CN108579770B - Method for degrading pollutants by using BiOCl nanoring - Google Patents
Method for degrading pollutants by using BiOCl nanoring Download PDFInfo
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- CN108579770B CN108579770B CN201810460524.7A CN201810460524A CN108579770B CN 108579770 B CN108579770 B CN 108579770B CN 201810460524 A CN201810460524 A CN 201810460524A CN 108579770 B CN108579770 B CN 108579770B
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000002063 nanoring Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000000593 degrading effect Effects 0.000 title claims abstract description 27
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 24
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims description 72
- 239000002135 nanosheet Substances 0.000 claims description 57
- 229920001223 polyethylene glycol Polymers 0.000 claims description 48
- 239000002202 Polyethylene glycol Substances 0.000 claims description 38
- 238000005530 etching Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 230000001699 photocatalysis Effects 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 26
- 239000000356 contaminant Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 19
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 19
- 229940012189 methyl orange Drugs 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 16
- 229940043267 rhodamine b Drugs 0.000 claims description 16
- 239000011941 photocatalyst Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- 238000001308 synthesis method Methods 0.000 claims description 8
- 150000003841 chloride salts Chemical class 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- FIMTUWGINXDGCK-UHFFFAOYSA-H dibismuth;oxalate Chemical compound [Bi+3].[Bi+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O FIMTUWGINXDGCK-UHFFFAOYSA-H 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229960003742 phenol Drugs 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 description 51
- 238000006731 degradation reaction Methods 0.000 description 51
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 230000007547 defect Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 8
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000002055 nanoplate Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920002562 Polyethylene Glycol 3350 Polymers 0.000 description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HWSISDHAHRVNMT-UHFFFAOYSA-N Bismuth subnitrate Chemical compound O[NH+]([O-])O[Bi](O[N+]([O-])=O)O[N+]([O-])=O HWSISDHAHRVNMT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 229960001482 bismuth subnitrate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 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
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to photocatalytic degradation and discloses a method for degrading pollutants by using BiOCl nanorings. The method for degrading pollutants has simple steps, and the BiOCl nano ring has high catalytic activity and catalytic stability and is convenient to recycle.
Description
Technical Field
The invention relates to photocatalytic degradation, in particular to a method for degrading pollutants by using BiOCl nanorings.
Background
Fossil fuels are indispensable in all the links of our lives, and non-renewable and gradually decreasing reserves have caused energy crisis and also accompanied serious environmental pollution when consumed. Currently, semiconductor photocatalytic technology is considered to be a promising technology to solve these two problems.
In recent years, the controllable synthesis of new BiOCl morphology and the research on the photocatalytic activity thereof have attracted great interest, mainly because BiOCl is used as an important semiconductor photocatalytic material in bismuth compounds and consists of a bismuth-oxygen layer [ Bi2O2]2+And bis [ Cl ]]-The ion layers are alternately arranged along the c-axis direction to form a unique layered structure which can be expressed in [ Bi ]2O2]2+Layer and [ Cl]-The internal electric field formed between the layers is beneficial to the separation of photo-generated electron-hole pairs, thereby having high catalytic performance.
However, most of the current reports are morphology such as BiOCl nanosheets, hierarchical structure microspheres and the like and photocatalytic activity of the morphology. The annular nano sheet (also called nano ring) is easy for fluid to pass through due to the center of the annular nano sheet, so that the dispersion of nano materials is facilitated on one hand, and the application is facilitated; on the other hand, the contact area of the BiOCl nanosheet with a fluid containing pollutants is increased, and the performance of the BiOCl nanosheet is improved. However, due to the reasons of material forward growth and the like in the synthesis process of the nanosheets, the nanoring synthesis is difficult, so that no report of BiOCl cyclic nanosheets exists in the prior art at present.
Disclosure of Invention
The invention aims to provide a method for degrading pollutants by using BiOCl nanorings, which has the advantages of simple steps, high catalytic activity and catalytic stability and convenience in recycling, and the BiOCl nanorings are simple in steps and easy to control, and the obtained BiOCl nanorings are neat in appearance and have high photocatalytic application value.
In order to achieve the above object, the present invention provides a method for degrading a contaminant using a BiOCl nanoring, comprising the step of contacting the BiOCl nanoring with water containing the contaminant under an illumination condition; the BiOCl nano-ring is obtained by the following synthesis method, wherein the synthesis method comprises the following steps: (1) will contain Bi3+、Cl-Carrying out heating reaction with a water solution of polyethylene glycol to obtain a BiOCl nanosheet; (2) etching the BiOCl nanosheets in acid liquor; wherein Cl is provided-The substance (b) is an alkali metal chloride salt; wherein the acid solution is a nitric acid solution, a sulfuric acid solution or a mixed solution of nitric acid and sulfuric acid.
