CN111185203B - Iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst and preparation method thereof - Google Patents
Iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- TWDJZUXQDJFLNE-UHFFFAOYSA-N O(Br)Br.[Bi+3].[O-2].[O-2].[Ti+4] Chemical compound O(Br)Br.[Bi+3].[O-2].[O-2].[Ti+4] TWDJZUXQDJFLNE-UHFFFAOYSA-N 0.000 title claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- 239000011630 iodine Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 39
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 10
- 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 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000593 degrading effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims 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 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 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 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 2
- 238000001179 sorption measurement Methods 0.000 abstract description 23
- 230000001699 photocatalysis Effects 0.000 abstract description 19
- 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 abstract description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 239000013335 mesoporous material Substances 0.000 abstract description 6
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
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- 239000002957 persistent organic pollutant Substances 0.000 description 4
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- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
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- 230000003197 catalytic effect Effects 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
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- 241000282414 Homo sapiens Species 0.000 description 1
- -1 Ti)4+ Chemical class 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- OLBRKKJBIBPJSE-UHFFFAOYSA-N bismuth;bromo hypobromite Chemical compound [Bi].BrOBr OLBRKKJBIBPJSE-UHFFFAOYSA-N 0.000 description 1
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
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- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention belongs to the field of inorganic nano photocatalytic materials, and particularly relates to an iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst and a preparation method thereof. The preparation method comprises the steps of taking mesoporous silica SBA-15 as a carrier, and respectively loading iodine, bismuth oxybromide and titanium dioxide in a certain proportion on the SBA-15 to prepare the iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst. The introduction of iodine can keep the composite material with higher adsorption capacity, ordered pore channel structure which is not easy to collapse, and can effectively prevent TiO2Agglomeration during heat treatment, and in addition iodine and bismuth oxybromide (BiOBr) can also reduce TiO2The forbidden band width of the catalyst can further improve the photocatalytic degradation performance; and BiOBr and TiO2Introduction into SiO2The surface of the mesoporous material can also play a role in synergetic photocatalysis, so that the photocatalysis performance of the composite material can be effectively improved, and the degradation rate of rhodamine B can reach 100% in 10min after the lamp is turned on.
Description
Technical Field
The invention belongs to the field of inorganic nano photocatalytic materials, and particularly relates to an iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst and a preparation method thereof.
Background
With the continuous acceleration of industrialization and agriculture, more and more organic waste compounds are discharged into water sources to cause serious water pollution, thereby seriously threatening the survival and development of human beings, and thus the environmental pollution is one of the problems to be urgently solved. The photocatalytic degradation of organic compounds is an economic, rapid and sustainable green technology and has great application potential.
In the existing research reports, it is found that a single mesoporous material such as silicon dioxide (SiO) is used2) Use of mesoporous materials in photocatalysisThe effect of degrading organic pollutants is not very desirable. Due to SiO2The mesoporous material has great amount of active sites on its surface for chemical modification and physical adsorption, so that it has photocatalytic metal ion or metal oxide (such as Ti)4+，Al3+And V5+) Carried on SiO2The surface of the mesoporous material can effectively improve the photocatalytic performance by exerting the synergistic effect. The commonly used metal oxide is TiO2But due to TiO2The forbidden band width of the material is large, the material is easy to inactivate and agglomerate, and the material can only be excited by ultraviolet light with the wavelength less than 387nm, so that the utilization rate of light is low, and the photocatalytic degradation efficiency is low.
Thus, how to incorporate TiO2The light response range is expanded to a visible light region, and TiO is improved2The adsorption and photocatalytic efficiency of pollutants become a difficult problem in the field of photocatalytic degradation.
Disclosure of Invention
In order to solve the technical problems, the invention provides an iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst and a preparation method thereof2Forbidden band width of (2) TiO 22The light response range is expanded to the visible light region.
The invention aims to provide an iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst, which is prepared by loading iodine-doped TiO on mesoporous silica2And then compounding with BiOBr to obtain the composite photocatalyst.
