CN108579770A - A method of carrying out degradation of contaminant using BiOCl nano-rings - Google Patents
A method of carrying out degradation of contaminant using BiOCl nano-rings Download PDFInfo
- Publication number
- CN108579770A CN108579770A CN201810460524.7A CN201810460524A CN108579770A CN 108579770 A CN108579770 A CN 108579770A CN 201810460524 A CN201810460524 A CN 201810460524A CN 108579770 A CN108579770 A CN 108579770A
- Authority
- CN
- China
- Prior art keywords
- biocl
- degradation
- rings
- nano
- solution
- 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
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000002063 nanoring Substances 0.000 title claims abstract description 78
- 230000015556 catabolic process Effects 0.000 title claims abstract description 76
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000000356 contaminant Substances 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 20
- 231100000719 pollutant Toxicity 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 238000010189 synthetic method Methods 0.000 claims abstract description 12
- 238000005286 illumination Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 75
- 229920001223 polyethylene glycol Polymers 0.000 claims description 46
- 239000002202 Polyethylene glycol Substances 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 26
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 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
- 239000000126 substance Substances 0.000 claims description 18
- 238000005530 etching Methods 0.000 claims description 17
- 239000003054 catalyst Substances 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
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000001103 potassium chloride Substances 0.000 claims description 11
- 235000011164 potassium chloride Nutrition 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000019441 ethanol Nutrition 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
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000002045 lasting effect Effects 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003403 water pollutant Substances 0.000 claims description 3
- 229960003742 phenol Drugs 0.000 claims description 2
- CEJZHMCGESPUGN-UHFFFAOYSA-N bismuth;oxalic acid Chemical compound [Bi].OC(=O)C(O)=O CEJZHMCGESPUGN-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 30
- 238000004064 recycling Methods 0.000 abstract description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 230000002950 deficient Effects 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- -1 alkali metal chlorine Salt Chemical class 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 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 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002562 Polyethylene Glycol 3350 Polymers 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
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- XWNOTOKFKBDMAP-UHFFFAOYSA-N [Bi].[N+](=O)(O)[O-] Chemical compound [Bi].[N+](=O)(O)[O-] XWNOTOKFKBDMAP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture 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
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/39—
-
- 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
Abstract
The step of the present invention relates to photocatalytic degradations, disclose a kind of method that BiOCl nano-rings carry out degradation of contaminant, and this method is included under illumination condition, BiOCl nano-rings and the water containing pollutant are contacted.The method and step of the degradation of contaminant is simple, and the BiOCl nano-rings have higher catalytic activity and catalytic stability, convenient for recycling, moreover, the BiOCl nano-rings synthetic method steps are simple, BiOCl nano-rings regular appearances that are easily controllable, obtaining have higher photocatalytic applications value.
Description
Technical field
The present invention relates to photocatalytic degradations, and in particular, to a kind of side carrying out degradation of contaminant using BiOCl nano-rings
Method.
Background technology
Fossil fuel is all indispensable in the links that we live, and the non-renewable and reserves that gradually decrease are
Through causing energy crisis, and also along with serious environmental pollution when consumption.Currently, Photocatalitic Technique of Semiconductor is considered
It is to solve the more promising technology of both of these problems.
In recent years, the controlledly synthesis of the new patterns of BiOCl and its photocatalytic activity research cause the great interest of people, main
It wants the reason is that BiOCl is as a kind of important conductor photocatalysis material in bismuth based compound, by bismuth oxygen layer [Bi2O2]2+With it is double
[Cl]-Sheath is alternately arranged along c-axis direction and constitutes unique layer structure, and this layer structure can be in [Bi2O2]2+Layer and
[Cl]-The separation that internal electric field is conducive to photo-generate electron-hole pair is formed between layer, to have high catalytic performance.
But report at present it is mostly be BiOCl nanometer sheets, hierarchical structure patterns and their photocatalysis such as micron ball
Activity.And cyclic annular nanometer sheet (also referred to as nano-rings) passes through because its center is easy to fluid, is on the one hand conducive to point of nano material
It dissipates, convenient for application；On the other hand it also will increase and the contact area of the fluid containing pollutant, the property of promotion BiOCl nanometer sheets
Energy.However, because material such as forward grows at the reasons to nanometer sheet in the synthesis process, cause nano-rings synthesis difficult, it is therefore, existing at present
Having technology does not have the report of BiOCl ring-type nanometer sheets.
Invention content
The object of the present invention is to provide a kind of method carrying out degradation of contaminant using BiOCl nano-rings, degradation of contaminant
Method and step it is simple, and the BiOCl nano-rings have higher catalytic activity and catalytic stability, convenient for recycle, no
Easily controllable only in this way, the BiOCl nano-rings synthetic method steps are simple, obtained BiOCl nano-rings regular appearances have
Higher photocatalytic applications value.
To achieve the goals above, the present invention provides it is a kind of using BiOCl nano-rings carry out degradation of contaminant method,
Under illumination condition, the step of BiOCl nano-rings and the water containing pollutant are contacted；Wherein, BiOCl nano-rings pass through
Following synthetic method obtains, wherein the synthetic method includes the following steps：(1) Bi will be contained3+、Cl-With the water of polyethylene glycol
Solution carries out heating reaction, obtains BiOCl nanometer sheets；(2) BiOCl nanometer sheets are etched in acid solution；Wherein, Cl is provided-'s
Substance is alkali metal chlorizated salt；Wherein, acid solution is the mixed solution of salpeter solution, sulfuric acid solution or nitric acid and sulfuric acid.
