CN112774686B - Bismuth ferrite/sepiolite composite visible light catalyst and preparation method thereof - Google Patents
Bismuth ferrite/sepiolite composite visible light catalyst and preparation method thereof Download PDFInfo
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- CN112774686B CN112774686B CN202110132635.7A CN202110132635A CN112774686B CN 112774686 B CN112774686 B CN 112774686B CN 202110132635 A CN202110132635 A CN 202110132635A CN 112774686 B CN112774686 B CN 112774686B
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- 239000004113 Sepiolite Substances 0.000 title claims abstract description 116
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 116
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 116
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 58
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 150000001621 bismuth Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 49
- 239000011941 photocatalyst Substances 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- 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 description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 5
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 23
- 230000015556 catabolic process Effects 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 9
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- 239000002957 persistent organic pollutant Substances 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 230000033558 biomineral tissue development Effects 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract description 2
- 230000004927 fusion Effects 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 13
- 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 12
- 229960000907 methylthioninium chloride Drugs 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229910002902 BiFeO3 Inorganic materials 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 3
- 229960003405 ciprofloxacin Drugs 0.000 description 3
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- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 3
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 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 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 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 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- B01J35/39—
-
- B01J35/613—
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The invention relates to a bismuth ferrite/sepiolite composite visible light catalyst and a preparation method thereof. The preparation method comprises the steps of taking soluble bismuth salt and ferric salt as raw materials, fully mixing the solutions, adjusting the pH value of the solution by using strong alkali, adding the treated purified sepiolite, carrying out ultrasonic stirring, fully mixing, and transferring to a polytetrafluoroethylene autoclave for hydrothermal reaction to generate the porous bismuth ferrite/sepiolite composite visible light catalyst with good appearance and based on the sepiolite. The bismuth ferrite is generated on line in the presence of the sepiolite, and the combined action of oxygen-containing groups and interface effects which are abundant on the surface of the sepiolite realizes the effective regulation and control of the structure and morphology of the generated bismuth ferrite, increases the fusion property of components and the stability of materials in the preparation of the bismuth ferrite/sepiolite composite visible light catalyst, reduces the recombination rate of energy band gaps and photo-generated carriers, and improves the visible light absorption utilization rate, the adsorption performance of organic pollutants, the visible light catalytic degradation performance of the organic pollutants and the mineralization effect.
Description
Technical Field
The invention belongs to the technical field of photocatalytic degradation of organic pollutants, and particularly relates to a bismuth ferrite/sepiolite composite visible light catalyst and a preparation method thereof.
Background
With the rapid development of the printing and dyeing industry, various dyes are widely used, resulting in a large amount of dye-containing wastewater being discharged into the environment. The printing and dyeing has complex structure, difficult degradation, high toxicity, bright color and the like, and is easy to cause serious pollution to the ecological environment when discharged into the environment, thus forming serious threat to human health. Various printing and dyeing wastewater treatment techniques have been developed, such as adsorption, reverse osmosis, biodegradation, chemical oxidation, advanced oxidation, photocatalytic degradation, and the like. Wherein the photocatalytic degradation technology utilizes a photo-energy excitation light catalyst to generate photo-generated hole/electron pairs so as to generate O 2 - (OH) and h + The method for decomposing dye molecules by using the iso-active species has the advantages of high degradation degree, high treatment efficiency, mild reaction condition, low cost and the like, and particularly has remarkable energy-saving effect by using the visible light catalyst excited by natural light, thereby being one of the most effective and most promising methods for treating printing and dyeing wastewater at present. Among the photocatalysts developed, the perovskite type photocatalyst has the advantages of good visible light absorption capacity, higher catalytic activity, low price, environmental friendliness and the like. Bismuth ferrite (BiFeO 3) is a typical bismuth perovskite material, has an energy band gap of about 2.5eV, can be excited under irradiation of visible light, and has good stability in an acidic environment, so that the bismuth ferrite material is widely valued. But pure phase BiFeO3 still has the defects of wider energy band, narrow visible spectrum absorption range, lower light absorptivity and quantum efficiency, higher photo-generated electron/hole pair recombination rate, lower specific surface area, unfavorable structural morphology for absorbing pollutants, absorbing and utilizing visible light and the like.
The modification of the pure phase photocatalyst is generally carried out by the following method: element doping such as Mn, N, ag, etc.; (2) Compounding with other substances such as graphene or reduced graphene oxide; (3) Forming heterojunction with other semiconductor materials such as TiO2, laCoO3, etc. Because Sepiolite (Sepiolite) has larger pore volume and specific surface area, a large number of acid-base centers exist, and abundant active sites and supporting sites can be provided for substances generated on the surface. Therefore, biFeO3 is generated on line in the presence of sepiolite, the stronger interface effect of the sepiolite can influence and promote the formation of the BiFeO3 microstructure, and the improvementBiFeO 3 The specific surface area of the sepiolite composite photocatalyst optimizes the structural morphology of light absorption, further reduces the energy band gap width and the recombination rate of photo-generated electron/hole pairs, and improves the spectral response performance of the sepiolite composite photocatalyst. At present, no related document discloses BiFeO 3 Sepiolite composite photocatalyst and its preparation method are provided.