Further, the preparation method comprises the following specific steps:
(1) preparation of mesoporous SiO2Material, named SBA-15;
(2) uniformly stirring aqueous solutions of iodic acid and tetrabutyl titanate at normal temperature, and calcining at 300-400 ℃ for 4-6 h; the yellow powder obtained was iodine-doped titanium dioxide, named I/TiO2(ii) a The molar ratio of the iodic acid to the tetrabutyl titanate is (1-4) to 5;
(3) the I/TiO obtained in the step (2)2Adding the mixture into a solution with the pH value of 1-6, stirring, and adding the SBA-1 obtained in the step (1)5, continuously stirring, washing with water, and drying to obtain a light yellow intermediate product named I/TiO2@ SBA-15; SBA-15 and I/TiO2The feeding mass ratio of (1): (3-6);
(4) the I/TiO obtained in the step (3)2@ SBA-15 addition to Bi (NO)3)·5H2Stirring the mixture evenly in a mixed solution of O and NaBr, then reacting for 20-30 h at 140-160 ℃, washing and drying to obtain a final product, namely I/TiO2-BiOBr @ SBA-15; wherein Bi (NO)3)·5H2O, NaBr and I/TiO2The molar ratio of Ti in the @ SBA-15 is 1 (2.5-3.5): (1-5).
Further, in the step (1), the preparation method of SBA-15 comprises the following steps: dissolving P123 in hydrochloric acid solution, stirring at constant temperature to obtain clear and transparent solution, dropwise adding tetraethoxysilane, continuously stirring, reacting, filtering, washing with water, drying, and calcining to obtain mesoporous SiO2Material, named SBA-15; wherein the molar ratio of the ethyl orthosilicate to the P123 to the hydrochloric acid is (58-65) to 1: 58.
Further, in the step (1), the stirring temperature of the P123 and the hydrochloric acid solution is 35-40 ℃.
Further, in the step (1), after ethyl orthosilicate is dripped, stirring is carried out for 20-48 h, the reaction temperature is 100-150 ℃, and the reaction time is 20-30 h.
Further, in the step (1), the drying temperature is 40-60 ℃.
Further, in the step (1), the calcining temperature is 600-700 ℃, and the time is 5-7 h.
Further, in the step (2), the stirring time of the aqueous solution of iodic acid and tetrabutyl titanate is 30-60 min.
Further, in the step (3), the solution is a nitric acid solution or a hydrochloric acid solution.
Further, in the step (3), the time for stirring twice is 3-5 hours respectively.
Further, in the step (4), the stirring time is 3-5 hours.
Further, in the step (4), the drying temperature is 60-80 ℃.
The second purpose of the invention is to propose the application of the composite photocatalyst in adsorbing or degrading organic pollutants, wherein the organic pollutants comprise one or more of rhodamine b, methyl orange and bisphenol A.
By the scheme, the invention at least has the following advantages:
(1) the invention provides an iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst (I/TiO)2BiOBr @ SBA-15), wherein the mesoporous material has higher adsorption capacity, ordered and difficultly collapsed pore channel structure, and can effectively prevent TiO2Agglomeration during heat treatment. Furthermore, TiO2The TiO can be reduced by doping iodine and loading BiOBr2The forbidden band width of BiOBr and TiO is promoted2The heterojunction structure is formed, and e can be effectively improved-And h+The transfer efficiency of the wastewater treatment system is improved, the photocatalytic activity of visible light is improved, and the degradation efficiency of organic pollutants in the wastewater is improved.
(2) I/TiO synthesized by the method2the-BiOBr @ SBA-15 photocatalyst material has strong adsorption and degradation capacity on rhodamine B, and the adsorption rate on rhodamine B can reach 65% after adsorption balance. In addition, under the irradiation of a xenon lamp, the degradation rate of the material to rhodamine B can reach 100% in 10 min.
(3) The process flow for preparing the composite photocatalyst is simple, the implementation cost is low, and the method has a good popularization prospect.
Drawings
FIG. 1 shows photocatalysts prepared in examples 1 to 4 and TiO prepared in comparative example 12@ SBA-15 DRS (ultraviolet diffuse reflectance Spectroscopy) curve.
