CN113198458B - Bismuth-chromium composite oxide semiconductor photocatalyst and preparation method and application thereof - Google Patents
Bismuth-chromium composite oxide semiconductor photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 59
- 239000004065 semiconductor Substances 0.000 title claims abstract description 51
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- PRTIWZOVTNONNN-UHFFFAOYSA-N [Bi].[Cr] Chemical compound [Bi].[Cr] PRTIWZOVTNONNN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011651 chromium Substances 0.000 claims abstract description 46
- 239000000725 suspension Substances 0.000 claims abstract description 14
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- 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 claims abstract description 10
- 230000031700 light absorption Effects 0.000 claims abstract description 7
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- 229910052797 bismuth Inorganic materials 0.000 description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
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- 230000000593 degrading effect Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
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- 238000010521 absorption reaction Methods 0.000 description 4
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 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 4
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- DHMGMTYGCBZFST-UHFFFAOYSA-N dibismuth;dioxido(dioxo)chromium Chemical compound [Bi+3].[Bi+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O DHMGMTYGCBZFST-UHFFFAOYSA-N 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
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- 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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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a bismuth-chromium composite oxide semiconductor photocatalyst and a preparation method and application thereof. The molecular formula of the photocatalyst is Cr2Bi3O11The maximum light absorption wavelength is 560 nm, the band gap is about 2.15 eV, the light absorption material is in a rod-shaped structure, the length is between 1 and 1.5 microns, and the diameter is about 150 nm. The preparation method comprises the following steps: dispersing bismuth nitrate pentahydrate in deionized water to obtain a white suspension; dissolving sodium chromate tetrahydrate in deionized water to obtain a yellow-green transparent solution; dropwise adding a sodium chromate solution into the bismuth nitrate suspension, and continuously stirring to obtain a yellow suspension; continuously stirring the obtained suspension for 0.5-24 hours, and naturally cooling to obtain yellow precipitate; filtering, washing, vacuum drying, grinding to obtain yellow powdery Cr2Bi3O11A semiconductor photocatalyst. Cr prepared by the invention2Bi3O11The semiconductor photocatalyst has a very wide light absorption wavelength range, so that the semiconductor photocatalyst has higher light utilization efficiency and can be used in environmental protection industries such as wastewater treatment and the like.
Description
Technical Field
The invention relates to a photocatalyst, in particular to a novel bismuth-chromium composite oxide semiconductor photocatalyst, a preparation method thereof and application thereof in the field of photocatalysis.
Background
Since the rattan island and the Honda discover that titanium dioxide has the capacity of decomposing water to produce hydrogen under ultraviolet irradiation, the photocatalytic technology is widely researched as an advanced redox technology with considerable prospect in the fields of hydrogen production by water splitting, environmental protection and the like. Titanium dioxide has become one of the hot spots of the leading research gradually due to its unique advantages, such as low cost and wide potential application range, and the photocatalytic technology based on the photocatalytic material has also been widely developed. The inherent electronic band structure of titanium dioxide, a typical photocatalyst, is a well-known drawback. Titanium dioxide is considered to be a less economical material given that its excessive bandwidth results in only ultraviolet light having sufficient energy to activate the titanium dioxide and initiate the photocatalytic process. In other common photocatalysts, the synthesis conditions are harsh, the cost is too high, the stability is poor, and the like are common defects. Therefore, it is very important to find a new photocatalyst with broad spectral response, easy preparation, low cost and good stability.
The bismuth-based semiconductor material has a layered microstructure, which is beneficial to the separation of photon-generated carriers, and meanwhile, the bismuth-based semiconductor material has simple and easy operation in synthesis steps, and the morphology of a reaction product can be regulated and controlled by controlling the synthesis reaction conditions, so that the photocatalytic activity of the photocatalytic material is improved by controlling the morphology. Currently, bismuth-based semiconductor materials that have been widely focused include Bi2WO6，Bi2MoO6，BiOX (X = Cl, Br, I)，BiPO4，BiVO4，(BiO)2CO3And the like. But the low photocatalytic activity under sunlight is a great obstacle to the difficulty of realizing industrial production. Therefore, the broadening of the spectral response range of the bismuth-based semiconductor material is helpful for promoting the rapid development of the field of solar drive photocatalysis, and is expected to realize the industrialization finally.
