GB2598977A - A preparation method of nanoflower titanium oxide by liquid circulation of chloridion - Google Patents
A preparation method of nanoflower titanium oxide by liquid circulation of chloridion Download PDFInfo
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- GB2598977A GB2598977A GB2103995.3A GB202103995A GB2598977A GB 2598977 A GB2598977 A GB 2598977A GB 202103995 A GB202103995 A GB 202103995A GB 2598977 A GB2598977 A GB 2598977A
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- titanium oxide
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- nanoflower
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000007788 liquid Substances 0.000 title claims abstract description 49
- 230000004087 circulation Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002057 nanoflower Substances 0.000 title claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000012530 fluid Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 230000001699 photocatalysis Effects 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011941 photocatalyst Substances 0.000 claims description 4
- VLYMIZRIGGBHSH-UHFFFAOYSA-N 5-(2-chloroethyl)-1h-imidazole;hydron;chloride Chemical compound Cl.ClCCC1=CNC=N1 VLYMIZRIGGBHSH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 claims 1
- FPSGJMRUEZMUNZ-UHFFFAOYSA-N ClCCN1C=NC(C1)=O Chemical compound ClCCN1C=NC(C1)=O FPSGJMRUEZMUNZ-UHFFFAOYSA-N 0.000 claims 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 2
- 238000003756 stirring Methods 0.000 abstract 2
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000008901 benefit Effects 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- -1 1-ethyl chloride-3-methylimidazolium chloride Chemical compound 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000001478 1-chloroethyl group Chemical group [H]C([H])([H])C([H])(Cl)* 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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
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- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/30—Particle morphology extending in three dimensions
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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
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Abstract
A method for preparing nanoparticle titanium oxide material is disclosed which comprises the following steps; chloridion liquid is mixed with an organic solvent, heating performed, then under stirring, tetrabutyl titanate added, then the mixture is transferred to a reaction still for a hydrothermal reaction, and after the hydrothermal reaction is finished, products washed with ethanol to recycle fluid containing the chloridion liquid, and then rotary evaporation is performed to condense volume to 50mL; the product is dried to be calcined to form titanium oxide material; the 50mL fluid recycled is placed in a beaker, and then under stirring, tetrabutyl titanate is added dropwise, the mixture is transferred to the reaction still for the hydrothermal reaction, and after the hydrothermal reaction is finished, products washed with the ethanol to recycle fluid containing the chloridion liquid, and then rotary evaporation is performed to condense volume to 50mL; the product is dried to be calcined, thereby titanium oxide material for the first circulation is obtained, ethanol cleanout fluid containing the chloridion liquid is reused for a preparation of the titanium oxide and the cycle can be repeated n times.
Description
A CIRCULATING PREPARATION METHOD OF NANOFLOWER TITANIUM OXIDE BY CHLORIDION LIQUID
TECHNICAL FIELD
[0001] The present invention relates to the technical field of titanium oxide preparation and photocatalysis, in particular to a dial lating preparation method of n an ofi ewer titanium oxide by chloridion
BACKGROUND OF THE INVENTION
[0002] The titanium oxide is one kind of photocatalysts which is widely studied with advantages like green and environmental protection, stable chemical nature and low cost, in recent years, the titanium oxide has developed a lot in fields of photocatalyst and purification of sewage, however, in practical applications, the titanium oxide is limited by electric conductivity of electrons and ions, thereby a photocatalytic reaction efficiency is affected; some measures like morphological structure design, nanoscale control, metal doping and material cladding are applied to improve a poor conductivity of the titanium oxide, however, processing methods like the metal doping and the material cladding are not only increasing a product cost of the titanium oxide, but also leading to problems like particle aggregation, disperse difficultly and low interface composite effect, thereby the conductivity of the material is reduced; moreover, when the morphological structure design and the nanoscale control are applied, some solvents are required to be added, thereby by-products are easily to be produced, which is not only reducing the productivity of the titanium oxide, but also polluting environment, therefore, to prepare the titanium oxide with a suitable method is what human need to explored for.
BRIEF SUMMARY OF THE INVENTION
[0003] The technical problem to be solved by the invention is to provide a circulating preparation method of rianollower titanium oxide by chloridion liquid so as to overcome the problems existing in the prior art, and the preparation method of the present invention specifically comprises the following steps: [0004] (1) Chloridion liquid is uniformly mixed with an organic solvent, an ultrasonic heating is performed at a temperature of 45-80°C for 15-30 minutes, and then under magnetic stirring, terabutyl titanate is added dropwise to be stirred for 10-20 minutes, and then a mixture is transferred to a reaction still for a hydrothermal reaction, and after the hydrothermal reaction is finished, products washed with ethanol are applied to recycle cleanout fluid containing the chloridion liquid, and then a rotary evaporation is performed to condense liquid volume to 50mL for a standby application; and then, the product is dried to be transferred to be calcined in a muffle furnace, thereby a nanoflower titanium oxide material is obtained, and the nanoflower titanium oxide material is named as PO.
