CN103252244A - Preparation method and application method of visible-light response type bismuth oxychloride photocatalyst - Google Patents
Preparation method and application method of visible-light response type bismuth oxychloride photocatalyst Download PDFInfo
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000004044 response Effects 0.000 title claims description 31
- 229940073609 bismuth oxychloride Drugs 0.000 title abstract 2
- 239000011941 photocatalyst Substances 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 36
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 26
- 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 claims abstract description 24
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 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 claims abstract 6
- AHUBLGVDRKDHAT-UHFFFAOYSA-N [Bi]=O.[Cl] Chemical compound [Bi]=O.[Cl] AHUBLGVDRKDHAT-UHFFFAOYSA-N 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 6
- 229940006461 iodide ion Drugs 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 241000370738 Chlorion Species 0.000 claims description 5
- 238000002835 absorbance Methods 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- 230000001603 reducing effect Effects 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000862 absorption spectrum Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 231100000331 toxic Toxicity 0.000 claims description 2
- 230000002588 toxic effect Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003256 environmental substance Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 abstract 3
- 230000003197 catalytic effect Effects 0.000 abstract 2
- 238000003760 magnetic stirring Methods 0.000 abstract 2
- SBQHRXFHJGZTCG-UHFFFAOYSA-M potassium iodide hydrochloride Chemical compound Cl.I[K] SBQHRXFHJGZTCG-UHFFFAOYSA-M 0.000 abstract 2
- 238000001179 sorption measurement Methods 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 239000001045 blue dye Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 20
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
一种可见光响应型氯氧铋光催化剂的制备及其应用方法，属于环境化工光催化水处理技术领域。其特征是将铋酸钠放置于无水乙醇中，在磁力搅拌下分散1～1.5h；配制1.2mol?L-1盐酸100mL，并称取与所配盐酸溶液中的氯离子等摩尔量的碘化钾溶于该盐酸溶液中，形成盐酸-碘化钾混合溶液；在磁力搅拌下将配制好的盐酸-碘化钾混合溶液以8～10分钟滴加1mL的速度加入到铋酸钠-无水乙醇分散体系中，搅拌时间1.5～2h，反应温度20～20.5℃，制得悬浮溶液，过滤，滤饼用蒸馏水和无水乙醇洗涤三次，在40～50℃温度下烘干即可，该催化剂用于吸附和光催化降解罗丹明B或者亚甲基蓝染料废水，在可见光下具有良好的吸附和光催化降解作用，催化活性稳定，重复利用率高，具有实际应用前景。
The preparation and application method of a visible light-responsive bismuth oxychloride photocatalyst belongs to the technical field of environmental chemical photocatalytic water treatment. It is characterized in that sodium bismuthate is placed in absolute ethanol and dispersed under magnetic stirring for 1 to 1.5 hours; 1.2mol?L -1 hydrochloric acid is prepared in 100mL, and an amount equivalent to the chloride ion in the hydrochloric acid solution is weighed. Dissolve potassium iodide in the hydrochloric acid solution to form a hydrochloric acid-potassium iodide mixed solution; under magnetic stirring, add the prepared hydrochloric acid-potassium iodide mixed solution dropwise at a rate of 1 mL in 8-10 minutes to the sodium bismuthate-absolute ethanol dispersion system , the stirring time is 1.5~2h, the reaction temperature is 20~20.5℃, the suspension solution is obtained, filtered, the filter cake is washed three times with distilled water and absolute ethanol, and it can be dried at 40~50℃. The catalyst is used for adsorption and light Catalytic degradation of rhodamine B or methylene blue dye wastewater has good adsorption and photocatalytic degradation effects under visible light, stable catalytic activity, high reuse rate, and has practical application prospects.
Description
Technical field
Preparation and the application process of a kind of visible-light response type chlorine of the present invention oxygen bismuth photochemical catalyst, belong to environmental chemical engineering photocatalysis water-treatment technology field, be specifically related to a kind of structure regulating action of utilizing iodide ion, the absorption spectrum of chlorine oxygen bismuth photochemical catalyst is widened visible region, is the technical scheme of feedstock production visible-light response type chlorine oxygen bismuth photochemical catalyst and application process thereof with sodium bismuthate, hydrochloric acid and KI.
