CN106745226A - Micro-nano titanium dioxide and preparation method and application based on eutectic solvent synthesis - Google Patents
Micro-nano titanium dioxide and preparation method and application based on eutectic solvent synthesis Download PDFInfo
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- CN106745226A CN106745226A CN201611083512.4A CN201611083512A CN106745226A CN 106745226 A CN106745226 A CN 106745226A CN 201611083512 A CN201611083512 A CN 201611083512A CN 106745226 A CN106745226 A CN 106745226A
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- 239000002904 solvent Substances 0.000 title claims abstract description 53
- 230000005496 eutectics Effects 0.000 title claims abstract description 45
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000010189 synthetic method Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 16
- 235000019743 Choline chloride Nutrition 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical group [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 16
- 229960003178 choline chloride Drugs 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 230000001699 photocatalysis Effects 0.000 claims description 15
- 238000007146 photocatalysis Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 238000006303 photolysis reaction Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 49
- 239000004408 titanium dioxide Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000003002 pH adjusting agent Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000003085 diluting agent Substances 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract 1
- 238000005287 template synthesis Methods 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 33
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 235000006408 oxalic acid Nutrition 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002077 nanosphere Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction 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
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention discloses the micro-nano titanium dioxide and preparation method and application that are synthesized based on eutectic solvent, using eutectic solvent as solvent and template synthesis micro-nano TiO2By the structure for adjusting hydrogen bond donor, without adding various diluents, pH adjusting agent and template and under conditions of avoiding high-temperature calcination, controllable preparation goes out the high-activity photocatalyst with different-shape, so as to develop the simple green of catalyst pattern easy-regulating, building-up process, the titanium dioxide new synthetic method that reaction condition is gentle, the reaction time is short and catalysis activity is high, this will provide a kind of effective route of synthesis for prepared by the green simple and easy to control of nano material.
Description
Technical field
The present invention relates to green, cleaning synthesis and photocatalysis technology field, and in particular to based on eutectic solvent synthesis
Micro-nano titanium dioxide and preparation method and application.
Background technology
Micro-nano titanium dioxide because physicochemical properties stabilization, fast light corrosive power it is strong, cheap, it is nontoxic be easy to get, environment
The features such as friendly and ultra-violet (UV) band photocatalysis performance is excellent and be widely used in photocatalytic pollutant degradation, photolysis water hydrogen, dyestuff
The fields such as the artificial light compositing of sensitization solar battery and solar energy fuel.However, titanium dioxide there is also as photochemical catalyst
Some shortcomings needs to overcome, such as the easily compound quantum efficiency for causing of photo-generate electron-hole is low and broad stopband caused by absorption spectrum
Narrow range.In face of these challenges, numerous studies improve electric charge transfer for the property of modified titanic oxide or expand visible ray
Absorption region, including noble metal or metal oxide deposition, nonmetalloid or ion doping, quantum dot load and electron carrier
Coupling.Except the above-mentioned strategy that extra elements are introduced in titanium dioxide, titanium dioxide of the exploitation with novel micro nanometer structure
It is the alternative for improving quantum efficiency.The intrinsic property of research verified anatase titania depend on its pattern,
Size and exposure crystal face, therefore, it is sudden and violent that substantial amounts of research starts to focus on the various patterns of controlledly synthesis, different size and particular crystal plane
The micro-nano-structure titanium dioxide of dew.Wherein, in terms of the Morphological control of micro-nano titanium dioxide, substantial amounts of work has been carried out,
And make great progress.But during pattern control synthesis, also facing some problems is needed to solve, and such as synthesis is walked
Rapid cumbersome, postorder often needs high-temperature calcination treatment, the building-up process also to need to add surfactant as pattern controlling agent, organic solvent
As diluent and inorganic acid as pH adjusting agent etc..Therefore, novel high-activity micro-nano titanium dioxide green easily preparation method
Exploitation is still the great challenge that micro-nano material synthesizes field.
Ionic liquid at room temperature is forced down because possessing steam, liquid journey is wide, nonflammable, electric conductivity is high, good stability, electrochemical window
Wide and zwitterion is adjustable grade for advantageous property, in the pretreatment of catalysis, organic synthesis, electrochemistry, materials chemistry, pharmacy and biomass
Etc. answering field.But in order to complete the exchange of anion in most of ionic liquid, it usually needs introduce substantial amounts of salt and solvent,
And in separation process, also commonly use organic solvent, therefore their building-up process be do not reach much it is environment-friendly.Together
When, the synthesis material price of general ionic liquid is high, causes the expensive of conventional ion liquid.These factors are seriously hindered
The process of industrialization of ionic liquid.Therefore, on the basis of ionic liquid necessity characteristic is ensured, the cheap raw material of selection safety,
Simplify synthetic schemes, the novel ion liquid for preparing more green economy be ionic liquid commercial application key issue it
One.
