CN112774706A - Bismuth oxycarbonate/sepiolite composite photocatalyst and preparation method thereof - Google Patents
Bismuth oxycarbonate/sepiolite composite photocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN112774706A CN112774706A CN202110132659.2A CN202110132659A CN112774706A CN 112774706 A CN112774706 A CN 112774706A CN 202110132659 A CN202110132659 A CN 202110132659A CN 112774706 A CN112774706 A CN 112774706A
- Authority
- CN
- China
- Prior art keywords
- sepiolite
- bismuth
- solution
- composite photocatalyst
- bismuth oxycarbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004113 Sepiolite Substances 0.000 title claims abstract description 111
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 104
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 102
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 title claims abstract description 40
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 45
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 39
- 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 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 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 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 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 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- GQLMQWWBIJYOFC-UHFFFAOYSA-M [Br-].C(CCCCCCCCCCCCCCC)[N+](C)(C)C.C(CO)O Chemical compound [Br-].C(CCCCCCCCCCCCCCC)[N+](C)(C)C.C(CO)O GQLMQWWBIJYOFC-UHFFFAOYSA-M 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000010979 pH adjustment Methods 0.000 claims 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 230000006798 recombination Effects 0.000 abstract description 8
- 238000005215 recombination Methods 0.000 abstract description 8
- 230000009471 action Effects 0.000 abstract description 6
- 230000031700 light absorption Effects 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 3
- 230000033558 biomineral tissue development Effects 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 description 18
- 230000015556 catabolic process Effects 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 9
- 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 9
- 229940043267 rhodamine b Drugs 0.000 description 9
- 239000002957 persistent organic pollutant Substances 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229940036358 bismuth subcarbonate Drugs 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 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 3
- 239000000047 product Substances 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 239000000126 substance Substances 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
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 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
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 1
- 229910002902 BiFeO3 Inorganic materials 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052610 inosilicate Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000007281 self degradation Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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 oxycarbonate/sepiolite composite photocatalyst and a preparation method thereof. The method comprises the steps of dissolving Cetyl Trimethyl Ammonium Bromide (CTAB) in Ethylene Glycol (EG) to prepare CTAB-EG solution as a template agent and a reducing agent, adding bismuth nitrate-ferric nitrate solution, adjusting the pH value of mixed solution by using strong alkali solution, adding purified sepiolite, fully mixing, transferring into a polytetrafluoroethylene autoclave, and carrying out hydrothermal reaction to generate the morphology-controllable porous bismuth oxycarbonate/sepiolite composite photocatalyst. By oxidizing and decomposing EG or CTAB under hydrothermal conditions to generate carbonate, and loading and growing bismuth oxycarbonate on sepiolite under the comprehensive action of the surface activity and template action of CTAB and the interface effect of sepiolite, the structure and the morphology of the sepiolite can be effectively controlled, the energy band gap and the recombination rate of photon-generated carriers are reduced, the visible light absorption utilization rate and the adsorption performance to organic matters are improved, and the photocatalytic degradation performance and the mineralization capability of the sepiolite are improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic degradation of organic pollutants, and particularly relates to a bismuth oxycarbonate/sepiolite composite photocatalyst and a preparation method thereof.
Background
Due to the rapid development of industrial and agricultural production and the continuous improvement of the living standard of people, organic pollutants discharged to the environment are increased day by day, and the water environment pollution is serious day by day. Heretofore, various treatment techniques have been developed to cope with the increasing organic contamination such as adsorption, flocculation, electrochemical methods, chemical reagent oxidation, ozone oxidation, Fenton oxidation, photo-Fenton oxidation, photocatalytic degradation and the like. In a plurality of treatment methods, the photocatalytic degradation can utilize light energy to oxidize and decompose organic pollutants at normal temperature, has strong capability of degrading the organic pollutants, complete degradation, high speed and no secondary pollution, can fully utilize natural light sources particularly in visible light catalytic degradation, and has low treatment cost. The semiconductor mesoporous structure photocatalytic material is beneficial to light reflection and refraction due to the excellent porous structure and the larger specific surface area, and can greatly improve the utilization rate of light; and the large specific surface area can provide enough active sites and places for pollutant molecule adsorption, and promote the high-efficiency mass transfer of pollutants, thereby improving the catalytic degradation effect of pollutants, and becoming a key point and a hotspot for research and development of environmental protection workers. At present, titanium dioxide is the most deeply researched, developed and widely applied photocatalyst, and has the advantages of good chemical stability, strong chemical pollutant resistance, environmental friendliness and the like. But because the energy band gap is higher than 3.2eV, the titanium dioxide powder can be effectively excited to generate electron/hole pairs only under the irradiation of ultraviolet rays (lambda is less than or equal to 387.5nm), and the titanium dioxide powder has the defects of high recombination rate of the electron/hole pairs, difficult separation of the titanium dioxide powder suspended in the solution and the like, thereby greatly limiting the popularization and the application of the titanium dioxide powder. Therefore, the research and development of the photocatalyst which has high light utilization rate, particularly the utilization of visible light, good catalytic degradation effect, low price and no toxicity per se is the key for promoting the application of the photocatalytic degradation technology in the treatment of organic pollutants.