[0005] (2) 50mL of cleanout fluid recycled in Step (1) is placed in a beaker, and then under magnetic stirring, the terabutyl titanate is added dropwise to be stirred for 10-20 minutes, and then the mixture is transferred to the reaction still for the hydrothermal reaction, and after the hydrothermal reaction is finished, products washed with the ethanol are applied to recycle the cleanout fluid containing the chloridion liquid, and then a rotary evaporation is performed to condense the fluid volume to 50mL for a standby application, and then, the product is dried to be transferred for being calcined in the muffle furnace, thereby the titanium oxide material for the first circulation is obtained, and the titanium oxide material for the first circulation is named as Pl.
[0006] (3) Ethanol cleanout fluid containing the chloridion liquid is reused for preparing the titanium oxide, and finally the titanium oxide material for n circulations is obtained, and the the titanium oxide material for n circulations is named as Pn [0007] As an optimized technical proposal, the organic solvent in Step (1) is one or more of the ethanol, isopropanol, ethylene glycol and acetone.
[0008] As an optimized technical proposal, the chloridion liquid in Step (1) is one or more of 1-ethyl chloride-3-methylimidazolium chloride, 4-(2-Chloroethyl) Imidazole chloride, 1-chl oroethyl -3-methyl imi dazol, 1-(2-Chl oroethyl)-2-Imidazoli none and N-(2-Chl oroethyl) 1 FlImi dazol e hydrochloride.
[0009] As an optimized technical proposal, a molar volume ratio of the chloridion liquid, the organic solvent and the terabutyl titanate in Step (1) is (1.5-10) mmol: 50 mL. (3-10) mmol.
[0010] As an optimized technical proposal, the hydrothermal reaction stated in Step (1), Step (2) or Step (3) is heated at 150-200t for 6-24 hours.
[0011] As an optimized technical proposal, the ethanol in Step (1) is 50-150 mL.
[0012] As an optimized technical proposal, the calcination stated in Step (I), Step (2) or Step (3) is heated to 200°C at a heating rate of 2r/min for I hour, and then heated to 250-400°C at a heating rate of 3 t/min for 1-3 hours.
[0013] As an optimized technical proposal, a scope of n in Step (4) is 1-5 times.
[0014] Furthermore, the titanium oxide material which is synthetic and recycled with above-stated method is applied in a field of photocatalytic hydrogen production as a photocatalyst.
[OW 5] The benefits of the invention are as follows: (1) the circulating preparation method of nanoldower titanium oxide by chloridion liquid provided by the present invention has some advantages like simple structure, easy to operate, green and environmental protection and no secondary pollution; moreover, when in a preparation process, a mixed liquor of the chloridion liquid and the organic solvent can be reused, thereby a system to prepare the titanium oxide circularly is formed, which is not only saving cost, but also benefit to a concept of green preparation and energy-saving, and at the same time, a new strategy is provided to prepare the titanium oxide; (2) as ionic liquid applied in the present invention has characteristics like electrical conductivity, difficult to volatilize, incombustible, electrochemical stability, high repeating utilization factor and pollution-free, when the chloridion liquid is applied to dissolve raw material as a secondary solvent for synthesizing the titanium oxide, which is not only accelerating a chemical reaction rate, but also forming a rodlike structure as the titanium oxide affected by the chloridion, thereby a nanoflower structure is constructed, which is benefit to process the light-catalyzed reaction; (3) the chloridion liquid applied in the present invention is also regarded as a cocatalyst, which is able to enhance an interaction among regents, thereby a photocatalytic hydrogen production performance with the titanium oxide is improved; moreover, raw material of the titanium oxide prepared and the titanium oxide prepared at an initial period have relative good photocatalytic hydrogen production performances.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 is a scanning electron micrograph of the prepared material in embodiment 1 and comparative example 1 of the present invention, wherein figure 1(a) is a scanning electron micrograph with low resolution of original sample PO in the embodiment 1; figure 1(b) is a scanning electron micrograph with high resolution of original sample PO in the embodiment]; figure 1(c) is a scanning electron micrograph of sample PI for the first circulation in embodiment 1; figure 1(d) is a scanning electron micrograph of sample P2 for the second circulation in embodiment 1; figure 1(e) is a scanning electron micrograph of sample P3 for the third circulation in embodiment 1; figure l(f) is a scanning electron micrograph of sample P4 for the fourth circulation in embodiment 1; figure 1(g) is a scanning electron micrograph of sample P5 for the fifth circulation in embodiment 1; figure 1(h) is a scanning electron micrograph of the comparative example 1.