Disclosure of Invention
Aiming at the defects existing in pure-phase BiFeO3, the invention aims to provide a bismuth ferrite/sepiolite composite visible light catalyst (BiFeO) 3 Sepiolite) is characterized by BiFeO 3 The porous material generated on line in the presence of sepiolite has the advantages of larger specific surface area, lower energy band gap, low recombination rate of photo-generated electrons and holes, higher absorption and utilization rate of visible light, stronger adsorption capacity of organic pollutants and high visible light catalytic degradation rate.
Another object of the present invention is to provide a preparation method for bismuth ferrite/sepiolite composite visible light catalyst, which is BiFeO 3 On-line generation in the presence of sepiolite to realize the generation of BiFeO 3 The structure and the morphology are regulated and optimized, the preparation method is simple and convenient, the process is easy to control, the three wastes are less discharged, the manufacturing cost is lower, and the large-scale production is easy to realize; the method specifically comprises the following steps:
(1) The mol ratio of the soluble bismuth salt to the ferric salt is 1:0.9-1.0, deionized water or dilute acid is respectively used for preparing bismuth salt and ferric salt solution, bi 3+ The concentration is 0.05 to 0.067mol/L, fe 3+ The concentration is 0.045-0.067 mol/L; then mixing the two solutions, and stirring the mixture for 1 to 2 hours by ultrasonic to obtain a bismuth salt-ferric salt solution, which is marked as a solution A;
(2) Regulating the pH value of the solution A obtained in the step (1) to 12.6-13.5, and continuing to stir ultrasonically at room temperature for 1-2 h to obtain a mixture B;
(3) Adding purified sepiolite into the mixture B obtained in the step (2) according to the mass ratio of sepiolite to bismuth salt of 0.082-0.41:1, and stirring for 1-1.5 h by ultrasonic to obtain a mixture C;
(4) Transferring the mixture C prepared in the step (3) into a polytetrafluoroethylene lining high-pressure reaction kettle, and reacting for 4-8 h at 150-200 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 2-5 times respectively, and drying at 60-80 ℃ to constant weight to obtain the bismuth ferrite/sepiolite composite visible light catalyst;
(5) And (3) regulating the pH value of the filtrate filtered in the step (4) to 8.0-9.0, precipitating for 1-2 hours, filtering, discharging the filtrate, and collecting filter residues for centralized treatment to recover valuable components.
Further, in the step (1), the soluble bismuth salt is one or more than two of bismuth sulfate, bismuth chloride or bismuth nitrate pentahydrate; the soluble ferric salt is one or more than two of ferric sulfate, ferric trichloride hexahydrate or ferric nitrate nonahydrate.
Further, in the step (1), the dilute acid is hydrochloric acid or nitric acid with the concentration of 0.1-0.2 mol/L.
Further, in the step (2), a strong alkali solution with the pH of 5-8 mol/L is adopted for adjusting the pH, and the strong alkali is KOH or NaOH.
Further, in the step (3), the purified sepiolite is treated by the following method: grinding sepiolite, sieving with 200-300 mesh sieve, soaking with 1-2 mol/L hydrochloric acid at 75-85deg.C under reflux for 0.5-1 hr, filtering, and washing with distilled water to neutrality; then preparing a mixture of sepiolite and 8-10 mmol/L hexadecyl trimethyl ammonium bromide (CTAB) solution with the solid-to-liquid ratio (g/mL) of 1:40-60, carrying out ultrasonic treatment for 0.5-1 h, filtering, washing with distilled water, drying to constant weight at 80-100 ℃, grinding, sieving with a 800-1000-mesh sieve, and taking a screen bottom for later use.
Further, in the step (5), sulfuric acid of 6 to 8mol/L is used for adjusting the pH.
Further, the ultrasonic stirring is ultrasonic auxiliary mechanical stirring, and the ultrasonic power is 200-250W.
Further, the reagents used were analytically pure bismuth nitrate pentahydrate, bismuth sulfate, bismuth chloride, ferric sulfate, ferric trichloride hexahydrate, ferric nitrate nonahydrate, KOH, naOH, ethanol, sulfuric acid, and hydrochloric acid.