In recent years, bismuth-based semiconductor materials, such as BiFeO3、BiVO4、Bi2WO6、Bi2MoO6And BiOX and the like, because the internal electric field generated by polarization is beneficial to the separation of photo-generated electrons and holes, the bismuth-based compound has higher photocatalytic performance, and because the bismuth-based compound is non-toxic and causes little pollution to the environment, the bismuth-based compound has become the key point of research and development of environmental protection workers. Wherein, bismuth oxycarbonate (Bi)2O2CO3) Is a typical Aurivillius-type oxide, belongs to a tetragonal system, and has unique composition of [ Bi2O2]2+And CO3 2-The inner electric field generated by polarization is beneficial to the separation of photoinduced electrons and holes, thereby improving Bi2O2CO3The photocatalytic performance of (a). However, the band gap value is between 3.2 and 3.5eV, the visible light absorption rate is low, the recombination rate of the photon-generated carrier particles (hole/electron pairs) is high, the quantum efficiency is low, and the popularization and the application of the photon-generated carrier particles are greatly limited. Therefore, appropriate measures must be taken to improve the structure and morphology of the material, reduce the energy band gap thereof, and improve the light absorption rate and light quantum efficiency and the adsorption performance to pollutants, thereby improving the photocatalytic degradation performance to pollutants.
Sepiolite (Sepiolite) is a magnesium-containing porous inosilicate mineral, has a unique nano-structure pore diameter, a large pore volume and a large specific surface area, is strong in adsorption capacity, light in weight and good in chemical stability, and particularly contains a large number of acid-base centers, so that other materials can be formed and grown on the Sepiolite by taking the Sepiolite as a support, and the purpose of regulating and controlling the structure and the morphology of the generated materials is achieved. Therefore, in-situ generation of the photocatalyst Bi in the presence of sepiolite is adopted2O2CO3Thereby preparing bismuth oxycarbonate/sepiolite (Bi)2O2CO3Sepiolite) composite photocatalyst, expected to improve the generated Bi2O2CO3The structure and the shape of the photocatalyst reduce the energy gap band, improve the absorption rate of visible light and the adsorption performance of pollution, and achieve the aim of improving the photocatalytic activityIn (1). So far, Bi has not been existed yet2O2CO3Research and report of a/Sepiolite composite photocatalyst.
Disclosure of Invention
In view of Bi2O2CO3Has the advantages of layered structure, no toxicity and the like, has the defects of high energy band gap, low light absorption rate, high recombination rate of photon-generated carriers, low photocatalytic efficiency and the like, and aims to provide Bi2O2CO3The Sepiolite composite photocatalyst has excellent structural morphology, lower energy gap band and photogenerated carrier recombination rate, higher visible light absorption utilization rate and quantum efficiency, and also has good adsorption performance on organic matters and excellent photocatalytic degradation performance.
Another object of the present invention is to provide a Bi2O2CO3Preparation method of/Sepiolite composite photocatalyst, and in-situ generation of Bi in the presence of Sepiolite2O2CO3To Bi2O2CO3The structure and the appearance of the product are effectively controlled, the preparation method is simple and convenient, the process is easy to control, the discharge of three wastes is less, the manufacturing cost is lower, and the large-scale production is easy to realize; the method specifically comprises the following steps:
(1) adding cetyl trimethyl ammonium bromide into ethylene glycol, and ultrasonically stirring for 20-40 min to prepare a cetyl trimethyl ammonium bromide-ethylene glycol solution with the concentration of 0.125-0.25 mol/L, and marking as a solution A;
(2) adding bismuth nitrate pentahydrate and ferric nitrate nonahydrate into deionized water according to the molar ratio of 1: 0.9-1.0, ultrasonically stirring for 20-40 min to dissolve and prepare a bismuth nitrate-ferric nitrate mixed solution, marking as a solution B, wherein Bi is3+The concentration of the Fe is 0.02-0.033 mol/L3+The concentration is 0.018-0.033 mol/L;
(3) slowly dropwise adding the solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 15-30 min, then adjusting the pH value to 10-10.5, and continuously ultrasonically stirring for 3-4 h at room temperature to obtain a mixture C;
(4) adding the purified sepiolite into the mixture C obtained in the step (3) according to the mass ratio of 0.082-0.41: 1 of the sepiolite to the bismuth nitrate pentahydrate, and carrying out ultrasonic stirring for 40-80 min to obtain a mixture D;
(5) transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 3-6 h at 180-250 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 2-5 times respectively, and drying at 100-120 ℃ to constant weight to obtain Bi2O2CO3A Sepiolite composite photocatalyst.
Further, in the step (3), a strong alkali solution of 8-12 mol/L is adopted for adjusting the pH, and the used strong alkali is KOH or NaOH.
Further, in the step (4), the purified sepiolite is processed by the following method: grinding sepiolite, sieving with a 200-300-mesh sieve, soaking in 1-2 mol/L hydrochloric acid at 75-85 ℃ for refluxing for 0.5-1 h, filtering, and washing with distilled water to be neutral; then preparing a mixture of sepiolite and 10mmol/L Cetyl 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 at 80-100 ℃ to constant weight, grinding and sieving with a 800-1000-mesh sieve, and taking undersize for later use.
Further, in the step (5), the high-pressure reaction kettle is a polytetrafluoroethylene-lined high-pressure reaction kettle.
Furthermore, the ultrasonic stirring is ultrasonic-assisted mechanical stirring, and the ultrasonic power is 200-250W.