[0017] Figure 2 is a fluorescence spectrogram of the prepared material in comparative example I and original sample PO in embodiment 1 of the present invention.
[0018] Figure 3 is a histogram of photocatalystic hydrogen production performance of the prepared materials in comparative examples 1-2, original sample PO, samples Pl, P2, P3, P4, PS in embodiment 1
DETAILED DESCRIPTION OF THE INVENTION
[0019] Embodiment I [0020] A circulating preparation method of narieflower titanium oxide by chloridion liquid, wherein the detailed preparation steps are as follows: [0021] (1) 10 mmol 1-ethyl chloride-3-methylimidazolium chloride is uniformly mixed with 50 nit of ethanol, and an ultrasonic heating is performed at a temperature of 60°C. for 20 minutes, and then under magnetic stirring, 10 mmol terabutyl titanate is added dropwise to be stirred for 20 minutes, and then a mixture is transferred to a reaction still for a hydrothermal reaction at 180°C for 12 hours, and after the hydrothermal reaction is finished, products washed with 100 rd. of the ethanol are applied to recycle cleanout fluid containing the chloridion liquid, a n a. rotary evaporation is peiThrrned to condense liquid o u e to 50mf. for a standby application; and then, the product is dried to be transferred to be heated to 200 'C for 1 hour at a heating rate of 2"C/min in a muffle furnace, and then organic matters on surface of the products are further removed by being heated to 300 'C at a heating rate of 3"Chnin for 1 hour, thereby a nanaflower titanium oxide material is Obtained, and the nanotlower titanium oxide material is named as PO.
[00221 50nth of cleanout fluid recycled in Step (I) is placed in a beaker, and then under magnetic stirring, 10 mmol the terabutyl titariate is added dropwi se to be stirred for 20 minutes, and then the mixture is transferred to the reaction still for the hydrothermal reaction at 180 'C for 12 hours, and after the hydrothermal reaction is finished, products washed with 100 mid of the ethanol are applied to recycle the cleanout fluid containing the chloridion liquid, and then the rotary evaporation is performed to condense the liquid volume to 50mL for a standby application, and then, the product is dried to be transferred for being heated to 200 "C at a heating rate of 2'Clinin for 1 hour in a muffle furnace, and then the organic matters on the surface of the products are further removed by being heated to 300 "C at a heating rate of 3cChnin for 1 hour, thereby a nanoflower titanium oxide material for the first circulation is obtained_ and the nand-lower titanium oxide material for the first circulation is named as Pi; [0023] (3) Ethanol cleanout fluid containing the chloridion liquid is reused for preparing the titanium oxide, and finally the titanium oxide material for n circulations is obtained(n-1,2,3,4,5), and the the titanium, oxide material for n circulations is named as Pn.
[0024] Comparative example 1 [0025] Compared with the embodiment 1, the comparative example.' does not add the chloridion liquid in the preparation process.
[0026] Comparative example 2 [0027] Commercial titanium oxide is selected by the comparative example 2 if the present invention.
100281 ZEISS Field Emission Scanning Electron Microscope of WOLFBN is applied to characterize morphology of original sample PO prepared in embodiment 1, five samples in circulations-P1, P2, P3, P4, P5 and the titanium oxide material prepared in comparative example 1 without adding the chloridion liquid, and an acceleration voltage is set to 10-30kV, and specific morphology are listed in figure 1.
[0029] Figure 1(a) and figure I(i) are respectively a scanning electron micrograph with low resolution of original sample PO and a scanning electron micrograph with high resolution of the original sample PO in the embodiment 1, which can conclude that the sample PO prepared is on flower-shaped structure composed of irons about 200nm long; figure 1(c), figure 1(d), figure 1(e), figure 1(4 figure 1(g), figure 1(h) are respectively the scanning electron micrograph of the sample P1 for the first circulation, the sample P2 for the second circulation, the sample P3 for the third circulation, the sample P4 for the fourth circulation, the sample P5 for the fifth circulation in the embodiment 1 and the comparative example 1, which can observed that the sample in early circulation period has kept same nanoflower shaped structure as PO, however, with the circulation times increase, the samples have irregularly-arranged bar structure instead of flower-shaped structures, and at the same time, a crystalline of the sample is becoming more and more poor, and particle sizes are gradually decreasing, and the morphology of the samples are closing to the morphology of the comparative example 1. Therefore, in synthetic processes of samples, the chloridion liquid is able to regulate the morphology and size of the materials, and with the circulation times increasing, components in the ionic liquid become less and less, thereby the materials no longer having controllable morphology with high crystallinity.