Through the technical scheme, the BiOCl nanoring is obtained, the blank in the synthesis aspect of the BiOCl nanoring is filled, and the obtained BiOCl nanoring has higher photocatalytic activity than a conventional BiOCl nanosheet with a hole-free center. Moreover, the synthesis method has simple steps and easy control, and the obtained BiOCl nano ring has regular appearance, higher scientific research value and higher photocatalytic application value. Moreover, the method for degrading the pollutants has simple steps, and the BiOCl nanoring is applied to the degradation of the pollutants for the first time, has higher catalytic activity and catalytic stability, is convenient to recycle, and has higher photocatalytic application value.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
figure 1 is the effect of different time etches on BiOCl nanorings: (a) SEM picture of 3h etching, (b) SEM picture of 6h etching; (c) a TEM image of a 6h etch; (d) etching corresponding XRD patterns at different times;
figure 2 is the effect of PEG of different molecular weights on BiOCl nanoplates: (a) PEG-3350, (b) PEG-4000, (c) PEG-6000, (d) PEG-10000;
fig. 3 is the effect of different acid solutions on etching of BiOCl nanosheets: (a) an HF solution, (b) an acetic acid solution, (c) a sulfuric acid solution, (d) a nitric acid solution;
figure 4 effect of different chlorine sources on synthesis of BiOCl nanoplates: (a) KCl, (b) HCl, (c) CTAC, (d) NaCl;
figure 5 is the effect of different amounts of PEG on the synthesis of BiOCl nanoplates: (a)0.05g, (b)0.1g, (c)0.15g, (d)0.2 g;
fig. 6 is a diagram of photocatalytic analysis in application example 1: (a) degradation curve of MO (10 mg/L); (b) when BiOCl nanorings are used as a photocatalyst, an ultraviolet-visible spectrum diagram of the MO solution is shown;
fig. 7 is a diagram of photocatalytic analysis in application example 2: (a) degradation profile of MO (30 mg/L); (b) when BiOCl nanorings are used as a photocatalyst, an ultraviolet-visible spectrum diagram of the MO solution is shown;
fig. 8 is a diagram of photocatalytic analysis in application example 3: (a) degradation curve of RhB (10 mg/L); (b) an ultraviolet-visible spectrum of the RhB solution when BiOCl nanorings are used as a photocatalyst;
fig. 9 is a diagram of photocatalytic analysis in application example 4: (a) degradation curve of RhB (30 mg/L); (b) an ultraviolet-visible spectrum of the RhB solution when BiOCl nanorings are used as a photocatalyst;
FIG. 10 is a graph showing the degradation curves of phenol (10mg/L) in the presence of different catalysts in application example 5;
FIG. 11 is a graph showing the recycling rate of BiOCl nanorings in application example 6 for photocatalytic degradation of 10mg/L methyl orange.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for degrading pollutants by using BiOCl nanorings, which comprises the step of contacting the BiOCl nanorings with water containing pollutants under the condition of illumination; the BiOCl nano-ring is obtained by the following synthesis method, wherein the synthesis method comprises the following steps: (1) will contain Bi3+、Cl-Carrying out heating reaction with a water solution of polyethylene glycol to obtain a BiOCl nanosheet; (2) etching the BiOCl nanosheets in acid liquor; wherein Cl is provided-The substance (b) is an alkali metal chloride salt; wherein the acid solution is a nitric acid solution, a sulfuric acid solution or a mixed solution of nitric acid and sulfuric acid.
Through the technical scheme, the BiOCl nanoring is obtained, the blank in the synthesis aspect of the BiOCl nanoring is filled, and the obtained BiOCl nanoring has higher photocatalytic activity than a conventional BiOCl nanosheet with a hole-free center. Moreover, the synthesis method has simple steps and easy control, and the obtained BiOCl nano ring has regular appearance, higher scientific research value and higher photocatalytic application value. Moreover, the method for degrading the pollutants has simple steps, and the BiOCl nanoring is applied to the degradation of the pollutants for the first time, has higher catalytic activity and catalytic stability, is convenient to recycle, and has higher photocatalytic application value.