FIG. 2 shows the photocatalysts prepared in examples 1 to 4, SBA-15 and I/TiO prepared in comparative example 12@SBA-15、TiO2-BiOBr@SBA-15、TiO2And @ SBA-15 is used for adsorbing rhodamine B and performing photocatalytic degradation.
FIG. 3 is a graph showing the adsorption and photocatalytic degradation cycle test of rhodamine B by the photocatalyst prepared in example 3.
Fig. 4 is a TEM image of the photocatalyst prepared in example 3.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
A preparation method of an iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst comprises the following steps:
(1) weighing 20g P123 in 650mL of water at 40 ℃, adding 100mL of 2mol/L hydrochloric acid solution, stirring until the solution is transparent, dropwise adding 45g of Tetraethoxysilane (TEOS), stirring at constant temperature for 24h, putting the mixture into a hydrothermal reaction kettle for reaction at 100 ℃ for 24h, filtering, washing, drying at 40 ℃, and calcining at 600 ℃ for 6h to obtain mesoporous SiO2The material was named SBA-15.
(2)36g HIO3And 345g of tetrabutyl titanate in 5000mL of H2Dissolving O for 30min, drying at 100 deg.C for 3 hr, calcining at 300 deg.C for 4 hr to obtain yellow powder of iodine-doped titanium dioxide 80g, named I/TiO2。
(3) Mixing 80g I/TiO2Adding into 15mL nitric acid solution with pH of 1, stirring for 3 hr, adding 26g SBA-15, stirring for 3 hr, washing with water, and drying at 60 deg.C to obtain 88g pale yellow powder named I/TiO2@SBA-15。
(4)3000mL glycerol, 3000mL H2O and 46g Bi (NO)3)·5H2Stirring O at normal temperature for 1h, adding 26g NaBr, stirring for 3h, and adding 8.23g of I/TiO in the step (3)2@ SBA-15 is continuously stirred for 3 hours, then poured into a hydrothermal reaction kettle to react for 24 hours at the temperature of 140 ℃, washed and dried at the temperature of 60 ℃ to obtain the iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst, which is named as 1-I/TiO2-BiOBr@SBA-15。
(5) The photocatalyst prepared in the present example was subjected to DRS test by an ultraviolet-visible near-infrared spectrophotometer to obtain a DRS curve, which is shown in fig. 1.
(6) The photocatalyst prepared in this example was subjected to adsorption and full spectrum photocatalytic activity tests.
Adsorption experiment: 0.1g of the photocatalyst prepared in this example was added to 100mL of rhodamine B (w/v, 10 mg/L) solution, stirred in the dark for 30min, samples were taken every 10 minutes, the samples taken each time were centrifuged, the supernatant was taken, the absorbance was measured at the optimum absorption wavelength (552nm) with an ultraviolet-visible spectrophotometer, the concentration at the sampling at different times was calculated from a standard curve, and the test results are shown in FIG. 2.
Photocatalytic activity experiment: and (3) carrying out photocatalytic reaction on the rhodamine B solution which is stirred for 30min and reaches adsorption/desorption balance, observing the color change of the dye by using a 300W xenon lamp as a light source under the irradiation of light of 200-800nm, and calculating the degradation rate, wherein the test result is shown in figure 2.
Example 2
A preparation method of an iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst comprises the following steps:
(1) the preparation method of step (1) is the same as in example 1.
(2)72gHIO3And 345g of tetrabutyl titanate in 5000mL of H2Dissolving O for 40min, drying at 100 deg.C for 3 hr, calcining at 350 deg.C for 4.5 hr to obtain yellow powder of iodine-doped titanium dioxide 90g, named I/TiO2。
(3) Mixing 90gI/TiO2Adding into 15mL nitric acid solution with pH of 3, stirring for 3 hr, adding 25g SBA-15, stirring for 3 hr, washing with water, and drying at 60 deg.C to obtain 91g pale yellow powder named I/TiO2@SBA-15。
(4)3000mL glycerol, 3000mL H2O and 44g Bi (NO)3)·5H2Stirring O at normal temperature for 1h, adding 27g NaBr, stirring for 3h, and adding 16.3g of I/TiO in the step (3)2Continuously stirring the @ SBA-15 for 3 hours, then pouring the mixture into a hydrothermal reaction kettle to react for 24 hours at the temperature of 145 ℃, washing the mixture with water, and drying the mixture at the temperature of 60 ℃ to obtain the iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst named as 2-I/TiO2-BiOBr@SBA-15。
(5) The photocatalyst prepared in the present example was subjected to DRS test by an ultraviolet-visible near-infrared spectrophotometer to obtain a DRS curve, which is shown in fig. 1.
