CN101037228A - Preparation of graduated nano-structural transition metal oxide by two-phase solvent soft interface process - Google Patents
Preparation of graduated nano-structural transition metal oxide by two-phase solvent soft interface process Download PDFInfo
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- CN101037228A CN101037228A CN 200710051589 CN200710051589A CN101037228A CN 101037228 A CN101037228 A CN 101037228A CN 200710051589 CN200710051589 CN 200710051589 CN 200710051589 A CN200710051589 A CN 200710051589A CN 101037228 A CN101037228 A CN 101037228A
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Abstract
The present invention provides a preparation method of gradate nanostructure transition metal oxide by a two phase solvent soft interface method which comprises the steps of that: metal salt or metal oxide is added into water, and the pH value of the solution is adjusted by acid or base, then the corresponding reactant precursor is obtained; another water insoluble organic solvent is added into the solution, and the whole mixture is subjected to solvothermal treatment, and then the solid product is obtained by pumping filter, finally, the corresponding gradate nanostructure transition metal oxide is obtained after scrubbing and drying. The transition metal oxide of the present invention has excellent gradate structure, for example, titanium dioxide has a main structure of micron order spheroidal particle which is formed by the ordered array of a plurality of nanorods. The titanium dioxide of the present invention has a high visible light photocatalysis activity, a simple synthetic route, an easy technology, available raw material, low cost and high yield, and is adapted to mass production.
Description
Technical field
The present invention relates to a kind of synthetic two-phase solvent soft interface method with transition metal oxide of graduation nanostructure, transition metal oxide comprises titanium dioxide, cupric oxide, zinc oxide, nickel oxide, tricobalt tetroxide, Vanadium Pentoxide in FLAKES, and the titanium dioxide that obtains has very high visible light photocatalysis active.
Background technology
At present, the research work of zero-dimension nano particle and 1-dimention nano village material has been carried out very deeply, how unit nano material (nanocrystalline, nano wire and nanotube etc.) is self-assembled into the nano material with graduation ordered structure, it is the important step that realizes nanometer system or nanodevice functionalization, material after the singularity of this graduation ordered structure may cause assembling and component units exist difference in the rerum natura of aspects such as electricity, magnetic and light, thereby give material new Application Areas.
Between immiscible liquid, biomolecules and solvent, liquids and gases, exist soft interface, the existence of soft interface may cause symmetric destruction, thereby make composition in the main body solution in the interface enrichment and the crystal growth point is provided, so the soft interface method is often used in the various nano materials of preparation.At present about utilizing the soft interface legal system to be equipped with in the research of nano material, or use surface additive, or use organometallics, or obtain the nano particle of self-assembly by at least two steps as precursor as the growth auxiliary agent.Shang Weijian has document and patent report using under any additives and the metal-organic prerequisite, utilizes one step of general two-phase solvent soft interface method to prepare titanium dioxide and other transition metal oxide with graded structure.
With the semiconductor nano material is catalyzer, and utilizing the photocatalytic oxidation degradation toxic pollutant is a kind of effective method for governing pollution.Titanium dioxide is with stable, the excellent optical property of its chemical property, and is nontoxic and can effectively remove the pollutent in the big G﹠W and become the ideal material that solves the energy and environmental problem.Titanium dioxide is of many uses, can be multiple organic pollutant photocatalytic degradation nontoxic micromolecular compound, as water, carbonic acid gas, mineral acid etc.; Photodissociation water is that hydrogen and oxygen obtain Hydrogen Energy; Sun power effectively is converted to chemical energy.But the forbidden band broad (Eg=3.2eV) of titanium dioxide, have only the short sunlight (λ≤387 nanometers) of wavelength just can be absorbed, and this part ultraviolet ray (300～400 nanometer) only accounts for and reaches 4%～6% of ground solar energy, and solar energy utilization ratio is very low.Therefore how making titanium dioxide have visible light photocatalysis active is the key problem in technology that improves solar energy utilization ratio.Simultaneously, the agent of development novel photocatalysis is still environment and material supplier author's important subject.
The inventive method is being lower than under 240 ℃ the temperature, adopt the method for two-phase solvent soft interface method to synthesize titanium dioxide and other transition metal oxide (cupric oxide, zinc oxide, nickel oxide, tricobalt tetroxide, Vanadium Pentoxide in FLAKES) with graded structure, energy consumption is low, and the photocatalytic activity of this method synthetic titanium dioxide under visible light is much higher than the P-25 powder P-25 (is example with the degraded rhodamine B) that the German Degussa company of the marketization produces, production technique is simple, and cost is low, is convenient to further enlarge produce.
Summary of the invention
The object of the present invention is to provide a kind of two-phase solvent soft interface legal system back-up hierarchical nanostructure titanium dioxide and other transition metal oxide (cupric oxide, zinc oxide, nickel oxide, tricobalt tetroxide, Vanadium Pentoxide in FLAKES), its method is that metal-salt is dissolved in aqueous phase, and the pH value of adding acid or alkali regulator solution, obtain its corresponding reactant precursor, add another kind of water-fast organic phase then, mixture obtains corresponding nano titanium oxide and transition metal oxide thereof through after the solvent heat treatment, the titanium dioxide of preparation has the microcosmic graded structure of " micron ball/nanometer rod ", and this titanium dioxide semiconductor catalyzer has very high photocatalytic activity under visible light.