In the above technical scheme, for Bi in the aqueous solution3+And Cl-The ratio of the amount of the BiOCl nanoring can be adjusted in a wide range, and the BiOCl nanoring can be obtained as long as the requirement of the technical scheme is met. In a more preferred embodiment of the present invention, in order to obtain a nanosheet with a defective center after step (1) and further obtain a BiOCl nanoring with a regular morphology, increase the synthesis efficiency, further increase the degradation efficiency and the degradation stability, preferably, Bi in an aqueous solution3+And Cl-The ratio of the amount of the substances in (A) is 1: 0.8-1.2.
Further, for Bi in aqueous solution3+At a concentration of Bi as defined above3+And Cl-The ratio of the amount of the substance(s) can be adjusted within a wide range, and in order to obtain BiOCl nanorings with regular morphology, improve the synthesis efficiency, further improve the degradation efficiency and the degradation stability, Bi in an aqueous solution is preferably selected3+The concentration of (A) is 20-50 mmol/L.
Similarly, the addition amount of polyethylene glycol can be adjusted in a wide range, and researches show that nano sheets with different sizes coexist with the increase of the dosage of polyethylene glycol, but the influence on the thickness and the central defect of the nano sheet is not obvious. In order to reduce the synthesis cost, improve the synthesis efficiency, and further improve the degradation efficiency and the degradation stability, preferably, in an aqueous solution: relative to 1mmol of Bi3+The mass content of the polyethylene glycol is 0.05-0.1 g.
In addition, the conditions of the heating reaction can be adjusted in a wide range, in order to obtain a regular-morphology BiOCl nanoring, improve the synthesis efficiency, and further improve the degradation efficiency and the degradation stability, preferably, the conditions of the heating reaction include: the temperature is 140 ℃ and 180 ℃.
Of course, the heating reaction time can be adjusted within a wide range, and in order to obtain a regular-morphology BiOCl nanoring, improve the synthesis efficiency, further improve the degradation efficiency and the degradation stability, the heating reaction time is preferably 8-15 h.
On the premise that the acid solution is a nitric acid solution, a sulfuric acid solution or a mixed solution of nitric acid and sulfuric acid, H in the acid solution+Concentration of (2)Can be adjusted within a wide range, and in order to obtain BiOCl nanorings with regular shapes, improve the synthesis efficiency, further improve the degradation efficiency and the degradation stability, H in the acid solution is preferably selected+The concentration of (B) is 0.8-1.5 mol/L.
Of course, the amount of the acid solution can be adjusted within a wide range, and in order to improve the reaction efficiency, further improve the degradation efficiency and the degradation stability, the amount of the acid solution is preferably 100-600mL relative to 1g of BiOCl nanosheet.
Moreover, the etching time can be adjusted within a wide range, and in order to obtain the nanoring with regular morphology and further improve the degradation efficiency and the degradation stability, the etching time is preferably 1-8 h.
Further preferably, in order to obtain regular-shaped BiOCl nanorings, the degradation efficiency and the degradation stability are further improved, and the etching time is preferably 3-6 h.
For the etching condition, the etching condition can be adjusted in a wide range, and can be performed by adopting various modes such as surface coating with acid liquor, soaking and the like on the nanosheets in the step (1), in a preferred embodiment of the present invention, in order to improve the etching efficiency and obtain nanorings with regular shapes, further improve the degradation efficiency and the degradation stability, preferably, the etching specific steps include: ultrasonically dispersing the BiOCl nanosheets into acid liquor, and continuously stirring.
In the above technical solution, for the Bi-containing component in the step (1)3+、Cl-The process of forming the aqueous solution of polyethylene glycol and the aqueous solution of polyethylene glycol can be adjusted within a wide range, for example, the material can be dissolved directly in a portion of water, or Bi can be supplied3+The substances, alkali metal chloride and polyethylene glycol are respectively dissolved in water, and then the three are mixed, or two of the three can be dissolved and then mixed, so that the invention can be realized. The invention is not required in the mixing process, and can be directly poured or dripped to realize the invention.
In a more preferred embodiment of the invention, in order to obtain the BiOCl nanosheet with the defective center, the morphology is further facilitated to obtainRegular BiOCl nanorings, further improving the degradation efficiency and the degradation stability, preferably containing Bi3+、Cl-And an aqueous solution of polyethylene glycol is obtained by: pre-dissolving alkali metal chloride and polyethylene glycol in water, ultrasonically dispersing, and then dropwise adding the mixture to the pre-dissolved Bi3+Mixing the above materials in water solution for 20-40 min.
