CN106179312A - The photocatalyst nano composite material prepared based on single-phase bismuth titanate - Google Patents
The photocatalyst nano composite material prepared based on single-phase bismuth titanate Download PDFInfo
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- CN106179312A CN106179312A CN201610514829.2A CN201610514829A CN106179312A CN 106179312 A CN106179312 A CN 106179312A CN 201610514829 A CN201610514829 A CN 201610514829A CN 106179312 A CN106179312 A CN 106179312A
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 31
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052797 bismuth Inorganic materials 0.000 claims description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 150000001621 bismuth Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 13
- 235000013877 carbamide Nutrition 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 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 12
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 3
- 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 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 22
- 238000007146 photocatalysis Methods 0.000 abstract description 18
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 4
- 229910002116 Bi12TiO20 Inorganic materials 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000001735 carboxylic acids Chemical class 0.000 description 9
- 238000006136 alcoholysis reaction Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910002118 Bi2Ti2O7 Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241001198704 Aurivillius Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- QAKMMQFWZJTWCW-UHFFFAOYSA-N bismuth titanium Chemical compound [Ti].[Bi] QAKMMQFWZJTWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002023 wood Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention is open a kind of based on single-phase bismuth titanate (Bi20TiO32) the photocatalyst nano composite material prepared, it is to prepare Bi by supercritical methanol technology20TiO32During add a small amount of Graphene and together react, make the Bi that reaction is formed20TiO32Being uniformly dispersed on graphene film, this is conducive to the diffusion of reactant and product, and then the raising of beneficially photocatalysis performance, and last fired crystallization forms Graphene Bi20TiO32Nano composite material.Preparation process reaction condition of the present invention is gentle, it is relatively low to realize cost, and the photocatalysis performance of the photocatalyst nano composite material prepared is better than single-phase bismuth titanate, and tool has a broad prospect of the use.
Description
The application is that Chinese patent application CN2014106737473 to November 20 in 2014 applying date is (based on single-phase titanium
The acid photocatalyst nano composite material prepared of bismuth) divisional application made.
Technical field
The present invention relates to photocatalysis technology, especially relate to a kind of photocatalyst nanometer prepared based on single-phase bismuth titanate again
Condensation material.
Background technology
Bi and Ti is because non-toxic inexpensive is referred to as " green metal ", Bi2Q3And TiQ2Compound can formation has multiple crystalline phase
Structure meet oxide.Bismuth titanates series is a kind of typical Aurivillius stratified material, and its crystal formation specifically includes that
Bi4Ti3O12、Bi2Ti2O7、Bi12TiO20、Bi20TiO32Deng.There are some researches show that molecular formula is Bi20TiO32Single-phase bismuth titanate
Nano material can be used as visible light-responded photocatalytic pollutant degradation.
Bi20TiO32Being the one of the bismuth titanates series material with photocatalytic activity, it disclosure satisfy that under sunlight still
There is this requirement of high photocatalysis performance, and this material itself is nontoxic, meet novel environmental friendly photocatalysis material
The requirement of material.
But, single-phase Bi20TiO32Have the drawback that as photocatalyst
1, under general condition, single-phase Bi20TiO32Be in a kind of metastable state, it only titanium bismuth mixed oxide to
Bi2Ti2O7Occur during transformation of crystal, by consulting Bi2O3-TiO2The phasor of system understands, under normal conditions
Bi20TiO32Being in metastable state, it can not be formed under conditions of temperature is less than 400 DEG C.Synthesis temperature in existing method
Higher, due to single-phase Bi20TiO32Synthesis condition harshness and metastability thereof, at present in addition to high temperature quenching method, also do not have it
He synthesizes the single-phase Bi with higher sunlight catalytic activity in a mild condition20TiO32The report of nano-photocatalyst material.
2, single-phase Bi20TiO32Nano-photocatalyst material is higher because of the recombination probability of photogenerated charge, causes its photocatalytic activity
Performance is the highest.To this end, improve the separation efficiency of bismuth titanates photo-generated carrier the most further and then improve its photocatalysis performance,
Become currently one of technical barrier needing research badly.
