CN106040227B - The photochemical catalyst nanocomposite prepared based on single-phase bismuth titanate - Google Patents
The photochemical catalyst nanocomposite prepared based on single-phase bismuth titanate Download PDFInfo
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- CN106040227B CN106040227B CN201610514260.XA CN201610514260A CN106040227B CN 106040227 B CN106040227 B CN 106040227B CN 201610514260 A CN201610514260 A CN 201610514260A CN 106040227 B CN106040227 B CN 106040227B
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 19
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 27
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 235000019441 ethanol Nutrition 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 150000001735 carboxylic acids Chemical class 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 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 10
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 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
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction 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
- 238000002156 mixing Methods 0.000 claims description 5
- 239000005456 alcohol based solvent Substances 0.000 claims description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims 1
- 238000005352 clarification Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 18
- 238000007146 photocatalysis Methods 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 14
- 150000001621 bismuth Chemical class 0.000 description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 description 2
- 229910002118 Bi2Ti2O7 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 2
- 230000000903 blocking effect Effects 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
- 230000002779 inactivation Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 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
- 238000004064 recycling Methods 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
- 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 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- QAKMMQFWZJTWCW-UHFFFAOYSA-N bismuth titanium Chemical compound [Ti].[Bi] QAKMMQFWZJTWCW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 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 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
- 239000012467 final product 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
- 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
- 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 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000719 pollutant Toxicity 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
- 238000000926 separation method 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
- 238000001179 sorption measurement Methods 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
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 discloses a kind of based on single-phase bismuth titanate (Bi20TiO32) prepare photochemical catalyst nanocomposite, be with supercritical methanol technology prepare Bi20TiO32A small amount of graphene is added in the process to react together, the Bi for making reaction be formed20TiO32It is uniformly dispersed on graphene film, this is conducive to the diffusion of reactants and products, and then is conducive to the raising of photocatalysis performance, and last fired crystallization forms graphene Bi20TiO32Nanocomposite.Preparation process reaction condition of the present invention is mild, cost of implementation is relatively low, and the photocatalysis performance for the photochemical catalyst nanocomposite being prepared is better than single-phase bismuth titanate, and tool has a broad prospect of the use.
Description
The application is the Chinese patent application CN2014106737473 to November 20 2014 applying date（Based on single-phase titanium
Photochemical catalyst nanocomposite prepared by sour bismuth）The divisional application made.
Technical field
The present invention relates to photocatalysis technologies, multiple more particularly, to a kind of photochemical catalyst nanometer prepared based on single-phase bismuth titanate
Condensation material.
Background technology
Bi and Ti is because non-toxic inexpensive is referred to as " green metal ", Bi2Q3And TiQ2It is compound to be formed with a variety of crystalline phases
Structure meets oxide.Bismuth titanates series is a kind of typical Aurivillius stratified materials, its crystal form includes mainly：
Bi4Ti3O12、Bi2Ti2O7、Bi12TiO20、Bi20TiO32Deng.Some researches show that molecular formula is Bi20TiO32Single-phase bismuth titanate
Nano material can be used as visible light-responded photocatalytic pollutant degradation.
Bi20TiO32It is one kind of the bismuth titanates series material with photocatalytic activity, it disclosure satisfy that under sunlight still
With this requirement of high photocatalysis performance, and the material itself is nontoxic, meets novel environmental friendly photocatalysis material
The requirement of material.
But single-phase Bi20TiO32It is had the disadvantage that as photochemical catalyst：
1, under general condition, single-phase Bi20TiO32In a kind of metastable state, it only titanium bismuth mixed oxide to
Bi2Ti2O7Occur during transformation of crystal, by consulting Bi2O3-TiO2 The phasor of system is it is found that in general
Bi20TiO32In metastable state, it cannot be formed under conditions of temperature is less than 400 DEG C.Synthesis temperature in existing method
It is higher, due to single-phase Bi20TiO32Synthesis condition harshness and its metastability, at present other than high temperature quenching method, there are no it
He synthesizes in a mild condition has the active single-phase Bi of higher sunlight catalytic20TiO32The report of nano-photocatalyst material.
2, single-phase Bi20TiO32Nano-photocatalyst material leads to its photocatalytic activity because the recombination probability of photogenerated charge is higher
Performance is not high.For this purpose, how to further increase the separative efficiency of bismuth titanates photo-generated carrier and then improve its photocatalysis performance,
Have become one of the technical barrier currently there is an urgent need for research.
Invention content
To overcome the deficiencies of existing technologies, the present invention proposes a kind of based on single-phase bismuth titanate（Bi20TiO32）The light of preparation is urged
Agent nanocomposite, preparation process reaction condition is mild, cost of implementation is relatively low, and the photochemical catalyst nanometer being 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：Based on single-phase bismuth titanate prepare photochemical catalyst nanocomposite,
It is to prepare Bi with supercritical methanol technology20TiO32A small amount of graphene is added in the process to react together, the Bi for making reaction be formed20TiO32
Even is dispersed on graphene film, and last fired crystallization forms graphene-Bi20TiO32Nanocomposite.
In one embodiment, the nano combined material of the photochemical catalyst is prepared by following steps：
Soluble bismuth salt is added in carboxylic acid, it is 1 to make bismuth/carboxylic acid molar ratio：50-70, stirring to bismuth salt are completely dissolved
After titanate esters are added, make titanium/bismuth molar ratio be 1：8-13 adds structure directing agent, makes the molar ratio of bismuth/structure directing agent
It is 1：3-4.5 is stirring evenly and then adding into urea, and it is 1 to make the molar ratio of bismuth/urea：0.5-3 obtains the first mixed solution；
First mixed solution is injected into alcoholic solvent, alcoholic solvent volume is every gram of soluble bismuth salt raw material of 25-45mL, and
The graphene of 0.5 ~ 2g is added in every 100ml alcoholic solvents, is transferred in autoclave after mixing, is passed through 8 ~ 12bar
Nitrogen is heated to 200-250 DEG C of holding 2-6h under its protection, makes bismuth salt complete hydrolysis or alcoholysis, then open deflation valve
Discharge solvent obtains dry presoma；
Presoma is washed repeatedly with ethyl alcohol and deionized water successively, crystallization 4-6h is roasted at 300-400 DEG C after dry,
Cooling photochemical catalyst graphene-Bi to obtain the final product20TiO32Nanocomposite.
Wherein, the soluble bismuth salt is bismuth nitrate or bismuth chloride.
Wherein, the titanate esters are butyl titanate or isopropyl titanate or the arbitrary proportion mixture of both.
Wherein, the structure directing agent be the tert-butyl alcohol, benzyl alcohol, benzyl carbinol and p nitrobenzyl alcohol in one kind or this four
The arbitrary proportion mixture of kind.
Wherein, alcoholic solvent is one kind or the arbitrary proportion mixture of these three in methanol, ethyl alcohol and propyl alcohol.
Compared with prior art, the present invention has the advantages that：
Photochemical catalyst nanocomposite of the present invention is to prepare Bi with supercritical methanol technology20TiO32A small amount of stone is added in the process
Black alkene reacts together, the Bi for making reaction be formed20TiO32It is uniformly dispersed on graphene film, this is conducive to reactants and products
Diffusion, and then be conducive to the raising of photocatalysis performance, last fired crystallization forms graphene-Bi20TiO32It is nano combined
Material.Photochemical catalyst graphene-the Bi prepared due to the present invention20TiO32Nanocomposite have prodigious surface area and
Higher porosity, to improve graphene-Bi20TiO32Pre- absorption of the nanocomposite to the contaminant molecule that is degraded
Ability, meanwhile, prodigious diffusion admittance is also formed, it can be with contaminant restraining to sky during single or multiple recyclings
The blocking of gap avoids graphene-Bi20TiO32The inactivation of nanocomposite, so as to keep higher photocatalysis to live
Property and stability.In addition, graphene-Bi20TiO32The photocatalysis performance of nanocomposite improves having derived from photogenerated charge
Effect separation and transmission, by synthesizing single-phase Bi20TiO32During a small amount of graphene is added, to reaction form graphene-
Bi20TiO32Nanocomposite, the graphene-Bi20TiO32Nanocomposite is in graphene and Bi20TiO32Between the two
The interface for foring close-coupled is conducive to the transmission of light induced electron, Jin Erti to construct good electron propagation ducts
The separative efficiency of high photo-generated carrier, to compare single-phase Bi20TiO32With more preferably photocatalysis performance.The present invention widens
Single-phase Bi20TiO32In the application of photocatalysis field, tool has a broad prospect of the use.
Description of the drawings
Fig. 1 is Bi20TiO32And graphene-Bi20TiO32XRD schematic diagrames.
Specific implementation mode
The molecular formula that the application meaning single-phase bismuth titanate is is Bi20TiO32, therefore mention in the context of this application
" single-phase bismuth titanate ", " single-phase Bi20TiO32" and " Bi20TiO32" meaning it is identical.
The present invention proposes that a kind of photochemical catalyst nanocomposite prepared based on single-phase bismuth titanate, preparation process react item
Part is mild, cost of implementation is relatively low, and the photocatalysis performance for the photochemical catalyst nanocomposite being prepared is better than single-phase metatitanic acid
Bismuth.
Photochemical catalyst nanocomposite of the present invention is to prepare Bi with supercritical methanol technology20TiO32A small amount of stone is added in the process
Black alkene reacts together, the Bi for making reaction be formed20TiO32It is uniformly dispersed on graphene film, this is conducive to reactants and products
Diffusion, and then be conducive to the raising of photocatalysis performance, last fired crystallization forms graphene-Bi20TiO32It is nano combined
Material.
It is prepared as follows：
1. the preparation of raw material：Soluble bismuth salt is added in small-molecular-weight carboxylic acid, it is 1 to make bismuth/carboxylic acid molar ratio：50-
70, it is stirred continuously to bismuth salt and is completely dissolved, then titanate esters are added dropwise into solution, it is 1 to make titanium/bismuth molar ratio：8-13, after
Continue and the larger alcohol of molecular weight is added after stirring to clarify thereto as structure directing agent, it is 1 to make bismuth/alcohol molar ratio：3-4.5
Urea can be added after stirring evenly thereto, it is 1 to make bismuth/urea mol ratio：0.5-3, stirs to clarify transparent, obtains first
Mixed solution；
2. supercritical reaction：By step, 1. the first mixed solution of gained is injected into the smaller alcoholic solvent of molecular weight, solvent
Volume is every gram of soluble bismuth salt raw material of 25-45mL, and the graphene of 0.5 ~ 2g is added in every 100ml solvents, is uniformly mixed
After be transferred in autoclave, be passed through 8 ~ 12bar nitrogen, be heated under its protection 200-250 DEG C holding 2-6h, make bismuth salt
Then complete hydrolysis or alcoholysis open deflation valve discharge solvent and obtain dry presoma；
3. crystallization shapes：By step, 2. presoma obtained washs repeatedly with ethyl alcohol and deionized water successively, after drying
Crystallization 4-6h is roasted at 300-400 DEG C, is taken out after being cooled to room temperature up to photochemical catalyst graphene-Bi20TiO32It is nano combined
Material.
Soluble bismuth salt is bismuth nitrate, bismuth chloride or bismuth sulfate etc. in above step, and small-molecular-weight carboxylic acid is formic acid, acetic acid
Or propionic acid etc., titanate esters are butyl titanate or isopropyl titanate etc., the larger alcohol of molecular weight is the tert-butyl alcohol, benzyl alcohol, benzene second
Alcohol or p nitrobenzyl alcohol etc., the smaller alcohol of molecular weight are methanol, ethyl alcohol or propyl alcohol 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 inhibit, and make obtained solution-stabilized and clarify, institute
The urea of addition can adjust the pattern of product and then influence its photocatalysis performance.
Also, photochemical catalyst graphene-Bi made from the method for the present invention20TiO32Nanocomposite, due to graphene
Content is less, still keeps single-phase Bi20TiO32Laminated structure with holes, be 20- with the visible chip size of transmission electron microscope observation
100nm, aperture is 8-10nm in piece.
Embodiment 1
It weighs 8g bismuth nitrates to be added in acetic acid, it is 1 to make bismuth/carboxylic acid molar ratio：70, it is stirred continuously completely molten to bismuth nitrate
Butyl titanate is added dropwise in Xie Houzai thereto, and it is 1 to make titanium/bismuth molar ratio：13, continue to stir to note thereto after clarified solution
Enter structure directing agent benzyl alcohol, it is 1 to make bismuth/alcohol molar ratio:4.5, urea finally is added into above-mentioned solution, bismuth/urea is made to rub
You are than being 1:3, it then stirs to solution clear.Obtained solution is injected into 360mL alcohol solvents, 1.8g is added
After graphene, stirs 4 hours, move into autoclave after mixing, 250 DEG C are heated under the protection of 12bar nitrogen
6h is kept, bismuth nitrate complete hydrolysis or alcoholysis are made, deflation valve discharge solvent is then opened and obtains dry presoma, then should
Presoma uses respectively washing 5 times of ethyl alcohol and deionized water successively, crystallization 4h is roasted at 400 DEG C after dry, after being cooled to room temperature
Take out to obtain photochemical catalyst graphene-Bi20TiO32Nanocomposite.
Embodiment 2
It weighs 8g bismuth nitrates to be added in acetic acid, it is 1 to make bismuth/carboxylic acid molar ratio：50, it is stirred continuously completely molten to bismuth nitrate
Butyl titanate is added dropwise in Xie Houzai thereto, and it is 1 to make titanium/bismuth molar ratio：8, continue to stir to note thereto after clarified solution
Enter structure directing agent benzyl alcohol, it is 1 to make bismuth/alcohol molar ratio:3, urea finally is added into above-mentioned solution, makes bismuth/urea mole
Than being 1:0.5, it then stirs to solution clear.Obtained solution is injected into 200mL alcohol solvents, 1g stones are added
It after black alkene, stirs 2 hours, moves into autoclave after mixing, 250 DEG C of holdings are heated under the protection of 8bar nitrogen
6h makes bismuth nitrate complete hydrolysis or alcoholysis, then opens deflation valve discharge solvent and obtains dry presoma, then by the forerunner
Body uses respectively washing 5 times of ethyl alcohol and deionized water successively, roasts crystallization 6h at 300 DEG C after dry, is taken out after being cooled to room temperature
Obtain photochemical catalyst graphene-Bi20TiO32Nanocomposite.
Embodiment 3
It weighs 8g bismuth nitrates to be added in acetic acid, it is 1 to make bismuth/carboxylic acid molar ratio：65, it is stirred continuously completely molten to bismuth nitrate
Butyl titanate is added dropwise in Xie Houzai thereto, and it is 1 to make titanium/bismuth molar ratio：12, continue to stir to note thereto after clarified solution
Enter structure directing agent benzyl alcohol, it is 1 to make bismuth/alcohol molar ratio:4, urea finally is added into above-mentioned solution, makes bismuth/urea mole
Than being 1:0.8, it then stirs to solution clear.Obtained solution is injected into 260mL alcohol solvents, 2.4g is added
After graphene, stirs 4 hours, move into autoclave after mixing, 200 DEG C are heated under the protection of 12bar nitrogen
6h is kept, bismuth nitrate complete hydrolysis or alcoholysis are made, deflation valve discharge solvent is then opened and obtains dry presoma, then should
Presoma uses respectively washing 5 times of ethyl alcohol and deionized water successively, crystallization 5h is roasted at 400 DEG C after dry, after being cooled to room temperature
Take out to obtain photochemical catalyst graphene-Bi20TiO32Nanocomposite.
From the Bi of Fig. 120TiO32And graphene-Bi20TiO32XRD schematic diagrames can be seen that and can successfully realize
Titanium ion and bismuth ion are to metastable state bismuth titanates (Bi20TiO32) conversion.In addition, from fig. 1, it can be seen that graphene-Bi20TiO32It is multiple
Condensation material maintains metastable state bismuth titanates (Bi20TiO32) crystal structure；Since graphene content is relatively low in complex, centainly
Amount the compound of graphene does not have an impact metastable state bismuth titanates (Bi20TiO32) crystal structure.
Weigh the catalyst graphene-Bi of the above-mentioned preparations of 0.1g20TiO32, disperseed the 1 × 10 of fourth 100ml-5M
In the beaker (250ml) of methyl orange solution, the magnetic agitation 60min under dark condition can reach suction-desorption equilibrium,
After tool balances, which is put into sun-drenched also side, the catalytic degradation of methyl orange is carried out under direct irradiation of sunlight.
Every certain reaction time, 5ml reaction solutions are taken, and detach by supercentrifuge, takes out supernatant.Centrifugate via
Ultraviolet-visible spectrophotometer detects, and observes the variation of maximum absorption peak intensity about at 464nm to speculate methyl
The concentration variation of orange degradation.The experimental results showed that graphene-Bi of the invention20TiO32Photocatalytic activity is far above Bi20TiO32
And commercialization P25 (titanium dioxide).Graphene-Bi20TiO32Catalyst is 98% in 75 minutes degradation rates；Bi20TiO32Light urges agent
It is 72% in 75 minutes degradation rates, it is degradable, it needs about 2.5 hours；And P25 only degraded 57% at 75 minutes, completely
Degradation then needs 3.5 hours.
In addition, photochemical catalyst graphene-Bi prepared by the present invention20TiO32Also have and preferably reuses characteristic.
Photochemical catalyst graphene-the Bi prepared due to the present invention20TiO32Nanocomposite has prodigious surface area
And higher porosity, to improve graphene-Bi20TiO32Nanocomposite is pre- to the contaminant molecule that is degraded
Adsorption capacity, meanwhile, prodigious diffusion admittance is also formed, it can be with contaminant restraining during single or multiple recyclings
Blocking to gap avoids graphene-Bi20TiO32The inactivation of nanocomposite, so as to keep higher light to urge
Change activity and stability.In addition, graphene-Bi20TiO32The photocatalysis performance of nanocomposite, which improves, is derived from photogenerated charge
Efficiently separate and transmit, by synthesizing Bi after a small amount of graphene is added20TiO32, to form graphene-Bi20TiO32Nanometer
Composite material, the graphene-Bi20TiO32Nanocomposite is in graphene and Bi20TiO32Close coupling is formd between the two
The interface of conjunction is conducive to the transmission of light induced electron, and then improve photo-generated carrier to construct good electron propagation ducts
Separative efficiency, to compare Bi20TiO32With more preferably photocatalysis performance.The present invention has widened Bi20TiO32It is led in photocatalysis
The application in domain, tool have a broad prospect of the use.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (1)
1. the photochemical catalyst nanocomposite prepared based on single-phase bismuth titanate, which is characterized in that the photochemical catalyst is nano combined
Material is prepared by following steps：It weighs 8g bismuth nitrates to be added in acetic acid, it is 1 to make bismuth/carboxylic acid molar ratio：65, be stirred continuously to
Butyl titanate is added dropwise after being completely dissolved in bismuth nitrate thereto again, and it is 1 to make titanium/bismuth molar ratio：12, continue to stir to obtain clarification
Injecting structure directed agents benzyl alcohol thereto after liquid, it is 1 to make bismuth/alcohol molar ratio:4, urea finally is added into above-mentioned solution, makes
Bismuth/urea mol ratio is 1:0.8, it then stirs to solution clear；Obtained solution is injected into 260mL alcohol solvents
In, after 2.4g graphenes are added, stir 4 hours, move into autoclave after mixing, under the protection of 12bar nitrogen
200 DEG C of holding 6h are heated to, bismuth nitrate complete hydrolysis or alcoholysis are made, before then opening deflation valve discharge solvent obtains drying
Body is driven, then the presoma is used to respectively washing 5 times of ethyl alcohol and deionized water successively, crystallization 5h is roasted at 400 DEG C after dry, waits for cold
But to taking out to obtain photochemical catalyst graphene-Bi after room temperature20TiO32Nanocomposite.
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