The invention relates to a bismuth ferrite/sepiolite composite visible light catalyst and a preparation method thereof. Bismuth nitrate and ferric nitrate are first prepared into solution of certain concentration, and then mixed thoroughly, and finally the solution is treated with alkali solutionRegulating the pH value of the mixed solution, and fully stirring; then adding the treated purified sepiolite into the mixture, ultrasonically stirring for a period of time, transferring into an autoclave with polytetrafluoroethylene lining, and performing hydrothermal reaction to obtain the porous bismuth ferrite/sepiolite composite visible light catalyst (BiFeO) with good appearance based on sepiolite 3 /Sepiolite). The technical proposal generates BiFeO by on-line hydrothermal method in the presence of sepiolite 3 The morphology and structure of the generated bismuth ferrite are well controlled under the action of rich oxygen-containing groups on the sepiolite surface and stronger interface effect, and the preparation of BiFeO is increased 3 The fusion property of the components and the stability of the materials in the Sepiolite composite photocatalyst reduce the recombination rate of energy band gaps and photogenerated carriers, improve the absorption and utilization rate of visible light and the adsorption performance of organic matters, and improve the photocatalytic degradation performance of organic pollution under visible light.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) The technical proposal of the invention adopts the on-line generation of BiFeO through hydrothermal reaction in the presence of sepiolite 3 The BiFeO is generated by the abundant active groups on the sepiolite surface and the strong interface effect 3 Effectively regulate and control the structure and the morphology of the BiFeO, and generates the BiFeO on line 3 Sepiolite is used as a support to form and grow, so that each component of the composite photocatalyst is fully fused, and the stability of the composite photocatalyst is improved.
(2) BiFeO prepared by the invention 3 The Sepiolite composite photocatalyst has a porous structure and a specific surface area ratio of BiFeO formed without Sepiolite 3 A significant increase; the adsorption capacity of the sepiolite on organic matters is increased through the synergistic effect of the sepiolite.
(3) BiFeO prepared by the invention 3 Sepiolite in the Sepiolite composite photocatalyst not only promotes and regulates BiFeO loaded on the Sepiolite through a special pore canal structure 3 The structure and the morphology of the catalyst are that the prepared composite photocatalyst is beneficial to the adsorption of organic pollutants and the absorption and utilization rate of light, and the energy band gap and the recombination rate of photo-generated electrons and holes are reduced, so that the photocatalytic degradation performance of the organic pollutants is improved.
(4) The product of the invention has excellent visible light catalytic degradation performance and mineralization capability on organic pollutants, has excellent catalytic decoloration performance on organic dye wastewater, is safe and nontoxic, is convenient to recycle, has good recycling performance, and is suitable for treating various organic pollution wastewater.
(5) The preparation method has the advantages of simple preparation process, easy operation and control of the process, less three-waste emission, lower manufacturing cost, and easy realization of large-scale production due to the conventional equipment, and has wide application prospect.
Drawings
FIG. 1 is a synthetic route diagram of bismuth ferrite/sepiolite composite visible light catalyst.
FIG. 2 shows a bismuth ferrite/sepiolite composite visible-light-driven photocatalyst (m (BiFeO) 3 ) XRD pattern of: (Sepilolite) =1:0.3).
FIG. 3 shows a bismuth ferrite/sepiolite composite visible-light-driven photocatalyst (m (BiFeO) 3 ) SEM image of: (Sepilolite) =1:0.3).
FIG. 4 shows a bismuth ferrite/sepiolite composite visible-light-driven photocatalyst (m (BiFeO) 3 ) Photocatalytic degradation efficiency profile for: (Sepilolite) =1:0.3).
FIG. 5 shows a bismuth ferrite/sepiolite composite visible-light-driven photocatalyst (m (BiFeO) 3 ) Cyclic usage effect graph of: (Sepilolite) =1:0.3).
Note that: m (BiFeO) 3 ) The ratio of the bismuth ferrite to the sepiolite is m.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples, but the invention is not limited thereto.
Example 1
(1) 2.70g of bismuth nitrate pentahydrate with the content of 99.0 percent is taken and dissolved in 110mL of deionized water to prepare Fe 3+ Dissolving 2.26g of ferric nitrate with the content of 98.5% in 122mL of deionized water to prepare Bi 3+ A concentration of 0.045mol/L solution; mixing the two solutions, and stirring the mixture for 2 hours by ultrasonic waves to obtain bismuth nitrate-ferric nitrate solution A.
(2) Adjusting the pH to 13.5 by using 8mol/L KOH solution, and continuously stirring for 2 hours at room temperature by ultrasonic waves to obtain a mixture B;
(3) Adding 0.27g of purified sepiolite into the mixture B, and stirring for 1.5h by ultrasonic to obtain a mixture C;
(4) Transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 6 hours at 200 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 3 times respectively, and drying at 80 ℃ to constant weight to obtain 1.97g of bismuth ferrite/sepiolite composite visible light catalyst.
(5) Adding 5mol/L sulfuric acid into the filtrate filtered in the step (4) to adjust the pH value to 8.8, precipitating for 2 hours, filtering, discharging the filtrate, and collecting filter residues for centralized treatment to recover valuable components.
