CN108187701A - A kind of AgCl/BiOCl photochemical catalyst preparation methods of tubulose AgCl structures - Google Patents
A kind of AgCl/BiOCl photochemical catalyst preparation methods of tubulose AgCl structures Download PDFInfo
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- CN108187701A CN108187701A CN201810088535.7A CN201810088535A CN108187701A CN 108187701 A CN108187701 A CN 108187701A CN 201810088535 A CN201810088535 A CN 201810088535A CN 108187701 A CN108187701 A CN 108187701A
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- Prior art keywords
- agcl
- biocl
- tubulose
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 title claims abstract description 126
- 229910021607 Silver chloride Inorganic materials 0.000 title claims abstract description 113
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000019441 ethanol Nutrition 0.000 claims abstract description 15
- 239000011941 photocatalyst Substances 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 4
- 239000011565 manganese chloride Substances 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 18
- 239000011541 reaction mixture Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 abstract description 3
- 235000002867 manganese chloride Nutrition 0.000 abstract description 3
- 229910001961 silver nitrate Inorganic materials 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 abstract description 2
- 229940099607 manganese chloride Drugs 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 15
- 229940012189 methyl orange Drugs 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002071 nanotube Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/027—Compounds of F, Cl, Br, I
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- 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
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- 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
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- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to photochemical catalyst preparing technical fields, it is related to a kind of preparation method of the AgCl/BiOCl photochemical catalysts of tubulose AgCl structures, preparing load for the first time using hydro-thermal method has the new A gCl/BiOCl photochemical catalysts of nanotube-shaped AgCl structures, using bismuth oxide, hydrochloric acid, silver nitrate and ethyl alcohol as raw material in specific preparation method, first prepare predecessor BiOCl, chlorine source (manganese chloride, iron chloride etc.) and silver-colored source are added, the AgCl BiOCl composite photo-catalysts of new structure are made with hydro-thermal method；Reinforced phase AgCl is tubular morphology structure in prepared AgCl/BiOCl photochemical catalysts, and tubulose AgCl and matrix BiOCl synusia are closely coupled；The preparation method science, preparation process is simple, and manufacturing cost is cheap, and product structure obtained is unique, and function admirable has a good application prospect.
Description
Technical field：
The invention belongs to photochemical catalyst preparing technical fields, are related to a kind of AgCl/BiOCl photochemical catalysts of novel pattern
Preparation method, in the AgCl/BiOCl photochemical catalysts prepared by this method, reinforced phase AgCl is tubular morphology and and matrix
BiOCl synusia are closely coupled, and tubulose AgCl can enhance the Photodegradation of Methyl Orange (Methyl that AgCl/BiOCl light urges agent in the structure
Orange:MO) performance.
Background technology：
Photocatalysis is one of most popular technology of current field of environmental improvement, is had in terms of environmental pollution improvement very excellent
Different effect.Compared to other pollutant abatement technologies, Photocatalitic Technique of Semiconductor have degrading organic pollutant type it is more,
The advantages such as degradation rate is high, property is stablized, and because it utilizes sunlight as light source, be more energy-saving and environmentally friendly.Traditional
Photochemical catalyst TiO2, ZnO forbidden bands it is wider, but without visible light-responded ability, so limiting their practical application.At present,
It is main to the research emphasis of photochemical catalyst that there are two aspects：First, to conventional Ti O2Photochemical catalyst is modified, as ion is mixed
Miscellaneous, noble-metal-supported, semiconductors coupling, surface modification etc.；Second, exploration can responding to visible light, degrade more efficient, energy savingly
The novel semi-conductor photochemical catalyst of pollutant.
