CN104437460B - The photochemical catalyst nano composite material prepared based on single-phase bismuth titanate - Google Patents
The photochemical catalyst nano composite material prepared based on single-phase bismuth titanate Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052797 bismuth Inorganic materials 0.000 claims description 30
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 21
- 150000001621 bismuth Chemical class 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 230000001476 alcoholic effect Effects 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 8
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 238000006136 alcoholysis reaction Methods 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 3
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- -1 phenmethylol Chemical compound 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 238000007146 photocatalysis Methods 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000001735 carboxylic acids Chemical class 0.000 description 9
- 239000002253 acid Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000047 product Substances 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
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 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
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 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
- 229910002116 Bi12TiO20 Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- XWNOTOKFKBDMAP-UHFFFAOYSA-N [Bi].[N+](=O)(O)[O-] Chemical compound [Bi].[N+](=O)(O)[O-] XWNOTOKFKBDMAP-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 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
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 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 1
- 239000004575 stone Substances 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
- 210000002700 urine Anatomy 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
Landscapes
- 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 photochemical catalyst 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 photochemical catalyst nano composite material prepared is better than single-phase bismuth titanate, and tool has a broad prospect of the use.
Description
Technical field
The present invention relates to photocatalysis technology, especially relate to a kind of photocatalysis prepared based on single-phase bismuth titanate
Agent nano composite material.
Background technology
Bi and Ti is because non-toxic inexpensive is referred to as " green metal ", Bi2Q3And TiQ2Compound can be formed many
Plant the composite oxides of crystal phase structure.Bismuth titanates series is a kind of typical Aurivillius stratified material, it
Crystal formation specifically include that Bi4Ti3O12、Bi2Ti2O7、Bi12TiO20、Bi20TiO32Deng.Study table
Bright molecular formula is Bi20TiO32Single-phase bismuth titanate nano-material can be used as visible light-responded photocatalytic degradation
Pollutant.
Bi20TiO32Being the one of the bismuth titanates series material with photocatalytic activity, it disclosure satisfy that at the sun
Still there is under light this requirement of high photocatalysis performance, and this material itself is nontoxic, meets novel
The requirement of environmentally friendly catalysis material.
But, single-phase Bi20TiO32Have the drawback that as photochemical catalyst
1, under general condition, single-phase Bi20TiO32Being in a kind of metastable state, it is only at titanium bismuth mixed oxidization
Thing is to Bi2Ti2O7Occur during transformation of crystal, by consulting Bi2O3-TiO2The phasor of system understands,
Bi under normal conditions20TiO32Being in metastable state, it is to be formed under conditions of temperature is less than 400 DEG C
's.Synthesis temperature in existing method is higher, due to single-phase Bi20TiO32Synthesis condition harshness and meta-stable thereof
Property, at present in addition to high temperature quenching method, also do not have other synthesize in a mild condition have higher too
The single-phase Bi of sun photocatalytic activity20TiO32The report of nano-photocatalyst material.
2, single-phase Bi20TiO32Nano-photocatalyst material is higher because of the recombination probability of photogenerated charge, causes its light
Catalysis activity performance is the highest.To this end, improve the separative efficiency of bismuth titanates photo-generated carrier the most further
And then improve its photocatalysis performance, it has also 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) system
Standby photochemical catalyst nano composite material, preparation process reaction condition is gentle, it is relatively low to realize cost, and system
The photocatalysis performance of the standby photochemical catalyst nano composite material obtained is better than single-phase bismuth titanate (Bi20TiO32)。
The present invention adopts the following technical scheme that realization: a kind of photochemical catalyst prepared based on single-phase bismuth titanate is received
Nano composite material, the nano combined material of this photochemical catalyst prepared by following steps:
Soluble bismuth salt being joined in carboxylic acid, making bismuth/carboxylic acid mol ratio is 1:50-70, and stirring is to bismuth salt
Adding titanate esters after being completely dissolved, the mol ratio making titanium/bismuth is 1:8-13, adds structure directing agent, makes
The mol ratio of bismuth/structure directing agent is 1:3-4.5, is stirring evenly and then adding into urea, make bismuth/urea mole
Ratio 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 the Graphene of 0.5～2g, it is transferred to high pressure after mixing anti-
Answer in still, be passed through 8～12bar nitrogen, under it is protected, be heated to 200-250 DEG C keep 2-6h, make bismuth salt complete
All-hydrolytic or alcoholysis, then open vent valve door row and go out the presoma that solvent obtains being dried；
Being washed repeatedly by ethanol and deionized water successively by presoma, at 300-400 DEG C, roasting is brilliant after drying
Change 4-6h, cool down and i.e. obtain photochemical catalyst Graphene-Bi20TiO32Nano composite material.
Wherein, described soluble bismuth salt is bismuth nitrate or bismuth chloride.