Example 2
(1) 2.70g of bismuth nitrate pentahydrate with the content of 99.0 percent is dissolved in 100ml of 0.1mol/L dilute nitric acid to prepare Bi 3+ The solution with the concentration of 0.055mol/L is taken, and 2.21g of ferric nitrate with the content of 98.5 percent is dissolved in 108ml of 0.1mol/L dilute nitric acid to prepare Fe 3+ A concentration of 0.050mol/L solution; mixing the two solutions, and stirring the mixture for 1.5 hours by ultrasonic to obtain bismuth nitrate-ferric nitrate solution A.
(2) Adjusting the pH to 13.0 by using 8mol/L KOH solution, and continuously stirring ultrasonically at room temperature for 1.5h to obtain a mixture B;
(3) Adding 0.22g of purified sepiolite into the mixture B, and stirring for 1.5h by ultrasonic to obtain a mixture C;
(4) Transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 7 hours at 190 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 4 times, and drying at 75 ℃ to constant weight to obtain 1.90g of bismuth ferrite/sepiolite composite visible light catalyst.
(5) Adding 6mol/L sulfuric acid into the filtrate filtered in the step (4) to adjust the pH value to 8.0, precipitating for 1.5 hours, filtering, discharging the filtrate, and collecting filter residues for centralized treatment to recover valuable components.
Example 3
(1) 2.70g of bismuth nitrate pentahydrate with the content of 99.0 percent is dissolved in 92mL of deionized water to prepare Bi 3+ Dissolving 2.21g of ferric nitrate with the content of 98.5% in 95mL of deionized water to prepare Fe, wherein the concentration of the ferric nitrate is 0.060mol/L 3+ The concentration is 0.055mol/L solution; mixing the two solutions, and stirring the mixture for 1h by ultrasonic to obtain bismuth nitrate-ferric nitrate solution A.
(2) Adjusting the pH to 12.6 by using a KOH solution with the concentration of 6mol/L, and continuously stirring for 1h at room temperature by ultrasonic to obtain a mixture B;
(3) Adding 0.54g of purified sepiolite into the mixture B, and stirring for 1h by ultrasonic to obtain a mixture C;
(4) Transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 8 hours at 180 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 4 times, and drying at 70 ℃ to constant weight to obtain 2.20g of bismuth ferrite/sepiolite composite visible light catalyst.
(5) Adding 7mol/L sulfuric acid into the filtrate filtered in the step (4) to adjust the pH value to 8.7, precipitating for 1h, filtering, discharging the filtrate, and collecting filter residues for centralized treatment to recover valuable components.
Samples were taken and assayed on a D8 advanced X-powder diffractometer (40 kV,40mA, bruce AXS, germany) and scanned at 10℃to 80℃using the MDI Jade 5.0 analyte phase, the results of which are shown in FIG. 2. As can be seen from FIG. 2, diffraction peaks at 22.5 °, 31.8 °, 32.1 °, 39.5 °, 45.8 °, 51.4 °, 57.0 °, and the like, and BiFeO 3 The standard card (JCPDS No. 20-0169) of (B) well-matched, indicating that BiFeO exists in the product 3 A phase; and the diffraction peak at 26.6 ° coincides with the sepiolite (080) crystal plane. Thus, the product is formed from BiFeO 3 Phase and sepiolite.
BiFeO prepared in the absence of sepiolite was determined using a S-4800-type field emission scanning electron microscope (FESEM, hitachi Co., japan) 3 And the morphology of the sample of this example, the results are shown in FIG. 3. FIG. 3 (a) shows BiFeO 3 Is composed of irregularly-shaped particles with different sizes; FIG. 3 (b) shows that BiFeO produced in the presence of sepiolite 3 The composite photocatalyst of Sepiolite is a network structure formed by stacking small particles. This indicates that the presence of sepiolite alters the coating BiFeO 3 The crystal structure of the catalyst is beneficial to improving the photoelectrochemical property of the photocatalyst, such as improving the light absorption performance, reducing the energy band gap, the recombination rate of photo-generated electrons and holes, and the like, and improving the adsorption capacity to pollutants.
Determination of BiFeO Using a specific surface area-pore volume Analyzer (BELSORP-mini II, microtracBEL, japan) 3 Is 67.34m 2 /g，BiFeO 3 The specific surface area of the Sepiolite composite photocatalyst is 81.27m 2 And/g. The diffuse reflection ultraviolet-visible spectrum (UV-vis DRS) was measured by a UV-2550 scanning ultraviolet-visible spectrophotometer (Shimadzu, japan), and calculated to obtain BiFeO 3 And BiFeO 3 Band gap E of Sepiolite sample g 2.39eV and 2.19eV, respectively, indicating BiFeO 3 BiFeO formed by compounding with sepiolite 3 E of Sepiolite composite photocatalyst g Obviously reduces the sepiolite, obviously improves the structure of the composite photocatalyst and reduces the energy band gap of the composite photocatalyst.
