CN106732684B - Double salt Hydrolyze method prepares high activity BiOX catalysis material - Google Patents
Double salt Hydrolyze method prepares high activity BiOX catalysis material Download PDFInfo
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- CN106732684B CN106732684B CN201611116749.8A CN201611116749A CN106732684B CN 106732684 B CN106732684 B CN 106732684B CN 201611116749 A CN201611116749 A CN 201611116749A CN 106732684 B CN106732684 B CN 106732684B
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 150000003839 salts Chemical class 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 15
- 230000000694 effects Effects 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 230000007062 hydrolysis Effects 0.000 claims abstract description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 18
- 150000001621 bismuth Chemical class 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims description 10
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 claims description 10
- 229940036358 bismuth subcarbonate Drugs 0.000 claims description 10
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- 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 2
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 description 13
- 238000002604 ultrasonography Methods 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AHUBLGVDRKDHAT-UHFFFAOYSA-N [Bi]=O.[Cl] Chemical compound [Bi]=O.[Cl] AHUBLGVDRKDHAT-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 238000011109 contamination Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- -1 hydrogen halogen Bismuth salt Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 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
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses double salt Hydrolyze method to prepare high activity BiOX catalysis material, comprise the following steps, it is clear state that bismuth salt, solvent, halogen acid solution, which are mixed, which makes bismuth salt be completely dissolved to mixed liquor, by mixed liquor as in reaction kettle, when 100 250 DEG C of reactions 6 20 are small, gained is deposited in normal pressure after completion of the reaction, when temperature is that 20 100 DEG C of hydrolysis 0.5 5 are small, then organic solvent washing is used, 50 100 DEG C dry to obtain BiOX.The BiOX catalysis material that the present invention is prepared by double salt Hydrolyze method has excellent visible light photocatalysis active.
Description
Technical field
The invention belongs to solar energy photocatalytic Material Field, and in particular to a kind of double salt Hydrolyze method prepares high activity zirconyl oxyhalides
Bismuth catalysis material.
Background technology
With the fast development of modernization industry, global problem of environmental pollution is also more and more prominent and serious, especially
That a large amount of of the organic pollution to human hazard, dyestuff, pesticide and bio-chemical etc. use and discharge, caused by environment
Pollution has to cause concern of the people to this problem, how to solve the problems, such as that this becomes many researchers are run into one
Hang-up.Therefore we there is an urgent need to some environmentally protective, efficient and free of contamination scientific methods to convert them to nothing
The compound of pollution.In recent years, for the processing of a large amount of organic pollutions, main means are that (absorption, filtering, coagulate various physics
Knot etc.) and chemistry (Photocatalitic Technique of Semiconductor, supercritical water oxidation, electrochemical method, enzymatic treatment) method.Wherein, partly lead
Body photocatalysis technology is considered as to solve most effective, the most economical technological means of organic contamination.
Traditional semiconductor light-catalyst TiO2, due to its with it is nontoxic, oxidation efficiency is high, non-selectivity and property
Stablize the features such as and be widely used.But TiO2But there are significant limitation, it can only under ultraviolet light respond and recycle tired
It is difficult.Therefore, in order to reduce the cost of photochemical catalyst, improve quantum yield and visible light utilization efficiency, a large amount of passes have been carried out both at home and abroad
In the research work for improving properties of catalyst.
In miscellaneous non-TiO2In photochemical catalyst, bismuth based semiconductor photochemical catalyst is because it has unique electronics knot
Structure and appropriately sized energy gap and it is noticeable.Wherein, BiOX (BiOX, X=Cl, Br, I) is due to suitable
Energy gap, the chemical property of stabilization, the layer structure of uniqueness (high anisotropy), and show higher photocatalysis and live
Property, particularly to visible light-responded obvious, solar energy can be made full use of, is expected to realize industrialized production.
By the BiOX catalysis material that distinct methods are prepared due to properties such as structure, pattern, sizes not
Together, there is also very big difference for its catalytic performance.Being used to prepare the method for BiOX photocatalyst at this stage includes hydrolysis
Method, solvent-thermal method, template, high temperature solid-state method etc..Wherein solvent-thermal method is due to can be by controlling reaction solution concentration, temperature
Degree, the time, change solvent and add different surfactants the methods of, and obtain different-shape, the BiOX light of size is urged
Agent and be widely used, the present invention is namely based on solvent-thermal method and is prepared double salt, then produces BiOX by double salt hydrolysis
Light urges agent.