Wherein, described titanate esters is butyl titanate or isopropyl titanate, or the arbitrary proportion of both mixes
Compound.
Wherein, during described structure directing agent is the tert-butyl alcohol, phenmethylol, benzyl carbinol and p nitrobenzyl alcohol
A kind of or the arbitrary proportion mixture of these four.
Wherein, the arbitrary proportion mixture of a kind of or these three during alcoholic solvent is methyl alcohol, ethanol and propyl alcohol.
Compared with prior art, there is advantages that
Photochemical catalyst nano composite material of the present invention is to prepare Bi by supercritical methanol technology20TiO32During add
A small amount of Graphene together reacts, and makes the Bi that reaction is formed20TiO32It is uniformly dispersed on graphene film, this
Be conducive to reactant and the diffusion of product, and then the raising of beneficially photocatalysis performance, last fired crystalline substance
Change and form Graphene-Bi20TiO32Nano composite material.The photochemical catalyst Graphene prepared due to the present invention-
Bi20TiO32Nano composite material has the biggest surface area and higher porosity, thus improves stone
Ink alkene-Bi20TiO32The nano composite material pre-adsorption capacity to the contaminant molecule that is degraded, meanwhile, also shape
Become the biggest diffusion admittance, can be with contaminant restraining to space during single or multiple recycles
Blocking, it is to avoid Graphene-Bi20TiO32The inactivation of nano composite material, such that it is able to keep higher
Photocatalytic activity and stability.It addition, Graphene-Bi20TiO32The photocatalysis performance of nano composite material carries
High source efficiently separating and transmitting in photogenerated charge, by synthesizing single-phase Bi20TiO32During add
A small amount of Graphene, thus react formation Graphene-Bi20TiO32Nano composite material, this Graphene-
Bi20TiO32Nano composite material is at Graphene and Bi20TiO32Define closely-coupled boundary between the two
Face, thus constructed the transmission of good electron propagation ducts, beneficially light induced electron, and then improve light
The separative efficiency of raw carrier, thus compare single-phase Bi20TiO32There is more preferably photocatalysis performance.This
Bright widen single-phase Bi20TiO32In 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 in the context of this application
" single-phase bismuth titanate ", " the single-phase Bi mentioned20TiO32" and " Bi20TiO32" all implications are identical.
The present invention proposes a kind of photochemical catalyst nano composite material prepared based on single-phase bismuth titanate, prepares
Journey reaction condition is gentle, it is relatively low to realize cost, and the light of the photochemical catalyst nano composite material prepared
Catalytic performance is better than single-phase bismuth titanate.
Photochemical catalyst nano composite material of the present invention is to prepare Bi by supercritical methanol technology20TiO32During add
A small amount of Graphene together reacts, and makes the Bi that reaction is formed20TiO32It is uniformly dispersed on graphene film, this
Be conducive to reactant and the diffusion of product, and then the raising of beneficially photocatalysis performance, last fired crystalline substance
Change and form Graphene-Bi20TiO32Nano composite material.
It is prepared as follows:
1. the preparation of raw material: soluble bismuth salt joined in small-molecular-weight carboxylic acid, makes bismuth/carboxylic acid mol ratio
For 1:50-70, it is stirred continuously to bismuth salt and is completely dissolved, then in solution, be added dropwise over titanate esters, make titanium/bismuth
Mol ratio is 1:8-13, and the alcohol being added thereto to molecular weight after continuing to stir to clarify bigger is led as structure
To agent, making bismuth/alcohol mol ratio is 1:3-4.5, can be added thereto to urea, make bismuth/urine after stirring
Element mol ratio is 1:0.5-3, stirs to clarify transparent, obtains the first mixed solution；
2. supercritical reaction: step 1. gained the first mixed solution is injected into the alcoholic solvent of molecular weight
In, solvent volume is 25-45mL every gram soluble bismuth salt raw material, and adds 0.5～2g in every 100ml solvent
Graphene, be transferred to after mixing in autoclave, be passed through 8～12bar nitrogen, its protect under
It is heated to 200-250 DEG C and keeps 2-6h, make bismuth salt complete hydrolysis or alcoholysis, then open vent valve door row and go out
Solvent obtains the presoma being dried；
3. crystallization shapes: presoma step 2. prepared washs repeatedly by ethanol and deionized water successively,
Dried roasting crystallization 4-6h at 300-400 DEG C, take out after being cooled to room temperature i.e. obtain photochemical catalyst Graphene-
Bi20TiO32Nano composite material.