Background technology
Along with the development of dye industry, its factory effluent has become one of current most important pollution source of water body.Dye wastewater has that color is dark, complicated component, the COD value is higher and characteristics such as difficult degradation, brings serious harm to ecological environment.The method of dye wastewater treatment using mainly contains at present: absorption method, membrane separation process, photocatalytic oxidation, electrochemical oxidation process, ultrasonic degradation technology etc.Photocatalytic oxidation has characteristics such as efficient energy-saving, contaminant degradation be thorough.TiO
2Be the photochemical catalyst that is most widely used, the light generation less than 387 nm responds to wavelength but its wideer band gap (～3.2 eV) makes it, and the wavelength that accounts for solar energy 45～50% is the not response of visible light of 400～750 nm.The highly anisotropic layer structure of chlorine oxygen bismuth (BiOCl) is convenient to the separation in light induced electron hole, has guaranteed the good stable photocatalytic activity of BiOCl.But broad-band gap (～3.4 eV) has limited the utilization of the visible light of BiOCl equally.Therefore, the band-gap energy of BiOCl is reduced, thereby can more fully effectively utilize solar energy to become the focus that people pay close attention to.At present, the correlative study of more existing enhancing BiOCl visible light response activity is by wide coverage.Xiong etc. have reported in the auxiliary employing down of sweet mellow wine Hydrothermal Preparation foursquare two-dimentional BiOCl nanometer sheet, and the band gap of this catalyst obviously reduces (～2.92 eV).This catalyst shows good photocatalytic activity to rhodamine B under visible light, and catalyst amount is 0.5 gL
-1The time, 10
-5MolL
-1The degraded fully in 8 minutes of rhodamine B solution (RSC Advances, 2011,1:1542-1553).The irradiation of people such as Ye by ultraviolet light is reduced to 2.65 eV with the band gap of BiOCl from 3.5 eV.This is because the irradiation of ultraviolet light makes the BiOCl caltalyst form the oxygen room in mutually.Under radiation of visible light, this catalyst to the degrading activity of the rhodamine B catalyst ground activity before than UV-irradiation improved nearly 20 times (Phys. Chem. Chem. Phys., 2012,14:82-85).People such as Chen are raw material with bismuth trichloride and nitric acid, have prepared BiOCl(～2.87 eV under the corrective action of l-lysine) photochemical catalyst.Narrow band gap may be because the pattern of nano flower-like and high (110) crystal face that exposes.After λ 〉=435 nm light sources shine 50 min, 10 mgL
-1RhB decolours fully, and its degradation rate constant reaches 0.1186 min
-1(Catalysis Communications, 2012,23:54-57).
Summary of the invention
The preparation of a kind of visible-light response type chlorine of the present invention oxygen bismuth photochemical catalyst and the purpose of application process are at the wide problem of BiOCl photochemical catalyst band gap, a kind of strong reducing property and selective absorption performance of utilizing iodide ion proposed, the BiOCl crystal is grown along the particular crystal orientation preferentially, and the absorption spectrum of BiOCl photochemical catalyst widened visible region, with sodium bismuthate, hydrochloric acid and KI are raw material, by redox, precipitation, separate, washing and drying steps prepare the method for visible-light response type chlorine oxygen bismuth photochemical catalyst and application thereof, this method is fully effectively utilized solar energy, and can solve environmental pollution problems.