Summary of the invention
For overcoming the defect of prior art, the present invention proposes a kind of based on single-phase bismuth titanate (Bi20TiO32) light prepared urges
Agent nano composite material, preparation process reaction condition is gentle, it is relatively low to realize cost, and the photocatalyst nanometer prepared is multiple
The photocatalysis performance of condensation material is better than single-phase bismuth titanate (Bi20TiO32)。
The present invention adopts the following technical scheme that realization: the photocatalyst nano composite material prepared based on single-phase bismuth titanate,
It is to prepare Bi by supercritical methanol technology20TiO32During add a small amount of Graphene and together react, make the Bi that reaction is formed20TiO32All
Even is dispersed on graphene film, and last fired crystallization forms Graphene-Bi20TiO32Nano composite material.
In one embodiment, the nano combined material of this photocatalyst is prepared by following steps:
Soluble bismuth salt being joined in carboxylic acid, making bismuth/carboxylic acid mol ratio is 1:50-70, and stirring to bismuth salt is completely dissolved
Rear addition titanate esters, the mol ratio making titanium/bismuth is 1:8-13, adds structure directing agent, makes the mol ratio of bismuth/structure directing agent
For 1:3-4.5, being stirring evenly and then adding into carbamide, the mol ratio making bismuth/carbamide is 1:0.5-3, obtains the first mixed solution；
Being injected in alcoholic solvent by first mixed solution, alcoholic solvent volume is 25-45mL every gram soluble bismuth salt raw material, and
In every 100ml alcoholic solvent add 0.5～2g Graphene, be transferred to after mix homogeneously in autoclave, be passed through 8～
12bar nitrogen, is heated to 200-250 DEG C under it is protected and keeps 2-6h, make bismuth salt complete hydrolysis or alcoholysis, then open venting
Valve discharges the presoma that solvent obtains being dried；
Presoma is used ethanol and deionized water wash repeatedly successively, roasting crystallization 4-6h at 300-400 DEG C after drying,
Cool down and i.e. obtain photocatalyst Graphene-Bi20TiO32Nano composite material.
Wherein, the arbitrary proportion of a kind of or these three during described soluble bismuth salt is bismuth nitrate, bismuth chloride and bismuth sulfate
Mixture.
Wherein, described titanate esters is butyl titanate or isopropyl titanate, or the arbitrary proportion mixture of both.
Wherein, one during described structure directing agent is the tert-butyl alcohol, benzyl alcohol, phenethanol and p nitrobenzyl alcohol or this four
The arbitrary proportion mixture planted.
Wherein, the arbitrary proportion mixture of a kind of or these three during alcoholic solvent is methanol, ethanol and propanol.
Compared with prior art, there is advantages that
Photocatalyst nano composite material of the present invention is to prepare Bi by supercritical methanol technology20TiO32During add a small amount of stone
Ink alkene together reacts, and makes the Bi that reaction is formed20TiO32Being uniformly dispersed on graphene film, this is conducive to reactant and product
Diffusion, and then the raising of beneficially photocatalysis performance, last fired crystallization forms Graphene-Bi20TiO32Nano combined material
Material.Photocatalyst Graphene-the Bi prepared due to the present invention12TiO20Nano composite material has the biggest surface area and relatively
High porosity, thus improve Graphene-Bi12TiO20The nano composite material preadsorption energy to the contaminant molecule that is degraded
Power, meanwhile, also form the biggest diffusion admittance, can be with contaminant restraining to space during single or multiple recycles
Blocking, it is to avoid Graphene-Bi12TiO20The inactivation of nano composite material, such that it is able to keep higher photocatalytic activity and
Stability.It addition, Graphene-Bi12TiO20The photocatalysis performance raising of nano composite material comes from efficiently separating of photogenerated charge
And transmission, by synthesizing single-phase Bi12TiO20During add a small amount of Graphene, thus react formation Graphene-
Bi12TiO20Nano composite material, this Graphene-Bi12TiO20Nano composite material is at Graphene and Bi12TiO20Shape between the two
Become closely-coupled interface, thus constructed the transmission of good electron propagation ducts, beneficially light induced electron, and then improved
The separation efficiency of photo-generated carrier, thus compare single-phase Bi12TiO20There is more preferably photocatalysis performance.The present invention has widened list
Phase Bi12TiO20In the application of photocatalysis field, tool has a broad prospect of the use.
Accompanying drawing explanation
Fig. 1 is Bi20TiO32And Graphene-Bi20TiO32XRD schematic diagram.