In above step, soluble bismuth salt is bismuth nitrate or bismuth chloride etc., and small-molecular-weight carboxylic acid is formic acid, second
Acid or propionic acid etc., titanate esters is butyl titanate or isopropyl titanate etc., and the alcohol that molecular weight is bigger is tertiary fourth
Alcohol, phenmethylol, benzyl carbinol or p nitrobenzyl alcohol etc., the alcohol of molecular weight is methyl alcohol, ethanol or third
Alcohol etc..Wherein, small-molecular-weight carboxylic acid is primary solvent, and it can make titanate esters and the hydrolytic process of bismuth salt
Slowing down and mutually suppress, make obtained solution-stabilized and clarify, the urea added can regulate product
Pattern so that affect its photocatalysis performance.
Further, the photochemical catalyst Graphene-Bi that the inventive method prepares20TiO32Nano composite material, by
Less in Graphene content, still keep single-phase Bi20TiO32Laminated structure with holes, use transmission electron microscope
Observing visible chip size is 20-100nm, and 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 nitric acid
Bismuth is added dropwise over butyl titanate after being completely dissolved the most wherein, and making titanium/bismuth mol ratio is 1:13, continues to stir
Mixing to obtain injecting structure directed agents phenmethylol wherein after clarified solution, making bismuth/alcohol mol ratio is 1:4.5, the most backward
Adding urea in above-mentioned solution, making bismuth/urea mol ratio is 1:3, then stirs to solution clear.Will
Obtained solution is injected in 360mL alcohol solvent, after adding 1.8g Graphene, stirs 4 hours, mixed
Move in autoclave after closing uniformly, under the protection of 12bar nitrogen, be heated to 250 DEG C keep 6h, make nitre
Acid bismuth complete hydrolysis or alcoholysis, then open vent valve door row and go out the presoma that solvent obtains being dried, then will
This presoma respectively washs 5 times by ethanol and deionized water successively, roasting crystallization 4h at 400 DEG C after drying,
Photochemical catalyst Graphene-Bi is taken out to obtain after being cooled to room temperature20TiO32Nano 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 nitre
Acid bismuth is added dropwise over butyl titanate after being completely dissolved the most wherein, and making titanium/bismuth mol ratio is 1:8, continues
Stirring to obtain injecting structure directed agents phenmethylol wherein after clarified solution, making bismuth/alcohol mol ratio is 1:3, the most backward
Adding urea in above-mentioned solution, making bismuth/urea mol ratio is 1:0.5, then stirs to solution clear.
Obtained solution is injected in 200mL alcohol solvent, after adding 1g Graphene, stirs 2 hours, mixed
Move in autoclave after closing uniformly, under the protection of 8bar nitrogen, be heated to 250 DEG C keep 6h, make nitre
Acid bismuth complete hydrolysis or alcoholysis, then open vent valve door row and go out the presoma that solvent obtains being dried, then will
This presoma respectively washs 5 times by ethanol and deionized water successively, roasting crystallization 6h at 300 DEG C after drying,
Photochemical catalyst Graphene-Bi is taken out to obtain after being cooled to room temperature20TiO32Nano 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 nitre
Acid bismuth is added dropwise over butyl titanate after being completely dissolved the most wherein, and making titanium/bismuth mol ratio is 1:12, continues
Stirring to obtain injecting structure directed agents phenmethylol wherein after clarified solution, making bismuth/alcohol mol ratio is 1:4, the most backward
Adding urea in above-mentioned solution, making bismuth/urea mol ratio is 1:0.8, then stirs to solution clear.
Obtained solution is injected in 260mL alcohol solvent, after adding 2.4g Graphene, stirs 4 hours,
Move in autoclave after mixing, 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
This presoma is respectively washed 5 times by ethanol and deionized water successively, roasting crystallization 5h at 400 DEG C after drying,
Photochemical catalyst Graphene-Bi is taken out to obtain after being cooled to room temperature20TiO32Nano composite material.
From the Bi of Fig. 120TiO32And Graphene-Bi20TiO32XRD schematic diagram it can be seen that can become
Merit realize titanium ion and bismuth ion to metastable state bismuth titanates (Bi20TiO32) conversion.Additionally, can from Fig. 1
Know, Graphene-Bi20TiO32Composite maintains metastable state bismuth titanates (Bi20TiO32) crystal structure；
Owing in complex, Graphene content is relatively low, the compound of a certain amount of Graphene does not affects metastable state metatitanic acid
Bismuth (Bi20TiO32) crystal structure.
Weigh the catalyst Graphene-Bi of the above-mentioned preparation of 0.1g20TiO32, disperseed the 1 of fourth 100ml
×10-5In the beaker (250ml) of M methyl orange solution, magnetic agitation 60min under dark condition so that it is
Suction-desorption equilibrium can be reached, after tool balance, this system is put into sun-drenched also side, at the sun
The catalytic degradation of methyl orange is carried out under light direct irradiation.Every certain reaction time, take 5ml reactant liquor,
And separated by supercentrifuge, take out supernatant.Centrifugate is examined via ultraviolet-visible spectrophotometer
Survey, and the change observing about maximum absorption peak intensity at 464nm speculates the dense of methyl orange degradation
Degree change.Test result indicate that, the Graphene-Bi of the present invention20TiO32Photocatalytic activity is far above
Bi20TiO32And commercialization P25 (titanium dioxide).Graphene-Bi20TiO32Catalyst at 75 minutes degradation rates is
98%；Bi20TiO32Light urges agent to be 72% at 75 minutes degradation rates, degradable, needs about 2.5 hours；
And P25 only degraded 57% when 75 minutes, degradable, need 3.5 hours.