Recently, there are reports in the literature (Z. Li, Z. Zhang, L. Wang, X. Meng, Bismuth chroma (Bi)2CrO6) A formulating semiconductor in photocatalysis, Journal of Catalysis, 382 (2020) 40-48.) found that Bi2CrO6Compared with Bi of the same kind2WO6，Bi2MoO6The semiconductor possesses a larger absorption range, which means that it has a higher solar light utilization efficiency than both. However, the bismuth chromate prepared by the reported hydrothermal method still has low photocatalytic activity compared with the conventional bismuth tungstate and bismuth molybdate, and still has a large improvement space in the aspects of synthesis methods and the like.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a bismuth-chromium composite oxide semiconductor photocatalyst having uniform size, wide light absorption range, high sunlight utilization rate, and high activity and stability.
The invention also aims to provide a preparation method of the bismuth-chromium composite oxide semiconductor photocatalyst, which has the advantages of mild condition, simple operation, strong repeatability and low requirements on instruments and equipment.
The third object of the present invention is to provide Cr as described above2Bi3O11The semiconductor photocatalyst is applied to various technical fields such as sewage treatment and the like.
The bismuth-chromium composite oxide semiconductor photocatalyst provided by the invention is characterized in that the molecular formula of the bismuth-chromium composite oxide semiconductor photocatalyst is Cr2Bi3O11。
The maximum light absorption wavelength of the bismuth-chromium composite oxide semiconductor photocatalyst is 560 nanometers, and the band gap is about 2.15 eV.
The bismuth-chromium composite oxide semiconductor photocatalyst is of a rod-shaped structure, the length of the bismuth-chromium composite oxide semiconductor photocatalyst is between 1 and 1.5 micrometers, and the diameter of the bismuth-chromium composite oxide semiconductor photocatalyst is about 150 nanometers.
The preparation method of the bismuth-chromium composite oxide semiconductor photocatalyst is characterized by comprising the following steps of:
(1) dispersing bismuth nitrate pentahydrate in deionized water at the temperature of 20-100 ℃ to obtain white turbid liquid;
(2) at room temperature, dissolving sodium chromate tetrahydrate in deionized water to obtain a yellow-green transparent solution;
(3) dropwise adding the sodium chromate solution obtained in the step (2) into the bismuth nitrate suspension obtained in the step (1), and continuously stirring to obtain a yellow suspension;
(4) continuously stirring the suspension liquid obtained in the step (3) for 0.5-24 hours at the temperature of 20-100 ℃, and naturally cooling to obtain yellow precipitate;
(5) filtering the precipitate in the step (4), collecting solid, fully washing with deionized water and ethanol, performing vacuum drying, and grinding to obtain yellow powdery Cr2Bi3O11A semiconductor photocatalyst.
The concentration of the pentahydrate bismuth nitrate in the step (1) is 0.01-0.10 mol/L.
The molar ratio of the bismuth nitrate pentahydrate to the sodium chromate in the step (3) is 1 (0.1-5.0).
And (5) drying at the temperature of 5-100 ℃ for 8-72 hours.
The application of the bismuth-chromium composite oxide semiconductor photocatalyst provided by the invention in degradation of organic pollutants comprises the following steps:
(1) adding Cr into waste water containing organic pollutants2Bi3O11The semiconductor photocatalyst is added, and the volume ratio of the added mass of the catalyst to the wastewater is 0.01-5 g/L;
(2) stirring thoroughly to make Cr2Bi3O11The semiconductor photocatalyst is uniformly dispersed in the wastewater;
(3) irradiating the wastewater by using light with the wavelength of 300-800 nm.
The invention has the advantages that:
(1) cr prepared by the invention2Bi3O11The semiconductor photocatalyst has a very wide light absorption wavelength range (the maximum absorption wavelength can reach about 560 nm), and has higher light utilization efficiency compared with a commercial titanium dioxide photocatalyst (P25) and typical bismuth-based semiconductors such as bismuth tungstate, bismuth molybdate and the like which are researched more in the past.
(2) The invention is prepared by a simple aqueous phase synthesis methodCr generation2Bi3O11The semiconductor photocatalyst has the advantages of mild condition, simple operation, strong repeatability and low requirement on instruments and equipment, and provides good technical basis and material guarantee for large-area application.
(3) Cr prepared by the invention2Bi3O11The photocatalyst can effectively complete the task of degrading organic pollutants under the broad-spectrum illumination, and has the capability of completing hydrogen production and oxygen production, heavy metal treatment, carbon dioxide reduction, desulfurization and denitrification, nitrogen fixation and other various tasks. Can be used in the environmental protection industries such as wastewater treatment and the like, and has the potential of assisting the self-restoration of the environment.
Drawings
FIG. 1 shows Cr prepared in example 12Bi3O11Powder X-ray diffraction pattern of the photocatalyst.
FIG. 2 shows Cr prepared in example 12Bi3O11Simulation structure diagram of photocatalyst.
FIG. 3 shows Cr prepared in example 12Bi3O11Scanning electron microscopy of the photocatalyst.