Furthermore, the reagents used, cetyl trimethyl ammonium bromide, ethylene glycol, bismuth nitrate pentahydrate, ferric nitrate nonahydrate, KOH, NaOH, ethanol and hydrochloric acid, were all analytically pure.
The invention relates to a bismuth oxycarbonate/sepiolite composite photocatalyst and a preparation method thereof. Dissolving cetyl trimethyl ammonium bromide in ethylene glycol to prepare a template-reducing agent solution, dissolving bismuth nitrate and ferric nitrate in deionized water simultaneously to prepare a bismuth nitrate-ferric nitrate mixed solution, dropwise adding the bismuth nitrate-ferric nitrate mixed solution into the template-reducing agent solution, adjusting the pH value of the mixed solution by using a strong base solution, and fully stirring to obtain a mixture; adding the processed purified sepiolite into the mixture, mixing thoroughly, and transferringAnd carrying out hydrothermal reaction in an autoclave with a polytetrafluoroethylene lining to generate the porous bismuth oxycarbonate/sepiolite composite photocatalyst which is supported by sepiolite and has good appearance. The ethylene glycol or hexadecyl trimethyl ammonium bromide is oxidatively decomposed by bismuth nitrate and ferric nitrate under hydrothermal conditions to generate carbonate radical, and the carbonate radical is reacted with Bi3+Bismuth oxycarbonate is generated under the alkaline condition, and the bismuth oxycarbonate is loaded and grows on the sepiolite under the comprehensive action of the surface activity and the template action of hexadecyl trimethyl ammonium bromide and the strong interface effect of the sepiolite. The shape and the structure of the generated bismuth subcarbonate are well controlled, the energy band gap and the recombination rate of photon-generated carriers are reduced, the visible light absorption utilization rate and the adsorption performance to organic matters are improved, and the photocatalytic degradation performance to organic pollution is obviously improved.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) cetyl trimethyl ammonium bromide-ethylene glycol solution is used as a template agent and a reducing agent, carbonate is obtained by oxidizing and decomposing cetyl trimethyl ammonium bromide or ethylene glycol through bismuth nitrate and ferric nitrate under hydrothermal conditions, the amount of carbonate in the reaction process can be effectively controlled, and accordingly Bi is controlled2O2CO3The formation speed of (c); the structure and the shape of the composite photocatalyst are effectively controlled by the surface activity or the template action of cetyl trimethyl ammonium bromide and ethylene glycol and the interface action of sepiolite.
(2) Bi prepared by the invention2O2CO3the/Sepiolite composite photocatalyst is a porous structure, and the specific surface area of the composite photocatalyst is not Bi generated by Sepiolite2O2CO3Large; the adsorption capacity to organic matters is enhanced through the synergistic effect with the sepiolite.
(3) Bi prepared by the invention2O2CO3Bi in Sepiolite composite photocatalyst2O2CO3The sepiolite is generated in the presence of sepiolite and grows by taking the sepiolite as a support, and the sepiolite have good fusion and stability; the sepiolite not only promotes and regulates Bi loaded on the sepiolite by using a special pore channel structure2O2CO3Formation of structure and morphology ofReducing the energy band gap and the recombination rate of photo-generated electrons and holes, and sepiolite and Bi2O2CO3The synergistic effect enhances the adsorption and absorption utilization rate of the organic pollutants on light and improves the photocatalytic degradation performance of the organic pollutants.
(4) The product of the invention has excellent visible light catalytic degradation performance and good mineralization capability on organic pollutants, and has good photocatalytic decoloration performance on organic dye wastewater; safe and nontoxic, convenient to recover and good in recycling performance, and is suitable for treating various organic polluted wastewater.
(5) The method has the advantages of simple preparation process, easy control of the process, less discharge of three wastes, lower manufacturing cost, conventional equipment as required, easy realization of large-scale production and wide application prospect.
Drawings
Fig. 1 is a synthesis route diagram of a bismuth oxycarbonate/sepiolite composite photocatalyst.
FIG. 2 shows a bismuth oxycarbonate/sepiolite composite photocatalyst (m (Bi)2O2CO3) XRD pattern of m (sepiolite) 1: 0.4).
FIG. 3 shows a bismuth oxycarbonate/sepiolite composite photocatalyst (m (Bi)2O2CO3) SEM image of m (Sepilolite) 1: 0.4).
FIG. 4 shows a bismuth oxycarbonate/sepiolite composite photocatalyst (m (Bi)2O2CO3) Graph of photocatalytic degradation efficiency for m (Sepilolate) 1: 0.4).
FIG. 5 shows a bismuth oxycarbonate/sepiolite composite photocatalyst (m (Bi)2O2CO3) M (Sepilolate) 1: 0.4).
Note: m (Bi)2O2CO3) M (Sepilolite) is the mass ratio of bismuth subcarbonate to sepiolite.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples, but the present invention is not limited thereto.