Further, an aqueous solution pre-dissolved with an alkali metal chloride and polyethylene glycol and pre-dissolved with a donor Bi3+The volume ratio of the aqueous solution of the substance can be adjusted in a wider range, in order to obtain the BiOCl nano-sheet with a defect at the center, the BiOCl nano-ring with regular morphology is further favorably obtained, the degradation efficiency and the degradation stability are further improved, and preferably, the aqueous solution pre-dissolved with alkali metal chloride and polyethylene glycol and the aqueous solution pre-dissolved with Bi-providing component are pre-dissolved3+The volume ratio of the aqueous solution of the substance (1: 0.8-1.2).
In a preferred embodiment of the present invention, in order to improve reaction efficiency, yield, degradation efficiency and degradation stability, it is preferable that the method further comprises the steps of cooling the product after the heating reaction in step (1), washing the product with distilled water and/or ethanol for a plurality of times, and drying the product.
In the above technical scheme, the skilled person is about providing Bi3+In order to further make the raw materials easily available and further improve the degradation efficiency and the degradation stability, it is preferable to provide Bi3+The substance(s) of (b) is/are bismuth nitrate and/or bismuth oxalate.
In the above technical solution, there are various choices for the alkali metal chloride salt, such as magnesium chloride, calcium chloride, aluminum chloride, potassium chloride, etc., and in order to further make the raw materials easily available and improve the reaction efficiency and yield, and further improve the degradation efficiency and stability of degradation, it is preferable that the alkali metal chloride salt is at least one of sodium chloride, potassium chloride, and lithium chloride.
The number average molecular weight of polyethylene glycol can be selected in a wider range, and through research, as the molecular weight of polyethylene glycol increases, the nanosheet is closer to a square shape, but the influence on the central defect part is small, which indicates that the molecular weight of PEG is not a main influence factor for obtaining the nano annular structure. In order to further make the raw materials easily available and improve the reaction efficiency and yield, further improve the degradation efficiency and the stability of degradation, it is preferable that the number average molecular weight of polyethylene glycol is 3350-10000.
There are many objects to which the method for photocatalytic degradation of contaminants is applicable, and in a preferred embodiment of the present invention, in order to rapidly degrade contaminants in water and improve the recycling rate of the BiOCl photocatalyst, the contaminants preferably include one or more of phenol, rhodamine B, and methyl orange.
In a preferred embodiment of the invention, in order to rapidly degrade the pollutants in the water and improve the recycling rate of the BiOCl nanorings, the concentration of the pollutants in the water containing the pollutants is preferably 10-30 mg/L.
The dosage of the BiOCl nanoring can be flexibly adjusted, and in order to save the degradation cost on the basis of high degradation efficiency, the dosage of the BiOCl photocatalyst with high photocatalytic activity is preferably 100mg relative to 100mL of water containing pollutants.
The contact condition of the BiOCl nanoring and water containing the pollutants can be flexibly adjusted, and in order to reduce the residues of the pollutants, the contact time is preferably 2-40 min.
In addition, the contact temperature of the BiOCl nanoring with water containing contaminants may not be required, and in order to improve the degradation efficiency, the contact temperature is preferably 30 to 50 ℃.
The present invention will be described in detail below by way of examples.
Example 1
1mmol of Bi (NO)3)3·5H2O was dissolved ultrasonically in 15mL of distilled water, labeled solution A. Adding 1mmol KCl into 15mL distilled water, ultrasonic dissolving, adding 0.1g polyethylene glycol (PEG-6000), ultrasonic dispersing, and labeling as B solution. The solution B was added dropwise to the solution a, and then the mixed solution was stirred for 30 minutes. Finally transferring the mixture into a 40mL high-pressure reaction kettleAnd heating at 160 deg.C for 12 hr. And after the reaction is finished, naturally cooling to room temperature, washing the product with distilled water and ethanol, and drying to constant weight, wherein the product is marked as BiOCl-S.
0.03g of the synthesized product is weighed and ultrasonically dispersed to 15mL of 1 mol.L-1HNO of (2)3And continuously stirring the solution for 6 hours to obtain a final product, wherein the product is marked as BiOCl-R.
Example 2
(1) Dissolving bismuth nitrate, sodium chloride and polyethylene glycol (number average molecular weight of 3350) in water to obtain a solution containing Bi3+、Cl-Carrying out heating reaction with a water solution of polyethylene glycol at 140 ℃ for 15h to obtain BiOCl nano-sheets; bi in aqueous solution3+Has a concentration of 20mmol/L and Bi in the aqueous solution3+And Cl-The amount ratio of the substances of (a) to (b) is 1: 0.8; relative to 1mmol of Bi3+The mass content of the polyethylene glycol is 0.05 g;
cooling the product after the heating reaction in the step (1), washing the product for many times by using distilled water and ethanol, and drying the product;
(2) ultrasonically dispersing BiOCl nano-sheets in 0.8mol/L nitric acid solution, continuously stirring, and etching for 3 hours; the amount of the nitric acid solution used was 100mL relative to 1g of BiOCl nanoplates.