The content of the invention
In view of this, it is an object of the invention to provide a kind of double salt Hydrolyze method to prepare high activity BiOX photocatalysis material
There is excellent visible light photocatalysis to live for material, the high activity BiOX catalysis material being prepared by double salt Hydrolyze method
Property.
For achieving the above object, the present invention provides following technical solution：
Double salt Hydrolyze method prepares high activity BiOX catalysis material, includes the following steps：By bismuth salt, solvent, hydrogen halogen
Bismuth salt is completely dissolved to mixed liquor be clear state for acid solution mixing, by mixed liquor as in reaction kettle, at 100-250 DEG C instead
When answering 6-20 small, gained is deposited in normal pressure after completion of the reaction, when temperature is 20-100 DEG C of hydrolysis 0.5-5 small, then with organic
Solvent washs, and 50-100 DEG C dries to obtain BiOX.
Preferably, the bismuth salt：Solvent：The molar ratio of halogen acid solution is 0.04~0.012：0.4~3：0.2~1.2.
Preferably, the bismuth salt is at least one of bismuth chloride, bismuth subcarbonate, bismuth sulfate, bismuth nitrate.
Preferably, the solvent is at least one of acetonitrile, pure water, alcohol, acetone, toluene.
Preferably, the halogen acid solution is at least one of hydrochloric acid solution, hydrobromic acid, hydroiodic acid and hydrofluoric acid.
Preferably, the mixing is mixed using ultrasonic wave.
Preferably, the reaction kettle is ptfe autoclave.
Preferably, the organic solvent is at least one of alcohol and acetone, and temperature is 10-50 DEG C.
Preferably, it is 6-7, electrical conductivity ＜ 20us/cm that the washing process, which need to be washed to pH value of solution,.
Preferably, the drying course is dried to BiOX moisture less than 0.5%.
Double salt is prepared using solvent-thermal method in the present invention, then produces BiOX light by double salt hydrolysis and urge agent, this work
The material that skill obtains is nano material, is uniformly dispersed, and pattern is also more regular, can effectively reduce photo-generated carrier and move to the interior in semiconductor
The recombination rate in light induced electron and hole during shifting, and specific surface area bigger, contact more abundant with reaction substrate, therefore photocatalysis
Performance higher, while sample purity is high, crystallinity is fine.
The beneficial effects of the present invention are：High activity BiOX light is prepared the invention discloses a kind of double salt Hydrolyze method to urge
Change material, there is the BiOX catalysis material that the present invention is prepared by double salt Hydrolyze method excellent visible light photocatalysis to live
Property.
Brief description of the drawings
In order to make the purpose of the present invention, technical solution and beneficial effect clearer, the present invention provides drawings described below：
A, c represent to scheme using the SEM of pure water (embodiment 8) bismoclite sample obtained by solvent in Fig. 1, and b, d are represented with pure
The SEM figures of acetonitrile (embodiment 1) bismoclite sample obtained by solvent；
Fig. 2 is represented with the XRD diagram of pure water (embodiment 8) and pure acetonitrile (embodiment 1) the bismoclite sample obtained by solvent；
Fig. 3 represents bismoclite sample and TiO under visible ray and simulated solar irradiation2Photocatalysis performance figure；
Fig. 4 is represented with the Fourier of pure water (embodiment 8) and pure acetonitrile (embodiment 1) the bismoclite sample obtained by solvent
Infrared spectrogram；
Fig. 5 represents kinetics of photocatalytic degradation curve of the bismuth oxybromide to rhodamine B (RhB)；
Fig. 6 represents to hydrolyze the XRD diagram of forward and backward gained bismuth oxybromide.
Embodiment
The preferred embodiment of the present invention is described in detail below.The experiment side of actual conditions is not specified in embodiment
Method, usually according to normal condition or according to the condition proposed by manufacturer.