In many novel semi-conductor photochemical catalysts, Bi-O-Cl photochemical catalysts have better photocatalysis performance, due to tool
There are unique layer structure and electronic structure, the separation of photo-generated carrier can be promoted, and reduce its recombination probability, thus become
One of research hotspot.But the absorption in visible-range of Bi-O-Cl photochemical catalysts is not high, it is therefore desirable to it
It is modified.In currently available technology, the method for modifying of BiOX catalysis material is common to have ion to mix method, noble metal
Modification method, composite heterogenous junction method etc., such as the research of 2013 Nian Yuchang woodss seminars are prepared for Pt/BiOCl nanometer sheets, and having can
See light absorpting ability；The AgCl/BiOCl composite photo-catalysts for being prepared for AgCl particle modifications are studied by 2016 Nian Liu rocs seminars,
Improve absorption of the photochemical catalyst in visible-range；The patent Zl2015106941060 of Fudan University in 2016 is disclosed
A kind of visible light catalyst Ag-AgCl-BiOCl and its preparation method and application, is obtained by AgCl and BiOCl coprecipitation methods
To composite photo-catalyst Ag-AgCl-BiOCl, crystal is made of BiOCl, AgCl and simple substance Ag in Ag-AgCl-BiOCl, and
Ag-AgCl is present in BiOCl intracells, and whole pattern is dispersant, sheet discrete particles structure.The present invention is based on grind above
Study carefully, research for the first time has prepared a kind of AgCl/BiOCl photochemical catalysts with novel pattern (from having no in currently available technology
Have relevant report), i.e. AgCl/BiOCl composite photo-catalysts nanometer tube modified AgCl have stronger photoresponse ability and light
Catalytic activity.
Invention content：
It is an object of the invention to overcome shortcoming of the existing technology, seek to design a kind of prepare with special construction
The method of AgCl/BiOCl photochemical catalysts, particularly a kind of AgCl/BiOCl photochemical catalysts with tubulose AgCl structures are (following
Abbreviation AgCl/BiOCl photochemical catalysts) preparation method.
To achieve these goals, the preparation method of the AgCl/BiOCl photochemical catalysts of research and design of the present invention includes following
Step：
(1) preparation of BiOCl
1. first to 0.01-0.05mol Bi2O3Middle dropwise addition 5-30mL hydrochloric acid, is evenly stirred until that above two mixture is complete
Dissolving forms clear solution, then ammonium hydroxide is added dropwise to adjust pH value to 5-10 into above-mentioned clear solution so that goes out in clear solution
Existing white precipitate forms suspension；
White colloidal is formed 2. suspension is placed in continuing magnetic force under 30-60 DEG C of temperature control and is stirred 20-60 minutes, uses deionization
Water and absolute ethyl alcohol to above-mentioned white colloidal centrifuge washing three times after, white colloidal is 24 hours dry at a temperature of 40-80 DEG C,
Collection obtains BiOCl white powders；
(2) preparation of AgCl/BiOCl
1. weigh 1.0-5.0g AgNO with electronic balance3Powder is placed in sky beaker, then 50-150ml is added dropwise into beaker
Then absolute ethyl alcohol adds in stirrer and is placed in stirring 10-60min formation solution As on magnetic stirrer；
2. weigh 20-100mg MnCl2Or FeCl3It is placed in sky beaker, then the anhydrous second of 50-150ml is added dropwise into beaker
Then alcohol adds in stirrer and 10-60 min formation solution Bs is stirred on magnetic stirrer；
3. it weighs BiOCl white powders obtained in 2-8g steps (1) to be placed in sky beaker, then 50- is added dropwise into beaker
Then beaker is placed in Ultrasound Instrument after ultrasound 10-60min, adds stirrer in magnetic stirrer by 150ml absolute ethyl alcohols
Upper stirring 10-60min forms solution C；
4. solution A, B are pipetted with pipette according to the amount that the molar ratio of AgCl and BiOCl is 2%, 5% or 10% respectively
Enter in water heating kettle with C, then water heating kettle is put into baking oven, adjusting oven temperature makes water heating kettle be warming up to 120-200 DEG C with stove, so
120-200 DEG C of heating 12-20h of temperature control obtains reaction mixture afterwards；
5. taking out water heating kettle after heating, take the mode of furnace cooling or water cooling that reaction mixture is cooled to room
Then reaction mixture is controlled rotating speed 8000-9000 r/min centrifugal treatings 5-8 minutes to remove ethyl alcohol by temperature using centrifuge tube；
Reaction mixture after centrifugal treating deionized water and ethyl alcohol are washed three times respectively；
6. the reaction mixture after washing is placed in culture dish, 30-80 DEG C of temperature control is 24 hours dry in drying box, and then
Obtaining load has the AgCl/BiOCl photocatalyst powders of nano tubular structure AgCl of different proportion (2%, 5% or 10%).
