO3/Cu9S5 composite.
FIG. 5 is a graph showing the comparison of the performance of Bi2O2CO3/Cu9S5、Bi2O2CO、Cu9S5 of the present invention in terms of the degradation of bisphenol A by visible light catalysis prepared in example 1 and comparative examples 1 and 2. As shown in fig. 5, the experimental results showed that: under the conditions that the catalyst addition amount is 0.5 g/L, the initial concentration of bisphenol A is 10 mg/L, and the initial temperature is room temperature, the degradation rates of a single Bi 2O2CO3/PMS/Vis system and a Cu 9S5/PMS/Vis system on bisphenol A in 30min are 8.28 percent and 39.69 percent respectively, and the Bi 2O2CO3/Cu9S5/PMS/Vis system on bisphenol A reaches 96.87 percent, which means that the composite material utilizes more visible light due to the existence of oxygen-enriched vacancies, and meanwhile, the interface charge transfer of a photo-generated carrier is effectively improved due to the construction of an S-type heterojunction, and the in-situ recombination of photo-generated electron hole pairs in two single photocatalysts is inhibited.
(II) continuous degradation experiment
After the first degradation reaction of Bi 2O2CO3/Cu9S5 prepared in example 1 is completed, the reacted solution is centrifugally washed, the recovered catalyst is dried in a freeze dryer to 48: 48 h, and then the catalyst is put into a reactor again to carry out the next degradation experiment, and the other degradation reaction conditions and the first photocatalytic degradation performance evaluation experiment setting program are kept consistent except the materials; after the second reaction is completed, repeating the steps, and carrying out three degradation experiments.
FIG. 6 is a graph showing the degradation of Bi 2O2CO3/Cu9S5 prepared in example 1 according to the present invention by the repeated use of bisphenol A by the visible light catalytic degradation. As shown in fig. 6, the degradation rate of bisphenol a was above 90% in three consecutive degradation experiments, which indicates that the photocatalytic activity of Bi 2O2CO3/Cu9S5 photocatalytic nanomaterial remained good after three cycles.
The heterojunction catalytic material rich in oxygen vacancies and covering the full visible spectrum through visible light absorption is successfully prepared by a one-pot hydrothermal method, and the existence of the oxygen vacancies enables the material to utilize light lower than band gap energy, so that the photo-generated electron transition distance is shortened, and the separation efficiency of interface carriers is improved when the heterojunction is constructed.
Claims (10)
1. The preparation method of the heterojunction catalytic material rich in oxygen vacancies is characterized by comprising the following steps:
A. Dissolving Bi (NO 3)3·5H2 O and sodium carbonate in ultrapure water respectively to prepare Bi (NO 3)3·5H2 O solution and Na 2CO3 solution), stirring, dripping Na 2CO3 solution into Bi (NO 3)3·5H2 O solution to obtain mixed solution, adding glyoxal solution into the mixed solution, stirring, centrifuging, collecting precipitate, washing, and drying to obtain Bi 2O2CO3 rich in oxygen vacancies;
B. Dispersing Bi 2O2CO3 rich in oxygen vacancies, anhydrous copper acetate and thiourea into deionized water, stirring, performing hydrothermal reaction, cooling reactants, filtering, washing and drying to obtain a product Bi 2O2CO3/Cu9S5, namely the heterojunction catalytic material rich in oxygen vacancies.
2. The method for preparing the heterojunction catalytic material rich in oxygen vacancies as claimed in claim 1, wherein: in step A, bi (NO 3)3·5H2 O to sodium carbonate molar ratio is 1:2-4.
3. The method for preparing the heterojunction catalytic material rich in oxygen vacancies as claimed in claim 1, wherein: in the step A, the volume ratio of the mixed solution to the glyoxal solution is 40:1-4.
4. The method for preparing the heterojunction catalytic material rich in oxygen vacancies as claimed in claim 1, wherein: in the step A, drying is carried out by adopting an oven, the drying temperature is 60-80 ℃, and the drying time is 12-24 h.
5. The method for preparing the heterojunction catalytic material rich in oxygen vacancies as claimed in claim 1, wherein: in the step B, the molar ratio of Bi 2O2CO3 to anhydrous copper acetate to thiourea is 0.01-0.1:1:1.
6. The method for preparing the heterojunction catalytic material rich in oxygen vacancies as claimed in claim 1, wherein: in the step B, the temperature of the hydrothermal reaction is 140-180 ℃, and the time of the hydrothermal reaction is 8-12 h.
7. The method for preparing the heterojunction catalytic material rich in oxygen vacancies as claimed in claim 1, wherein: in the step B, drying is carried out by adopting an oven, the drying temperature is 60-80 ℃, and the drying time is 8-12h.
8. A heterojunction catalytic material rich in oxygen vacancies, characterized in that: a method of preparing the oxygen vacancy-rich heterojunction catalytic material of any one of claims 1 to 7.
9. Use of the oxygen vacancy-rich heterojunction catalytic material of claim 8 for photocatalytic degradation of contaminants.
10. Use of the oxygen vacancy-rich heterojunction catalytic material of claim 9 for photocatalytic degradation of contaminants, characterized in that: the contaminants include bisphenol a.
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| US20190127883A1 (en) * | 2017-10-26 | 2019-05-02 | Soochow University | Iodine doped bismuthyl carbonate nanosheet and molybdenum disulfide modified carbon nanofiber composites, preparation method and application thereof |
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