[0030] Fluorescence spectrophotometer is applied to characterize the original sample in embodiment 1 and prepared materials in comparative example 1, thereby to further analyze a function of the chloridion liquid in material synthesis, and wave length is set as 300-550 nm, and the fluorescence spectrophotometer is shown in figure 2.
[0031] As observed in figure 2, there are five similar characteristic peaks among PO of embodiment 1 and sample of comparative example 1 in a scope of 300-550 nm, which can be ascribed to peak of the titanium oxide, however, a characteristic peak of the PO in embodiment 1 has a relative low strength with a clear peak shape, which demonstrates that the regents have a strong interaction as adding the chloridion liquid, thereby an electron transportation is accelerated and a separation of a photo-generated electron-hole is promoted, thereby a photocatalytic performance is enhanced.
[0032] PerfectLight 6A automatic photocatalytic hydrogen production instrument, Agilent gas chromarograph integrated unit and xenon lamps are applied in this experiment to jointly detect a rate of photocatalytic hydrogen production, and the specific steps are as follows: 40 mL of deionized water, 40 mL of methanol and 20 mg of prepared materials are being sonicated for 5 mm, and then to transfer into a gas-phase reactor, and then the gas-phase reactor is sealed for being exhausted to keep a vacuum state, and then a distance between the xenon lamps and the reaction liquid level is 10 cm, and then a magnetic stirring apparatus and the xenon lamps are started to do an automatic photocatalytic hydrogen production test for 3 hours continuously; after the automatic photocatalytic hydrogen production test is finished, a gas chromatography is conducted to the produced hydrogen for a quantitative analysis, and the specific data are shown in figure 3 [0033] Figure 3 is a histogram for photocatalytic hydrogen production performance of original sample PO in embodiment 1 and five circulating samples Pl, P2, P3, P4, P5, and prepared materials in comparative examples 1-2; as can be observed in figure 3, the hydrogen-production rates are respectively 2.75 mmol/g/h, 2.70 mmol/g/h, 2.27 mmol/g/h, 1.79 mmol/g/h, 1.15 mmol/g/h, 0.42 mmol/g/h, 0.29 mmol/g/h and 0.38 mmol/g/h, wherein PO has the highest photocatalytic hydrogen production rate, which is nine times as the prepared liquid material free of the chloridion liquid in comparative example 1 and seven times as the commercial titanium oxide applied in comparative example 2, and above-stated are contributed to a efficient function of the chloridion liquid, which is not only accelerating a chemical reaction rate, but also speed up an electron transport in a catalytic reaction, thereby the materials have an excellent photocatalytic hydrogen production performance; when the material for circularly preparing the titanium oxide by the chloridion liquid is recycled, the materials showed good performance in an initial state, and the PI for the first circulation almost has a same hydrogen production rate as the original sample PO; however, when in the fourth circulation, the hydrogen production rate of the sample has decreased greatly, compared with the PO, the hydrogen production rate of the P4 decreases by 58.2% and the the hydrogen production rate of the PS decreases by 84.7%, and moreover, the PS and the samples prepared by the comparative example 1 without adding the chloridion liquid have similar hydrogen production rate, which demonstrates that the chloridion liquid no longer work as a content of the chloridion liquid has decreased greatly when in fifth circulation.
[0034] The above is only the preferable embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and any changes or substitutions without creative efforts shall fall within the protection scope of the present invention. Therefore, the claimed protection extent of the invention shall be determined with reference to the appended claims.