Example 3
(1) Dissolving bismuth nitrate, potassium chloride and polyethylene glycol (number average molecular weight of 10000) in water to obtain a solution containing Bi3+、Cl-Carrying out heating reaction with a water solution of polyethylene glycol at 180 ℃ for 8h to obtain BiOCl nanosheets; bi in aqueous solution3+Has a concentration of 50mmol/L and Bi in the aqueous solution3+And Cl-The ratio of the amount of the substances of (a) to (b) is 1: 1.2; relative to 1mmol of Bi3+The mass content of the polyethylene glycol is 0.1 g;
cooling the product after the heating reaction in the step (1), washing with ethanol for multiple times and drying;
(2) ultrasonically dispersing BiOCl nano sheets in 0.5mol/L sulfuric acid solution, continuously stirring, and etching for 8 hours; the amount of the nitric acid solution used was 600mL relative to 1g of BiOCl nanosheets.
Example 4
(1) Adding bismuth oxalatePotassium chloride and polyethylene glycol (number average molecular weight: 4000) in water to obtain a solution containing Bi3+、Cl-Carrying out heating reaction with a water solution of polyethylene glycol at 160 ℃ for 10h to obtain BiOCl nano-sheets; bi in aqueous solution3+Has a concentration of 30mmol/L and Bi in the aqueous solution3+And Cl-The ratio of the amounts of the substances of (a) to (b) is 1: 1; relative to 1mmol of Bi3+The mass content of the polyethylene glycol is 0.05 g;
cooling the product after the heating reaction in the step (1), washing with distilled water for many times and drying;
(2) ultrasonically dispersing BiOCl nano-sheets in 1mol/L nitric acid solution, continuously stirring, and etching for 1 h; the amount of the nitric acid solution used was 300mL relative to 1g of BiOCl nanoplates.
Example 5
BiOCl nanorings were synthesized as in example 1, except that the etching time was 3 h. The BiOCl nanorings obtained in example 1 and example 5 were examined and the results are shown in FIG. 1, in FIG. 1: (a) an SEM (scanning electron microscope) image of a BiOCl nanoring obtained by etching for 3h in example 5, and (b) an SEM image of a BiOCl nanoring obtained by etching for 6h in example 1; (c) a TEM (transmission electron microscope) image of the BiOCl nanoring obtained in example 1 by etching for 6 h; (d) XRD (X-ray diffraction) patterns corresponding to BiOCl nanorings in example 5 and example 1 are used for studying the influence of etching time on the morphology of the sample.
As seen from the SEM image in FIG. 1, the sample is of a nano ring structure, and the central hole of the nano sheet is obviously larger than the central hole of the nano sheet etched for 3 hours after 6 hours of etching. The TEM images further confirmed that the sample was a nanocyclic structure. As can be seen from the given XRD pattern, the diffraction peaks of the etched sample all correspond to BiOCl (JCPDS No.06-0249), and no other impurity peaks are detected, indicating that the synthesized product is purer and free of impurities.
Similarly, the nanoring structures appeared in the SEM images of the BiOCl nanorings in examples 2-4, which were compared with BiOCl (JCPDS No.06-0249), and no other impurity peaks were detected.
We speculate that the reaction mechanism of the present invention is: bismuth oxalate and bismuth nitrate are easy to hydrolyze in water to generate basic bismuth nitrate and release a large amount of hydrogen ions to dissolveThe liquid is in an acidic environment. After adding a polyethylene glycol solution of alkali metal chloride, chloride ions attack bismuth subnitrate to generate BiOCl crystal nuclei. Hydrogen ions in the solution are adsorbed on the (001) crystal face of the BiOCl crystal nucleus through H-O bonds, and then grow anisotropically into a sheet-shaped structure exposing the (001) crystal face. PEG is a nonionic surfactant, is coordinated with bismuth through a hydroxyl oxygen atom, and is adsorbed on a BiOCl (001) crystal face, and finally a BiOCl nanosheet with a defective (001) crystal face is formed. When defective BiOCl is put into HNO3Or sulfuric acid solution, the etching reaction starts due to the higher reactivity of the defect sites. With the prolonging of the etching time, the etching degree is deepened, and the BiOCl nano-ring is gradually formed.