FIG. 4 shows Cr prepared in example 12Bi3O11The total distribution spectrum of the elements of the photocatalyst.
FIG. 5 shows Cr prepared in example 12Bi3O11The X-ray photoelectron spectrum of the photocatalyst.
FIG. 6 shows Cr prepared in example 12Bi3O11High resolution X-ray photoelectron spectroscopy of the photocatalyst.
FIG. 7 shows Cr prepared in example 12Bi3O11Uv-visible diffuse reflectance spectrum of photocatalyst.
FIG. 8 shows Cr prepared in example 12Bi3O11The performance of the catalyst is compared with that of the similar catalyst for degrading phenol.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings by way of specific examples, and materials, reagents and the like used in the following examples are commercially available.
Example 1: cr (chromium) component2Bi3O11Preparation of semiconductor photocatalysts
(1) Dispersing bismuth nitrate pentahydrate in deionized water at 60 ℃ to obtain a white suspension, wherein the concentration of the bismuth nitrate pentahydrate is 0.025 mol/L;
(2) at room temperature, dissolving sodium chromate tetrahydrate in deionized water to enable the molar ratio of the sodium chromate tetrahydrate in the aqueous solution to the bismuth nitrate pentahydrate in the step (1) to be 1:2, and obtaining a yellow-green transparent solution;
(3) dropwise adding the solution obtained in the step (2) into the suspension obtained in the step (1), and continuously stirring to obtain a yellow suspension;
(4) continuously stirring the suspension obtained in the step (3) for 1 hour at the temperature of 60 ℃, and naturally cooling to obtain yellow precipitate;
(5) filtering the precipitate in the step (4), collecting the solid, fully washing with deionized water and ethanol, performing vacuum drying at 60 ℃ for 12 hours, and grinding to obtain yellow powdery Cr2Bi3O11A photocatalyst.
As can be seen from the powder X-ray diffraction spectrum of FIG. 1, the prepared product and the chromium-oxygen-bismuth type compound Cr in the open source material simulation database2Bi3O11Consistent structure (mp-1196207, material project. org), the major facets have been noted in the figure. Through further calculation, a structure model of the prepared product is simulated as shown in fig. 2, and the small ball model sequentially represents bismuth, chromium and oxygen atoms from large to small. As can be seen from the scanning electron micrograph of FIG. 3, synthesized Cr2Bi3O11The semiconductor photocatalyst sample has good uniformity and a rod-shaped structure, and the length of the micro rod is generally between 1 and 1.5 micrometers and the diameter of the micro rod is about 150 nanometers through measurement and calculation. FIG. 4 shows Cr2Bi3O11The distribution of elements in the composite oxide, the specific mass percentage of the elements and the atomic number percentage are shown in the table1, it can be seen that the atomic ratio (Cr: Bi: O = 8.42: 25.11: 66.47 ≈ 1: 3: 8) calculated by the experimental data and the result of the X-ray diffraction spectrum (Cr: Bi: O = 8.42: 25.11: 66.47 ≈ 1: 3: 8)2Bi3O11And Cr: bi: o = 2:3: 11) are relatively close, validating each other. In the X-ray photoelectron spectrum of fig. 5, it can be seen that no other elements except bismuth, chromium and oxygen are found in the catalyst, and the purity of the sample is high. In the X-ray photoelectron fine spectrum of fig. 6, only one set of double peaks appears in the bismuth and chromium scanning spectra of the material, and the two peaks in the oxygen scanning spectra are respectively assigned to the oxygen atoms bonded with the chromium and the bismuth, which indicates that the material has only one chemical state. The UV-Vis Diffuse reflectance spectrum of FIG. 7 shows Cr2Bi3O11The semiconductor photocatalyst has a wide absorption range in the visible region, a maximum absorption wavelength of about 560 nm, and a bandwidth of about 2.15 eV, which is estimated by calculation, indicating that Cr of the present invention2Bi3O11The semiconductor photocatalyst has good light utilization efficiency and good oxidation-reduction capability.
TABLE 1 Cr2Bi3O11Elemental composition distribution in semiconductor catalysts
Example 2: cr (chromium) component2Bi3O11Semiconductor photocatalyst for degrading waste water containing colored pollutants
(1) 0.1g of Cr is added into 100 mL of wastewater with the concentration of 5 mg/L of mixed rhodamine B/methylene blue/methyl orange2Bi3O11A semiconductor photocatalyst;
(2) stirring thoroughly to mix Cr2Bi3O11The catalyst is uniformly dispersed in the wastewater;
(3) and (3) irradiating the wastewater in the step (2) by using a light source with the wavelength of 300-800 nm for 1 hour.