Example 1
(1) Adding 5.47g of hexadecyl trimethyl ammonium bromide into 120mL of glycol, and ultrasonically stirring for 20min to prepare a hexadecyl trimethyl ammonium bromide-glycol solution A with the concentration of 0.125 mol/L;
(2) respectively adding 2.94g of 99.0 percent bismuth nitrate pentahydrate and 2.46g of 98.5 percent ferric nitrate nonahydrate into 300mL of deionized water, and ultrasonically stirring for 20min to dissolve into Bi3+The concentration is 0.02mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.020 mol/L;
(3) slowly dropwise adding the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 15min, then adjusting the pH to 10.5 by using 10mol/L KOH solution, and continuously ultrasonically stirring for 4h at room temperature to obtain a mixture C;
(4) adding 0.24g of purified sepiolite into the mixture C obtained in the step (3), and ultrasonically stirring for 40min to obtain a mixture D;
(5) transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 3 hours at 250 ℃; and cooling to room temperature, filtering, washing filter residues for 3 times respectively by using deionized water and ethanol, and drying at 120 ℃ to constant weight to obtain 1.75g of bismuth oxycarbonate/sepiolite composite photocatalyst.
Example 2
(1) Adding 5.47g of hexadecyl trimethyl ammonium bromide into 100mL of ethylene glycol, and ultrasonically stirring for 25min to prepare a hexadecyl trimethyl ammonium bromide-ethylene glycol solution A with the concentration of 0.15 mol/L;
(2) respectively adding 2.94g of 99.0 percent bismuth nitrate pentahydrate and 2.41g of 98.5 percent ferric nitrate nonahydrate into 240mL of deionized water, and ultrasonically stirring for 25min to dissolve into Bi3+The concentration is 0.025mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.024 mol/L;
(3) slowly dropwise adding the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 20min, then adjusting the pH to 10.3 by using a KOH solution of 12mol/L, and continuously ultrasonically stirring for 3.5h at room temperature to obtain a mixture C;
(4) adding 0.29g of purified sepiolite into the mixture C obtained in the step (3), and ultrasonically stirring for 50min to obtain a mixture D;
(5) transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 4 hours at 230 ℃; and cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 4 times respectively, and drying at 115 ℃ to constant weight to obtain 1.78g of the bismuth oxycarbonate/sepiolite composite photocatalyst.
Example 3
(1) Adding 5.47g of hexadecyl trimethyl ammonium bromide into 75mL of glycol, and ultrasonically stirring for 30min to prepare a hexadecyl trimethyl ammonium bromide-glycol solution A with the concentration of 0.20 mol/L;
(2) respectively adding 2.94g of 99.0 percent bismuth nitrate pentahydrate and 2.34g of 98.5 percent ferric nitrate nonahydrate into 200mL of deionized water, and ultrasonically stirring for 25min to dissolve into Bi3+The concentration is 0.030mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.0285 mol/L;
(3) slowly dropwise adding the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 25min, then adjusting the pH to 10.1 by using 11mol/L KOH solution, and continuously ultrasonically stirring for 3h at room temperature to obtain a mixture C;
(4) adding 0.59g of purified sepiolite into the mixture C obtained in the step (3), and ultrasonically stirring for 60min to obtain a mixture D;
(5) transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 4.5 hours at 220 ℃; and cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ to constant weight to obtain 2.04g of the bismuthyl carbonate/sepiolite composite photocatalyst.
The phase was determined on a D8 Advance X-powder diffractometer (40kV,40mA, Bruker 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, Bi2O2CO3The diffraction pattern of the/Sepiolite XRD is between 23.9 degrees, 30.3 degrees, 32.7 degrees and 48.9 degrees and Bi2O2CO3The standard card (JCPDS No.41-1488) is well matched, and the 26.6-degree diffraction peak and the sepiolite (080) crystal face structure indicate that the product is Bi2O2CO3Sepiolite composite。
Bi prepared in the absence of sepiolite was determined using a field emission scanning electron microscope (FESEM, Hitachi Co., Japan) model S-48002O2CO3And the morphology of the sample of this example, the results are shown in FIG. 3. As can be seen from FIG. 3(a), Bi formed in the absence of sepiolite2O2CO3Is composed of long granular particles with different sizes; as can be seen from FIG. 3(b), Bi formed in the presence of sepiolite2O2CO3the/Sepiolite composite photocatalyst is porous large particles formed by stacking fine spherical particles. This indicates that the presence of sepiolite alters the coating layer Bi2O2CO3The crystal structure of the photocatalyst is beneficial to improving the photoelectrochemical properties of the photocatalyst, such as improving the absorption performance of light, reducing the energy band gap, the recombination rate of photo-generated electrons and holes and the like, and improving the adsorption capacity of pollutants.
Bi determination with a specific surface area-pore volume analyzer (BELSORP-mini II, MicrotracBEL, Japan)2O2CO3Has a specific surface area of 49.01m2/g，Bi2O2CO3Specific surface area of/Sepiolite composite photocatalyst is 77.86m2(ii) in terms of/g. Measuring diffuse reflection ultraviolet-visible spectrum (UV-vis DRS) by using UV-2550 scanning ultraviolet-visible spectrophotometer (Shimadzu, Japan), and calculating to obtain Bi2O2CO3And Bi2O2CO3Energy band gap E of/Sepiolite sampleg3.39eV and 3.14eV, respectively, indicating that Bi2O2CO3Bi formed by compounding with sepiolite2O2CO3E of/Sepiolite composite photocatalystgObviously reduces the content of the sepiolite, obviously improves the structure of the composite photocatalyst and reduces the energy band gap of the composite photocatalyst.