Reinforced phase AgCl is tubular morphology in the AgCl/BiOCl photochemical catalysts of tubulose AgCl structures prepared in the present invention
Structure, a diameter of 4-6nm of pipe, the wall thickness of pipe is 1.5 ± 0.5nm, closely coupled with matrix BiOCl synusia；The light of the structure
Catalyst has the specific surface area of bigger, is more advantageous to light induced electron and hole is transferred to surface, urged so as to substantially increase light
Change efficiency.
Load has 2%AgCl, 5%AgCl or 10% respectively in the AgCl/BiOCl photochemical catalysts that the present invention is prepared
AgCl, the load percentage 2%, 5% or 10% refer to the molar ratio of AgCl and BiOCl in AgCl/BiOCl photochemical catalysts；Its
The middle performance for loading degradation of contaminant methyl orange under the AgCl/BiOCl photochemical catalyst visible rays for having 5%AgCl is best, for matter
The methyl orange solution of a concentration of 80mg/L is measured, the degradation rate of methyl orange can reach 91% after sixty minutes under visible light.
Compared with prior art, the present invention preparing load for the first time using hydro-thermal method has the new of nanotube-shaped AgCl structures
Type AgCl/BiOCl photochemical catalysts, AgCl nanotubes are combined closely with BiOCl lamellas；The catalyst has stronger photoresponse energy
Power and photocatalytic activity have good degradation property to pollutant methyl orange；In specific preparation method with bismuth oxide, hydrochloric acid,
Silver nitrate and ethyl alcohol first prepare predecessor BiOCl, add chlorine source (manganese chloride, iron chloride etc.) and silver-colored source, use as raw material
The AgCl-BiOCl composite photo-catalysts of new structure are made in hydro-thermal method；The preparation method science, preparation process is simple, is prepared into
This is cheap, and product structure obtained is unique, and function admirable has a good application prospect.
Description of the drawings：
Fig. 1 is the X ray diffracting spectrum of AgCl/BiOCl photochemical catalysts of the present invention.
Fig. 2 is shape appearance figure of the AgCl/BiOCl photochemical catalysts of the present invention under transmission electron microscope (TEM).
Fig. 3 is the selective electron diffraction figure (SAED of AgCl nanotubes in AgCl/BiOCl photochemical catalysts of the present invention
Figure).
Fig. 4 is the energy spectrum diagram (EDS figures) of AgCl/BiOCl photochemical catalysts of the present invention.
Fig. 5 is the high power transmission electron microscope picture (TEM of AgCl nanotubes in AgCl/BiOCl photochemical catalysts of the present invention
Figure).
Fig. 6 is the UV-vis DRS spectrogram (DRS) of AgCl/BiOCl photochemical catalysts of the present invention.
Fig. 7 is that load of the present invention has the AgCl/BiOCl photochemical catalysts of different proportion AgCl under visible light to first
The degradation curve schematic diagram of base orange.
Specific embodiment：
The invention will be further described by way of example and in conjunction with the accompanying drawings.