(6) The photocatalyst prepared in this example was subjected to adsorption and full spectrum photocatalytic activity tests. The procedure of the test was the same as in example 1, and the results are shown in FIG. 2.
Example 3
A preparation method of an iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst comprises the following steps:
(1) the preparation method of step (1) is the same as in example 1.
(2)106g HIO3And 345g of tetrabutyl titanate in 5000mL of H2Dissolving O for 50min, drying at 100 deg.C for 3 hr, calcining at 380 deg.C for 5 hr to obtain yellow powder of iodine-doped titanium dioxide 100g, named I/TiO2。
(3) Mixing 100g I/TiO2Adding into 15mL nitric acid solution with pH of 5, stirring for 3 hr, adding 24g SBA-15, stirring for 3 hr, washing with water, and drying at 60 deg.C to obtain 101g pale yellow powder named I/TiO2@SBA-15。
(4)3000mL glycerol, 3000mL H2O and 49g Bi (NO)3)·5H2Stirring O at normal temperature for 1h, adding 32g NaBr, stirring for 3h, adding 30.2g I/TiO in the step (3)2Continuously stirring the @ SBA-15 for 3 hours, then pouring the mixture into a hydrothermal reaction kettle to react for 24 hours at the temperature of 150 ℃, washing the mixture with water, and drying the mixture at the temperature of 60 ℃ to obtain the iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst named as 3-I/TiO2-BiOBr@SBA-15。
(5) The photocatalyst prepared in the present example was subjected to DRS test by an ultraviolet-visible near-infrared spectrophotometer to obtain a DRS curve, which is shown in fig. 1.
(6) The photocatalyst prepared in this example was subjected to adsorption and full spectrum photocatalytic activity tests. The procedure of the test was the same as in example 1, and the results are shown in FIG. 2.
(7) The photocatalyst prepared in the embodiment is used for carrying out cyclic tests on rhodamine B adsorption and photocatalytic degradation, and the specific test method comprises the following steps: accurately measuring 100.0mL of 10mg/L rhodamine B aqueous solution in a beaker, weighing 0.10g of the catalyst prepared in the experiment, slowly stirring in a dark place for 30min to achieve adsorption balance, then turning on a 300W xenon lamp light source, keeping the solution slowly stirring, placing the solution at a position 15cm under the light source, and sampling at intervals. Centrifuging the sample, taking the supernatant, pouring the supernatant into a cuvette, and measuring the absorbance of the supernatant by using an ultraviolet-visible spectrophotometer at 552 nm. And then washing and drying the centrifuged precipitate, and putting 100.0mL of 10mg/L rhodamine B aqueous solution again for adsorption and photocatalytic degradation tests, and circulating for 7 times in this way, wherein the test result is shown in figure 3.
As can be seen from FIG. 3, the photocatalyst prepared in this example still maintains 95% of degradation rate after 7 cycles, which indicates that the sample has good stability.
(6) A TEM image of the photocatalyst prepared in this example is shown in FIG. 4.
As can be seen from FIG. 4, the channels of the mesoporous silica are almost covered by BiOBr and TiO2Nano particle full, TiO2The size of the nano particles is about 15-20nm, the BiOBr presents a sheet structure, the size is about 140-280nm, and the lattice spacing is 0.35nm and 0.28nm respectively.
Example 4
A preparation method of an iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst comprises the following steps:
(1) the preparation method of step (1) is the same as in example 1.