Embodiment 1
Take 0.1M bismuth chlorides to add in 50g acetonitrile solutions, and add the hydrochloric acid solution of 0.5M, ultrasound makes bismuth chloride all molten
Solution is clarified in solution to solution.The solution configured is poured into the ptfe autoclave of 100ml, 160 DEG C of reactions
12h, after the completion of question response, normal pressure is deposited in by gained, temperature for 50 DEG C of hydrolysis 5 it is small when, then washed with acetone, 60 DEG C of bakings
Do to obtain bismoclite.It is 6-7, electrical conductivity ＜ 20us/cm that the washing process, which need to be washed to pH value of solution,.The drying course drying
It is less than 0.5% to bismoclite moisture.
Embodiment 2
Take 0.1M bismuth chlorides to add in 50g acetonitrile solutions, and add the hydrochloric acid solution of 1.0M, ultrasound makes bismuth chloride all molten
Solution is clarified in solution to solution.The solution configured is poured into the ptfe autoclave of 100ml, 160 DEG C of reactions
12h, is deposited in normal pressure by gained after completion of the reaction, when temperature is that 80 DEG C of hydrolysis 3 are small, is then washed with acetone, 60 DEG C dry
Bismoclite.It is 6-7, electrical conductivity ＜ 20us/cm that the washing process, which need to be washed to pH value of solution,.The drying course is dried to chlorine
Bismuth oxide moisture is less than 0.5%.
Embodiment 3
Take 0.1M bismuth chlorides to add in 50g acetonitrile solutions, and add the hydrochloric acid solution of 0.35M, ultrasound makes bismuth chloride whole
It is dissolved in solution to solution and clarifies.The solution configured is poured into the ptfe autoclave of 100ml, 160 DEG C anti-
8h is answered, gained is deposited in normal pressure after completion of the reaction, when temperature is that 90 DEG C of hydrolysis 3 are small, is then washed with acetone, 60 DEG C of drying
Obtain bismoclite.It is 6-7, electrical conductivity ＜ 20us/cm that the washing process, which need to be washed to pH value of solution,.The drying course is dried to
Bismoclite moisture is less than 0.5%.
Embodiment 4
Take 0.1M bismuth chlorides to add in 50g acetonitrile solutions, and add the hydrochloric acid solution of 0.35M, ultrasound makes bismuth chloride whole
It is dissolved in solution to solution and clarifies.The solution configured is poured into the ptfe autoclave of 100ml, 160 DEG C anti-
Answer 12h, gained be deposited in normal pressure after completion of the reaction, temperature for 40 DEG C of hydrolysis 2 it is small when, then with organic solvent washing, 70 DEG C
Dry to obtain bismoclite.It is 6-7, electrical conductivity ＜ 20us/cm that the washing process, which need to be washed to pH value of solution,.The drying course dries
Do to bismoclite moisture and be less than 0.5%.
Embodiment 5
Take 0.1M bismuth chlorides to add in 50g acetonitrile solutions, and add the hydrochloric acid solution of 0.35M, ultrasound makes bismuth chloride whole
It is dissolved in solution to solution and clarifies.The solution configured is poured into the ptfe autoclave of 100ml, 160 DEG C anti-
12h is answered, gained is deposited in normal pressure after completion of the reaction, when temperature is that 50 DEG C of hydrolysis 2 are small, is then washed with acetone, 50 DEG C of drying
Obtain bismoclite.It is 6-7, electrical conductivity ＜ 20us/cm that the washing process, which need to be washed to pH value of solution,.The drying course is dried to
Bismoclite moisture is less than 0.5%.
Embodiment 6
Take 0.1M bismuth chlorides to add in 50g acetonitrile solutions, and add the hydrochloric acid solution of 0.35M, ultrasound makes bismuth chloride whole
It is dissolved in solution to solution and clarifies.The solution configured is poured into the ptfe autoclave of 100ml, 180 DEG C anti-
12h is answered, gained is deposited in normal pressure after completion of the reaction, when temperature is that 60 DEG C of hydrolysis 1 are small, then with ethanol wash, 60 DEG C of drying
Obtain bismoclite.It is 6-7, electrical conductivity ＜ 20us/cm that the washing process, which need to be washed to pH value of solution,.The drying course is dried to
Bismoclite moisture is less than 0.5%.