Detailed description of the invention
The application indication single-phase bismuth titanate molecular formula i.e. is Bi20TiO32, therefore mention in the context of this application
" single-phase bismuth titanate ", " single-phase Bi20TiO32" and " Bi20TiO32" all implications are identical.
The present invention proposes a kind of photocatalyst nano composite material prepared based on single-phase bismuth titanate, preparation process reaction bar
Part is gentle, it is relatively low to realize cost, and the photocatalysis performance of the photocatalyst nano composite material prepared is better than single-phase metatitanic acid
Bismuth.
Photocatalyst nano composite material of the present invention is to prepare Bi by supercritical methanol technology20TiO32During add a small amount of stone
Ink alkene together reacts, and makes the Bi that reaction is formed20TiO32Being uniformly dispersed on graphene film, this is conducive to reactant and product
Diffusion, and then the raising of beneficially photocatalysis performance, last fired crystallization forms Graphene-Bi20TiO32Nano combined material
Material.
It is prepared as follows:
1. the preparation of raw material: soluble bismuth salt joined in small-molecular-weight carboxylic acid, making bismuth/carboxylic acid mol ratio is 1:50-
70, it is stirred continuously to bismuth salt and is completely dissolved, then in solution, be added dropwise over titanate esters, making titanium/bismuth mol ratio is 1:8-13, continues
Being added thereto to the bigger alcohol of molecular weight after stirring to clarify as structure directing agent, making bismuth/alcohol mol ratio is 1:3-4.5, stirs
Can be added thereto to carbamide after mixing uniformly, making bismuth/urea mol ratio is 1:0.5-3, stirs to clarify transparent, obtains the first mixing
Solution；
2. supercritical reaction: step 1. gained the first mixed solution is injected in the alcoholic solvent of molecular weight, solvent
Volume is 25-45mL every gram soluble bismuth salt raw material, and adds the Graphene of 0.5～2g, mix homogeneously in every 100ml solvent
After be transferred in autoclave, be passed through 8～12bar nitrogen, its protect under be heated to 200-250 DEG C keep 2-6h, make bismuth
Salt complete hydrolysis or alcoholysis, then open vent valve door row and go out the presoma that solvent obtains being dried；
3. crystallization shapes: presoma step 2. prepared uses ethanol and deionized water wash repeatedly successively, exists after drying
Roasting crystallization 4-6h at 300-400 DEG C, takes out after being cooled to room temperature and i.e. obtains photocatalyst Graphene-Bi20TiO32Nano combined material
Material.
In above step, soluble bismuth salt is bismuth nitrate, bismuth chloride or bismuth sulfate etc., and small-molecular-weight carboxylic acid is formic acid, acetic acid
Or propanoic acid etc., titanate esters is butyl titanate or isopropyl titanate etc., and the alcohol that molecular weight is bigger is the tert-butyl alcohol, benzyl alcohol, benzene second
Alcohol or p nitrobenzyl alcohol etc., the alcohol of molecular weight is methanol, ethanol or propanol etc..Wherein, small-molecular-weight carboxylic acid is main
Solvent, it can make the hydrolytic process of titanate esters and bismuth salt slow down and mutually suppress, and makes obtained solution-stabilized and clarifies, institute
The carbamide added can regulate the pattern of product and then affect its photocatalysis performance.
Further, the photocatalyst Graphene-Bi that the inventive method prepares20TiO32Nano composite material, owing to Graphene contains
Measure less, still keep single-phase Bi20TiO32Laminated structure with holes, be 20-with chip size seen from transmission electron microscope observation
100nm, sheet mesoporous is 8-10nm.
Embodiment 1
Weighing 8g bismuth nitrate and join in acetic acid, making bismuth/carboxylic acid mol ratio is 1:70, is stirred continuously to bismuth nitrate the most molten
Xie Houzai is added dropwise over butyl titanate wherein, and making titanium/bismuth mol ratio is 1:13, continues to stir to note wherein after clear liquor
Entering structure directing agent benzyl alcohol, making bismuth/alcohol mol ratio is 1:4.5, finally adds carbamide in above-mentioned solution, makes bismuth/carbamide rub
That ratio is 1:3, then stirs to solution clear.Obtained solution is injected in 360mL alcohol solvent, adds 1.8g
After Graphene, stir 4 hours, move in autoclave after mix homogeneously, under the protection of 12bar nitrogen, be heated to 250 DEG C
Keep 6h, make bismuth nitrate complete hydrolysis or alcoholysis, then open vent valve door row and go out the presoma that solvent obtains being dried, then should
Presoma respectively washs 5 times with ethanol and deionized water successively, and roasting crystallization 4h at 400 DEG C after drying, after being cooled to room temperature
Take out to obtain photocatalyst Graphene-Bi20TiO32Nano composite material.