Claims (1)
- CLAIMS1 A preparation method of nanoflower titanium oxide by liquid circulation of chloridion, wherein the method comprises the following steps: (1) chloridion liquid is uniformly mixed with an organic solvent, an ultrasonic heating is performed at a temperature of 45-80°C for 15-30 minutes, and then under magnetic stirring, terabutyl titanate is added dropwise to be stirred for 10-20 minutes, and then a mixture is transferred to a reaction still for a hydrothermal reaction, and after the hydrothermal reaction is finished, products washed with ethanol are applied to recycle cleanout fluid containing the chloridion liquid, and then a rotary evaporation is performed to condense volume to 50mL for a standby application; and then, the product is dried to be transferred to be calcined in a muffle furnace, thereby a nanoflower Titanium oxide material is obtained, and the nanoflower titanium oxide material is named as PO; (2) 50mL cleanout fluid recycled in Step (1) is placed in a beaker, and then under magnetic stirring, the terabutyl titanate is added dropwise to be stirred for 10-20 minutes, and then the mixture is transferred to the reaction still for the hydrothermal reaction, and after the hydrothermal reaction is finished, products washed with the ethanol are applied to recycle the cleanout fluid containing the chloridion liquid, and then a rotary evaporation is performed to condense volume to 50mL for a standby application; and then, the product is dried to be transferred to be calcined in the muffle furnace, thereby a titanium oxide material for the first circulation is obtained, and the titanium oxide material for the first circulation is named as PI; (3) ethanol cleanout fluid containing the chloridion liquid is reused for a preparation of the titanium oxide, and finally the titanium oxide material for n circulations is obtained, and the the titanium oxide material for n circulations is named as Pn 2. The Preparation method of nanoflower titanium oxide by liquid circulation of chloridion defined in claim 1, wherein the organic solvent is one or more of Ethanol, Isopropanol, Ethylene glycol and Acetone 3. The Preparation method of nanoflower titanium oxide by liquid circulation of chloridion defined in claim 1, wherein the chloridion liquid in Step (1) is one or more of I-ethyl chloride-3-methylimidazolium chloride, 4-(2-Chloroethyl) Imidazole chloride, 1-chloroethy1-3-methylimidazol, 1-(2-Chloroethyl)-2-Imidazolinone and N-(2-Chloroethyl) 1H-Imidazole hydrochloride.4. The Preparation method of nanoflower titanium oxide by liquid circulation of chloridion defined in claim 1, wherein a molar volume ratio of the chloridion liquid, the organic solvent and the terabutyl titanate in Step (1) is (1.5-10) mmol: 50 mL: (310) mmol.5. The Preparation method of nanoflower titanium oxide by liquid circulation of chloridion defined in claim 1, wherein the hydrothermal reaction stated in Step (1), Step (2) or Step (3) is heated at 150-200°C for 6-24 hours.6 The Preparation method of nanoflower titanium oxide by liquid circulation of chloridion defined in claim 1, wherein the ethanol in Step (1) is 50-150 mL 7. The Preparation method of nanoflower titanium oxide by liquid circulation of chloridion defined in claim 1, wherein the calcination stated in Step (1), Step (2) or Step (3) is heated to 200°Cat a heating rate of 2°C/min for 1 hour, and then heated to 250-400°C for 13 hours at a heating rate of 3°C/min.8 The Preparation method of nanoflower titanium oxide by liquid circulation of chloridion defined in claim 1, wherein a scope of n in Step (4) is 1-5 times.9. One kind of the titanium oxide material which is synthetic and recycled is prepared with any one of methods in claims 1-8.The titanium oxide material which is synthetic and recycled defined in claim 9 is applied in a field of photocatalytic hydrogen production as a photocatalyst.
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| CN202110499059.XA CN113428894A (en) | 2021-03-23 | 2021-05-08 | Method for circularly preparing nano flower-shaped titanium dioxide by using chloride ion liquid |
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| CN105540655A (en) * | 2015-12-21 | 2016-05-04 | 河南师范大学 | Three-dimensional dendritic structure TiO2 array preparation method |
| CN107381632A (en) * | 2017-08-15 | 2017-11-24 | 齐鲁工业大学 | A kind of preparation method of three-dimensional flower-shaped titanium dioxide nano material |
| CN111847505A (en) * | 2020-06-17 | 2020-10-30 | 山东师范大学 | Method for preparing titanium dioxide based on ternary eutectic solvent, titanium dioxide material and application |
| CN113428894A (en) * | 2021-03-23 | 2021-09-24 | 嘉兴市湘荣化工贸易有限公司 | Method for circularly preparing nano flower-shaped titanium dioxide by using chloride ion liquid |
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| CN101580275B (en) * | 2008-05-15 | 2012-07-04 | 中国科学院过程工程研究所 | Method for preparing titanium dioxide hollow spherical powder |
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| CN104772149B (en) * | 2015-04-07 | 2017-01-18 | 大连理工大学 | Bi2O3/BiFeO3/TiO2 nano-flower photocatalytic material and preparation method thereof |
| CN106115777A (en) * | 2016-06-15 | 2016-11-16 | 南开大学 | The preparation method of a kind of titanium dioxide ultrathin nanometer page and the application in lithium ion battery thereof |
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| CN113428894A (en) * | 2021-03-23 | 2021-09-24 | 嘉兴市湘荣化工贸易有限公司 | Method for circularly preparing nano flower-shaped titanium dioxide by using chloride ion liquid |
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