Example 4
(1) 1.97g of bismuth sulfate with 98.5 percent content is dissolved in 82ml of 0.1mol/L dilute nitric acid to prepare Bi 3+ Dissolving 1.00g of ferric sulfate with the content of 99.0 percent in 83ml of 0.1mol/L dilute nitric acid to prepare Fe with the concentration of 0.067mol/L solution 3+ A concentration of 0.060mol/L solution; mixing the two solutions, and stirring the mixture for 1.5 hours by ultrasonic to obtain bismuth sulfate-ferric sulfate solution A.
(2) Adjusting the pH to 12.8 by using a KOH solution with the concentration of 5mol/L, and continuously stirring for 1h at room temperature by ultrasonic to obtain a mixture B;
(3) Adding 0.81g of purified sepiolite into the mixture B, and stirring for 1.5h by ultrasonic to obtain a mixture C;
(4) Transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 6 hours at 170 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 5 times respectively, and drying at 60 ℃ to constant weight to obtain 2.44g of bismuth ferrite/sepiolite composite visible light catalyst.
(5) Adding 8mol/L sulfuric acid into the filtrate filtered in the step (4) to adjust the pH value to 8.2, precipitating for 1h, filtering, discharging the filtrate, and collecting filter residues for centralized treatment to recover valuable components.
Example 5
(1) 1.77g of bismuth chloride with the content of 98.0 percent is dissolved in 102ml of 0.1mol/L dilute hydrochloric acid to prepare Bi 3+ A solution with a concentration of 0.054mol/L was taken, and 1.43g of hexahydrate with a content of 99.5% was takenFerric chloride is dissolved in 101ml of 0.1mol/L dilute hydrochloric acid to prepare Fe 3+ A concentration of 0.052mol/L solution; mixing the two solutions, and stirring the mixture for 2 hours by ultrasonic to obtain bismuth chloride-ferric trichloride solution A.
(2) Adjusting the pH to 12.9 by using 6mol/L NaOH solution, and continuously stirring ultrasonically at room temperature for 1.5h to obtain a mixture B;
(3) Adding 0.62g of purified sepiolite into the mixture B, and stirring for 1.5h by ultrasonic to obtain a mixture C;
(4) Transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 4 hours at 200 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 2 times respectively, and drying at 80 ℃ to constant weight to obtain 2.33g of bismuth ferrite/sepiolite composite visible light catalyst.
(5) Adding 7.5mol/L sulfuric acid into the filtrate filtered in the step (4) to adjust the pH value to 8.7, precipitating for 1h, filtering, discharging the filtrate, and collecting filter residues for centralized treatment to recover valuable components.
Example 6
(1) 1.77g of bismuth chloride with the content of 98.0 percent is dissolved in 95ml of 0.2mol/L dilute hydrochloric acid to prepare Bi 3+ Dissolving 1.39g of ferric trichloride hexahydrate with the content of 99.5 percent in 76ml of 0.2mol/L dilute hydrochloric acid to prepare Fe 3+ A concentration of 0.067mol/L solution; mixing the two solutions, and stirring the mixture for 2 hours by ultrasonic to obtain bismuth chloride-ferric trichloride solution A.
(2) Adjusting the pH to 13.2 by using 8mol/L NaOH solution, and continuously stirring for 2 hours at room temperature by ultrasonic waves to obtain a mixture B;
(3) Adding 0.53g of purified sepiolite into the mixture B, and stirring for 1.5h by ultrasonic to obtain a mixture C;
(4) Transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 7 hours at 160 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 3 times respectively, and drying at 80 ℃ to constant weight to obtain 2.22g of bismuth ferrite/sepiolite composite visible light catalyst.
(5) Adding 5mol/L sulfuric acid into the filtrate filtered in the step (4) to adjust the pH value to 8.0, precipitating for 2 hours, filtering, discharging the filtrate, and collecting filter residues for centralized treatment to recover valuable components.
Examples 7 to 10 are examples of photocatalytic degradation performance tests
Example 7
The photocatalytic performance test conditions were as follows: bismuth ferrite/sepiolite composite visible light catalyst (BiFeO) prepared in example 3 was used as a light source at room temperature using a 300W xenon lamp 3 /Sepiolite，m(BiFeO 3 ) Preparation of bismuth ferrite (BiFeO) under the same conditions in the presence of: m (Sepilolite) =1:0.3) 3 ) As a test sample, the degradation rate of Methylene Blue (MB) was used as an evaluation index. The specific operation steps are as follows: 50mg of photocatalyst sample and 50mL of 60mg/L MB solution were added to a clean 100mL jacketed beaker, each kept at equal distance from the light source. Standing for 30min in the dark to ensure that the adsorption and desorption of MB on the surface of the sample reach equilibrium; during the illumination, samples were taken every 15min, with a sampling volume of 2mL. The samples were poured into a centrifuge tube and centrifuged to obtain a supernatant, the concentration of the supernatant was measured at 665nm by a UV-3600 ultraviolet-visible spectrophotometer (Shimazu, japan), and the degradation rates at different degradation times were calculated and plotted as degradation graphs, as shown in FIG. 4. Taking a water sample with illumination for 90min, measuring total organic carbon in a TOC-LCPH type total organic carbon analyzer (Shimadzu, japan), and calculating the degradation rate of the total organic carbon.