Example 4
(1) Adding 5.47g of hexadecyl trimethyl ammonium bromide into 60mL of ethylene glycol, and ultrasonically stirring for 40min to prepare a hexadecyl trimethyl ammonium bromide-ethylene glycol solution A with the concentration of 0.25 mol/L;
(2) respectively taking 2.94g of 99.0 percent pentahydrate bismuth nitrate and 2.21 g ofAdding 98.5% g ferric nitrate nonahydrate into 182mL deionized water, and ultrasonically stirring for 25min to dissolve into Bi3+The concentration is 0.033mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.030 mol/L;
(3) slowly dropwise adding the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 30min, then adjusting the pH to 10.0 by using 8mol/L KOH solution, and continuously ultrasonically stirring for 3.5h at room temperature to obtain a mixture C;
(4) adding 0.88g of purified sepiolite into the mixture C obtained in the step (3), and ultrasonically stirring for 70min to obtain a mixture D;
(5) transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 5 hours at 210 ℃; and cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 5 times respectively, and drying at 105 ℃ to constant weight to obtain 2.33g of the bismuthyl carbonate/sepiolite composite photocatalyst.
Example 5
1) Adding 5.47g of hexadecyl trimethyl ammonium bromide into 110mL of ethylene glycol, and ultrasonically stirring for 25min to prepare a hexadecyl trimethyl ammonium bromide-ethylene glycol solution A with the concentration of 0.14 mol/L;
(2) respectively adding 2.94g of 99.0 percent bismuth nitrate pentahydrate and 2.46g of 98.5 percent ferric nitrate nonahydrate into 182mL of deionized water, and ultrasonically stirring for 25min to dissolve into Bi3+The concentration is 0.033mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.033 mol/L;
(3) slowly dropwise adding the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 25min, then adjusting the pH to 10.2 by using 8mol/L NaOH solution, and continuously ultrasonically stirring for 4h at room temperature to obtain a mixture C;
(4) adding 1.21g of purified sepiolite into the mixture C obtained in the step (3), and ultrasonically stirring for 80min to obtain a mixture D;
(5) transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 5.5 hours at 200 ℃; and cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 2 times respectively, and drying at 100 ℃ to constant weight to obtain 2.64g of the bismuthyl carbonate/sepiolite composite photocatalyst.
Example 6
1) Adding 5.47g of hexadecyl trimethyl ammonium bromide into 100mL of ethylene glycol, and ultrasonically stirring for 35min to prepare a hexadecyl trimethyl ammonium bromide-ethylene glycol solution A with the concentration of 0.15 mol/L;
(2) respectively adding 2.94g of 99.0 percent bismuth nitrate pentahydrate and 2.34g of 98.5 percent ferric nitrate nonahydrate into 220mL of deionized water, and ultrasonically stirring for 25min to dissolve into Bi3+The concentration is 0.027mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.026 mol/L;
(3) slowly dropwise adding the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 30min, then adjusting the pH to 10.5 by using a 12mol/L NaOH solution, and continuously ultrasonically stirring for 3.5h at room temperature to obtain a mixture C;
(4) adding 1.18g of purified sepiolite into the mixture C obtained in the step (3), and ultrasonically stirring for 80min to obtain a mixture D;
(5) transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 6 hours at 180 ℃; and cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 4 times respectively, and drying at 100 ℃ to constant weight to obtain 2.67g of the bismuthyl carbonate/sepiolite composite photocatalyst.
Examples 7 to 9 are photocatalytic degradation performance test examples
Example 7
The photocatalytic performance test conditions were as follows: the bismuth oxycarbonate/sepiolite composite photocatalyst prepared in example 3 (Bi) was used as a light source at room temperature under a 300W xenon lamp2O2CO3/Sepiolite，m(Bi2O2CO3) M (Sepilolite) 1: 0.4 and preparation of bismuth subcarbonate (Bi) in the absence of sepiolite under identical conditions2O2CO3) As a test sample, the degradation rate of rhodamine B (RhB) is used as an evaluation index. The specific operation steps are as follows: a clean 100mL jacketed beaker was charged with 50mg photocatalyst sample and 50mL of 60mg/L RhB solution, each at equal distances from the light source. Standing in dark for 30min to ensure that RhB is in the sampleThe surface adsorption and desorption reach equilibrium; and (3) degrading under the illumination of a 300W xenon lamp, and sampling once every 15min in the degradation process, wherein the sampling volume is 2 mL. The sample was injected into a centrifuge tube and centrifuged to take out the supernatant, the concentration was measured at 554nm in a UV-3600 UV-visible spectrophotometer (Shimazu, Japan), the degradation rates at different degradation times were calculated, and a degradation curve graph was obtained by plotting the degradation rates against time, as shown in FIG. 4. A water sample with illumination for 90min is taken to determine the total organic carbon in a TOC-LCPH type total organic carbon analyzer (Shimadzu, Japan), and the degradation rate of the total organic carbon is calculated.
As can be seen from fig. 4, the adsorption/desorption equilibrium was reached at 30min in the dark room, with a decrease in RhB concentration of about 5.8%; the light irradiation is carried out for 90min without adding the photocatalyst, and the self-degradation rate is very low; with sample Bi2O2CO3/Sepiolite(m(Bi2O2CO3) M (Sepilolite) is 1: 0.4) as catalyst, the degradation rate of Rh B reaches 99.1 percent; and Bi2O2CO3As a catalyst, the degradation rate of RhB is only 62.5 percent after the irradiation for 90 min. Thus, Bi2O2CO3/Sepiolite(m(Bi2O2CO3) M (sepiolite) 1: 0.4) has excellent photocatalytic degradation properties for RhB.