TABLE 2 Cr2Bi3O11Degradation rate of semiconductor photocatalyst to colored pollutant wastewater within 1 hour
| Contaminants | Rhodamine B | Methylene blue | Methyl orange |
| Percent of degradation/%) | 85.43 | 40.09 | 79.66 |
It can be seen that Cr2Bi3O11The rhodamine B degrading agent has good degrading capability on colored organic pollutants such as organic dyes, and the degrading rate of rhodamine B in one hour reaches 85.43 percent to the maximum.
Example 3: cr (chromium) component2Bi3O11Semiconductor photocatalyst for degrading phenol wastewater
(1) 0.1g of Cr was added to 100 mL of wastewater containing 10 mg/L of phenol2Bi3O11A semiconductor photocatalyst;
(2) stirring thoroughly to mix Cr2Bi3O11The photocatalyst is uniformly dispersed in the wastewater;
(3) and (3) irradiating the wastewater in the step (2) by using a light source with the wavelength of 300-800 nm for 6 hours.
TABLE 3 Cr2Bi3O11Degradation rate of semiconductor photocatalyst to colorless phenol wastewater within 6 hours
| Contaminants | Phenol and its preparation |
| Percent of degradation/%) | 27.50 |
| Total organic carbon removal rate/%) | 11.41 |
It can be seen that Cr2Bi3O11The degradation capability to colorless phenol is also realized, and the degradation rates of phenol and total organic carbon in 6 hours reach 27.50 percent and 11.41 percent respectively. The degradation capacities of the same bismuth molybdate and bismuth tungstate to phenol were compared within 2 hours, 4 hours and 6 hours, as shown in FIG. 8. As can be seen from the figure, Cr2Bi3O11The activity of (A) reaches 95.36 mu mol gcat within two hours-1·h-1About 4.8 and 2.8 times as much as bismuth molybdate and tungstate.
The present invention is not limited to the above embodiments, and any changes or modifications made to the present invention should be covered within the scope of the present invention.
Claims (6)
1. A bismuth-chromium composite oxide semiconductor photocatalyst is characterized in that the molecular formula of the bismuth-chromium composite oxide semiconductor photocatalyst is Cr2Bi3O11The optical fiber is in a rod-shaped structure, the length is between 1 and 1.5 micrometers, the diameter is 150 nanometers, the maximum light absorption wavelength is 560 nanometers, and the band gap is 2.15 eV.
2. A method for preparing the bismuth-chromium composite oxide semiconductor photocatalyst as claimed in claim 1, which is characterized by comprising the following steps:
(1) dispersing bismuth nitrate pentahydrate in deionized water at the temperature of 20-100 ℃ to obtain white turbid liquid;
(2) at room temperature, dissolving sodium chromate tetrahydrate in deionized water to obtain a yellow-green transparent solution;
(3) dropwise adding the sodium chromate solution obtained in the step (2) into the bismuth nitrate suspension obtained in the step (1), and continuously stirring to obtain a yellow suspension;
(4) continuously stirring the suspension liquid obtained in the step (3) for 0.5-24 hours at the temperature of 20-100 ℃, and naturally cooling to obtain yellow precipitate;
(5) filtering the precipitate in the step (4), collecting solid, fully washing with deionized water and ethanol, performing vacuum drying, and grinding to obtain yellow powdery Cr2Bi3O11A semiconductor photocatalyst.
3. The method for preparing the bismuth-chromium composite oxide semiconductor photocatalyst as claimed in claim 2, wherein the concentration of bismuth nitrate pentahydrate in the step (1) is 0.01-0.10 mol/L.
4. The preparation method of the bismuth-chromium composite oxide semiconductor photocatalyst as claimed in claim 2, wherein the molar ratio of bismuth nitrate pentahydrate to sodium chromate in the step (3) is 1 (0.1-5.0).
5. The method for preparing a bismuth-chromium composite oxide semiconductor photocatalyst as claimed in claim 2, wherein the drying temperature in the step (5) is 5 to 100 ℃ and the drying time is 8 to 72 hours.
6. The use of a bismuth chromium composite oxide semiconductor photocatalyst as claimed in claim 1 for the degradation of organic contaminants comprising the steps of:
(1) adding C into waste water containing organic pollutantsr2Bi3O11The semiconductor photocatalyst is added, and the volume ratio of the added mass of the catalyst to the wastewater is 0.01-5 g/L;
(2) stirring thoroughly to make Cr2Bi3O11The semiconductor photocatalyst is uniformly dispersed in the wastewater;
(3) irradiating the wastewater by using light with the wavelength of 300-800 nm.
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