As can be seen from fig. 4, the adsorption/desorption equilibrium is reached in the dark room for 30min, and the MB concentration is reduced by about 6.7%; when the photocatalyst is not added for illumination for 90min, the self-degradation rate is very small; in the form of BiFeO sample 3 /Sepiolite(m(BiFeO 3 ) M (Sepilolite) =1:0.3) is catalyst illumination 90min, and the degradation rate of MB reaches 99.9%; in the form of BiFeO 3 As a catalyst, the degradation rate of MB only reaches 60.8% after 90min of irradiation. Thus, biFeO 3 /Sepiolite(m(BiFeO 3 ) M (Sepilolite) =1:0.3) has excellent photocatalytic degradation properties for MB.
After 90min of measurement irradiation, biFeO 3 /Sepiolite(m(BiFeO 3 ) M (Sepilolite) =1:0.3) and BiFeO 3 The Total Organic Carbon (TOC) removal rates were 85.71% and 31.95%, respectively. Thus, biFeO 3 /Sepiolite(m(BiFeO 3 ) M (Sepilolite) =1:0.3) has excellent mineralization ability to MB.
Example 8
To degrade BiFeO 3 The Sepiolite composite photocatalyst was separated and recovered and used as the photocatalyst for the next round of experiments. The experimental conditions and procedures and test methods were the same as in example 7. The cycle was repeated 5 times, and the change in degradation rate was as shown in FIG. 5.
As can be seen from FIG. 5, the BiFeO is recycled 5 times 3 The catalytic degradation rate of the composite visible light catalyst of/Sepiolite on MB is reduced from 99.9% of the 1 st time to 97.5% of the 5 th time, and is reduced by only 2.4%. The result shows that the BiFeO prepared by the invention 3 The Sepiolite composite visible light catalyst has excellent recovery and recycling performance.
Example 9
This example is an example of photocatalytic decolorization performance, and the test conditions are as follows: 10mg of Methyl Orange (MO), methylene Blue (MB) and rhodamine (RhB) are respectively taken and dissolved in 1L of distilled water to prepare a simulated mixed solution (MO-MB-RhB), and the bismuth ferrite/sepiolite composite visible light catalyst (BiFeO) prepared in example 3 is used 3 /Sepiolite，m(BiFeO 3 ) Bismuth ferrite (BiFeO) prepared under the same conditions in the presence of: m (Sepilolite) =1:0.3) and no sepiolite 3 ) Is a photocatalyst sample. A clean 200mL jacketed beaker was charged with 100mg of the photocatalyst sample and 100mL of MO-MB-RhB solution. Standing in the dark for 30min, then carrying out degradation under 300W xenon lamp illumination, sampling every 15min in the degradation process, sampling 2mL in volume, and measuring the chromaticity of the solution by a dilution fold method after centrifugal separation, wherein the result is shown in Table 1.
TABLE 1 variation of solution chromaticity with time of illumination
Table 1 shows that BiFeO 3 /Sepiolite(m(BiFeO 3 ) The dye has excellent photocatalytic decoloring capability to mixed dye solution, and becomes colorless basically after 90min of irradiation, which is obviously superior to BiFeO without sepiolite 3 。
Example 10
This example is an example of the catalytic degradation performance of a prepared sample on an antibiotic. The photocatalyst used and experimental conditions were the same as in example 7, and the degradation subjects were the common antibiotics Ciprofloxacin (CIP), norfloxacin (NFX) and tetracycline hydrochloride (TC-H). Preparing CIP, NFX and TC-H into 10mg/L solution, performing degradation test according to the method and steps of example 7, illuminating for 90min, sampling, measuring the concentration of the solution on a UV-3600 ultraviolet-visible spectrophotometer (Shimazu, japan) at 272nm, 273nm and 357nm respectively, and calculating the degradation rate of the illumination for 90 min; meanwhile, the total organic carbon was measured in a TOC-LCPH total organic carbon analyzer (Shimadzu, japan), and the degradation rate of the total organic carbon was calculated, and the results are shown in Table 2.
Table 2 degradation effect of the prepared photocatalyst on antibiotics
Table 2 shows that BiFeO was prepared 3 /Sepiolite(m(BiFeO 3 ) The degradation rate and mineralization rate of the composite material to m (Sepilolite) =1:0.3) on 3 antibiotics are higher and obviously superior to those of BiFeO 3 . It can be seen that the presence of sepiolite provides a significant improvement in the performance of the prepared photocatalyst. The foregoing is only a preferred embodiment of the invention, and various modifications and changes may be made thereto by those skilled in the art in light of the above teachings, for example, combinations of ratios and process conditions may be made within the scope of the invention as defined by the appended claims, and similar such changes and modifications are intended to be included within the spirit of the invention.