Through the above technical solutions, the present invention has obtained BiOCl nano-rings, BiOCl nano-rings synthesis side has not only been filled up
The blank in face, and the obtained more conventional center of BiOCl nano-rings not apertures BiOCl nanometer sheets with higher photocatalysis live
Property.Moreover, the synthetic method step is simple, easily controllable, obtained BiOCl nano-rings regular appearances, not only have compared with
High scientific research value also has higher photocatalytic applications value.Moreover, the method and step of the degradation of contaminant is simple,
And BiOCl nano-rings are applied to the degradation of pollutant for the first time, which has higher catalytic activity and catalysis steady
It is qualitative, convenient for recycling, there is higher photocatalytic applications value.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is influence of the different time etching to BiOCl nano-rings：(a) the SEM figures of 3h etchings, (b) SEM of 6h etchings
Figure；(c) the TEM figures of 6h etchings；(d) different time etches corresponding XRD diagram；
Fig. 2 is influences of the PEG of different molecular weight to BiOCl nanometer sheets：(a) PEG-3350, (b) PEG-4000, (c)
PEG-6000, (d) PEG-10000；
Fig. 3 is influence of the different acid solutions to etching BiOCl nanometer sheets：(a) HF solution, (b) acetic acid solution, (c) sulfuric acid is molten
Liquid, (d) salpeter solution；
Influence of the difference chlorine sources Fig. 4 to synthesis BiOCl nanometer sheets：(a)KCl,(b)HCl,(c)CTAC,(d)NaCl；
Fig. 5 is influences of the PEG of different amounts to synthesis BiOCl nanometer sheets：(a) 0.05g, (b) 0.1g, (c) 0.15g,
(d)0.2g；
Fig. 6 is the photocatalysis analysis chart in application examples 1：(a) degradation curve of MO (10mg/L)；(b) with BiOCl nano-rings
For photochemical catalyst when, the UV-visible spectrum of MO solution；
Fig. 7 is the photocatalysis analysis chart in application examples 2：(a) degradation curve of MO (30mg/L)；(b) with BiOCl nano-rings
For photochemical catalyst when, the UV-visible spectrum of MO solution；
Fig. 8 is the photocatalysis analysis chart in application examples 3：(a) degradation curve of RhB (10mg/L)；(b) with BiOCl nanometers
When ring is photochemical catalyst, the UV-visible spectrum of RhB solution；
Fig. 9 is the photocatalysis analysis chart in application examples 4：(a) degradation curve of RhB (30mg/L)；(b) with BiOCl nanometers
When ring is photochemical catalyst, the UV-visible spectrum of RhB solution；
Figure 10 is the degradation curve of phenol (10mg/L) in the presence of the different catalysts in application examples 5；
Figure 11 is BiOCl nano-rings in application examples 6 to 10mg/L Photocatalytic Degradation of Methyl Orange recycling rate of waterused figures.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of methods carrying out degradation of contaminant using BiOCl nano-rings, will under illumination condition
The step of BiOCl nano-rings are contacted with the water containing pollutant；Wherein, BiOCl nano-rings are synthesized by the following way method and obtain
It arrives, wherein the synthetic method includes the following steps：(1) Bi will be contained3+、Cl-With the aqueous solution of polyethylene glycol heat anti-
It answers, obtains BiOCl nanometer sheets；(2) BiOCl nanometer sheets are etched in acid solution；Wherein, Cl is provided-Substance be alkali metal chlorine
Salt dissolving；Wherein, acid solution is the mixed solution of salpeter solution, sulfuric acid solution or nitric acid and sulfuric acid.
Through the above technical solutions, the present invention has obtained BiOCl nano-rings, BiOCl nano-rings synthesis side has not only been filled up
The blank in face, and the obtained more conventional center of BiOCl nano-rings not apertures BiOCl nanometer sheets with higher photocatalysis live
Property.Moreover, the synthetic method step is simple, easily controllable, obtained BiOCl nano-rings regular appearances, not only have compared with
High scientific research value also has higher photocatalytic applications value.Moreover, the method and step of the degradation of contaminant is simple,
And BiOCl nano-rings are applied to the degradation of pollutant for the first time, which has higher catalytic activity and catalysis steady
It is qualitative, convenient for recycling, there is higher photocatalytic applications value.
In the above-mentioned technical solutions, for Bi in aqueous solution3+And Cl-The ratio between the amount of substance, can in wider range into
Row adjustment, as long as meeting the requirement of above-mentioned technical proposal, can be obtained target BiOCl nano-rings.It is a kind of more excellent in the present invention
In the embodiment of choosing, in order to obtain the defective nanometer sheet in center after step (1) and further obtain regular appearance
BiOCl nano-rings improve combined coefficient, further increase the stability of degradation efficiency and degradation, it is preferable that Bi in aqueous solution3+
And Cl-The ratio between the amount of substance be 1:0.8-1.2.
Further, for Bi in aqueous solution3+Concentration, in above-mentioned Bi3+And Cl-The feelings that determine of the ratio between the amount of substance
It under condition, can be adjusted in wider range, in order to obtain the BiOCl nano-rings of regular appearance, improve combined coefficient, further
Improve the stability of degradation efficiency and degradation, it is preferable that Bi in aqueous solution3+A concentration of 20-50mmol/L.