Example 6
The preparation was carried out according to the method of example 1, except that polyethylene (PEG-6000) was changed to PEG-3350, PEG-4000 and PEG-10000, respectively, i.e., PEG number average molecular weights were 3350, 4000 and 10000, respectively.
Performing SEM analysis on the BiOCl nanosheets obtained in the step (1) to obtain a picture 2, wherein in the picture 2: (a) PEG-3350, (b) PEG-4000, (c) PEG-6000 and (d) PEG-10000, so as to study the influence of PEG (3350-10000) with different molecular weights on the central defect part of the nano-sheet. As seen in fig. 2, as the molecular weight of PEG increased, the nanoplatelets approached more and more the square, but had less effect on the central defect site. Indicating that the molecular weight of PEG is not a major factor in obtaining the nanocyclic structure. After etching, BiOCl nanorings can be obtained.
Example 7
The preparation was carried out as in example 1, except that the amount of polyethylene (PEG-6000) was changed to 0.1g, 0.15g and 0.2g, respectively.
Performing SEM analysis on the BiOCl nanosheet obtained in the step (1) to obtain a picture 5, wherein the dosage of PEG-6000 in the picture 5 is respectively as follows: (a)0.05g, (b)0.1g, (c)0.15g and (d)0.2g, so as to study the influence of different PEG dosage on the morphology of the nanosheets. As seen from the SEM image, when the amount of PEG is small (0.05g,0.1g), square nanosheets with uniform morphology and size can be obtained. With the increase of the dosage, the nano sheets with different sizes coexist, but the influence on the thickness and the central defect of the nano sheet is not obvious. After acid liquor etching, the nano-ring can be obtained.
Comparative example 1
Prepared according to the synthesis of example 1 except that the nitric acid solution was replaced with HF solution.
Comparative example 2
Prepared according to the synthetic method of example 1 except that the nitric acid solution was replaced with acetic acid solution.
SEM analysis of the products of example 1 and example 3 and comparative examples 1 and 2 gave different acid solutions (monobasic acid concentration of 1 mol. L)-1The concentration of sulfuric acid is 0.51 mol.L-1) The SEM image of the etching of the nano-sheets in the step (1) shows that: (a) the acid solution is HF solution, (b) the acid solution is acetic acid solution, (c) the acid solution is sulfuric acid solution, and (d) the acid solution is nitric acid solution. Figure 3 shows the BiOCl nanoplates under four different acid etches. From fig. 3, it is found that after the sample is stirred in HF and acetic acid for 6h, the center of the BiOCl nanosheet is not etched, and remains as it is. After stirring in a sulfuric and nitric acid solution for 6h, the central portion of the wafer was successfully etched to form a ring structure. The BiOCl nanosheet precursor can be etched into a ring by sulfuric acid etching and nitric acid etching.
Comparative example 3
Prepared according to the synthetic method of example 1 except that potassium chloride was replaced with hydrochloric acid.
Comparative example 4
Prepared according to the synthetic method of example 1, except that potassium chloride was replaced with cetyltrimethylammonium chloride (CTAC).
The SEM analysis of the products of step (1) in examples 1 and 2 and comparative examples 3 and 4 was performed to investigate the effect of using different chlorine sources on the morphology of the nanoplatelets, and the results are shown in fig. 4, in fig. 4: (a) KCl, (b) HCl, (c) CTAC, (d) NaCl; from SEM pictures, it is seen that both KCl and NaCl can be used to obtain BiOCl nanosheets with uniform morphology, and the centers of the nanosheets have defects; when hydrochloric acid and cetyltrimethylammonium chloride (CTAC) are used, the BiOCl nanosheet with a defect in the center and uniform morphology cannot be obtained. After further acid etching, the nanoplatelets obtained with hydrochloric acid and cetyltrimethylammonium chloride (CTAC) failed to form nanorings.
Application example 1
BiOCl-S and BiOCl-R in example 1, each 0.04g, were contacted with 40mL of an aqueous solution containing Methyl Orange (MO) (10mg/L) at 30 ℃ under light. The results are shown in FIG. 6, which is (a) a degradation curve of MO (10 mg/L); (b) when BiOCl-R (BiOCl nano-ring) is taken as a photocatalyst, the ultraviolet-visible spectrum of the MO solution is shown, and the photocatalytic duration corresponding to the curve from top to bottom in the graph is from short to long; as can be seen, the BiOCl-R nanoring sample shows higher photocatalytic activity, 100% of MO (10mg/L) can be completely degraded within 2 minutes under the irradiation of sunlight, and the degradation rate of the BiOCl-R nanoring is twice that of the nanosheet BiOCl-S.