Embodiment 2
Weighing 8g bismuth nitrate and join in acetic acid, making bismuth/carboxylic acid mol ratio is 1:50, is stirred continuously to bismuth nitrate the most molten
Xie Houzai is added dropwise over butyl titanate wherein, and making titanium/bismuth mol ratio is 1:8, continues to stir to note wherein after clear liquor
Entering structure directing agent benzyl alcohol, making bismuth/alcohol mol ratio is 1:3, finally adds carbamide in above-mentioned solution, makes bismuth/carbamide mole
Ratio is 1:0.5, then stirs to solution clear.Obtained solution is injected in 200mL alcohol solvent, adds 1g stone
After ink alkene, stir 2 hours, move in autoclave after mix homogeneously, under the protection of 8bar nitrogen, be heated to 250 DEG C of holdings
6h, makes bismuth nitrate complete hydrolysis or alcoholysis, then opens vent valve door row and goes out the presoma that solvent obtains being dried, then by this forerunner
Body respectively washs 5 times with ethanol and deionized water successively, roasting crystallization 6h at 300 DEG C after drying, takes out after being cooled to room temperature
Obtain photocatalyst Graphene-Bi20TiO32Nano composite material.
Embodiment 3
Weighing 8g bismuth nitrate and join in acetic acid, making bismuth/carboxylic acid mol ratio is 1:65, is stirred continuously to bismuth nitrate the most molten
Xie Houzai is added dropwise over butyl titanate wherein, and making titanium/bismuth mol ratio is 1:12, continues to stir to note wherein after clear liquor
Entering structure directing agent benzyl alcohol, making bismuth/alcohol mol ratio is 1:4, finally adds carbamide in above-mentioned solution, makes bismuth/carbamide mole
Ratio is 1:0.8, then stirs to solution clear.Obtained solution is injected in 260mL alcohol solvent, adds 2.4g
After Graphene, stir 4 hours, move in autoclave after mix homogeneously, under the protection of 12bar nitrogen, be heated to 200 DEG C
Keep 6h, make bismuth nitrate complete hydrolysis or alcoholysis, then open vent valve door row and go out the presoma that solvent obtains being dried, then should
Presoma respectively washs 5 times with ethanol and deionized water successively, and roasting crystallization 5h at 400 DEG C after drying, after being cooled to room temperature
Take out to obtain photocatalyst Graphene-Bi20TiO32Nano composite material.
From the Bi of Fig. 120TiO32And Graphene-Bi20TiO32XRD schematic diagram it can be seen that can successfully realize titanium from
Son and bismuth ion to metastable state bismuth titanates (Bi20TiO32) conversion.Additionally, from fig. 1, it can be seen that Graphene-Bi20TiO32Composite wood
Material maintains metastable state bismuth titanates (Bi20TiO32) crystal structure；Owing in complex, Graphene content is relatively low, a certain amount of stone
The compound of ink alkene does not affects metastable state bismuth titanates (Bi20TiO32) crystal structure.
Weigh the catalyst Graphene-Bi of the above-mentioned preparation of 0.1g12TiO20, it is scattered in the 1 × 10 of 100ml-5M methyl
In the beaker (250ml) of orange solution, magnetic agitation 60min under dark condition so that it is suction-desorption equilibrium can be reached, wait have
After balance, this system is put into sun-drenched also side, under direct irradiation of sunlight, carries out the catalytic degradation of methyl orange.Every
In certain response time, take 5ml reactant liquor, and separated by high speed centrifuge, take out supernatant.Centrifugal liquid via ultraviolet-
Visible spectrophotometer detects, and the change observing about maximum absorption peak intensity at 464nm speculates methyl orange degradation
Concentration change.Test result indicate that, the Graphene-Bi of the present invention12TiO20Photocatalytic activity is far above Bi12TiO20And it is commercial
P25 (titanium dioxide).Graphene-Bi12TiO20Catalyst is 98% at 75 minutes degradation rates；Bi12TiO20Light urges agent at 75 minutes
Degradation rate is 72%, degradable, needs about 2.5 hours；And P25 only degraded 57% when 75 minutes, degradable, need
3.5 hour.