Embodiment 1：
The preparation method of the AgCl/BiOCl photochemical catalysts of tubulose AgCl structures that the present embodiment is related to includes the following steps：
(1) preparation of BiOCl
1. first to 0.01-0.05mol bismuth oxides (Bi2O3) in be added dropwise 5-30mL hydrochloric acid (HCl), stir evenly above two
Mixture is completely dissolved to form clear solution, then ammonium hydroxide (NH is added dropwise into above-mentioned clear solution3·H2O) to adjust pH value to 5-
10 so that occur white precipitate in clear solution and form suspension；
White colloidal is formed 2. suspension is placed in continuing magnetic force under 30-60 DEG C of temperature control and is stirred 20-60 minutes, uses deionization
Water and absolute ethyl alcohol (C2H5OH) to above-mentioned white colloidal centrifuge washing three times after, white colloidal is dry at a temperature of 40-80 DEG C
24 hours, collection obtained BiOCl white powders；
(2) preparation of AgCl/BiOCl
1. weigh 1.0-5.0g silver nitrates (AgNO with electronic balance3) powder is placed in sky beaker, then is added dropwise into beaker
50-150ml absolute ethyl alcohols (C2H5OH), then add in stirrer and 10-60min formation solution As are stirred on magnetic stirrer；
2. weigh 20-100mg manganese chlorides (MnCl2) or iron chloride (FeCl3) be placed in sky beaker, then be added dropwise into beaker
50-150ml absolute ethyl alcohols (C2H5OH), then add in stirrer and 10-60min formation solution Bs are stirred on magnetic stirrer；
3. it weighs BiOCl white powders obtained in 2-8g steps (1) to be placed in sky beaker, then 50- is added dropwise into beaker
150ml absolute ethyl alcohols (C2H5OH), then beaker is placed in Ultrasound Instrument after ultrasound 10-60min, adds stirrer in magnetic force
10-60min is stirred on blender and forms solution C；
4. solution A, B are pipetted with pipette according to the amount that the molar ratio of AgCl and BiOCl is 2%, 5% or 10% respectively
Enter in water heating kettle with C, then water heating kettle is put into baking oven, adjusting oven temperature makes water heating kettle be warming up to 120-200 DEG C with stove, so
120-200 DEG C of heating 12-20h of temperature control obtains reaction mixture afterwards；
5. taking out water heating kettle after heating, take the mode of furnace cooling or water cooling that reaction mixture is cooled to room
Then reaction mixture is controlled rotating speed 8000-9000 r/min centrifugal treatings 5-8 minutes to remove ethyl alcohol by temperature using centrifuge tube；
Reaction mixture after centrifugal treating deionized water and ethyl alcohol are washed three times respectively；
6. the reaction mixture after washing is placed in culture dish, 30-80 DEG C of temperature control is 24 hours dry in drying box, and then
Obtaining load has the AgCl/BiOCl photocatalyst powders of nano tubular structure AgCl of different proportion (2%, 5% or 10%).
Chemical reagent title and molecular formula involved in the present embodiment is as shown in table 1.
Table 1
Experimental facilities title and model involved in the present embodiment is as shown in table 2.
Table 2
The AgCl/BiOCl photochemical catalysts prepared in the present embodiment have unique tubulose AgCl support structures, AgCl nanometers
Pipe is combined closely with BiOCl lamellas；A diameter of 4-6nm of AgCl nanotubes, the wall thickness of pipe is 1.5 ± 0.5nm；Above structure
AgCl/BiOCl photochemical catalysts there is the characteristics of specific surface area is high, and activity is strong, be conducive to the separation in light induced electron and hole, energy
More effectively improve light degradation rate and photocatalytic activity.
The object of AgCl/BiOCl photochemical catalysts manufactured in the present embodiment is mutually understood through x-ray powder diffraction instrument (XRD) test
(as shown in Figure 1 specific), the 2 θ values at the peak of arrow meaning are corresponding to the standard card of AgCl in collection of illustrative plates.