The preparation method of a kind of visible-light response type chlorine of the present invention oxygen bismuth photochemical catalyst, it is characterized in that it being a kind of strong reducing property and selective absorption performance of utilizing iodide ion, the BiOCl crystal is grown along the particular crystal orientation preferentially, and the absorption spectrum of BiOCl photochemical catalyst widened visible region, be raw material with sodium bismuthate, hydrochloric acid and KI, prepare the method for visible-light response type chlorine oxygen bismuth photochemical catalyst by redox, precipitation, separation, washing and drying steps, its concrete preparation process is:
(1) sodium bismuthate is positioned in the absolute ethyl alcohol, under magnetic agitation, disperses 1～1.5 h; Prepare 1.2 molL
-1Hydrochloric acid 100 mL, and take by weighing with the hydrochloric acid solution of preparing in the KI of chlorion equimolar amounts be dissolved in 1.2 molL that prepare
-1In the hydrochloric acid solution, it is standby to form hydrochloric acid-KI mixed solution;
(2) the standby hydrochloric acid-KI mixed solution that with the speed that dripped 1mL in 8～10 minutes step (1) is prepared under magnetic agitation joins in sodium bismuthate-absolute ethyl alcohol suspension, stirring reaction times 1.5～2 h, reaction temperature control is at 20～20.5 ℃, and it is standby to make aaerosol solution;
(3) the standby aaerosol solution that step (2) is obtained filters, and filter cake usefulness distilled water and absolute ethanol washing three times are dried under 40～50 ℃ of temperature then, namely make visible-light response type BiOCl photochemical catalyst.
The preparation method of above-mentioned a kind of visible-light response type chlorine oxygen bismuth photochemical catalyst, it is characterized in that strong reducing property and selective absorption performance by iodide ion, make BiOCl crystal preferred growth on the particular crystal direction, and the band gap of BiOCl is decreased to 2.3 eV, thereby make it not only produce response to ultraviolet light, simultaneously visible light is also produced response.
The application process of above-mentioned a kind of visible-light response type chlorine oxygen bismuth photochemical catalyst, it is characterized in that prepared visible-light response type BiOCl photochemical catalyst is used for the degradation water organic matter, the particularly processing of the harmful hardly degraded organic substance rhodamine B of trace toxic or methylene blue in the water, concrete degradation step is:
Step (1): accurately take by weighing rhodamine B or the methylene blue solid of 7 mg, it is dissolved in the distilled water, and is settled to 1000 mL, make 7 mgL
-1Rhodamine B or methylene blue solution;
Step (2): accurately pipette rhodamine B that 100 mL steps (1) obtain or methylene blue solution to reactor with pipette, and add 0.03～0.05 g BiOCl photochemical catalyst, temperature of reaction system control is at 20～20.5 ℃, under half-light, adsorb 1～1.5 h earlier, make it reach the adsorption/desorption balance;
Step (3): with the 350W xenon lamp as visible light source, step (2) gained solution is carried out the photocatalytic degradation reaction under illumination, every interval 5～30min time sampling, and measure the absorbance of rhodamine B or methylene blue and calculate its conversion ratio with UV-VIS spectrophotometry.
Preparation method and the advantages of application thereof of a kind of visible-light response type chlorine of the present invention oxygen bismuth photochemical catalyst are:
(1) it is wide to have remedied chlorine oxygen bismuth photochemical catalyst band gap, can not take full advantage of the defective of solar energy.The band gap of chlorine oxygen bismuth is decreased to 2.3 eV from 3.4 eV, has increased the utilization ratio of chlorine oxygen bismuth photochemical catalyst to visible light;
(2) adopt conventional inorganic raw material as reactant, raw material is cheap and easy to get; Preparation process remains on room temperature, does not need high-temperature roasting, and the preparation condition gentleness is simple; This preparation method is environmentally friendly simultaneously, does not produce the poisonous and harmful accessory substance;
(3) visible-light response type chlorine oxygen bismuth photochemical catalyst has good photocatalytic activity under visible light, and can utilize solar energy more fully efficiently, and this utilizes significant to environmental improvement and green energy resource.
Description of drawings
Fig. 1 is the XRD figure of the visible-light response type chlorine oxygen bismuth photochemical catalyst of embodiment of the present invention 1 preparation.
Fig. 2 is the DRS figure of the visible-light response type chlorine oxygen bismuth photochemical catalyst of embodiment of the present invention 1 preparation.