It addition, photochemical catalyst Graphene-Bi prepared by the present invention20TiO32Also have and preferably reuse spy
Property.
Photochemical catalyst Graphene-the Bi prepared due to the present invention20TiO32Nano composite material has the biggest
Surface area and higher porosity, thus improve Graphene-Bi20TiO32Nano composite material is to being dropped
Solve the pre-adsorption capacity of contaminant molecule, meanwhile, also form the biggest diffusion admittance, at single or many
During secondary recycling can be with the contaminant restraining blocking to space, it is to avoid Graphene-Bi20TiO32Receive
The inactivation of nano composite material, such that it is able to keep higher photocatalytic activity and stability.It addition, graphite
Alkene-Bi20TiO32The photocatalysis performance raising of nano composite material comes from efficiently separating and passing of photogenerated charge
Defeated, by synthesizing Bi after adding a small amount of Graphene20TiO32, thus form Graphene-Bi20TiO32Nanometer is multiple
Condensation material, this Graphene-Bi20TiO32Nano composite material is at Graphene and Bi20TiO32Formed between the two
Closely-coupled interface, thus constructed the biography of good electron propagation ducts, beneficially light induced electron
Defeated, and then the separative efficiency of raising photo-generated carrier, thus compare Bi20TiO32There is more preferably photocatalysis
Performance.The present invention has widened Bi20TiO32In the application of photocatalysis field, 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 at this
Any amendment, equivalent and the improvement etc. made within the spirit of invention and principle, should be included in this
Within the protection domain of invention.
Claims (5)
1. the photochemical catalyst nano composite material prepared based on single-phase bismuth titanate, it is characterised in that this light is urged
The nano combined material of agent 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 is to bismuth salt
Adding titanate esters after being completely dissolved, the mol ratio making titanium/bismuth is 1:8-13, adds structure directing agent, makes
The mol ratio of bismuth/structure directing agent is 1:3-4.5, is stirring evenly and then adding into urea, make bismuth/urea mole
Ratio 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 the Graphene of 0.5～2g, it is transferred to high pressure after mixing anti-
Answer in still, be passed through 8～12bar nitrogen, under it is protected, be heated to 200-250 DEG C keep 2-6h, make bismuth salt complete
All-hydrolytic or alcoholysis, then open vent valve door row and go out the presoma that solvent obtains being dried；
Being washed repeatedly by ethanol and deionized water successively by presoma, at 300-400 DEG C, roasting is brilliant after drying
Change 4-6h, cool down and i.e. obtain photochemical catalyst Graphene-Bi20TiO32Nano composite material.
The photochemical catalyst nano composite material prepared based on single-phase bismuth titanate the most according to claim 1,
It is characterized in that, described soluble bismuth salt is bismuth nitrate or bismuth chloride.
The photochemical catalyst nano composite material prepared based on single-phase bismuth titanate the most according to claim 1,
It is characterized in that, described titanate esters is butyl titanate or isopropyl titanate, or the arbitrary proportion of both
Mixture.
The photochemical catalyst nano composite material prepared based on single-phase bismuth titanate the most according to claim 1,
It is characterized in that, described structure directing agent is in the tert-butyl alcohol, phenmethylol, benzyl carbinol and p nitrobenzyl alcohol
A kind of or arbitrary proportion mixture of these four.
The photochemical catalyst nano composite material prepared based on single-phase bismuth titanate the most according to claim 1,
It is characterized in that, alcoholic solvent is the arbitrary proportion mixing of a kind of or these three in methyl alcohol, ethanol and propyl alcohol
Thing.
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| CN201610514260.XA CN106040227B (en) | 2014-11-20 | 2014-11-20 | The photochemical catalyst nanocomposite prepared based on single-phase bismuth titanate |
| CN201610514932.7A CN106179313A (en) | 2014-11-20 | 2014-11-20 | The photocatalyst nano composite material prepared based on single-phase bismuth titanate |
| CN201410673747.3A CN104437460B (en) | 2014-11-20 | 2014-11-20 | The photochemical catalyst nano composite material prepared based on single-phase bismuth titanate |
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| CN201610514260.XA Division CN106040227B (en) | 2014-11-20 | 2014-11-20 | The photochemical catalyst nanocomposite prepared based on single-phase bismuth titanate |
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