After measuring and irradiating for 90min, Bi2O2CO3/Sepiolite(m(Bi2O2CO3) M (Sepilolite) 1: 0.4) and Bi2O2CO3The Total Organic Carbon (TOC) removal was 71.23% and 29.76%, respectively. Thus, Bi2O2CO3/Sepiolite(m(Bi2O2CO3) M (sepiolite) 1: 0.4) has excellent mineralization ability on RhB.
Example 8
Bi after degradation2O2CO3And separating and recycling the/Sepiolite composite photocatalyst to be used as the photocatalyst for the next experiment. The experimental conditions and procedures and test methods were the same as in example 7. The degradation rate was varied by 5 cycles as shown in FIG. 5.
As can be seen from FIG. 5, Bi is recycled for 5 times2O2CO3The catalytic degradation rate of the/Sepiolite composite photocatalyst to RhB is reduced from 99.1% at the 1 st time to 94.7% at the 5 th time, and is only reduced by 4.4%. The results show that the Bi prepared by the invention2O2CO3the/Sepiolite composite photocatalyst has excellent recycling and recycling performance.
Example 9
This example is an example of photocatalytic bleaching performance, with the following test conditions: 10mg of Methyl Orange (MO), Methylene Blue (MB) and Fluorescein (FS) were dissolved in 1L of distilled water to prepare a simulated mixed solution (MO-MB-FS), and the bismuth oxycarbonate/sepiolite composite photocatalyst (Bi) prepared in example 3 was used2O2CO3/Sepiolite，m(Bi2O2CO3) M (Sepilolite) 1: 0.4 and bismuth subcarbonate (Bi) prepared under the same conditions in the absence of sepiolite2O2CO3) Is a photocatalyst sample. A clean 200mL jacketed beaker was charged with 100mg of photocatalyst sample and 100mL of MO-MB-FS solution. Standing in the dark for 30min, then degrading under the illumination of a 300W xenon lamp, sampling once every 15min in the degradation process, wherein the sampling volume is 2mL, and measuring the solution chroma by a dilution multiple method after centrifugal separation, wherein the results are shown in Table 1.
TABLE 1 change in solution color with time of illumination
The results in Table 1 show that Bi2O2CO3the/Sepiolite has excellent photocatalytic decoloring capability on mixed dye solution, can be completely decolored after being irradiated for 90min, and is obviously superior to Bi without Sepiolite2O2CO3. The above is only a preferred embodiment of the present invention, and those skilled in the art can make various modifications and changes to the above concept, for example, the composition and process conditions are combined and changed within the scope of the composition and process conditions given by the present invention, and such changes and modifications are all within the spirit of the present invention.
Claims (7)
1. The bismuth oxycarbonate/sepiolite composite photocatalyst is characterized in that bismuth oxycarbonate is generated on line in the presence of sepiolite to form a porous material with the sepiolite being supported by bismuth oxycarbonate and coating the sepiolite, and the mass ratio of the components of the bismuth oxycarbonate to the components of the sepiolite is 1: 0.16-0.78.
2. The preparation method of the bismuth oxycarbonate/sepiolite composite photocatalyst as claimed in claim 1, which is characterized by comprising the following steps:
(1) adding cetyl trimethyl ammonium bromide into ethylene glycol, and ultrasonically stirring for 20-40 min to prepare a cetyl trimethyl ammonium bromide-ethylene glycol solution with the concentration of 0.125-0.25 mol/L, and marking as a solution A;
(2) adding bismuth nitrate pentahydrate and ferric nitrate nonahydrate into deionized water according to the molar ratio of 1: 0.9-1.0, ultrasonically stirring for 20-40 min to dissolve and prepare a bismuth nitrate-ferric nitrate mixed solution, marking as a solution B, wherein Bi is3+The concentration of the Fe is 0.02-0.033 mol/L3+The concentration is 0.018-0.033 mol/L;
(3) slowly dropwise adding the solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 15-30 min, then adjusting the pH value to 10-10.5, and continuously ultrasonically stirring for 3-4 h at room temperature to obtain a mixture C;
(4) adding the purified sepiolite into the mixture C obtained in the step (3) according to the mass ratio of 0.082-0.41: 1 of the sepiolite to the bismuth nitrate pentahydrate, and carrying out ultrasonic stirring for 40-80 min to obtain a mixture D;
(5) transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 3-6 h at 180-250 ℃; and cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 2-5 times respectively, and drying at 100-120 ℃ to constant weight to obtain the bismuthyl carbonate/sepiolite composite photocatalyst.
3. The method for preparing the bismuth oxycarbonate/sepiolite composite photocatalyst according to claim 2, wherein in the step (3), a strong alkali solution with a concentration of 8-12 mol/L is adopted for pH adjustment, and the strong alkali is KOH or NaOH.
4. The method for preparing the bismuth oxycarbonate/sepiolite composite photocatalyst according to claim 2, wherein in the step (4), the purified sepiolite is processed by the following method: grinding sepiolite, sieving with a 200-300-mesh sieve, soaking in 1-2 mol/L hydrochloric acid at 75-85 ℃ for refluxing for 0.5-1 h, filtering, and washing with distilled water to be neutral; then preparing a mixture of sepiolite and 8-10 mmol/L Cetyl Trimethyl Ammonium Bromide (CTAB) solution with the 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 at 80-100 ℃ to constant weight, grinding and sieving with a 800-1000-mesh sieve, and taking undersize for later use.