Embodiment 7
Take 0.1M bismuth chlorides to add 25g acetonitrile solutions and 25g deionized water solutions, and add the hydrochloric acid solution of 1.0M, surpass
Sound makes bismuth chloride be fully dissolved in solution to solution clarification.The polytetrafluoroethylene (PTFE) that the solution configured is poured into 100ml is anti-
Answer in kettle, 160 DEG C of reaction 12h, gained is deposited in normal pressure after completion of the reaction, when temperature is that 80 DEG C of hydrolysis 4 are small, then uses alcohol
Washing, 70 DEG C dry to obtain bismoclite.It is 6-7, electrical conductivity ＜ 20us/cm that the washing process, which need to be washed to pH value of solution,.It is described
Drying course is dried to bismoclite moisture less than 0.5%.
Embodiment 8
0.05M bismuth chlorides are added in 50g deionized waters, and add the hydrochloric acid solution of 1.0M, and ultrasound makes bismuth chloride all molten
Solution is clarified in solution to solution.The solution configured is poured into the ptfe autoclave of 100ml, 160 DEG C of reactions
12h, is deposited in normal pressure, when temperature is that 70 DEG C of hydrolysis 1 are small, then with ethanol wash, 60 DEG C dry by gained after completion of the reaction
Bismoclite.It is 6-7, electrical conductivity ＜ 20us/cm that the washing process, which need to be washed to pH value of solution,.The drying course is dried to chlorine
Bismuth oxide moisture is less than 0.5%.
Embodiment 9
Take 0.05M bismuth subcarbonate add 50g acetonitriles in, and add 0.5M hydrochloric acid solution and 0.5M hydrobromic acid it is molten
Liquid, ultrasound make bismuth subcarbonate be fully dissolved in solution to solution clarification.The solution configured is poured into the polytetrafluoro of 100ml
In ethylene reaction kettle, 180 DEG C of reaction 12h, are deposited in normal pressure, when temperature is that 80 DEG C of hydrolysis 4 are small, then by gained after completion of the reaction
With ethanol wash, 70 DEG C dry to obtain BiOX.It is 6-7, electrical conductivity ＜ 20us/ that the washing process, which need to be washed to pH value of solution,
cm.The drying course is dried to BiOX moisture less than 0.5%.
Embodiment 10
Take 0.05M bismuth subcarbonate add 50g acetonitriles in, and add 0.25M hydrochloric acid solution and 0.75M hydrobromic acid it is molten
Liquid, ultrasound make bismuth subcarbonate be fully dissolved in solution to solution clarification.The solution configured is poured into the polytetrafluoro of 100ml
In ethylene reaction kettle, 180 DEG C of reaction 12h, are deposited in normal pressure, when temperature is that 80 DEG C of hydrolysis 4 are small, then by gained after completion of the reaction
With ethanol wash, 70 DEG C dry to obtain bismuth oxybromide.It is 6-7, electrical conductivity ＜ 20us/ that the washing process, which need to be washed to pH value of solution,
cm.The drying course is dried to bismuth oxybromide moisture less than 0.5%.
Embodiment 11
Take the bismuth subcarbonate of 0.05M to add in 50g acetonitriles, and add the hydrobromic acid solution of 1.0M, ultrasound makes bismuth subcarbonate
It is fully dissolved in solution to solution and clarifies.The solution configured is poured into the ptfe autoclave of 100ml, 200
DEG C reaction 16h, is deposited in normal pressure by gained after completion of the reaction, temperature for 80 DEG C of hydrolysis 3 it is small when, then washed with acetone, 60 DEG C
Dry to obtain bismuth oxybromide.It is 6-7, electrical conductivity ＜ 20us/cm that the washing process, which need to be washed to pH value of solution,.The drying course dries
Do to bismuth oxybromide moisture and be less than 0.5%.