Similarly, it for the additive amount of polyethylene glycol, can be adjusted in wider range, it has been investigated that, with poly- second
The increase of glycol dosage has various sizes of nanometer sheet to coexist, but the influence unobvious of the thickness and central defect to nanometer sheet.
In order to reduce synthesis cost, combined coefficient is improved, further increases the stability of degradation efficiency and degradation, it is preferable that aqueous solution
In：Bi relative to 1mmol3+, the mass content of polyethylene glycol is 0.05-0.1g.
In addition, for the condition of heating reaction, it can be adjusted in wider range, in order to obtain regular appearance
BiOCl nano-rings improve combined coefficient, further increase the stability of degradation efficiency and degradation, it is preferable that heat the item of reaction
Part includes：Temperature is 140-180 DEG C.
Certainly, it for the time of heating reaction, can be adjusted in wider range, in order to obtain regular appearance
BiOCl nano-rings, improve combined coefficient, further increase the stability of degradation efficiency and degradation, it is preferable that heat reaction when
Between be 8-15h.
Under the premise of acid solution is the mixed solution of salpeter solution, sulfuric acid solution or nitric acid and sulfuric acid, for H in acid solution+
Concentration, can be adjusted in wider range, in order to obtain the BiOCl nano-rings of regular appearance, improve combined coefficient, into one
Step improves the stability of degradation efficiency and degradation, it is preferable that H in acid solution+A concentration of 0.8-1.5mol/L.
Certainly, it for the dosage of acid solution, can be adjusted in wider range, in order to improve reaction efficiency, further carry
The stability of high degradation efficiency and degradation, it is preferable that relative to 1g BiOCl nanometer sheets, the dosage of acid solution is 100-600mL.
Moreover, it for etch period, can be adjusted in wider range, in order to obtain the nanometer of regular appearance
Ring further increases the stability of degradation efficiency and degradation, it is preferable that etch period 1-8h.
It is further preferred that BiOCl nano-rings of regular appearance in order to obtain, further increase degradation efficiency and degradation
Stability, it is preferable that etch period 3-6h.
It for the operating mode of etching, can be adjusted in wider range, surface can be used by the nanometer sheet in step (1)
It coats the various ways such as acid solution, immersion to carry out, in a kind of preferred embodiment of the present invention, in order to improve etching efficiency and obtain
To the nano-rings of regular appearance, the stability of degradation efficiency and degradation is further increased, it is preferable that the specific steps packet of etching
It includes：By in BiOCl nanometer sheet ultrasonic disperses to acid solution, persistently stir.
In technical solution above, for containing Bi in step (1)3+、Cl-It was formed with the aqueous solution of polyethylene glycol
Journey can be adjusted in wider range, such as can will also provide Bi directly by material dissolution in a water3+Substance,
Alkali metal chlorizated salt and polyethylene glycol difference are soluble in water, then three is mixed, and can also dissolve, then remix two-by-two,
Realize the present invention.Certainly for mixed process, the present invention is also not required, and can directly be toppled over, and can also be added dropwise, and can be achieved
The present invention.
In a kind of more preferred embodiment of the present invention, defective BiOCl nanometer sheets in center in order to obtain, more into
One step is conducive to obtain the BiOCl nano-rings of regular appearance, further increases the stability of degradation efficiency and degradation, it is preferable that
Contain Bi3+、Cl-It is obtained in the following manner with the aqueous solution of polyethylene glycol：Alkali metal chlorizated salt and polyethylene glycol are pre-dissolved in
In water, then ultrasonic disperse is added dropwise to predissolve and is provided with Bi3+Substance aqueous solution in, mix 20-40min.
Further, Bi is provided with dissolved with the aqueous solution of alkali metal chlorizated salt and polyethylene glycol and predissolve in advance3+Object
The volume ratio of the aqueous solution of matter can be adjusted in wider range, in order to obtain the defective BiOCl nanometer sheets in center, more into
One step is conducive to obtain the BiOCl nano-rings of regular appearance, further increases the stability of degradation efficiency and degradation, it is preferable that
In advance Bi is provided with dissolved with the aqueous solution of alkali metal chlorizated salt and polyethylene glycol and predissolve3+The volume ratio of aqueous solution of substance be
1:0.8-1.2。
In a kind of preferred embodiment of the present invention, in order to improve reaction efficiency, yield is improved, degradation is further increased
The stability of efficiency and degradation, it is preferable that further include being cooled down to the product after heating reaction in step (1), use distilled water
And/or ethyl alcohol repeatedly washs and dry step.
In the above-mentioned technical solutions, those skilled in the art are for providing Bi3+Substance can be adjusted in wider range
It is whole, in order to further make raw material simple and easy to get, further increase the stability of degradation efficiency and degradation, it is preferable that provide Bi3+'s
Substance is bismuth nitrate and/or bismuth oxalate.