The AgCl/BiOCl photocatalyst applications scanning electron microscope (TEM) prepared in the present embodiment is observed its basic pattern and is understood
(as shown in Figure 2), the strong position of contrast are BiOCl synusia, and contrast weak part in edge is " one-dimensional nano structure " of AgCl；Root
According to the selective electron diffraction collection of illustrative plates (as shown in Figure 3) of " one-dimensional nano structure " of AgCl/BiOCl photochemical catalysts, corresponding to AgCl,
It is possible thereby to determine that the object for being somebody's turn to do " one-dimensional nano structure " is mutually AgCl；According to energy spectrum diagram (as shown in Figure 4), it can be verified that AgCl and
The object phase of BiOCl；The high power transmission electricity of the tubulose AgCl structures loaded in the AgCl/BiOCl photochemical catalysts that the present embodiment is related to
It can be clearly seen in mirror figure (as shown in Figure 5) and judge to obtain " one-dimensional nano structure " in Fig. 2 to be nanotube-shaped, from
And determine unique knot that there is AgCl/BiOCl photochemical catalysts the BiOCl of AgCl nanotubes and lamellar to be closely linked
Structure.
Embodiment 2：
The present embodiment carries out the AgCl/BiOCl photochemical catalysts of load different proportion AgCl obtained in embodiment 1 purple
Outer visible diffusing reflection (DRS) test, test result are as shown in Figure 6：In the range of 360-800nm, load 2%AgCl's
The light absorpting ability of the AgCl/BiOCl of AgCl/BiOCl, the AgCl/BiOCl for loading 5%AgCl and load 10%AgCl are high
In pure BiOCl, it can thus be appreciated that AgCl/BiOCl photochemical catalysts made from embodiment 1 are in visible-range (390-760nm)
With stronger visible light-responded ability.
Embodiment 3：
The present embodiment is using methyl orange as target contaminant, using AgCl/BiOCl photocatalysis of the visible light source to preparation
The photodegradation of agent carries out experimental study.The load respectively for confirming to develop in embodiment 1 has 2%AgCl, 5%AgCl and 10%
The AgCl/BiOCl photochemical catalysts of AgCl are respectively provided with methyl orange preferable degradation, wherein load has 5%AgCl's
The performance of AgCl/BiOCl photocatalyst for degrading pollutant methyl oranges is 80mg/L for mass concentration preferably (as shown in Figure 7)
Methyl orange solution, the degradation rate of methyl orange can reach 91% after sixty minutes, and the degradation rate of pure BiOCl is only under the same terms
It is 15%.
For the present embodiment with methyl orange (MO) for catabolite, specific degradation experiment is as follows：
The MO aqueous solutions of a concentration of 80mg/L of initial mass are prepared, AgCl/BiOCl light is then added in into MO aqueous solutions urges
Agent, a concentration of 2mg/mL；The environment of photocatalytic degradation is simulated using photochemical reaction case.Start light-catalyzed reaction it
Before, MO aqueous solutions are stirred 30 minutes in the dark to reach adsorption-desorption balance；Then MO aqueous solutions are exposed to visible ray
Under (xenon lamp is used to filter out ultraviolet light using optical filter with simulated visible light light source as light source), in continuous ventilation and stirring
Lower photocatalysis Decomposition MO finally carries out the calculating of degradation rate.
The results are shown in Figure 7 for comparative analysis, and the absorption property of AgCl/BiOCl photochemical catalysts is better than the light of unsupported AgCl
Catalyst.Wherein, the absorption property for loading the AgCl/BiOCl photochemical catalysts of 5%AgCl is best, can be adsorbed when secretly adsorbing 30min
40%, after illumination 60min, degradation rate can reach 91%, and the degradation rate of pure BiOCl is only about 15%, that is, loads 5%
Degradation rate of the AgCl/BiOCl photochemical catalysts of AgCl when degrading 60min is 6 times of BiOCl.
In conclusion AgCl/BiOCl photochemical catalysts obtained have excellent photocatalysis under visible light in embodiment 1
Activity.Principle is：First, AgCl/BiOCl photochemical catalysts have stronger visible light-responded ability；Secondly as AgCl nanometers
Tubular structure improves the specific surface area of AgCl/BiOCl photocatalyst materials, enhances AgCl/BiOCl photocatalyst materials
Absorption property, more contaminant molecules can be adsorbed；The AgCl nano tubular structures of load cause AgCl/ simultaneously
The active site of BiOCl photocatalyst materials surface reaction increases, and photo-generated carrier is enable quickly to be moved to surface and is reacted,
So as to reduce the recombination probability of light induced electron and hole, and then improve photocatalysis performance.