Embodiment 12
Take the bismuth subcarbonate of 0.05M to add in 50g acetonitriles, and add the hydrobromic acid solution of 1.0M, ultrasound makes bismuth subcarbonate
It is fully dissolved in solution to solution and clarifies.The solution configured is poured into the ptfe autoclave of 100ml, 200
DEG C reaction 16h, is deposited in normal pressure by gained after completion of the reaction, temperature for 90 DEG C of hydrolysis 3 it is small when, then washed with acetone, 60 DEG C
Dry to obtain bismuth oxybromide.It is 6-7, electrical conductivity ＜ 20us/cm that the washing process, which need to be washed to pH value of solution,.The drying course dries
Do to bismuth oxybromide moisture and be less than 0.5%.
A, c represent to scheme using the SEM of pure water (embodiment 8) bismoclite sample obtained by solvent in Fig. 1, and b, d are represented with pure
The SEM figures of acetonitrile (embodiment 1) bismoclite sample obtained by solvent.As seen from Figure 1, the gained BiOCl in pure water solvent
Crystal is formed for the accumulation of a large amount of flaky precipitates；Gained BiOCl is by the tiny flaky precipitate of largely about 10nm thickness in pure acetonitrile
The spherical nano material formed is accumulated, is uniformly dispersed, pattern is also more regular, and this characteristic can effectively reduce photo-generated carrier half
The recombination rate in light induced electron and hole when leading vivo migration, and specific surface area bigger, contact more abundant with reaction substrate, because
This photocatalysis performance higher.
Fig. 2 represents the XRD diagram for solvent gained bismoclite sample with pure water (embodiment 8) and pure acetonitrile (embodiment 1),
As seen from the figure, either in pure water or pure acetonitrile solvent gained sample, corresponding to tetragonal system BiOCl (001),
(002), (003), (113) crystal face (show) that there is very strong spread out at place according to its standard card JCPDS card No.85-0861
Peak is penetrated, shows gained sample for the higher BiOCl crystal of purity, from the point of view of the acuity at high-strength peak, gained BiOCl sample knots
Brilliant degree is fine.The XRD diffraction maximums of gained BiOCl are less in pure water, are due to that gained crystal sheet is larger, crystal is flat, crystal
Orientation arrange so that some diffraction maximums weaken even disappears.
For relatively gained BiOCl and commodity (P25) TiO2Photocatalysis efficiency, by the BiOCl samples synthesized by embodiment 1
Product and commodity (P25) TiO2Light degradation is carried out to RhB dyestuffs under visible ray/simulated solar irradiation, final data is shown in after processing
Fig. 3, from the figure 3, it may be seen that either under visible ray or simulated solar irradiation, the photocatalysis performance of BiOCl is obvious obtained by this experiment
Better than commodity (P25) TiO2.Under visible ray, after 35min gained BiOCl to the degradation rate of RhB up to 100%, and TiO2The bottom of to
The degradation rate of thing is less than 1%；Under simulated solar, degradeds of the BiOCl to substrate is up to more than 99% after 25min, and commodity (P25)
TiO2Only 40% or so.
Fig. 4 is represented with the Fourier of pure water (embodiment 8) and pure acetonitrile (embodiment 1) the bismoclite sample obtained by solvent
Infrared spectrogram, as seen from the figure, in the infrared spectrum using acetonitrile as sample obtained by solvent, 531cm-1There is very strong absorption at place
(it is 525cm when pure water is solvent-1), this is attributed to the vibration of Bi-O keys in BiOCl；1040cm-1(it is 1035cm in pure water-1)、
1445cm-1Also there is stronger absorption at place, is respectively the symmetrical and asymmetric stretching vibration of Bi-Cl keys in BiOCl；1625cm-1、
3450cm-1Corresponding absorption H respectively2The flexural vibrations of H-O and stretching vibration (respectively 1640cm when pure water is solvent in O-1、
3395cm-1).Therefore, either BiOCl crystal has been obtained using pure acetonitrile or pure water as solvent.
Fig. 5 represents kinetics of photocatalytic degradation curve of the bismuth oxybromide to rhodamine B (RhB), as seen from Figure 5, most
The photocatalysis efficiency of hydrolysis gained bismuth oxybromide photocatalyst is high after good condition is reaction time 16h, reaction temperature is 200 DEG C,
Photocatalysis efficiency reaches 100% in 15min.