In the above-mentioned technical solutions, for alkali metal chlorizated salt can there are many selections, such as magnesium chloride, calcium chloride, chlorine
Change aluminium, potassium chloride etc., in order to further make raw material simple and easy to get and improve reaction efficiency and yield, further increases degradation efficiency
With the stability of degradation, it is preferable that alkali metal chlorizated 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 wider range, through research, with polyethylene glycol point
The increase of son amount, nanometer sheet become closer to square, but little on the influence of center rejected region, and explanation will obtain nano-rings
The molecular weight of shape structure, PEG is not major influence factors.In order to further make raw material simple and easy to get and improve reaction efficiency and production
Rate further increases the stability of degradation efficiency and degradation, it is preferable that the number-average molecular weight of polyethylene glycol is 3350-10000.
For the method for the photocatalytic pollutant degradation applicable object there are many kinds of, implement of the invention a kind of preferred
In mode, for the pollutant in fast degradation water, and the BiOCl photochemical catalyst recycling rates of waterused are improved, it is preferable that the dirt
It includes one or more in phenol, rhodamine B and methyl orange to contaminate object.
In a kind of preferred embodiment of the present invention, for the pollutant in fast degradation water, and improves the BiOCl and receive
The recycling rate of waterused of meter Huan, it is preferable that a concentration of 10-30mg/L of the water pollutant containing pollutant.
The dosage of BiOCl nano-rings can be adjusted flexibly, in order on the basis of with high degradation efficiency, save degradation
Cost, it is preferable that relative to the water containing pollutant of 100mL, the dosage of the BiOCl photochemical catalysts with highlight catalytic active
For 100mg.
It for the contact conditions that BiOCl nano-rings are contacted with the water containing pollutant, can be adjusted flexibly, in order to subtract
Of low pollution object remains, it is preferable that time of contact 2-40min.
In addition, can be not required for the Contact Temperature that BiOCl nano-rings are contacted with the water containing pollutant, it is
Raising degradation efficiency, it is preferable that Contact Temperature is 30-50 DEG C.
The present invention will be described in detail by way of examples below.
Embodiment 1
By 1mmol Bi (NO3)3·5H2In O ultrasonic dissolutions to 15mL distilled water, it is labeled as solution A.1mmol KCl are added
Into 15mL distilled water, 0.1g polyethylene glycol (PEG-6000) is added after ultrasonic dissolution, ultrasonic disperse is labeled as B solution.B is molten
Drop is added in solution A, then stirs mixed solution 30 minutes.It is finally transferred in the autoclave of 40mL, 160 DEG C add
Heat 12 hours.After reaction, cooled to room temperature, product distilled water, ethyl alcohol wash, dry to constant weight, Product Labeling
For BiOCl-S.
Above-mentioned synthetic product is weighed into 0.03g ultrasonic disperses to 15mL 1molL-1HNO3In solution, continuously stir
6h obtains final product, Product Labeling BiOCl-R.
Embodiment 2
(1) bismuth nitrate, sodium chloride and polyethylene glycol (number-average molecular weight 3350) is soluble in water, Bi will be contained3+、Cl-
140 DEG C of heating reaction 15h are carried out at the aqueous solution of polyethylene glycol, obtain BiOCl nanometer sheets；Bi in aqueous solution3+It is a concentration of
20mmol/L, Bi in aqueous solution3+And Cl-The ratio between the amount of substance be 1:0.8；Bi relative to 1mmol3+, the matter of polyethylene glycol
Amount content is 0.05g；
Product after heating reaction in step (1) is cooled down, is repeatedly washed with distilled water and ethyl alcohol and dry；
(2) lasting to stir by BiOCl nanometer sheets ultrasonic disperse in the salpeter solution of 0.8mol/L, etch 3h；Relative to
The dosage of 1g BiOCl nanometer sheets, salpeter solution is 100mL.
Embodiment 3
(1) bismuth nitrate, potassium chloride and polyethylene glycol (number-average molecular weight 10000) is soluble in water, Bi will be contained3+、Cl-
180 DEG C of heating reaction 8h are carried out at the aqueous solution of polyethylene glycol, obtain BiOCl nanometer sheets；Bi in aqueous solution3+It is a concentration of
50mmol/L, Bi in aqueous solution3+And Cl-The ratio between the amount of substance be 1:1.2；Bi relative to 1mmol3+, the matter of polyethylene glycol
Amount content is 0.1g；
Product after heating reaction in step (1) is cooled down, is repeatedly washed with ethyl alcohol and dry；
(2) lasting to stir by BiOCl nanometer sheets ultrasonic disperse in the sulfuric acid solution of 0.5mol/L, etch 8h；Relative to
The dosage of 1g BiOCl nanometer sheets, salpeter solution is 600mL.
Embodiment 4
(1) bismuth oxalate, potassium chloride and polyethylene glycol (number-average molecular weight 4000) is soluble in water, Bi will be contained3+、Cl-
160 DEG C of heating reaction 10h are carried out at the aqueous solution of polyethylene glycol, obtain BiOCl nanometer sheets；Bi in aqueous solution3+It is a concentration of
30mmol/L, Bi in aqueous solution3+And Cl-The ratio between the amount of substance be 1:1；Bi relative to 1mmol3+, the quality of polyethylene glycol
Content is 0.05g；
Product after heating reaction in step (1) is cooled down, is repeatedly washed with distilled water and dry；
(2) lasting to stir by BiOCl nanometer sheets ultrasonic disperse in the salpeter solution of 1mol/L, etch 1h；Relative to 1g
The dosage of BiOCl nanometer sheets, salpeter solution is 300mL.