Claims (2)
1. the AgCl/BiOCl photochemical catalyst preparation methods of a kind of tubulose AgCl structures, it is characterised in that include the following steps：
(1) preparation of BiOCl
1. first to 0.01-0.05mol Bi2O3Middle dropwise addition 5-30mL hydrochloric acid, is evenly stirred until that above two mixture is completely dissolved
Clear solution is formed, then ammonium hydroxide is added dropwise to adjust pH value to 5-10 into above-mentioned clear solution so that is occurred in clear solution white
Color precipitates to form suspension；
Form white colloidal 2. suspension is placed under 30-60 DEG C of temperature control continuing magnetic force and is stirred 20-60 minute, with deionized water with
Absolute ethyl alcohol to above-mentioned white colloidal centrifuge washing three times after, by white colloidal dry 24 hours at a temperature of 40-80 DEG C, collect
Obtain BiOCl white powders；
(2) preparation of AgCl/BiOCl
1. weigh 1.0-5.0g AgNO with electronic balance3Powder is placed in sky beaker, then dropwise addition 50-150ml is anhydrous into beaker
Then ethyl alcohol adds in stirrer and is placed in stirring 10-60min formation solution As on magnetic stirrer；
2. weigh 20-100mg MnCl2Or FeCl3It is placed in sky beaker, then 50-150ml absolute ethyl alcohols is added dropwise into beaker, so
Stirrer is added in afterwards, and 10-60min formation solution Bs are stirred on magnetic stirrer；
3. it weighs BiOCl white powders obtained in 2-8g steps (1) to be placed in sky beaker, then 50-150ml is added dropwise into beaker
Then beaker is placed in Ultrasound Instrument after ultrasound 10-60min, adds stirrer and stirred on magnetic stirrer by absolute ethyl alcohol
10-60min forms solution C；
4. solution A, B and C are pipetted with pipette according to the amount that the molar ratio of AgCl and BiOCl is 2%, 5% or 10% respectively
Enter in water heating kettle, then water heating kettle is put into baking oven, adjusting oven temperature makes water heating kettle be warming up to 120-200 DEG C with stove, then
120-200 DEG C of heating 12-20h of temperature control obtains reaction mixture；
5. taking out water heating kettle after heating, the mode of furnace cooling or water cooling is taken to be cooled to room temperature reaction mixture, so
Reaction mixture is controlled into rotating speed 8000-9000r/min centrifugal treatings 5-8 minutes to remove ethyl alcohol using centrifuge tube afterwards；To centrifugation
Reaction mixture deionized water that treated and ethyl alcohol wash three times respectively；
6. the reaction mixture after washing is placed in culture dish, 30-80 DEG C of temperature control is 24 hours dry in drying box, and then obtains
Load has the AgCl/BiOCl photocatalyst powders of 2%, 5% or 10% nano tubular structure AgCl respectively.
2. the AgCl/BiOCl photochemical catalyst preparation methods of tubulose AgCl structures according to claim 1, it is characterised in that
In the AgCl/BiOCl photochemical catalysts of the tubulose AgCl structures of preparation reinforced phase AgCl be tubular morphology structure, a diameter of 4- of pipe
6nm, the wall thickness of pipe is 1.5 ± 0.5nm, and tubulose AgCl and matrix BiOCl synusia are closely coupled；The AgCl/ of tubulose AgCl structures
The load percentage of tubulose AgCl is respectively 2%, 5% or 10% in BiOCl photochemical catalysts, the load percentage 2%, 5% or
10% refers to the molar ratio of AgCl and BiOCl in AgCl/BiOCl photochemical catalysts.
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