The BiOCl nanorings in the examples 1-7 are also detected to have significantly better photocatalytic degradation efficiency than the nanosheets with no pores in the center.
Therefore, the BiOCl nano ring has better photocatalytic activity, and the method for degrading pollutants by photocatalysis has the characteristic of high efficiency.
Application example 2
BiOCl-S and BiOCl-R in example 1, each 0.04g, were contacted with 40mL of an aqueous solution containing Methyl Orange (MO) (30mg/L) at 30 ℃ under light. The results are shown in FIG. 7, which is (a) a degradation curve of MO (30 mg/L); (b) when BiOCl-R (BiOCl nano-ring) is taken as a photocatalyst, the ultraviolet-visible spectrum of the MO solution is shown, and the photocatalytic duration corresponding to the curve from top to bottom in the graph is from short to long; as can be seen, the BiOCl-R nanoring sample shows higher photocatalytic activity, 100% of MO (30mg/L) can be completely degraded within 10 minutes under the irradiation of sunlight, and the degradation efficiency of the BiOCl-R nanoring sample is obviously superior to that of a nanosheet BiOCl-S.
Application example 3
BiOCl-S and BiOCl-R in example 1, each 0.04g, were contacted with 40mL of an aqueous solution containing rhodamine B (RhB) (10mg/L) at 30 ℃ under light irradiation. The results are shown in FIG. 8, (a) degradation curve of RhB (10 mg/L); (b) when BiOCl-R (BiOCl nano-ring) is taken as a photocatalyst, the ultraviolet-visible spectrum of the RhB solution is shown, and the photocatalytic duration corresponding to the curve from top to bottom in the graph is from short to long; as can be seen, the BiOCl-R nanoring sample shows higher photocatalytic activity, 100% of RhB (10mg/L) can be completely degraded within 4 minutes under the irradiation of sunlight, and the degradation rate of the BiOCl-R nanoring is 2.5 times that of the nanosheet BiOCl-S.
Application example 4
BiOCl-S and BiOCl-R in example 1, each 0.04g, were contacted with 40mL of an aqueous solution containing rhodamine B (RhB) (30mg/L) at 30 ℃ under light irradiation. The results are shown in FIG. 9, (a) degradation curve of RhB (30 mg/L); (b) when BiOCl-R (BiOCl nano-ring) is taken as a photocatalyst, the ultraviolet-visible spectrum of the RhB solution is shown, and the photocatalytic duration corresponding to the curve from top to bottom in the graph is from short to long; as can be seen, the BiOCl-R nanoring sample shows higher photocatalytic activity, 100% of RhB (10mg/L) can be completely degraded within 14 minutes under the irradiation of sunlight, and the catalytic activity of the BiOCl-R nanoring is obviously superior to that of the BiOCl-S nanosheet.
Application example 5
The catalytic activity of the BiOCl-R, BiOCl-S nanosheets was compared as in application example 1, except that MO was changed to 10mg/L phenol, and the results are shown in FIG. 10, where it can be seen that the catalytic activity of BiOCl-R was superior to that of the BiOCl-S sample, and phenol was degraded by the BiOCl-R catalyst by 90% in 40 minutes.
The BiOCl nanorings in the examples 1-7 are also detected to have significantly better photocatalytic degradation efficiency than the nanosheets with no pores in the center.
Therefore, the BiOCl nano ring has better photocatalytic activity, and the method for degrading pollutants by photocatalysis has the characteristic of high efficiency.
Application example 6
According to the method of application example 1, 0.04g of BiOCl-R sample in example 1 is applied to carry out repeated degradation on 40mL of 10mg/L methyl orange aqueous solution through photocatalytic degradation for 5 times, and the degradation efficiency after repeated utilization is observed, as shown in FIG. 11, the BiOCl nanoring of BiOCl-R has good stability and high repeated utilization rate in the photocatalytic process.
The diffraction patterns of the BiOCl-R photocatalyst before and after five times of circulation are analyzed by X-ray diffraction, and the results show that the diffraction peaks of the BiOCl-R photocatalyst before and after five times of circulation are basically changed little, so that the BiOCl-R photocatalyst is good in stability and high in repeated utilization rate in the photocatalytic process.
Similarly, the BiOCl nanorings in the embodiments 1-7 have the advantages of better stability and higher repeated utilization rate through detection.