The specific embodiment
Embodiment 1
Take by weighing 3.16 g sodium bismuthates, it is dispersed in the 40 mL absolute ethyl alcohols.Prepare 1.2 molL
-1Watery hydrochloric acid 40 mL, take by weighing with institute complex salt acid solution in the KI of chlorion equimolar amounts be dissolved in this hydrochloric acid and form hydrochloric acid-KI mixed solution, this mixed solution is joined in sodium bismuthate-absolute ethyl alcohol suspension with the speed that dripped 1mL in 8 minutes, obtain aaerosol solution behind stirring reaction 1.5 h.Aaerosol solution is carried out suction filtration, and with distilled water and absolute ethanol washing filter cake three times, 40 ℃ of oven dry down, namely get visible-light response type BiOCl photochemical catalyst then.
The gained photochemical catalyst is used for oxidation processes rhodamine B or aqueous solution of methylene blue.Degradation step is:
Step (1): accurately take by weighing rhodamine B or the methylene blue solid of 7 mg, it is dissolved in the distilled water, and is settled to 1000 mL, make 7 mgL
-1Rhodamine B or methylene blue solution;
Step (2): accurately pipette rhodamine B that 100 mL steps (1) obtain or methylene blue solution to reactor with pipette, and add 0.03 g BiOCl photochemical catalyst, temperature of reaction system control is adsorbed 1 h earlier at 20～20.5 ℃ under half-light, make it reach the adsorption/desorption balance;
Step (3): as visible light source, step (2) gained solution is carried out the photocatalytic degradation reaction under illumination with xenon lamp (350W).Every interval 5～30min time sampling, and measure the absorbance of rhodamine B or methylene blue and calculate its conversion ratio with UV-VIS spectrophotometry, the results are shown in Table 1.
Take by weighing 6.32 g sodium bismuthates, it is dispersed in the 80 mL absolute ethyl alcohols.Prepare 1.2 molL
-1Watery hydrochloric acid 80 mL, take by weighing with institute complex salt acid solution in the KI of chlorion equimolar amounts be dissolved in this hydrochloric acid and form hydrochloric acid-KI mixed solution, this mixed solution is joined in sodium bismuthate-absolute ethyl alcohol suspension with the speed that dripped 1mL in 10 minutes, obtain aaerosol solution behind stirring reaction 2 h.Aaerosol solution is carried out suction filtration, and with distilled water and absolute ethanol washing filter cake three times, 50 ℃ of oven dry down, namely get visible-light response type BiOCl photochemical catalyst then.
The gained photochemical catalyst is used for oxidation processes rhodamine B or aqueous solution of methylene blue.Degradation step is:
Step (1): accurately take by weighing rhodamine B or the methylene blue solid of 7 mg, it is dissolved in the distilled water, and is settled to 1000 mL, make 7 mgL
-1Rhodamine B or methylene blue solution.
Step (2): accurately pipette rhodamine B that 100 mL steps (1) obtain or methylene blue solution to reactor with pipette, and add 0.03 g BiOCl photochemical catalyst, temperature of reaction system control is adsorbed 1.5 h earlier at 20～20.5 ℃ under half-light, make it reach the adsorption/desorption balance;
Step (3): as visible light source, step (2) gained solution is carried out the photocatalytic degradation reaction under illumination with xenon lamp (350W).Every interval 5～30min time sampling, and measure the absorbance of rhodamine B or methylene blue and calculate its conversion ratio with UV-VIS spectrophotometry, the results are shown in Table 1.
Take by weighing 1.58 g sodium bismuthates, it is dispersed in the 20 mL absolute ethyl alcohols.Prepare 1.2 molL
-1Watery hydrochloric acid 20 mL, take by weighing with institute complex salt acid solution in the KI of chlorion equimolar amounts be dissolved in this hydrochloric acid and form hydrochloric acid-KI mixed solution, this mixed solution is joined in sodium bismuthate-absolute ethyl alcohol suspension with the speed that dripped 1mL in 9 minutes, obtain aaerosol solution behind stirring reaction 1.5 h.Aaerosol solution is carried out suction filtration, and with distilled water and absolute ethanol washing filter cake three times, 45 ℃ of oven dry down, namely get visible-light response type BiOCl photochemical catalyst then.
The gained photochemical catalyst is used for oxidation processes rhodamine B or aqueous solution of methylene blue.Degradation step is:
Step (1): accurately take by weighing rhodamine B or the methylene blue solid of 7 mg, it is dissolved in the distilled water, and is settled to 1000 mL, make 7 mgL
-1Rhodamine B or methylene blue solution.