The content of the invention
To overcome the defect of prior art, the invention provides the micro-nano titanium dioxide and system that are synthesized based on eutectic solvent
Preparation Method and application, the simple green of its building-up process, reaction condition are gentle, the reaction time is short, and the titanium dioxide pattern of preparation is easy
Regulation and control, activity are high.
To achieve the above object, the technical scheme is that：
Application of the eutectic solvent in micro-nano titanium dioxide is synthesized.
Eutectic solvent refers to by hydrogen bond receptor (such as quaternary ammonium salt) and hydrogen-bond donor (such as acid amides, carboxylic acid and polyalcohol
Compound) two components that combine or three component eutectic mixtures, its freezing point is substantially less than the molten of each component pure material
Point.Eutectic solvent not only has heat endurance, insignificant vapour pressure, the electrochemical potential window wider of conventional ion liquid
The advantages of, also with being readily synthesized, low in raw material price, nontoxic and biodegradable advantage.In addition, the conjunction of eutectic solvent
It is easy to operate and without purifying into 100% Atom economy, it is more suitable for industrialization.
Heretofore described micro-nano titanium dioxide is the titanium dioxide with micro-nano structure, and the micro-nano structure is micron
The hierarchical structure that structure, nanostructured or both are combined.
In the present invention, eutectic solvent has (1) stronger solvent borne；(2) property of conventional ion liquid；(3) in
Portion's hydrogen bond network structure makes it have Supramolecular property, so as to soft template effect can be played；(4) can by adjust hydrogen bond donor and
The species of hydrogen bond receptor, adjusts its structure and performance so that when micro-nano titanium dioxide is prepared, without add various diluents,
PH adjusting agent and template and high-temperature calcination is avoided, so that controllable preparation goes out the micro-nano titanium dioxide with highlight catalytic active.
Preferably, the eutectic solvent is synthesized into for Choline Chloride with hydrogen-bond donor.
It is further preferred that the hydrogen-bond donor is to contain carboxyl, carbonyl or hydroxyl organic matter.
Still more preferably, the hydrogen-bond donor is oxalic acid, citric acid, tartaric acid, urea, ethylene glycol or glycerine.
It is further preferred that the Choline Chloride is 1 with the mol ratio of hydrogen-bond donor:1-4.
It is further preferred that the synthesis condition is：- 100 DEG C of temperature 60 C, time 1h-8h.
A kind of synthetic method of the micro-nano titanium dioxide based on eutectic solvent synthesis, using the organic compound of titanium as titanium
Source, adds eutectic solvent to carry out ion thermal synthesis so as to obtain based on eutectic solvent synthesis with the mixture of little water
Micro-nano titanium dioxide.
The present invention adds eutectic solvent as solvent and template so that various dilutions need not be added in building-up process
Agent, pH adjusting agent and template, it also avoid the subsequent treatments such as high-temperature calcination, the simple green of building-up process, reaction condition be gentle,
Reaction time is short；Meanwhile, control preparation micro-nano titanium dioxide with different patterns, such as micro-nano-sphere, nanometer rods, nanometer
Bar, nanometer sheet, nanometer rods intert into flower and cash strings day scape shape etc..Using eutectic solvent synthesis with different pattern micro-nanos
Titanium dioxide is respectively provided with high activity photocatalysis performance.
The organic compound of the titanium used in the present invention is butyl titanate, tetraisopropyl titanate or tetraethyl titanate etc..
It is preferred that butyl titanate.
Preferably, the eutectic solvent is synthesized into for quaternary ammonium salt with hydrogen-bond donor.
It is further preferred that the quaternary ammonium salt is Choline Chloride.Choline Chloride is used as a kind of very cheap, biodegradable
And nontoxic quaternary ammonium salt, can extract from biomass or easily use fossil energy by a kind of technique of efficient economizing
Source carries out synthetically prepared.
It is further preferred that the hydrogen-bond donor is to contain carboxyl, carbonyl or hydroxyl organic matter.
Still more preferably, the hydrogen-bond donor is oxalic acid, citric acid, tartaric acid, urea, ethylene glycol or glycerine.
By use different hydrogen-bond donors so that control prepare micro-nano titanium dioxide with different patterns, enter
And control the photocatalysis performance of micro-nano titanium dioxide.