(2)144g HIO3And 345g of tetrabutyl titanate in 5000mL of H2Dissolving O for 60min, drying at 100 deg.C for 3 hr, calcining at 400 deg.C for 6 hr to obtain yellow powder of iodine-doped titanium dioxide 110g, named I/TiO2。
(3) Mixing 110g I/TiO2Adding into 15mL nitric acid solution with pH of 6, stirring for 3 hr, adding 21g SBA-15, stirring for 3 hr, washing with water, and drying at 60 deg.C to obtain 98g pale yellow powder named I/TiO2@SBA-15。
(4)3000mL glycerol, 3000mL H2O and 41g Bi (NO)3)·5H2Stirring O at normal temperature for 1h, adding 30g NaBr, stirring for 3h, adding 33g I/TiO in the step (3)2Continuously stirring for 3h at @ SBA-15, then pouring into a hydrothermal reaction kettle for reacting for 24h at 160 ℃, washing with water, and drying at 60 ℃ to obtain the iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst named as 4-I/TiO2-BiOBr@SBA-15。
(5) The photocatalyst prepared in the present example was subjected to DRS test by an ultraviolet-visible near-infrared spectrophotometer to obtain a DRS curve, which is shown in fig. 1.
(6) The photocatalyst prepared in this example was subjected to adsorption and full spectrum photocatalytic activity tests. The procedure of the test was the same as in example 1, and the results are shown in FIG. 2.
Comparative example 1
SBA-15 was prepared in the same manner as in example 1. The prepared SBA-15 was subjected to adsorption and full spectrum photocatalytic activity tests, the test procedures were the same as those of the adsorption and full spectrum photocatalytic test in example 1, and the test results are shown in FIG. 2.
Preparation of I/TiO2@ SBA-15, preparation of I/TiO I example 12The same procedure is applied to @ SBA-15. For the prepared I/TiO2@ SBA-15 was subjected to the adsorption and full spectrum photocatalytic activity tests, which were the same as those in example 1, and the test results are shown in FIG. 2.
Preparation of TiO2BiOBr @ SBA-15, preparation of I/TiO as in example 12The procedure of-BiOBr @ SBA-15 is the same except that no HIO is added3. For the prepared TiO2BiOBr @ SBA-15 was subjected to the same adsorption and full spectrum photocatalytic activity tests as those in example 1, and the test results are shown in FIG. 2.
Preparation of TiO2@ SBA-15, preparation of I/TiO I example 12The procedure of @ SBA-15 is the same except that no HIO is added3. The obtained TiO is2@ SBA-15 DRS test was performed by UV-visible near-IR spectrophotometer to obtain DRS curve, see FIG. 1. For the prepared TiO2@ SBA-15 was subjected to the adsorption and full spectrum photocatalytic activity tests, which were the same as those in example 1, and the test results are shown in FIG. 2.
As can be seen from FIG. 1, compared with TiO not doped with iodine and loaded with bismuth oxybromide2Sample @ SBA-15, photocatalyst prepared in examples 1-4The absorption intensity of light in the visible region (400nm to 760nm) is increased. This is because the original TiO is doped with bismuth oxybromide and iodine in titanium dioxide2The numerical value of the forbidden band width of (A) is reduced, so that the absorption of light by red shift of absorption wavelength is enhanced.