Claims (8)
1. The bismuth ferrite/sepiolite composite visible light catalyst is characterized in that bismuth ferrite is generated on line in the presence of sepiolite to form a porous material of which sepiolite is coated by bismuth ferrite based on sepiolite, and the mass ratio of the bismuth ferrite to the sepiolite is 1:0.12-0.63;
the preparation method of the bismuth ferrite/sepiolite composite visible light catalyst is characterized by comprising the following steps of:
(1) The mol ratio of the soluble bismuth salt to the ferric salt is 1:0.9-1.0, deionized water or dilute acid is respectively used for preparing bismuth salt and ferric salt solution, bi 3+ The concentration is 0.05-0.067 mol/L, fe 3+ The concentration is 0.045-0.067 mol/L; then mixing the two solutions, and stirring the mixture for 1 to 2 hours by ultrasonic to obtain a bismuth salt-ferric salt solution, and marking the bismuth salt-ferric salt solution as a solution A;
(2) Adjusting the pH value of the solution A obtained in the step (1) to 12.6-13.5, and continuously stirring for 1-2 hours at room temperature by ultrasonic to obtain a mixture B;
(3) Adding purified sepiolite into the mixture B obtained in the step (2) according to the mass ratio of sepiolite to bismuth salt of 0.082-0.41:1, and stirring for 1-1.5 h by ultrasonic to obtain a mixture C; the purified sepiolite is treated by the following method: grinding sepiolite, sieving with a 200-300 mesh sieve, soaking with 1-2 mol/L hydrochloric acid at 75-85 ℃ under reflux for 0.5-1 h, filtering, and washing with distilled water to neutrality; then preparing a mixture of sepiolite and 8-10 mmol/L hexadecyl trimethyl ammonium bromide, namely CTAB solution with a solid-to-liquid ratio of 1:40-60 g/mL, carrying out ultrasonic treatment for 0.5-1 h, filtering, washing with distilled water, drying to constant weight at 80-100 ℃, grinding, sieving with a 800-1000 mesh sieve, and taking a screen lower product for later use;
(4) Transferring the mixture C prepared in the step (3) into a polytetrafluoroethylene lining high-pressure reaction kettle, and reacting for 4-8 h at 150-200 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 2-5 times respectively, and drying at 60-80 ℃ to constant weight to obtain the bismuth ferrite/sepiolite composite visible light catalyst;
(5) And (3) regulating the pH value of the filtrate filtered in the step (4) to 8.0-9.0, precipitating for 1-2 hours, filtering, discharging the filtrate, and collecting filter residues for centralized treatment to recover valuable components.
2. The method for preparing the bismuth ferrite/sepiolite composite visible light catalyst as claimed in claim 1, which is characterized by comprising the following steps:
(1) The mol ratio of the soluble bismuth salt to the ferric salt is 1:0.9-1.0, deionized water or dilute acid is respectively used for preparing bismuth salt and ferric salt solution, bi 3+ The concentration is 0.05-0.067 mol/L, fe 3+ The concentration is 0.0450.067mol/L; then mixing the two solutions, and stirring the mixture for 1 to 2 hours by ultrasonic to obtain a bismuth salt-ferric salt solution, and marking the bismuth salt-ferric salt solution as a solution A;
(2) Adjusting the pH value of the solution A obtained in the step (1) to 12.6-13.5, and continuously stirring for 1-2 hours at room temperature by ultrasonic to obtain a mixture B;
(3) Adding purified sepiolite into the mixture B obtained in the step (2) according to the mass ratio of sepiolite to bismuth salt of 0.082-0.41:1, and stirring for 1-1.5 h by ultrasonic to obtain a mixture C; the purified sepiolite is treated by the following method: grinding sepiolite, sieving with a 200-300 mesh sieve, soaking with 1-2 mol/L hydrochloric acid at 75-85 ℃ under reflux for 0.5-1 h, filtering, and washing with distilled water to neutrality; then preparing a mixture of sepiolite and 8-10 mmol/L hexadecyl trimethyl ammonium bromide, namely CTAB solution with a solid-to-liquid ratio of 1:40-60 g/mL, carrying out ultrasonic treatment for 0.5-1 h, filtering, washing with distilled water, drying to constant weight at 80-100 ℃, grinding, sieving with a 800-1000 mesh sieve, and taking a screen lower product for later use;
(4) Transferring the mixture C prepared in the step (3) into a polytetrafluoroethylene lining high-pressure reaction kettle, and reacting for 4-8 h at 150-200 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 2-5 times respectively, and drying at 60-80 ℃ to constant weight to obtain the bismuth ferrite/sepiolite composite visible light catalyst;
(5) And (3) regulating the pH value of the filtrate filtered in the step (4) to 8.0-9.0, precipitating for 1-2 hours, filtering, discharging the filtrate, and collecting filter residues for centralized treatment to recover valuable components.