5. The method for preparing the bismuth oxycarbonate/sepiolite composite photocatalyst as claimed in claim 2, wherein in the step (5), the high-pressure reaction kettle is a polytetrafluoroethylene-lined high-pressure reaction kettle.
6. The preparation method of the bismuth oxycarbonate/sepiolite composite photocatalyst according to claim 2, wherein the ultrasonic stirring is ultrasonic-assisted mechanical stirring, and the ultrasonic power is 200-250W.
7. The method for preparing the bismuth oxycarbonate/sepiolite composite photocatalyst according to any one of claims 2 to 6, wherein the reagents used are cetyltrimethylammonium bromide, ethylene glycol, bismuth nitrate pentahydrate, ferric nitrate nonahydrate, KOH, NaOH, ethanol and hydrochloric acid, all of which are analytically pure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110132659.2A CN112774706B (en) | 2021-01-31 | 2021-01-31 | Bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110132659.2A CN112774706B (en) | 2021-01-31 | 2021-01-31 | Bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112774706A true CN112774706A (en) | 2021-05-11 |
| CN112774706B CN112774706B (en) | 2023-10-24 |
Family
ID=75760166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110132659.2A Active CN112774706B (en) | 2021-01-31 | 2021-01-31 | Bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112774706B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113546650A (en) * | 2021-07-20 | 2021-10-26 | 辽宁大学 | Bismuth tungstate-bismuth oxyfluoride composite photocatalyst and preparation method and application thereof |
| CN115028200A (en) * | 2022-05-16 | 2022-09-09 | 大连理工大学 | Preparation method of bismuth oxide/bismuth oxycarbonate composite electrode material |
| CN115634702A (en) * | 2021-07-20 | 2023-01-24 | 南昌航空大学 | Bismuth oxycarbonate/biochar composite photocatalyst and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09183620A (en) * | 1995-12-27 | 1997-07-15 | Dowa Mining Co Ltd | Bismuth oxycarbonate powder and its production |
| CN103769185A (en) * | 2014-02-11 | 2014-05-07 | 南京信息工程大学 | Preparation method of nanoscale square flaky bismuth oxycarbonate photocatalyst |
| CN105749945A (en) * | 2016-03-16 | 2016-07-13 | 湖北文理学院 | Fe(III)/Bi2O2CO3 photocatalyst preparation method |
| CN106268895A (en) * | 2016-08-23 | 2017-01-04 | 扬州天辰精细化工有限公司 | A kind of preparation method of iron sesquioxide bismuthyl carbonate composite photo-catalyst |
| CN106694013A (en) * | 2016-12-15 | 2017-05-24 | 湘潭大学 | Sepiolite-bismuth subcarbonate catalyst and application thereof in organic wastewater treatment |
| CN106732705A (en) * | 2016-12-29 | 2017-05-31 | 江苏大学 | A kind of Fe3O4@C@(BiO)2CO3The Preparation method and use of composite photo-catalyst |
| CN107029770A (en) * | 2017-04-27 | 2017-08-11 | 中南大学 | A kind of preparation method of metastable phase bismuth oxide and its application in photocatalysis degradation organic contaminant |
| CN108212187A (en) * | 2018-01-26 | 2018-06-29 | 湖北文理学院 | Fe adulterates Bi2O2CO3Preparation method and Fe the doping Bi of photochemical catalyst2O2CO3Photochemical catalyst |
| CN110575841A (en) * | 2019-09-11 | 2019-12-17 | 哈尔滨理工大学 | Novel photocatalyst material for degrading methylene blue light and preparation method thereof |
-
2021
- 2021-01-31 CN CN202110132659.2A patent/CN112774706B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09183620A (en) * | 1995-12-27 | 1997-07-15 | Dowa Mining Co Ltd | Bismuth oxycarbonate powder and its production |
| CN103769185A (en) * | 2014-02-11 | 2014-05-07 | 南京信息工程大学 | Preparation method of nanoscale square flaky bismuth oxycarbonate photocatalyst |
| CN105749945A (en) * | 2016-03-16 | 2016-07-13 | 湖北文理学院 | Fe(III)/Bi2O2CO3 photocatalyst preparation method |
| CN106268895A (en) * | 2016-08-23 | 2017-01-04 | 扬州天辰精细化工有限公司 | A kind of preparation method of iron sesquioxide bismuthyl carbonate composite photo-catalyst |
| CN106694013A (en) * | 2016-12-15 | 2017-05-24 | 湘潭大学 | Sepiolite-bismuth subcarbonate catalyst and application thereof in organic wastewater treatment |
| CN106732705A (en) * | 2016-12-29 | 2017-05-31 | 江苏大学 | A kind of Fe3O4@C@(BiO)2CO3The Preparation method and use of composite photo-catalyst |
| CN107029770A (en) * | 2017-04-27 | 2017-08-11 | 中南大学 | A kind of preparation method of metastable phase bismuth oxide and its application in photocatalysis degradation organic contaminant |
| CN108212187A (en) * | 2018-01-26 | 2018-06-29 | 湖北文理学院 | Fe adulterates Bi2O2CO3Preparation method and Fe the doping Bi of photochemical catalyst2O2CO3Photochemical catalyst |
| CN110575841A (en) * | 2019-09-11 | 2019-12-17 | 哈尔滨理工大学 | Novel photocatalyst material for degrading methylene blue light and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| LIJUN CHENG ET AL.: ""Template-induced Bi2O2CO3 microstructure self-assembled by nanosheets with exposed {001} facets"", vol. 5, pages 7 - 8 * |