Still more preferably, the hydrogen-bond donor is oxalic acid.It is hydrogen-bond donor to use oxalic acid, can control the micro- of preparation
Receive the structure with special cash strings day scape shape of titanium dioxide, the photocatalysis performance of the micro-nano titanium dioxide with the structure is more
It is good.
It is further preferred that the Choline Chloride is 1 with the mol ratio of hydrogen-bond donor:1-4.
It is further preferred that the synthesis condition is：- 100 DEG C of temperature 60 C, time 1h-8h.
Preferably, eutectic solvent and the volume ratio of water are 1:0.0025-0.1.Water is added in eutectic solvent, can
Butyl titanate is hydrolyzed, and in the range of this, micro-nano titanium dioxide can be controlled to possess the pattern of more preferable photocatalysis performance.
Preferably, the temperature of Hydrothermal Synthesiss is 100 DEG C -180 DEG C.System can be also controlled by controlling the time of Hydrothermal Synthesiss
Standby micro-nano titanium dioxide with different patterns, and then control the photocatalysis performance of micro-nano titanium dioxide.
It is further preferred that the temperature of Hydrothermal Synthesiss is 130-180 DEG C.The micro-nano dioxy for preparing can be controlled at this temperature
Change the structure with special cash strings day scape shape of titanium, the photocatalysis performance of the micro-nano titanium dioxide with the structure is more preferable.
Preferably, the time of Hydrothermal Synthesiss is 1h-48h.The photocatalysis of the micro-nano titanium dioxide prepared in the generated time
Performance is more preferable.
Micro-nano titanium dioxide prepared by a kind of above method.Micro-nano titanium dioxide prepared by the above method can have difference
Special construction.
Application of the above-mentioned micro-nano titanium dioxide in photocatalysis.
A kind of catalyst, is prepared by the above method.The catalysis of micro-nano titanium deoxide catalyst prepared by the above method
Effect is more preferable than the catalytic effect of presently commercially available nano titanium oxide P25.
A kind of method that photocatalytic water prepares hydrogen, photodissociation is carried out using above-mentioned catalyst.
Preferably, the consumption of the catalyst is the 1.25%-10% of solvent quality.
Beneficial effects of the present invention are：
1. the present invention uses eutectic solvent as solvent and template so that need not be added when preparing titanium dioxide various
Diluent, pH adjusting agent and template, it also avoid the subsequent treatments such as high-temperature calcination, the simple green of building-up process, reaction condition
Gently, the reaction time is short；
2. preparation method of the invention can control prepare micro-nano titanium dioxide with different patterns, such as micro-nano
Ball, nanometer rods, nano strip, nanometer sheet, nanometer rods intert into flower and cash strings day scape shape etc..Using having that eutectic solvent synthesizes
Different pattern micro-nano titanium dioxide are respectively provided with high activity photocatalysis performance.
Brief description of the drawings
Fig. 1 is the shape appearance figure of cash strings day scape；
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 3；
Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment 3.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment the invention will be further described.
Embodiment 1
Choline Chloride and oxalic acid are mixed, both mol ratios 2:1,70 DEG C are heated to, 6h is reacted under certain rotating speed, then
Eutectic solvent is obtained by drying 8h under -0.09MPa.
With butyl titanate as titanium source, 19.5mL eutectic solvents and 0.5mL water are added in the small beaker of 50mL, small
Beaker is placed on magnetic stirring apparatus and is stirred, and to butyl titanate is added dropwise in small beaker, then the solution for preparing
In the stainless steel hydrothermal reaction kettle of the polytetrafluoro liner for pouring into 25mL, good seal is put into baking oven.It is naturally cold after reacting 8h at 160 DEG C
But to room temperature, then separated with supercentrifuge with respectively washing three times of water and ethanol respectively, the solid powder of acquisition is 50
DEG C baking oven under dry 6h, you can obtain finished product titanium dioxide.
10mg catalyst is added in capacity is for the quartz reaction bottle of 18.5ml, 8ml water, 2ml methyl alcohol is subsequently adding, ultrasound
5min, is then evacuated to vacuum by quartz reaction bottle, then to nitrogen is filled with quartzy bottle, reaches the inner and outer boundary's air of bottle and flattens
Weighing apparatus.Quartzy bottle is transferred in light-catalyzed reaction instrument, ultraviolet light 6h is used, then taken out, with gas Chromatographic Determination generation
Hydrogen content.