Therefore, the BiOCl nanoring has excellent photocatalytic activity and reusability, is a ring-shaped result, is convenient to disperse in liquid, can reduce use conditions, and is a high-efficiency photocatalyst with practical value.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (15)
1. A method for degrading pollutants by using BiOCl nanorings is characterized by comprising the step of contacting the BiOCl nanorings with water containing pollutants under the condition of illumination; the BiOCl nano-ring is obtained by the following synthesis method, wherein the synthesis method comprises the following steps:
(1) will contain Bi3+、Cl-Carrying out heating reaction with a water solution of polyethylene glycol to obtain a BiOCl nanosheet;
(2) etching the BiOCl nanosheets in acid liquor;
wherein Cl is provided-The substance (b) is an alkali metal chloride salt;
wherein the acid solution is a nitric acid solution, a sulfuric acid solution or a mixed solution of nitric acid and sulfuric acid;
wherein, H in the acid liquor+The concentration of (A) is 0.8-1.5 mol/L; the etching time is 1-8 h;
wherein the contaminants comprise one or more of phenol, rhodamine B, and methyl orange.
2. A method of degrading a contaminant according to claim 1 wherein Bi is in an aqueous solution3+And Cl-The ratio of the amount of the substances in (A) is 1: 0.8-1.2.
3. A method of degrading a contaminant according to claim 2 wherein Bi is in aqueous solution3+The concentration of (A) is 20-50 mmol/L.
4. A method of degrading contaminants according to claim 3 wherein in the aqueous solution: relative to 1mmol of Bi3+The mass content of the polyethylene glycol is 0.05-0.1 g.
5. A method of degrading contaminants according to claim 1 wherein the conditions of the heating reaction include: the temperature is 140 ℃ and 180 ℃;
and/or the time is 8-15 h.
6. The method for degrading pollutants according to claim 1, wherein the amount of the acid solution is 100-600mL relative to 1g of BiOCl nanosheets;
the etching time is 3-6 h.
7. A method for degrading contaminants according to claim 6, wherein the etching comprises: ultrasonically dispersing the BiOCl nanosheets into acid liquor, and continuously stirring.
8. A method of degrading a contaminant according to any one of claims 1 to 7 wherein Bi is present3+、Cl-And polyethylene glycolIs obtained by the following method:
pre-dissolving alkali metal chloride and polyethylene glycol in water, ultrasonically dispersing, and then dropwise adding the mixture to the pre-dissolved Bi3+Mixing the above materials in water solution for 20-40 min.
9. A method of degrading a contaminant according to claim 8 wherein the aqueous solution having the alkali metal chloride salt and the polyethylene glycol pre-dissolved therein is pre-dissolved with the provided Bi3+The volume ratio of the aqueous solution of the substance (1: 0.8-1.2).
10. A method of degrading contaminants according to claim 8 further comprising the step of cooling the heated reaction product, washing it with distilled water and/or ethanol multiple times and drying it.
11. A method of degrading a contaminant according to claim 8 wherein Bi is provided3+The substance(s) is (are) bismuth nitrate and/or bismuth oxalate;
and/or the alkali metal chloride salt is at least one of sodium chloride, potassium chloride and lithium chloride;
and/or the polyethylene glycol has a number average molecular weight of not more than 10000.
12. A method of degrading contaminants according to claim 11 wherein the number average molecular weight of the polyethylene glycol is 3350-10000.
13. A method of degrading contaminants according to claim 8 wherein the concentration of contaminants in the contaminant-containing water is 10-30 mg/L.
14. A method of degrading contaminants according to claim 13, wherein the concentration of contaminants in the contaminant-containing water is 10-40mg/L and the amount of BiOCl photocatalyst having high photocatalytic activity is 100mg per 100mL of contaminant-containing water.
15. A method of degrading contaminants according to claim 13 wherein the conditions of contacting comprise: the contact time is 2-40 min; and/or the contact temperature is 30-50 ℃.
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| CN107840366A (en) * | 2017-11-29 | 2018-03-27 | 安徽师范大学 | Exposure（110）The BiOX micron bars and its synthetic method of crystal face |
| CN107857333A (en) * | 2017-11-29 | 2018-03-30 | 安徽师范大学 | The method of photocatalytic pollutant degradation |
| CN107876069A (en) * | 2017-11-29 | 2018-04-06 | 安徽师范大学 | BiOCl photochemical catalysts and its synthetic method with highlight catalytic active |
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| CN107840366A (en) * | 2017-11-29 | 2018-03-27 | 安徽师范大学 | Exposure（110）The BiOX micron bars and its synthetic method of crystal face |
| CN107857333A (en) * | 2017-11-29 | 2018-03-30 | 安徽师范大学 | The method of photocatalytic pollutant degradation |
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