| RUIRUI LIU ET AL.: ""Honeycomb-like micro-mesoporous structure TiO2/sepiolite composite for combined chemisorption and photocatalytic elimination of formaldehyde"", vol. 248, pages 234 - 245, XP085008890, DOI: 10.1016/j.micromeso.2017.04.029 * |
| 周慧;王磊;沈明;樊璐;: "片状氧化铋的软模板法制备及其光催化降解性能", 扬州大学学报(自然科学版), no. 04, pages 33 - 37 * |
| 李桂水;胡旭敏;程丽君;郝亮;: "表面活性剂修饰碳酸氧铋的制备及光催化性能", 应用化学, no. 06, pages 87 - 94 * |
| 杨秋月: ""Bi基复合材料的制备及其可见光催化性能研究"", no. 2, pages 027 - 996 * |
| 胡丹单: ""Fe2O3/Bi2O2CO3复合纳米材料的合成及其光催化性质的研究"", no. 6, pages 32 - 33 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113546650A (en) * | 2021-07-20 | 2021-10-26 | 辽宁大学 | Bismuth tungstate-bismuth oxyfluoride composite photocatalyst and preparation method and application thereof |
| CN115634702A (en) * | 2021-07-20 | 2023-01-24 | 南昌航空大学 | Bismuth oxycarbonate/biochar composite photocatalyst and preparation method and application thereof |
| CN115028200A (en) * | 2022-05-16 | 2022-09-09 | 大连理工大学 | Preparation method of bismuth oxide/bismuth oxycarbonate composite electrode material |
| CN115028200B (en) * | 2022-05-16 | 2023-02-21 | 大连理工大学 | Preparation method of bismuth oxide/bismuth oxycarbonate composite electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112774706B (en) | 2023-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rohokale et al. | A novel two-step co-precipitation approach of CuS/NiMn2O4 heterostructured nanocatalyst for enhanced visible light driven photocatalytic activity via efficient photo-induced charge separation properties | |
| CN112774706B (en) | Bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof | |
| CN107497456B (en) | Preparation method and application of layered bismuth oxychloride visible-light-driven photocatalyst | |
| Zhao et al. | Study on the photocatalysis mechanism of the Z-scheme cobalt oxide nanocubes/carbon nitride nanosheets heterojunction photocatalyst with high photocatalytic performances | |
| CN111604077B (en) | g-C for degrading ammonia nitrogen3N4/Gr/TiO2Z-system photocatalytic material and preparation method and application thereof | |
| CN110776049B (en) | Method for treating organic wastewater by activating peroxymonosulfate with functionalized zirconium-based metal organic framework/protonated carbon nitride composite material | |
| CN105126917B (en) | A kind of preparation method of copper/cuprous oxide/cyclization polyacrylonitrile visible light catalyst | |
| CN107790157A (en) | A kind of ternary bismuthino composite photo-catalyst Bi/Bi4O5Br2/ BiOI and its preparation method and application | |
| CN106552651A (en) | A kind of Bi12O17Br2The synthesis of photochemical catalyst and application process | |
| CN111686770B (en) | Metal ion co-doped BiOBr microsphere, preparation method and application thereof | |
| CN111604083B (en) | Graphite type carbon nitride composite photocatalytic material with oxygen vacancy bismuth tungstate/oxygen-enriched structure and preparation method and application thereof | |
| Xie et al. | Enhancing visible light photocatalytic activity by transformation of Co3+/Co2+ and formation of oxygen vacancies over rationally Co doped ZnO microspheres | |
| CN110180565A (en) | A kind of photochemical catalyst Bi5O7The synthetic method and its application of Br | |
| CN114933709A (en) | Preparation method and application of high-yield UiO-66 metal organic framework material | |
| CN114762826A (en) | High index crystal plane Cu2Preparation method and application of O photocatalyst | |
| CN113101980A (en) | TiO with visible light catalytic activity2Preparation method and application of/UiO-66 composite material | |
| CN112808287B (en) | Magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof | |
| CN111545211A (en) | Graphene oxide-lanthanum oxide-cobalt hydroxide composite material, and synthesis method and application thereof | |
| CN113976107B (en) | Method for preparing Mn-based composite catalyst by using organic waste liquid and application of Mn-based composite catalyst in decomposition of indoor formaldehyde | |
| CN107973367B (en) | Fe-doped coated TiO2Process for degrading wastewater by using photocatalyst | |
| CN115301225A (en) | Preparation method and application of bismuth/titanium dioxide photocatalytic degradation material with hollow microsphere structure | |
| CN112657555B (en) | Monodisperse Fe-O cluster doped Ni-based metal organic framework composite photocatalyst and preparation method and application thereof | |
| CN114433132A (en) | Method for synthesizing Z-type heterojunction catalytic material by ultrasonic-assisted method | |
| CN113786839A (en) | ZnO/CuO/GO heterojunction photocatalyst with composite microsphere structure and preparation method and application thereof | |
| CN112774686B (en) | Bismuth ferrite/sepiolite composite visible light catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |