CN104437460A - Photocatalyst nanocomposite prepared based on single-phase bismuth titanate - Google Patents
Photocatalyst nanocomposite prepared based on single-phase bismuth titanate Download PDFInfo
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- CN104437460A CN104437460A CN201410673747.3A CN201410673747A CN104437460A CN 104437460 A CN104437460 A CN 104437460A CN 201410673747 A CN201410673747 A CN 201410673747A CN 104437460 A CN104437460 A CN 104437460A
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- bismuth
- graphene
- photochemical catalyst
- tio
- titanate
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 36
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 title abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 29
- 229910052797 bismuth Inorganic materials 0.000 claims description 25
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 21
- 150000001621 bismuth Chemical class 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 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
- 238000001035 drying Methods 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
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 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
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 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
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 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
- 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
- 238000002156 mixing Methods 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
- 238000005406 washing Methods 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 150000001735 carboxylic acids Chemical class 0.000 description 9
- 230000008569 process Effects 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 235000011054 acetic acid Nutrition 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 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
- 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
- 238000011160 research Methods 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 241000258920 Chilopoda Species 0.000 description 1
- 241000270322 Lepidosauria Species 0.000 description 1
- 241000239226 Scorpiones Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 241000271897 Viperidae Species 0.000 description 1
- 238000010521 absorption reaction 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003795 desorption Methods 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
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect 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
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 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
- 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
- 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
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a photocatalyst nanocomposite prepared based on single-phase bismuth titanate (Bi20TiO32). A small amount of graphene is added for reaction in a supercritical preparation process of Bi20TiO32, Bi20TiO32 formed by reaction is uniformly dispersed on a graphene sheet to facilitate dispersion of both a reactant and a product and further facilitate improvement of photocatalytic performance, and a graphene-Bi20TiO32 nanocomposite is finally formed by roasting crystallization. According to the photocatalyst nanocomposite, a preparation process is mild in reaction condition and lower in implementation cost, and the prepared photocatalyst nanocomposite has photocatalytic performance higher than that of single-phase bismuth titanate, and has a broad application prospect.
Description
Technical field
The present invention relates to photocatalysis technology, especially relate to a kind of photochemical catalyst nano composite material prepared based on single-phase bismuth titanate.
Background technology
Bi and Ti is because the cheap five poisonous creatures: scorpion, viper, centipede, house lizard, toad are called as " green metal ", Bi
2q
3and TiQ
2what compound can form the multiple crystal phase structure of local meets oxide.Bismuth titanates series is a kind of typical Aurivillius stratified material, and its crystal formation mainly comprises: Bi
4ti
3o
12, Bi
2ti
2o
7, Bi
12tiO
20, Bi
20tiO
32deng.There are some researches show that molecular formula is Bi
20tiO
32single-phase bismuth titanate nano-material can be used as visible light-responded photocatalytic pollutant degradation.
Bi
20tiO
32be the one of the bismuth titanates series material with photocatalytic activity, it can meet still have this requirement of high photocatalysis performance under sunshine, and this material itself is nontoxic, meets the requirement of novel environmental friendly catalysis material.
But, single-phase Bi
20tiO
32as photochemical catalyst, there is following defect:
1, under general condition, single-phase Bi
20tiO
32be in a kind of metastable state, it only at titanium bismuth mixed oxide to Bi
2ti
2o
7occur in the process of transformation of crystal, by consulting Bi
2o
3-TiO
2the phasor of system is known, under normal conditions Bi
20tiO
32be in metastable state, it can not be formed under the condition of temperature lower than 400 DEG C.Synthesis temperature in existing method is higher, due to single-phase Bi
20tiO
32harsh and the metastability of synthesis condition, at present except quench hot method, does not also have other to synthesize in a mild condition to have the single-phase Bi of higher sunlight catalytic activity
20tiO
32the report of nano-photocatalyst material.
2, single-phase Bi
20tiO
32nano-photocatalyst material is higher because of the recombination probability of photogenerated charge, causes its photocatalytic activity performance not high.For this reason, how to improve the separative efficiency of bismuth titanates photo-generated carrier further and then to improve its photocatalysis performance, to have become one of current 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 (Bi
20tiO
32) the photochemical catalyst nano composite material prepared, preparation process reaction condition is gentle, it is lower to realize cost, and the photocatalysis performance of the photochemical catalyst nano composite material prepared is better than single-phase bismuth titanate (Bi
20tiO
32).
The present invention adopts following technical scheme to realize: a kind of photochemical catalyst nano composite material prepared based on single-phase bismuth titanate, and the nano combined material of this photochemical catalyst is prepared by following steps:
Soluble bismuth salt is joined in carboxylic acid, bismuth/carboxylic acid mol ratio is made to be 1:50-70, be stirred to after bismuth salt dissolves completely and add titanate esters, the mol ratio of titanium/bismuth is made to be 1:8-13, add structure directing agent again, the mol ratio making bismuth/structure directing agent is 1:3-4.5, adds urea after stirring, the mol ratio making bismuth/urea is 1:0.5-3, obtains the first mixed solution;
First mixed solution is injected in alcoholic solvent, 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, be transferred to after mixing in autoclave, pass into 8 ~ 12bar nitrogen, under its protection, 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 drying;
By presoma successively with ethanol and deionized water washing repeatedly, after drying at 300-400 DEG C roasting crystallization 4-6h, cool and obtain photochemical catalyst Graphene-Bi
20tiO
32nano composite material.
Wherein, described soluble bismuth salt is a kind of or this three kinds the arbitrary proportion mixture in bismuth nitrate, bismuth chloride and bismuth sulfate.
Wherein, described titanate esters is butyl titanate or isopropyl titanate, or this arbitrary proportion mixture of two kinds.
Wherein, described structure directing agent is a kind of or this four kinds the arbitrary proportion mixture in the tert-butyl alcohol, phenmethylol, benzyl carbinol and p nitrobenzyl alcohol.
Wherein, alcoholic solvent is a kind of or this three kinds the arbitrary proportion mixture in methyl alcohol, ethanol and propyl alcohol.
Compared with prior art, the present invention has following beneficial effect:
Photochemical catalyst nano composite material of the present invention is preparing Bi by supercritical methanol technology
20tiO
32add a small amount of Graphene in process together to react, make the Bi that reaction is formed
20tiO
32be dispersed in uniformly on graphene film, this is conducive to the diffusion of reactant and product, and then is conducive to the raising of photocatalysis performance, forms Graphene-Bi finally by roasting crystallization
20tiO
32nano composite material.Due to photochemical catalyst Graphene-Bi prepared by the present invention
12tiO
20nano composite material has very large surface area and higher porosity, thus improves Graphene-Bi
12tiO
20nano composite material, to the pre-adsorption capacity of the contaminant molecule that is degraded, meanwhile, also form very large diffusion admittance, single or multiple to recycle in process can contaminant restraining to the blocking in space, avoid Graphene-Bi
12tiO
20the inactivation of nano composite material, thus higher photocatalytic activity and stability can be kept.In addition, Graphene-Bi
12tiO
20the photocatalysis performance of nano composite material improves the effective separation and the transmission that come from photogenerated charge, by synthesizing single-phase Bi
12tiO
20process in add a small amount of Graphene, thus reaction forms Graphene-Bi
12tiO
20nano composite material, this Graphene-Bi
12tiO
20nano composite material is at Graphene and Bi
12tiO
20define closely-coupled interface between the two, thus construct and play good electron propagation ducts, be beneficial to the transmission of light induced electron, and then improve the separative efficiency of photo-generated carrier, thus compare single-phase Bi
12tiO
20there is better photocatalysis performance.The present invention has widened single-phase Bi
12tiO
20in the application of photocatalysis field, tool has a broad prospect of the use.
Accompanying drawing explanation
Fig. 1 is Bi
20tiO
32and Graphene-Bi
20tiO
32xRD schematic diagram.
Detailed description of the invention
The molecular formula that the application's indication single-phase bismuth titanate is is Bi
20tiO
32, therefore " single-phase bismuth titanate " mentioned in the context of this application, " single-phase Bi
20tiO
32" and " Bi
20tiO
32" all implication is identical.
The present invention proposes a kind of photochemical catalyst nano composite material prepared based on single-phase bismuth titanate, and preparation process reaction condition is gentle, it is lower to realize cost, and the photocatalysis performance of the photochemical catalyst nano composite material prepared is better than single-phase bismuth titanate.
Photochemical catalyst nano composite material of the present invention is preparing Bi by supercritical methanol technology
20tiO
32add a small amount of Graphene in process together to react, make the Bi that reaction is formed
20tiO
32be dispersed in uniformly on graphene film, this is conducive to the diffusion of reactant and product, and then is conducive to the raising of photocatalysis performance, forms Graphene-Bi finally by roasting crystallization
20tiO
32nano composite material.
Be prepared as follows:
1. the preparation of raw material: soluble bismuth salt is joined in small-molecular-weight carboxylic acid, bismuth/carboxylic acid mol ratio is made to be 1:50-70, constantly be stirred to bismuth salt to dissolve completely, dropwise titanate esters is added again in solution, titanium/bismuth mol ratio is made to be 1:8-13, continue to add the larger alcohol of molecular weight after stirring to clarify wherein as structure directing agent, bismuth/alcohol mol ratio is made to be 1:3-4.5, urea can be added wherein after stirring, bismuth/urea mol ratio is made to be 1:0.5-3, stir to clarify transparent, obtain the first mixed solution;
2. supercritical reaction: by step 1. gained first mixed solution be injected in the alcoholic solvent of molecular weight, solvent volume is 25-45mL every gram soluble bismuth salt raw material, and in every 100ml solvent, add the Graphene of 0.5 ~ 2g, be transferred to after mixing in autoclave, pass into 8 ~ 12bar nitrogen, under its protection, 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 drying;
3. crystallization be shaped: the presoma that 2. step is obtained successively with ethanol and deionized water washing repeatedly, after drying at 300-400 DEG C roasting crystallization 4-6h, take out after being cooled to room temperature and obtain photochemical catalyst Graphene-Bi
20tiO
32nano composite material.
In above step, soluble bismuth salt is bismuth nitrate, bismuth chloride or bismuth sulfate etc., small-molecular-weight carboxylic acid is formic acid, acetic acid or propionic acid etc., titanate esters is butyl titanate or isopropyl titanate etc., the alcohol that molecular weight is larger is the tert-butyl alcohol, phenmethylol, benzyl carbinol or p nitrobenzyl alcohol etc., and the alcohol of molecular weight is methyl alcohol, ethanol or propyl alcohol etc.Wherein, small-molecular-weight carboxylic acid is primary solvent, and it can make the hydrolytic process of titanate esters and bismuth salt slow down and mutually suppress, and make obtained solution-stabilized and clarify, the urea added can regulate the pattern of product and then affect its photocatalysis performance.
Further, the photochemical catalyst Graphene-Bi that the inventive method is obtained
20tiO
32nano composite material, because Graphene content is less, still keeps single-phase Bi
20tiO
32laminated structure with holes, be 20-100nm with the visible chip size of transmission electron microscope observation, sheet mesoporous is 8-10nm.
Embodiment 1
Taking 8g bismuth nitrate joins in acetic acid, bismuth/carboxylic acid mol ratio is made to be 1:70, constantly be stirred to after bismuth nitrate dissolves completely and dropwise add butyl titanate wherein again, titanium/bismuth mol ratio is made to be 1:13, continue to stir obtaining injecting structure directed agents phenmethylol wherein after clarified solution, make bismuth/alcohol mol ratio be 1:4.5, finally in above-mentioned solution, add urea, make bismuth/urea mol ratio be 1:3, be then stirred to solution clear.Obtained solution is injected in 360mL alcohol solvent; after adding 1.8g Graphene; stir 4 hours; mix in rear immigration autoclave, 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 drying; again this presoma is respectively washed 5 times by ethanol and deionized water successively, after drying at 400 DEG C roasting crystallization 4h, to be cooledly to room temperature, take out to obtain photochemical catalyst Graphene-Bi
20tiO
32nano composite material.
Embodiment 2
Taking 8g bismuth nitrate joins in acetic acid, bismuth/carboxylic acid mol ratio is made to be 1:50, constantly be stirred to after bismuth nitrate dissolves completely and dropwise add butyl titanate wherein again, titanium/bismuth mol ratio is made to be 1:8, continue to stir obtaining injecting structure directed agents phenmethylol wherein after clarified solution, make bismuth/alcohol mol ratio be 1:3, finally in above-mentioned solution, add urea, make bismuth/urea mol ratio be 1:0.5, be then stirred to solution clear.Obtained solution is injected in 200mL alcohol solvent; after adding 1g Graphene; stir 2 hours; mix in rear immigration autoclave, under the protection of 8bar 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 drying; again this presoma is respectively washed 5 times by ethanol and deionized water successively, after drying at 300 DEG C roasting crystallization 6h, to be cooledly to room temperature, take out to obtain photochemical catalyst Graphene-Bi
20tiO
32nano composite material.
Embodiment 3
Taking 8g bismuth nitrate joins in acetic acid, bismuth/carboxylic acid mol ratio is made to be 1:65, constantly be stirred to after bismuth nitrate dissolves completely and dropwise add butyl titanate wherein again, titanium/bismuth mol ratio is made to be 1:12, continue to stir obtaining injecting structure directed agents phenmethylol wherein after clarified solution, make bismuth/alcohol mol ratio be 1:4, finally in above-mentioned solution, add urea, make bismuth/urea mol ratio be 1:0.8, be then stirred to solution clear.Obtained solution is injected in 260mL alcohol solvent; after adding 2.4g Graphene; stir 4 hours; mix in rear immigration autoclave, 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 drying; again this presoma is respectively washed 5 times by ethanol and deionized water successively, after drying at 400 DEG C roasting crystallization 5h, to be cooledly to room temperature, take out to obtain photochemical catalyst Graphene-Bi
20tiO
32nano composite material.
From the Bi of Fig. 1
20tiO
32and Graphene-Bi
20tiO
32xRD schematic diagram can find out, successfully can realize titanium ion and bismuth ion to metastable state bismuth titanates (Bi
20tiO
32) conversion.In addition, as can be seen from Figure 1, Graphene-Bi
20tiO
32composite maintains metastable state bismuth titanates (Bi
20tiO
32) crystal structure; Because in complex, Graphene content is lower, the compound of a certain amount of Graphene does not affect metastable state bismuth titanates (Bi
20tiO
32) crystal structure.
Take the catalyst Graphene-Bi of the above-mentioned preparation of 0.1g
12tiO
20, disperseed 1 × 10 of fourth 100ml
-5in the beaker (250ml) of M methyl orange solution, stir 60min at dark condition lower magnetic force, suction-desorption equilibrium can be reached, after tool balance, this system is put into sun-drenched also side, under direct irradiation of sunlight, carries out the catalytic degradation of methyl orange.Every certain reaction time, get 5ml reactant liquor, and be separated by supercentrifuge, take out supernatant.Centrifugate detects via ultraviolet-visible spectrophotometer, and observes the change about the maximum absorption peak intensity at 464nm place infer the change in concentration of methyl orange degradation.Experimental result shows, Graphene-Bi of the present invention
12tiO
20photocatalytic activity is far above Bi
12tiO
20and commercial P25 (titanium dioxide).Graphene-Bi
12tiO
20catalyst is 98% at 75 minutes degradation rates; Bi
12tiO
20light urges agent to be 72% at 75 minutes degradation rates, degradable, needs about 2.5 hours; And P25 only degraded 57% 75 minutes time, degradable, need 3.5 hours.
In addition, the photochemical catalyst Graphene-Bi for preparing of the present invention
12tiO
20also have and preferably reuse characteristic.
Due to photochemical catalyst Graphene-Bi prepared by the present invention
12tiO
20nano composite material has very large surface area and higher porosity, thus improves Graphene-Bi
12tiO
20nano composite material, to the pre-adsorption capacity of the contaminant molecule that is degraded, meanwhile, also form very large diffusion admittance, single or multiple to recycle in process can contaminant restraining to the blocking in space, avoid Graphene-Bi
12tiO
20the inactivation of nano composite material, thus higher photocatalytic activity and stability can be kept.In addition, Graphene-Bi
12tiO
20the photocatalysis performance of nano composite material improves the effective separation and the transmission that come from photogenerated charge, after adding a small amount of Graphene, synthesize Bi
12tiO
20, thus form Graphene-Bi
12tiO
20nano composite material, this Graphene-Bi
12tiO
20nano composite material is at Graphene and Bi
12tiO
20define closely-coupled interface between the two, thus construct and play good electron propagation ducts, be beneficial to the transmission of light induced electron, and then improve the separative efficiency of photo-generated carrier, thus compare Bi
12tiO
20there is better photocatalysis performance.The present invention has widened Bi
12tiO
20in the application of photocatalysis field, tool has a broad prospect of the use.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. based on photochemical catalyst nano composite material prepared by single-phase bismuth titanate, it is characterized in that, the nano combined material of this photochemical catalyst is prepared by following steps:
Soluble bismuth salt is joined in carboxylic acid, bismuth/carboxylic acid mol ratio is made to be 1:50-70, be stirred to after bismuth salt dissolves completely and add titanate esters, the mol ratio of titanium/bismuth is made to be 1:8-13, add structure directing agent again, the mol ratio making bismuth/structure directing agent is 1:3-4.5, adds urea after stirring, the mol ratio making bismuth/urea is 1:0.5-3, obtains the first mixed solution;
First mixed solution is injected in alcoholic solvent, 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, be transferred to after mixing in autoclave, pass into 8 ~ 12bar nitrogen, under its protection, 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 drying;
By presoma successively with ethanol and deionized water washing repeatedly, after drying at 300-400 DEG C roasting crystallization 4-6h, cool and obtain photochemical catalyst Graphene-Bi20TiO32 nano composite material.
2. the photochemical catalyst of a kind of Graphene-bismuth titanates composite according to claim 1, it is characterized in that, described soluble bismuth salt is a kind of or this three kinds the arbitrary proportion mixture in bismuth nitrate, bismuth chloride and bismuth sulfate.
3. the photochemical catalyst of a kind of Graphene-bismuth titanates composite according to claim 1, it is characterized in that, described titanate esters is butyl titanate or isopropyl titanate, or this arbitrary proportion mixture of two kinds.
4. the photochemical catalyst of a kind of Graphene-bismuth titanates composite according to claim 1, it is characterized in that, described structure directing agent is a kind of or this four kinds the arbitrary proportion mixture in the tert-butyl alcohol, phenmethylol, benzyl carbinol and p nitrobenzyl alcohol.
5. the photochemical catalyst of a kind of Graphene-bismuth titanates composite according to claim 1, it is characterized in that, alcoholic solvent is a kind of or this three kinds the arbitrary proportion mixture in methyl alcohol, ethanol and propyl alcohol.
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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 |
| CN201610514829.2A CN106179312A (en) | 2014-11-20 | 2014-11-20 | The photocatalyst nano composite material prepared based on single-phase bismuth titanate |
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| CN105731584A (en) * | 2016-03-25 | 2016-07-06 | 郑州航空工业管理学院 | Method for removing micropollutant ibuprofen in water |
| WO2017106963A1 (en) * | 2015-12-22 | 2017-06-29 | Envision Sq Inc. | Photocatalytic composite material for the decomposition of air pollutants |
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| CN101862649A (en) * | 2010-03-23 | 2010-10-20 | 中南民族大学 | Preparation method and application of single-phase bismuth titanate nano-material |
| WO2011012935A2 (en) * | 2009-07-29 | 2011-02-03 | Universidade Do Minho | Photocatalytic coating for the controlled release of volatile agents |
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| WO2011012935A2 (en) * | 2009-07-29 | 2011-02-03 | Universidade Do Minho | Photocatalytic coating for the controlled release of volatile agents |
| CN101862649A (en) * | 2010-03-23 | 2010-10-20 | 中南民族大学 | Preparation method and application of single-phase bismuth titanate nano-material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017106963A1 (en) * | 2015-12-22 | 2017-06-29 | Envision Sq Inc. | Photocatalytic composite material for the decomposition of air pollutants |
| US10888847B2 (en) | 2015-12-22 | 2021-01-12 | Envision Sq Inc. | Photocatalytic composite material for the decomposition of air pollutants |
| CN105731584A (en) * | 2016-03-25 | 2016-07-06 | 郑州航空工业管理学院 | Method for removing micropollutant ibuprofen in water |
| CN105731584B (en) * | 2016-03-25 | 2018-04-17 | 郑州航空工业管理学院 | A kind of method for removing micropollutants brufen in water removal |
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| CN106179313A (en) | 2016-12-07 |
| CN106040227A (en) | 2016-10-26 |
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Application publication date: 20150325 Assignee: JINING JINGZE INFORMATION TECHNOLOGY CO.,LTD. Assignor: Jining high tech Keda Technology Project Service Co.,Ltd. Contract record no.: X2023980048428 Denomination of invention: Preparation of photocatalyst nanocomposites based on single-phase bismuth titanate Granted publication date: 20160831 License type: Common License Record date: 20231204 |