Step (2): accurately pipette rhodamine B that 100 mL steps (1) obtain or methylene blue solution to reactor with pipette, and add 0.05 g BiOCl photochemical catalyst, temperature of reaction system control is adsorbed 1.5 h earlier at 20～20.5 ℃ under half-light, make it reach the adsorption/desorption balance;
Step (3): as visible light source, step (2) gained solution is carried out the photocatalytic degradation reaction under illumination with xenon lamp (350W).Every interval 5～30min time sampling, and measure the absorbance of rhodamine B or methylene blue and calculate its conversion ratio with UV-VIS spectrophotometry, the results are shown in Table 1.
It is pure that used medicine and reagent is analysis in the above embodiment.
The degraded situation of table 1 visible-light response type BiOCl photochemical catalyst under different embodiments
Claims (3)
1. the preparation method of a visible-light response type chlorine oxygen bismuth photochemical catalyst, it is characterized in that it being a kind of strong reducing property and selective absorption performance of utilizing iodide ion, the BiOCl crystal is grown along the particular crystal orientation preferentially, and the absorption spectrum of BiOCl photochemical catalyst widened visible region, be raw material with sodium bismuthate, hydrochloric acid and KI, prepare the method for visible-light response type chlorine oxygen bismuth photochemical catalyst by redox, precipitation, separation, washing and drying steps, its concrete preparation process is:
(1) sodium bismuthate is positioned in the absolute ethyl alcohol, under magnetic agitation, disperses 1～1.5 h; Prepare 1.2 molL
-1Hydrochloric acid 100 mL, and take by weighing with the hydrochloric acid solution of preparing in the KI of chlorion equimolar amounts be dissolved in 1.2 molL that prepare
-1In the hydrochloric acid solution, it is standby to form hydrochloric acid-KI mixed solution;
(2) the standby hydrochloric acid-KI mixed solution that with the speed that dripped 1mL in 8～10 minutes step (1) is prepared under magnetic agitation joins in sodium bismuthate-absolute ethyl alcohol suspension, stirring reaction times 1.5～2 h, reaction temperature control is at 20～20.5 ℃, and it is standby to make aaerosol solution;
(3) the standby aaerosol solution that step (2) is obtained filters, and filter cake usefulness distilled water and absolute ethanol washing three times are dried under 40～50 ℃ of temperature then, namely make visible-light response type BiOCl photochemical catalyst.
2. according to the preparation method of the described a kind of visible-light response type chlorine oxygen bismuth photochemical catalyst of claim 1, it is characterized in that strong reducing property and selective absorption performance by iodide ion, make BiOCl crystal preferred growth on the particular crystal direction, and the band gap of BiOCl is decreased to 2.3 eV, thereby make it not only produce response to ultraviolet light, simultaneously visible light is also produced response.
3. the application process of the described a kind of visible-light response type chlorine oxygen bismuth photochemical catalyst of claim 1, it is characterized in that prepared visible-light response type BiOCl photochemical catalyst is used for the degradation water organic matter, the particularly processing of the harmful hardly degraded organic substance rhodamine B of trace toxic or methylene blue in the water, concrete degradation step is:
Step (1): accurately take by weighing rhodamine B or the methylene blue solid of 7 mg, it is dissolved in the distilled water, and is settled to 1000 mL, make 7 mgL
-1Rhodamine B or methylene blue solution;
Step (2): accurately pipette rhodamine B that 100 mL steps (1) obtain or methylene blue solution to reactor with pipette, and add 0.03～0.05 g BiOCl photochemical catalyst, temperature of reaction system control is at 20～20.5 ℃, under half-light, adsorb 1～1.5 h earlier, make it reach the adsorption/desorption balance;
Step (3): with the 350W xenon lamp as visible light source, step (2) gained solution is carried out the photocatalytic degradation reaction under illumination, every interval 5～30min time sampling, and measure the absorbance of rhodamine B or methylene blue and calculate its conversion ratio with UV-VIS spectrophotometry.
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