Embodiment 5
BiOCl nano-rings are synthesized according to the method for embodiment 1, the difference is that etch period is 3h.To embodiment 1 and implement
Gained BiOCl nano-rings are detected in example 5, the result is shown in Figure 1, in Fig. 1：(a) it is the BiOCl for etching 3h in embodiment 5 and obtaining
SEM (scanning electron microscope) figure of nano-rings (b) etches the BiOCl nano-rings SEM figures that 6h is obtained in embodiment 1；(c) in embodiment 1
TEM (transmission electron microscope) figure for the BiOCl nano-rings that etching 6h is obtained；(d) BiOCl nanometers in embodiment 5 and embodiment 1
Ring corresponding XRD (X-ray diffraction) figure, to study influence of the etch period to sample topography.
Found out by SEM figures in Fig. 1, sample is nanometer cyclic structure, and nanometer sheet centre bore is significantly greater than etching after etching 6h
3h.TEM figures further confirm that sample is nanometer cyclic structure.Spreading out for etched rear sample is can be seen that from the XRD spectrum provided
It penetrates peak and both corresponds to BiOCl (JCPDS No.06-0249), and do not detect other impurity peaks, illustrate that synthetic product is purer
Free from admixture.
Similarly, there is nanometer cyclic structure, warp and BiOCl in the SEM figures of the BiOCl nano-rings in embodiment 2-4
(JCPDS No.06-0249) is compareed, and does not detect other impurity peaks.
It is presumed that reaction mechanism of the invention is：Bismuth oxalate, bismuth nitrate are susceptible to hydrolysis in water, generate alkali formula nitric acid
Bismuth, while a large amount of hydrogen ions are discharged, so that solution is in acidic environment.After the polyglycol solution of alkali metal chlorizated salt is added, chlorine
Ion attack basic bismuth nitrate generates BiOCl nucleus.Hydrogen ion is adsorbed on BiOCl nucleus (001) crystalline substance by H-O keys in solution
Face, then anisotropic growth is the laminated structure of exposure (001) crystal face.PEG is nonionic surfactant, passes through hydroxyl oxygen
Atom is coordinated with bismuth, is adsorbed on BiOCl (001) crystal face, ultimately forms the defective BiOCl nanometer sheets of (001) crystal face.When
Defective BiOCl is put into HNO3Or in sulfuric acid solution after, thus rejected region is opened due to higher reactivity, etching reaction
Begin.As etch period extends, etching degree is deepened, and BiOCl nano-rings are gradually formed.
Embodiment 6
It is prepared according to the method for embodiment 1, the difference is that polyethylene (PEG-6000) is changed to PEG- respectively
3350, PEG-4000, PEG-10000, i.e. PEG number-average molecular weights are respectively 3350,4000,10000.
To the carry out sem analysis for the BiOCl nanometer sheets that step (1) obtains, Fig. 2 is obtained, in Fig. 2：(a) PEG-3350, (b)
PEG-4000, (c) PEG-6000, (d) PEG-10000 study the PEG (3350-10000) of different molecular weight to nanometer sheet with this
The influence at central defect position.As seen from Figure 2, with the increase of PEG molecular weight, nanometer sheet becomes closer to square, but
Center rejected region is influenced little.Illustrate to obtain a nanometer cyclic structure, the molecular weight of PEG is not major influence factors.
After etched, BiOCl nano-rings can be obtained.
Embodiment 7
It is prepared according to the method for embodiment 1, the difference is that the dosage of polyethylene (PEG-6000) is replaced with respectively
0.1g, 0.15g, 0.2g.
To the carry out sem analysis for the BiOCl nanometer sheets that step (1) obtains, Fig. 5 is obtained, the dosage point of PEG-6000 in Fig. 5
It is not：(a) 0.05g, (b) 0.1g, (c) 0.15g, (d) 0.2g, to study influence of the different PEG dosages to nanometer sheet pattern.From
SEM figures can be seen that, as PEG dosages less (0.05g, 0.1g), the more uniform square nanometer sheet of appearance and size can be obtained.
With the increase of dosage, there is various sizes of nanometer sheet to coexist, but the influence unobvious of the thickness and central defect to nanometer sheet.
After acid solution etches, nano-rings can be obtained.
Comparative example 1
It is prepared according to the synthetic method of embodiment 1, unlike, salpeter solution is replaced with into HF solution.
Comparative example 2
It is prepared according to the synthetic method of embodiment 1, unlike, salpeter solution is replaced with into acetic acid solution.
Through carrying out sem analysis to the product in embodiment 1, embodiment 3 and comparative example 1, comparative example 2, different acid solutions are obtained
(a concentration of 1molL of monoacid-1, a concentration of 0.51molL of sulfuric acid-1) SEM that nanometer sheet in step (1) etches is schemed,
The results are shown in Figure 3：(a) acid solution is HF solution, and (b) acid solution is acetic acid solution, and (c) acid solution is sulfuric acid solution, and (d) acid solution is nitre
Acid solution.Fig. 3 gives the BiOCl nanometer sheets under four kinds of different acid etches.It is found by Fig. 3, sample stirs in HF and acetic acid
After 6h, BiOCl nanometer sheets center is not etched, and keeps original state.After 6h being stirred in sulfuric acid and salpeter solution, the central part of piece
Divide and successfully etched, forms cyclic structure.Show that the BiOCl nanometer sheets presoma of this paper can be by sulfuric acid quarter, Nitric acid etching cyclization.