Hydrogen-producing speed=x × residue gaseous phase volume ÷ reaction time ÷ sample qualities,
Wherein, the unit of hydrogen-producing speed：Mmol ﹒ g-1﹒ h-1, the unit of remaining gaseous phase volume：ML, the unit in reaction time：
H, the unit of sample quality：G,
X extracts the hydrogen content that 1mL gases are measured in gas-chromatography in representing bottle, and unit is mmol/mL.
With this understanding, cash strings day scape shape titanium dioxide has been prepared, its hydrogen-producing speed is up to 0.87mmol ﹒ g-1﹒ h-1,
Hydrogen-producing speed (0.25mmol ﹒ g higher than P25 under the same terms-1﹒ h-1)。
Embodiment 2
With butyl titanate as titanium source, 19.5mL eutectic solvents and 0.5mL water, synthesis are added in the small beaker of 50mL
The raw material of eutectic solvent is Choline Chloride and oxalic acid, both mol ratios 2:1.Small beaker is placed on magnetic stirring apparatus and is stirred
Mix, and to butyl titanate is added dropwise in small beaker, then the solution for preparing is poured into 25mL polytetrafluoro liner it is stainless
In steel hydrothermal reaction kettle, good seal is put into baking oven.Room temperature is naturally cooled to after reacting 6h at 160 DEG C.With this understanding, prepare
Cash strings day scape shape titanium dioxide, its hydrogen-producing speed is up to 0.81mmol ﹒ g-1﹒ h-1。
Embodiment 3
With butyl titanate as titanium source, 19.5mL eutectic solvents and 0.5mL water, synthesis are added in the small beaker of 50mL
The raw material of eutectic solvent is Choline Chloride and oxalic acid, both mol ratios 2:1.Small beaker is placed on magnetic stirring apparatus and is stirred
Mix, and to butyl titanate is added dropwise in small beaker, then the solution for preparing is poured into 25mL polytetrafluoro liner it is stainless
In steel hydrothermal reaction kettle, good seal is put into baking oven.Room temperature is naturally cooled to after reacting 24h at 160 DEG C.With this understanding, prepare
Cash strings day scape shape titanium dioxide is gone out, as Figure 2-3, its pattern is similar with the pattern of the cash strings day scape of Fig. 1, uses the cash strings
The hydrogen-producing speed of its scape shape titanium dioxide is up to 1.14mmol ﹒ g-1﹒ h-1, it is nano titanium oxide P25 product hydrogen speed under the same terms
4.6 times of rate.
Embodiment 4
With butyl titanate as titanium source, 19.5mL eutectic solvents and 0.5mL water, synthesis are added in the small beaker of 50mL
The raw material of eutectic solvent is Choline Chloride and oxalic acid, both mol ratios 2:1.Small beaker is placed on magnetic stirring apparatus and is stirred
Mix, and to butyl titanate is added dropwise in small beaker, then the solution for preparing is poured into 25mL polytetrafluoro liner it is stainless
In steel hydrothermal reaction kettle, good seal is put into baking oven.Room temperature is naturally cooled to after reacting 24h at 140 DEG C.With this understanding, prepare
The similar cash strings day scape of titanium dioxide pattern for going out, its hydrogen-producing speed is up to 0.72mmol ﹒ g-1﹒ h-1。
Embodiment 5
With butyl titanate as titanium source, 19.5mL eutectic solvents and 0.5mL water, synthesis are added in the small beaker of 50mL
The raw material of eutectic solvent is Choline Chloride and oxalic acid, both mol ratios 2:1.Small beaker is placed on magnetic stirring apparatus and is stirred
Mix, and to butyl titanate is added dropwise in small beaker, then the solution for preparing is poured into 25mL polytetrafluoro liner it is stainless
In steel hydrothermal reaction kettle, good seal is put into baking oven.Room temperature is naturally cooled to after reacting 48h at 100 DEG C.With this understanding, prepare
The titanium dioxide pattern for going out is micro-nano-sphere, and its hydrogen-producing speed is up to 0.39mmol ﹒ g-1﹒ h-1。
Embodiment 6
With butyl titanate as titanium source, 19.5mL eutectic solvents and 0.5mL water, synthesis are added in the small beaker of 50mL
The raw material of eutectic solvent is Choline Chloride and oxalic acid, both mol ratios 2:1.Small beaker is placed on magnetic stirring apparatus and is stirred
Mix, and to butyl titanate is added dropwise in small beaker, then the solution for preparing is poured into 25mL polytetrafluoro liner it is stainless
In steel hydrothermal reaction kettle, good seal is put into baking oven.Room temperature is naturally cooled to after reacting 1.5h at 180 DEG C.With this understanding, prepare
The titanium dioxide pattern for going out is cash strings day scape shape, and its hydrogen-producing speed is up to 0.56mmol ﹒ g-1﹒ h-1。