It addition, photocatalyst Graphene-Bi prepared by the present invention12TiO20Also have and preferably reuse characteristic.
Photocatalyst Graphene-the Bi prepared due to the present invention12TiO20Nano composite material have the biggest surface area with
And higher porosity, thus improve Graphene-Bi12TiO20The nano composite material pre-suction to the contaminant molecule that is degraded
Attached ability, meanwhile, also form the biggest diffusion admittance, can be with contaminant restraining pair during single or multiple recycles
The blocking in space, it is to avoid Graphene-Bi12TiO20The inactivation of nano composite material, such that it is able to keep higher photocatalysis to live
Property and stability.It addition, Graphene-Bi12TiO20The photocatalysis performance raising of nano composite material comes from the effective of photogenerated charge
Separate and transmission, by synthesizing Bi after adding a small amount of Graphene12TiO20, thus form Graphene-Bi12TiO20Nano combined material
Material, this Graphene-Bi12TiO20Nano composite material is at Graphene and Bi12TiO20Define closely-coupled boundary between the two
Face, thus constructed the transmission of good electron propagation ducts, beneficially light induced electron, and then improve the separation of photo-generated carrier
Efficiency, thus compare Bi12TiO20There is more preferably photocatalysis performance.The present invention has widened Bi12TiO20Answering in photocatalysis field
With, tool has a broad prospect of the use.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.
Claims (5)
1. the photocatalyst nano composite material prepared based on single-phase bismuth titanate, it is characterised in that this photocatalyst is nano combined
Material is prepared by following steps:
Soluble bismuth salt being joined in carboxylic acid, making bismuth/carboxylic acid mol ratio is 1:50-70, and stirring adds after being completely dissolved to bismuth salt
Entering titanate esters, the mol ratio making titanium/bismuth is 1:8-13, adds structure directing agent, and the mol ratio making bismuth/structure directing agent is 1:
3-4.5, is stirring evenly and then adding into carbamide, and the mol ratio making bismuth/carbamide is 1:0.5-3, obtains the first mixed solution；
Being injected in alcoholic solvent by first mixed solution, alcoholic solvent volume is 25-45mL every gram soluble bismuth salt raw material, and often
100ml alcoholic solvent adds the Graphene of 0.5～2g, after mix homogeneously, uses supercritical methanol technology to prepare Bi20TiO32, facing with super
Boundary's method prepares Bi20TiO32During make the Bi that reaction formed20TiO32It is uniformly dispersed on Graphene, last fired crystallization
Form Graphene-Bi20TiO32Nano composite material.
A kind of photocatalyst of Graphene-bismuth titanates composite, it is characterised in that described can
Dissolubility bismuth salt is the arbitrary proportion mixture of a kind of or these three in bismuth nitrate, bismuth chloride and bismuth sulfate.
The photocatalyst of a kind of Graphene-bismuth titanates composite, it is characterised in that described titanium
Acid esters is butyl titanate or isopropyl titanate, or the arbitrary proportion mixture of both.
The photocatalyst of a kind of Graphene-bismuth titanates composite, it is characterised in that described knot
Structure directed agents is the arbitrary proportion mixture of a kind of or these four in the tert-butyl alcohol, benzyl alcohol, phenethanol and p nitrobenzyl alcohol.
The photocatalyst of a kind of Graphene-bismuth titanates composite, it is characterised in that alcoholic solvent
Arbitrary proportion mixture for a kind of or these three in methanol, ethanol and propanol.
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| CN103990447A (en) * | 2014-02-26 | 2014-08-20 | 南京工业大学 | Bismuth titanate catalyst with sunlight photocatalytic activity |
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| WAN GUO ET AL.: "Self-assembled hierarchical Bi12TiO20-graphene nanoarchitectures with excellent simulated sunlight photocatalytic activity", 《PHYS. CHEM. CHEM. PHYS.》 * |
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