Comparative example 3
It is prepared according to the synthetic method of embodiment 1, unlike, potassium chloride is replaced with into hydrochloric acid.
Comparative example 4
It is prepared according to the synthetic method of embodiment 1, unlike, potassium chloride is replaced with into hexadecyltrimethylammonium chloride
(CTAC)。
Sem analysis, research are carried out through the product to the step (1) in embodiment 1, embodiment 2 and comparative example 3, comparative example 4
Influence using different chlorine sources to nanometer sheet pattern, the results are shown in Figure 4, in Fig. 4：(a) KCl, (b) HCl, (c) CTAC, (d)
NaCl；Find out from SEM figures, the uniform BiOCl nanometer sheets of pattern can be obtained using KCl and NaCl, and piece center is defective；
And when with hydrochloric acid and hexadecyltrimethylammonium chloride (CTAC), then it cannot get the BiOCl that piece center is defective and pattern is uniform
Nanometer sheet.After further acid etching, the nanometer sheet that is obtained with hydrochloric acid and hexadecyltrimethylammonium chloride (CTAC), which cannot be formed, to be received
Meter Huan.
Application examples 1
In the case where temperature is 30 DEG C and illumination condition by the BiOCl-S and each 0.04g of BiOCl-R in embodiment 1, respectively with
Aqueous solution 40mL containing methyl orange (MO) (10mg/L) is contacted.The results are shown in Figure 6, the degradation of (a) MO (10mg/L)
Curve；(b) when being photochemical catalyst with BiOCl-R (BiOCl nano-rings), the UV-visible spectrum of MO solution, in figure curve from
The corresponding photocatalysis duration of top to bottm is from short to long；As it can be seen that BiOCl-R nano-rings samples show higher photocatalytic activity,
100% MO (10mg/L) can be degradable in 2 minutes under sunlight irradiation, and BiOCl-R nano-rings degradation rates are
Twice of nanometer sheet BiOCl-S.
After testing, the BiOCl nano-rings in embodiment 1-7 equally have the light for being substantially better than the center not nanometer sheet of apertures
Catalytic degradation efficiency.
As it can be seen that the BiOCl nano-rings of the present invention have preferable photocatalytic activity, photocatalytic pollutant degradation of the invention
Method have the characteristics that it is efficient.
Application examples 2
In the case where temperature is 30 DEG C and illumination condition by the BiOCl-S and each 0.04g of BiOCl-R in embodiment 1, respectively with
Aqueous solution 40mL containing methyl orange (MO) (30mg/L) is contacted.The results are shown in Figure 7, the degradation of (a) MO (30mg/L)
Curve；(b) when being photochemical catalyst with BiOCl-R (BiOCl nano-rings), the UV-visible spectrum of MO solution, in figure curve from
The corresponding photocatalysis duration of top to bottm is from short to long；As it can be seen that BiOCl-R nano-rings samples show higher photocatalytic activity,
100% MO (30mg/L) can be degradable in 10 minutes under sunlight irradiation, hence it is evident that is better than the drop of nanometer sheet BiOCl-S
Solve efficiency.
Application examples 3
In the case where temperature is 30 DEG C and illumination condition by the BiOCl-S and each 0.04g of BiOCl-R in embodiment 1, respectively with
Aqueous solution 40mL containing rhodamine B (RhB) (10mg/L) is contacted.The results are shown in Figure 8, the drop of (a) RhB (10mg/L)
Solution curve；(b) when being photochemical catalyst with BiOCl-R (BiOCl nano-rings), the UV-visible spectrum of RhB solution is bent in figure
Corresponding photocatalysis duration is from short to long from top to bottom for line；It lives as it can be seen that BiOCl-R nano-rings samples show higher photocatalysis
Property, 100% RhB (10mg/L) can be degradable in 4 minutes under sunlight irradiation, and BiOCl-R nano-rings degradation speed
Rate is 2.5 times of nanometer sheet BiOCl-S.
Application examples 4
In the case where temperature is 30 DEG C and illumination condition by the BiOCl-S and each 0.04g of BiOCl-R in embodiment 1, respectively with
Aqueous solution 40mL containing rhodamine B (RhB) (30mg/L) is contacted.The results are shown in Figure 9, the drop of (a) RhB (30mg/L)
Solution curve；(b) when being photochemical catalyst with BiOCl-R (BiOCl nano-rings), the UV-visible spectrum of RhB solution is bent in figure
Corresponding photocatalysis duration is from short to long from top to bottom for line；It lives as it can be seen that BiOCl-R nano-rings samples show higher photocatalysis
Property, 100% RhB (10mg/L) can be degradable in 14 minutes under sunlight irradiation, and the catalysis of BiOCl-R nano-rings
Activity is substantially better than BiOCl-S nanometer sheets.
Application examples 5
The catalytic activity of BiOCl-R, BiOCl-S nanometer sheet is compareed according to application examples 1, unlike, MO is become
More 10mg/L phenol, the results are shown in Figure 10, it is seen then that the catalytic activity of BiOCl-R is better than BiOCl-S samples, in 40 minutes
Phenol is by BiOCl-R catalyst degradations 90%.