As can be seen from FIG. 2, the photocatalysts prepared in examples 1 to 4 have better adsorption and photodegradation properties on rhodamine B, and the degradation on rhodamine B after adsorption for 30min and illumination for 10min is up to 100%, which is because the separation efficiency of photo-generated electrons and holes is improved by adding iodine and BiOBr. And the SBA-15 material has no photocatalytic activity and only adsorbability. I/TiO2@SBA-15、TiO2-BiOBr@SBA-15、TiO2The catalytic effect of @ SBA-15 is far less than that of the photocatalyst prepared in examples 1-4, and the synergistic effect between the iodine-doped titanium dioxide and the bismuth oxybromide can be seen, so that the catalytic effect of the photocatalyst can be obviously improved.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. The iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst is characterized by comprising the following steps: TiO doped with iodine is loaded on mesoporous silicon dioxide2Then compounding with BiOBr to obtain a composite photocatalyst;
the preparation method of the iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst comprises the following specific steps:
(1) preparation of mesoporous SiO2Material, named SBA-15;
(2) uniformly stirring aqueous solution of iodic acid and tetrabutyl titanate at normal temperature, calcining at 300-400 ℃ for 4-6h to obtain iodine-doped titanium dioxide named I/TiO2(ii) a The molar ratio of the iodic acid to the tetrabutyl titanate is (1-4) to 5;
(3) the I/TiO obtained in the step (2)2Is added toStirring the solution with the pH of 1-6, adding the SBA-15 obtained in the step (1), continuously stirring for 3-5 hours, washing with water, and drying to obtain a light yellow intermediate product named I/TiO2@ SBA-15; SBA-15 and I/TiO2The feeding mass ratio of (1): (3-6);
(4) the I/TiO obtained in the step (3)2@ SBA-15 addition to Bi (NO)3)·5H2Stirring for 3-5 h to be uniform in a mixed solution of O and NaBr, then reacting for 20-30 h at 140-160 ℃, washing with water, and drying at 60-80 ℃ to obtain a final product, namely I/TiO2-BiOBr @ SBA-15; wherein Bi (NO)3)·5H2O, NaBr and I/TiO2The molar ratio of Ti in the @ SBA-15 is 1 (2.5-3.5): (1-5).
2. The iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst as claimed in claim 1, wherein in the step (1), the preparation method of SBA-15 comprises the following steps: dissolving P123 in hydrochloric acid solution, stirring at constant temperature to obtain clear and transparent solution, dropwise adding tetraethoxysilane, continuously stirring, reacting, filtering, washing with water, drying, and calcining to obtain mesoporous SiO2Material, named SBA-15; wherein the molar ratio of the ethyl orthosilicate to the P123 to the hydrochloric acid is (58-65) to 1: 58.
3. The iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst as claimed in claim 1, wherein in the step (3), the solution is a nitric acid solution or a hydrochloric acid solution.
4. Use of the composite photocatalyst as claimed in any one of claims 1 to 3 for adsorbing or degrading organic contaminants, wherein the organic contaminants comprise one or more of rhodamine b, methyl orange, bisphenol A.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1555914A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Preparation method of photocatalytic active iodine adulterated titanium dioxide material |
| CN1555919A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Iodine adulterated photocatalytic multicrystal material possessing photocatalytic performance under visible light |
| CN101653732A (en) * | 2009-09-29 | 2010-02-24 | 福州大学 | Molecular sieve loaded BiOX photocatalyst, preparation method and application thereof |
| CN104785280A (en) * | 2015-04-14 | 2015-07-22 | 济南大学 | Flaky titanium dioxide/bismuth oxybromide composite photocatalyst and preparation method thereof |
-
2020
- 2020-02-11 CN CN202010085795.6A patent/CN111185203B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1555914A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Preparation method of photocatalytic active iodine adulterated titanium dioxide material |
| CN1555919A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Iodine adulterated photocatalytic multicrystal material possessing photocatalytic performance under visible light |
| CN101653732A (en) * | 2009-09-29 | 2010-02-24 | 福州大学 | Molecular sieve loaded BiOX photocatalyst, preparation method and application thereof |
| CN104785280A (en) * | 2015-04-14 | 2015-07-22 | 济南大学 | Flaky titanium dioxide/bismuth oxybromide composite photocatalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Effect of Different Calcination Temperatures on the Structural and Photocatalytic Performance of Bi-TiO2/SBA-15;Jing Ma et al.;《International Journal of Photoenergy》;20131231;第1-11页 * |
| Hybrid BiOBr-TiO2 nanocomposites with high visible light photocataytic activity for water treatment;Xian-Xian Wei et al.;《Journal of Hazardous Materials》;20131022;第263卷;第650-658页 * |
| Titania based nanocomposites as a photocatalyst: A review;Madhuri Sharon et al.;《AIMS Materials Science》;20160823;第3卷(第3期);第1236-1254页 * |
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