3. The method for preparing the bismuth ferrite/sepiolite composite visible light catalyst according to claim 2, wherein in the step (1), the soluble bismuth salt is one or more of bismuth sulfate, bismuth chloride or bismuth nitrate pentahydrate; the soluble ferric salt is one or more than two of ferric sulfate, ferric trichloride hexahydrate or ferric nitrate nonahydrate.
4. The method for preparing the bismuth ferrite/sepiolite composite visible light catalyst according to claim 2, wherein in the step (1), the dilute acid is 0.1-0.2 mol/L hydrochloric acid or nitric acid.
5. The method for preparing the bismuth ferrite/sepiolite composite visible light catalyst according to claim 2, wherein in the step (2), a strong alkali solution with the pH of 5-8 mol/L is adopted for adjusting the pH, and the strong alkali is KOH or NaOH.
6. The preparation method of the bismuth ferrite/sepiolite composite visible light catalyst according to claim 2, wherein in the step (5), 6-8 mol/L sulfuric acid is adopted for regulating the pH.
7. The preparation method of the bismuth ferrite/sepiolite composite visible light catalyst according to claim 2, wherein the ultrasonic stirring is ultrasonic-assisted mechanical stirring, and the ultrasonic power is 200-250W.
8. The method for preparing a bismuth ferrite/sepiolite composite visible-light-driven photocatalyst according to any one of claims 2 to 7, wherein the reagents used are analytically pure bismuth nitrate pentahydrate, bismuth sulfate, bismuth chloride, ferric sulfate, ferric trichloride hexahydrate, ferric nitrate nonahydrate, KOH, naOH, ethanol, sulfuric acid and hydrochloric acid.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626634A (en) * | 2012-03-30 | 2012-08-08 | 南京理工大学 | Bismuth ferrite-graphene compounding magnetism visible light catalyst, as well as preparation method and application of same |
| CN102941103A (en) * | 2012-09-24 | 2013-02-27 | 清华大学 | Bismuth ferrite-graphene nanometer composite material for the filed of photocatalysis and preparation method thereof |
| CN105688918A (en) * | 2016-01-18 | 2016-06-22 | 常州大学 | Preparation method of clay-perovskite composite material and application thereof |
| CN105772003A (en) * | 2016-04-12 | 2016-07-20 | 中国计量大学 | Rapid synthesis method of single-phase bismuth ferrite visible-light-driven photocatalyst |
| CN106179424A (en) * | 2016-07-13 | 2016-12-07 | 湘潭大学 | A kind of PVP auxiliary prepares method and the application of composite catalyst of flower-shaped BiOBr/ meerschaum composite catalyst |
| CN106944064A (en) * | 2017-03-15 | 2017-07-14 | 辽宁大学 | Ferrite cladding sepiolite composite catalyst and its preparation method and application |
| WO2018045790A1 (en) * | 2016-09-09 | 2018-03-15 | 南京大学 | Mesoporous manganese ferrite fenton-like catalyst, preparation method therefor, and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9409791B2 (en) * | 2014-12-29 | 2016-08-09 | Council Of Scientific & Industrial Research | Photocatalytic degradation of pharmaceutical drugs and dyes using visible active biox photocatalyst |
-
2021
- 2021-01-31 CN CN202110132635.7A patent/CN112774686B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626634A (en) * | 2012-03-30 | 2012-08-08 | 南京理工大学 | Bismuth ferrite-graphene compounding magnetism visible light catalyst, as well as preparation method and application of same |
| CN102941103A (en) * | 2012-09-24 | 2013-02-27 | 清华大学 | Bismuth ferrite-graphene nanometer composite material for the filed of photocatalysis and preparation method thereof |
| CN105688918A (en) * | 2016-01-18 | 2016-06-22 | 常州大学 | Preparation method of clay-perovskite composite material and application thereof |
| CN105772003A (en) * | 2016-04-12 | 2016-07-20 | 中国计量大学 | Rapid synthesis method of single-phase bismuth ferrite visible-light-driven photocatalyst |
| CN106179424A (en) * | 2016-07-13 | 2016-12-07 | 湘潭大学 | A kind of PVP auxiliary prepares method and the application of composite catalyst of flower-shaped BiOBr/ meerschaum composite catalyst |
| WO2018045790A1 (en) * | 2016-09-09 | 2018-03-15 | 南京大学 | Mesoporous manganese ferrite fenton-like catalyst, preparation method therefor, and application thereof |
| CN106944064A (en) * | 2017-03-15 | 2017-07-14 | 辽宁大学 | Ferrite cladding sepiolite composite catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 安俊健 ; 王梦玲 ; 黄梦璇 ; 王鹏 ; 张光彦 ; .纳米铁酸铋及其改性物的环境催化性能.化学进展.2018,(09),全文. * |
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