After testing, the BiOCl nano-rings in embodiment 1-7 equally have the light for being substantially better than the center not nanometer sheet of apertures
Catalytic degradation efficiency.
As it can be seen that the BiOCl nano-rings of the present invention have preferable photocatalytic activity, photocatalytic pollutant degradation of the invention
Method have the characteristics that it is efficient.
Application examples 6
According to the method for application examples 1, using the BiOCl-R samples in 0.04g embodiments 1 to 40mL10mg/L methyl orange water
Solution photocatalytic degradation carries out repeating to degrade 5 times, the degradation efficiency after observation recycling, as a result as shown in figure 11, it is seen then that
Stability is preferable in the photocatalytic process for the BiOCl nano-rings of BiOCl-R, and recycling rate of waterused is higher.
Five forward and backward diffraction patterns of cycle are being carried out using X-ray diffraction analysis BiOCl-R photochemical catalysts, are being found
BiOCl-R photochemical catalysts recycle for five times forward and backward diffraction maximum change substantially it is small, it is seen then that BiOCl-R photochemical catalysts are urged in light
Stability is preferable during change, and recycling rate of waterused is higher.
Similarly, after testing, the BiOCl nano-rings in embodiment 1-7 all have that stability is preferable, and recycling rate of waterused is higher
A little.
It can be seen that it is ring that the BiOCl nano-rings of the present invention, which have excellent photocatalytic activity and reusing and its,
Shape can reduce use condition, therefore, this product is that there is the efficiency light of practical value to urge as a result, convenient for disperseing in a liquid
Agent.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of method carrying out degradation of contaminant using BiOCl nano-rings, which is characterized in that under illumination condition, by BiOCl
The step of nano-rings are contacted with the water containing pollutant；Wherein, BiOCl nano-rings are synthesized by the following way method and obtain,
In, the synthetic method includes the following steps：
(1) Bi will be contained3+、Cl-Heating reaction is carried out with the aqueous solution of polyethylene glycol, obtains BiOCl nanometer sheets；
(2) BiOCl nanometer sheets are etched in acid solution；
Wherein, Cl is provided-Substance be alkali metal chlorizated salt；
Wherein, acid solution is the mixed solution of salpeter solution, sulfuric acid solution or nitric acid and sulfuric acid.
2. the method for degradation of contaminant according to claim 1, wherein Bi in aqueous solution3+And Cl-The ratio between the amount of substance
It is 1:0.8-1.2；
Preferably, Bi in aqueous solution3+A concentration of 20-50mmol/L.
It is further preferred that in aqueous solution：Bi relative to 1mmol3+, the mass content of polyethylene glycol is 0.05-0.1g.
3. the method for degradation of contaminant according to claim 1, wherein the condition for heating reaction includes：Temperature is 140-
180℃；
And/or time 8-15h.
4. the method for degradation of contaminant according to claim 1, wherein H in acid solution+A concentration of 0.8-1.5mol/L；Its
In, relative to 1g BiOCl nanometer sheets, the dosage of acid solution is 100-600mL；
And/or etch period 1-8h；
Preferably, etch period 3-6h.
5. the method for degradation of contaminant according to claim 4, wherein the specific steps of etching include：By BiOCl nanometers
It is lasting to stir in piece ultrasonic disperse to acid solution.
6. according to the method for claim 1-5 any one of them degradation of contaminant, wherein contain Bi3+、Cl-And polyethylene glycol
Aqueous solution obtain in the following manner：
Alkali metal chlorizated salt and polyethylene glycol are pre-dissolved in water, ultrasonic disperse, are then added dropwise to predissolve and are provided with Bi3+Object
In the aqueous solution of matter, 20-40min is mixed；
Preferably, Bi is provided with dissolved with the aqueous solution of alkali metal chlorizated salt and polyethylene glycol and predissolve in advance3+Substance it is water-soluble
The volume ratio of liquid is 1:0.8-1.2.
7. the method for degradation of contaminant according to claim 6, wherein further include cold to the product progress after heating reaction
But, with distilled water and/or the multiple washing of ethyl alcohol and dry step.
8. the method for degradation of contaminant according to claim 6, wherein provide Bi3+Substance be bismuth nitrate and/or oxalic acid
Bismuth；
And/or alkali metal chlorizated salt is at least one of sodium chloride, potassium chloride and lithium chloride；
And/or the number-average molecular weight of polyethylene glycol is not more than 10000；
Preferably, the number-average molecular weight of polyethylene glycol is 3350-10000.
9. the method for degradation of contaminant according to claim 6, wherein the water pollutant containing pollutant it is a concentration of
10-30mg/L；
Preferably, the pollutant includes one or more in phenol, rhodamine B and methyl orange；
Preferably, a concentration of 10-40mg/L of the water pollutant containing pollutant, relative to 100mL containing pollutant
The dosage of water, the BiOCl photochemical catalysts with highlight catalytic active is 100mg.