Fig. 6 represents to hydrolyze the XRD diagram of forward and backward gained bismuth oxybromide, the bismuth oxybromide after hydrolyzing it can be seen from XRD diagram
There is very strong diffraction maximum at (102), (110), (200), (212) place, show that gained sample purity is higher, and by not passing through
Though the double salt of hydrolysis also have several stronger diffraction maximums compared with standard bismuth oxybromide only several peaks relatively, explanation
Gained sample is entirely different before hydrolysis and after hydrolysis.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (6)
1. double salt Hydrolyze method prepares high activity BiOX catalysis material, it is characterised in that includes the following steps：By bismuth salt,
Solvent, halogen acid solution mixing make bismuth salt be completely dissolved to mixed liquor to be clear state, mixed liquor is placed in reaction kettle,
When 100-250 DEG C of reaction 6-20 is small, gained is deposited in normal pressure after completion of the reaction, when temperature is 20-100 DEG C of hydrolysis 0.5-5 small,
Then organic solvent washing is used, 50-100 DEG C dries to obtain BiOX；The solvent is acetonitrile, the organic solvent for alcohol and
At least one of acetone；The bismuth salt：Solvent：The molar ratio of halogen acid solution is 0.04 ~ 0.012：0.4~3：0.2~1.2；
Halogen acid solution is hydrobromic acid.
2. double salt Hydrolyze method prepares high activity BiOX catalysis material according to claim 1, it is characterised in that described
Bismuth salt is at least one of bismuth chloride, bismuth subcarbonate, bismuth sulfate, bismuth nitrate.
3. double salt Hydrolyze method prepares high activity BiOX catalysis material according to claim 1, it is characterised in that described
Mixing is mixed using ultrasonic wave.
4. double salt Hydrolyze method prepares high activity BiOX catalysis material according to claim 1, it is characterised in that described
Reaction kettle is ptfe autoclave.
5. double salt Hydrolyze method prepares high activity BiOX catalysis material according to claim 1, it is characterised in that described
It is 6-7, electrical conductivity ＜ 20us/cm that washing process, which need to be washed to pH value of solution,.
6. double salt Hydrolyze method prepares high activity BiOX catalysis material according to claim 1, it is characterised in that described
Drying course is dried to BiOX moisture less than 0.5%.
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| CN101024188A (en) * | 2007-02-15 | 2007-08-29 | 中国科学院上海硅酸盐研究所 | Halogen-oxide photocatalytic material and preparing method |
| CN101890354A (en) * | 2010-07-27 | 2010-11-24 | 北京师范大学 | Method for preparing bismuth ferrite photocatalyst |
| CN104014352A (en) * | 2014-05-14 | 2014-09-03 | 太原理工大学 | Multivariate controllable synthesis method of BiOCl photocatalyst |
| CN104226339A (en) * | 2014-09-18 | 2014-12-24 | 玉林师范学院 | Visible-light-induced photocatalyst Bi4O5Br2 and preparation method thereof |
| CN106040268A (en) * | 2016-04-14 | 2016-10-26 | 燕园众欣纳米科技（北京）有限公司 | Preparation method and application of small-size bismuth oxychloride/bismuth oxybromide chip |
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| CN101024188A (en) * | 2007-02-15 | 2007-08-29 | 中国科学院上海硅酸盐研究所 | Halogen-oxide photocatalytic material and preparing method |
| CN101890354A (en) * | 2010-07-27 | 2010-11-24 | 北京师范大学 | Method for preparing bismuth ferrite photocatalyst |
| CN104014352A (en) * | 2014-05-14 | 2014-09-03 | 太原理工大学 | Multivariate controllable synthesis method of BiOCl photocatalyst |
| CN104226339A (en) * | 2014-09-18 | 2014-12-24 | 玉林师范学院 | Visible-light-induced photocatalyst Bi4O5Br2 and preparation method thereof |
| CN106040268A (en) * | 2016-04-14 | 2016-10-26 | 燕园众欣纳米科技（北京）有限公司 | Preparation method and application of small-size bismuth oxychloride/bismuth oxybromide chip |
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