Embodiment 7
With butyl titanate as titanium source, 19mL eutectic solvents and 1mL water are added in the small beaker of 50mL, synthesized low common
The raw material of molten solvent is Choline Chloride and oxalic acid, both mol ratios 2:1.Small beaker is placed on magnetic stirring apparatus and is stirred,
And to butyl titanate is added dropwise in small beaker, then the solution for preparing is poured into the stainless steel water of the polytetrafluoro liner of 25mL
In thermal response kettle, good seal is put into baking oven.Room temperature is naturally cooled to after reacting 24h at 150 DEG C.With this understanding, prepare
The similar cash strings day scape of titanium dioxide pattern, its hydrogen-producing speed is up to 0.83mmol.g-1.h-1。
Embodiment 8
With butyl titanate as titanium source, 19.5mL eutectic solvents and 0.5mL water, synthesis are added in the small beaker of 50mL
The raw material of eutectic solvent is Choline Chloride and urea, both mol ratios 2:1.Small beaker is placed on magnetic stirring apparatus and is stirred
Mix, and to butyl titanate is added dropwise in small beaker, then the solution for preparing is poured into 25mL polytetrafluoro liner it is stainless
In steel hydrothermal reaction kettle, good seal is put into baking oven.Room temperature is naturally cooled to after reacting 24h at 130 DEG C.With this understanding, prepare
The titanium dioxide pattern for going out is micro-nano-sphere, and its hydrogen-producing speed is up to 0.47mmol ﹒ g-1﹒ h-1。
Embodiment 9
With butyl titanate as titanium source, 19.5mL eutectic solvents and 0.5mL water, synthesis are added in the small beaker of 50mL
The raw material of eutectic solvent is Choline Chloride and ethylene glycol, both mol ratios 2:1.Small beaker is placed on magnetic stirring apparatus to be carried out
Stirring, and to butyl titanate is added dropwise in small beaker, the polytetrafluoro liner that the solution for preparing then is poured into 25mL is not
In rust steel hydrothermal reaction kettle, good seal is put into baking oven.Room temperature is naturally cooled to after reacting 24h at 180 DEG C.With this understanding, make
It is micro-nano rod for the titanium dioxide for going out, its hydrogen-producing speed is up to 0.59mmol ﹒ g-1﹒ h-1。
Although above-mentioned be described with reference to accompanying drawing to specific embodiment of the invention, not to invention protection domain
Limitation, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not required to
The various modifications or deformation made by paying creative work are still within the scope of the present invention.
Claims (10)
1. application of the eutectic solvent in micro-nano titanium dioxide is synthesized.
2. it is a kind of based on eutectic solvent synthesis micro-nano titanium dioxide synthetic method, it is characterized in that, with the organic compound of titanium
Thing adds eutectic solvent to carry out Hydrothermal Synthesiss so as to obtain based on eutectic solvent synthesis with the mixture of water as titanium source
Micro-nano titanium dioxide.
3. synthetic method as claimed in claim 2, it is characterized in that, the eutectic solvent is that quaternary ammonium salt synthesizes with hydrogen-bond donor
And obtain；
Preferably, the quaternary ammonium salt is Choline Chloride；
Preferably, the hydrogen-bond donor is to contain carboxyl, carbonyl or hydroxyl organic matter；
Preferably, the Choline Chloride and the mol ratio of hydrogen-bond donor are 1:1-4；
Preferably, the synthesis condition is：Temperature 60 C~100 DEG C, time 1h-8h.
4. synthetic method as claimed in claim 2, it is characterized in that, eutectic solvent is 1 with the volume ratio of water:0.0025-
0.1。
5. synthetic method as claimed in claim 2, it is characterized in that, the temperature of Hydrothermal Synthesiss is 100 DEG C -180 DEG C；
Preferably, the temperature of Hydrothermal Synthesiss is 130-180 DEG C.
6. synthetic method as claimed in claim 2, it is characterized in that, the time of Hydrothermal Synthesiss is 1h-48h.
7. the micro-nano titanium dioxide that prepared by a kind of above method.
8. application of the micro-nano titanium dioxide described in claim 7 in photocatalysis.
9. a kind of catalyst, it is characterized in that, it is prepared by the above method.
10. a kind of method that photocatalytic water prepares hydrogen, it is characterized in that, photodissociation is carried out using the catalyst described in claim 9；
Preferably, the consumption of the catalyst is the 1.25%-10% of solvent quality.
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