10. the method for degradation of contaminant according to claim 9, wherein the condition of contact includes：Time of contact is 2-
40min；And/or Contact Temperature is 30-50 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810460524.7A CN108579770B (en) | 2018-05-15 | 2018-05-15 | Method for degrading pollutants by using BiOCl nanoring |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810460524.7A CN108579770B (en) | 2018-05-15 | 2018-05-15 | Method for degrading pollutants by using BiOCl nanoring |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108579770A true CN108579770A (en) | 2018-09-28 |
| CN108579770B CN108579770B (en) | 2020-03-24 |
Family
ID=63631201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810460524.7A Active CN108579770B (en) | 2018-05-15 | 2018-05-15 | Method for degrading pollutants by using BiOCl nanoring |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108579770B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225282A (en) * | 2018-10-24 | 2019-01-18 | 福建师范大学 | A kind of p-n junction CdWO4/ BiOCl heterojunction photocatalyst, preparation method and its usage |
| CN110302811A (en) * | 2019-08-05 | 2019-10-08 | 南京工业大学 | A kind of bismuthyl chloride flaky material and preparation method and application with rayed split |
| CN110302826A (en) * | 2019-06-21 | 2019-10-08 | 长沙学院 | Basic bismuth nitrate and iodine oxygen bismuth composite photo-catalyst and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464175A (en) * | 2013-09-29 | 2013-12-25 | 南开大学 | Method for preparing visible light photocatalyst BiOCl nanometer sheet |
| 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 |
-
2018
- 2018-05-15 CN CN201810460524.7A patent/CN108579770B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464175A (en) * | 2013-09-29 | 2013-12-25 | 南开大学 | Method for preparing visible light photocatalyst BiOCl nanometer sheet |
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225282A (en) * | 2018-10-24 | 2019-01-18 | 福建师范大学 | A kind of p-n junction CdWO4/ BiOCl heterojunction photocatalyst, preparation method and its usage |
| CN110302826A (en) * | 2019-06-21 | 2019-10-08 | 长沙学院 | Basic bismuth nitrate and iodine oxygen bismuth composite photo-catalyst and its preparation method and application |
| CN110302826B (en) * | 2019-06-21 | 2022-04-15 | 长沙学院 | Basic bismuth nitrate and bismuth oxyiodide composite photocatalyst and preparation method and application thereof |
| CN110302811A (en) * | 2019-08-05 | 2019-10-08 | 南京工业大学 | A kind of bismuthyl chloride flaky material and preparation method and application with rayed split |
| CN110302811B (en) * | 2019-08-05 | 2020-07-31 | 南京工业大学 | Bismuth oxychloride sheet material with radial cracks and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108579770B (en) | 2020-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108502926B (en) | BiOCl nano-rings and its synthetic method | |
| CN105040025B (en) | Compound porous pucherite optoelectronic pole of double-metal hydroxide and preparation method thereof | |
| CN102963934B (en) | Preparation method of bismuth tungstate quantum dot and preparation method of bismuth tungstate quantum dot-graphene composite material | |
| CN108579770A (en) | A method of carrying out degradation of contaminant using BiOCl nano-rings | |
| CN109092343A (en) | A kind of visible-light response type g-C3N4/BiVO4The preparation method and applications of heterojunction material | |
| CN108435194B (en) | Bismuth ferrite/bismuth tungstate heterojunction photocatalysis material and preparation method thereof | |
| CN104108753A (en) | Preparation for visible-light responsible BiVO4 catalyst | |
| CN105772048A (en) | Molybdenum carbide and titanium dioxide compounded photocatalytic water-decomposing hydrogen production catalyst and preparation method of molybdenum carbide and titanium dioxide compounded photocatalytic water-decomposing hydrogen production catalyst | |
| CN107162051B (en) | The preparation method of flower-shaped BiOCl photochemical catalyst and BiOCl photochemical catalyst obtained and application | |
| CN105688899A (en) | Preparation method and application for ternary composite photocatalyst | |
| CN105478142A (en) | Indium-sulfide mesoporous hollow microsphere photocatalyst, and preparation method and uses thereof | |
| CN105645459A (en) | Surface modified urchin-shaped ZnO/TiO2 composite material and preparation method thereof | |
| CN105126885A (en) | Composite visible light photocatalytic material and preparation method and application thereof | |
| CN106390986A (en) | Preparation method of bismuth vanadate/strontium titanate composite photocatalyst | |
| CN107876069A (en) | BiOCl photochemical catalysts and its synthetic method with highlight catalytic active | |
| CN104772134A (en) | Method for massively preparing mesoporous BiVO4/Bi2O3 composite micro-rod p-n heterojunction photocatalyst | |
| CN104128180B (en) | The method of Electron Beam Irradiation synthesis cuprous oxide/Graphene photocatalysis composite nano materials | |
| CN105833860A (en) | CQDs/Bi2WO6 composite photocatalyst and preparation method thereof | |
| CN114950502B (en) | Preparation method of nano rod-shaped red phosphorus photocatalyst with photocatalytic hydrogen evolution activity and stability | |
| CN103480395A (en) | Preparation and application of core-shell-structure bismuth sulfide@bismuth oxide composite microspheres | |
| CN106582722A (en) | Composite photocatalysis system, and preparation method and application thereof | |
| CN103785429B (en) | A kind of silver orthophosphate/Graphene/titanic oxide nano compound material and preparation method | |
| CN107626297A (en) | A kind of tiny balloon shape bismuth/composite bismuth vanadium photocatalyst and its preparation method and application | |
| CN104857975A (en) | Preparation method and application of CdIn2S4-graphene composite photocatalyst | |
| CN103785425A (en) | Preparation method and application of flower-like Bi2O(OH)2SO4 photocatalyst |
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 |