The present invention for achieving the above object, the technical scheme of employing is as follows:
Have the preparation method of the transition metal oxide of graduation nanostructure, it is characterized in that the preparation method is the two-phase solvent soft interface method, its preparation process is:
Step 3, adding and the immiscible organic solvent of water in the solution that step 2 prepares, the volume ratio of organic solvent and water is 1: 1～1: 100;
After step 5, step 4 finish, filter, and the solid product that filtration is obtained is with distilled water or repeatedly drip washing of ethanol, product was 30～100 ℃ of following vacuum-dryings 3～12 hours, 200～500 ℃ of following thermal treatment 0～5 hour promptly obtains the transition metal oxide that it has the graduation nanostructure accordingly;
The transition metal oxide that wherein has the graduation nanostructure is meant titanium dioxide, cupric oxide, zinc oxide, nickel oxide, tricobalt tetroxide, Vanadium Pentoxide in FLAKES.
Above-mentioned, the transition metal salt described in the step 2 is the muriate of its metal, sulfide, nitrate, vitriol, phosphatic one or more combination.Described GOLD FROM PLATING SOLUTION belongs to ionic content and is preferably 0.02～0.5 mol.
Described in the step 3 with the immiscible organic solvent of water be toluene, propyl carbinol, tetracol phenixin, chloroform, hexanaphthene, pentamethylene, ethylene dichloride, methylene dichloride, ethyl acetate, ether, normal heptane, normal hexane, methylethylketone, octane-iso, pentane, tetrachloroethane, dipropyl ether or trichloroethane.The volume ratio of described organic solvent and water is preferably 1: 1～and 1: 12.5.
Mixed solution solvent heat treatment preferred process temperature is 100～200 ℃ in the step 4, and the time is 10～36 hours.
Advantage of the present invention is:
1. can synthesize titanium dioxide and transition metal oxide with graduation nanostructure under the two-phase solvent heat condition, method has good versatility;
2. synthetic titanium dioxide has the microcosmic graded structure of " micron ball/nanometer rod ", and this titanium dioxide semiconductor catalyzer has very high photocatalytic activity under visible light;
3. one step of entire synthesis process finishes, and synthetic route is simple, and whole technological process is controlled easily, the needs of realistic production.
Description of drawings
Fig. 1 is the XRD figure of the various transition metal oxide powder of preparation.
Fig. 2 is the titanium dioxide SEM figure of preparation, and b figure is the enlarged photograph of a figure.
Fig. 3 is the SEM figure of the various transition metal oxide powder of preparation, and 3a is ZnO among the figure; 3b is Co
3O
43c is V
2O
53d is CuO; 3e is NiO.
Fig. 4 is under the existence condition of synthetic titanium dioxide, and different time visible light (λ 〉=420 nanometers) irradiation is the ultraviolet-visible spectrogram of the rhodamine B aqueous solution down.
Fig. 5 is under the different time radiation of visible light, has degrade the respectively effect of rhodamine B of the titanium dioxide of spherical secondary structure and commercially available Degussa P25, show in visible wavelength range (λ 〉=420 nanometers) that the prepared titanium dioxide sample of the present invention has higher catalyzed degradation activity than Degussa P25.
Embodiment
Further specify the processing step and the condition of two-phase solvent soft interface legal system back-up hierarchical nanostructure transition metal oxide below by example.But organic solvent is not defined as the toluene in the example, chloroform.All be suitable for the immiscible organic solvent toluene of water, propyl carbinol, tetracol phenixin, chloroform, hexanaphthene, pentamethylene, ethylene dichloride, methylene dichloride, ethyl acetate, ether, normal heptane, normal hexane, methylethylketone, octane-iso, pentane, tetrachloroethane, dipropyl ether or trichloroethane.
The preparation of graduation nanometer titania.Preparation process is:
Step 3, in the solution that step 2 prepares, add 20 milliliters of chloroforms;
Carry out solvent heat treatment in step 4, the solution that step 3 is prepared, temperature is 100 ℃, and the time is 36 hours;
After step 5, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 6, product under vacuum condition 60 ℃ dry 12 hours down, promptly obtain white titania powder.
The SEM figure of this titania powder sees Fig. 2.
As seen from the figure, its agent structure of titanium dioxide of preparation is micron-sized spheroidal particle, and each spheroidal particle is formed by a large amount of nanometer rod ordered arrangement, have the microcosmic hierarchy of " micron ball/nanometer rod ", the titanium dioxide semiconductor catalyzer of this structure has very high photocatalytic activity under visible light.
The preparation of graduation nanometer titania.Preparation process is:
Step 3, in the solution that step 2 prepares, add 4 milliliters of chloroforms;
Carry out solvent heat treatment in step 4, the solution that step 3 is prepared, temperature is 100 ℃, and the time is 36 hours;
After step 5, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 6, product under vacuum condition 60 ℃ dry 12 hours down, promptly obtain white titania powder.
The SEM figure of this titania powder sees Fig. 2.
Embodiment 3
The preparation of graduation nanometer titania.Preparation process is:
Step 3, in the solution that step 2 prepares, add 4 milliliters of chloroforms;
Carry out solvent heat treatment in step 4, the solution that step 3 is prepared, temperature is 100 ℃, and the time is 96 hours;
After step 5, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 6, product under vacuum condition 100 ℃ dry 3 hours down, promptly obtain white titania powder.
The SEM figure of this titania powder sees Fig. 2.
The preparation of graduation nanometer titania.Preparation process is:
Step 3, in the solution that step 2 prepares, add 50 milliliters of chloroforms;
Carry out solvent heat treatment in step 4, the solution that step 3 is prepared, temperature is 200 ℃, and the time is 12 hours;
After step 5, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 6, product under vacuum condition 80 ℃ dry 6 hours down, promptly obtain white titania powder.
The SEM figure of this titania powder sees Fig. 2.
Embodiment 5
The preparation of graduation nanometer titania.Preparation process is:
Step 3, in the solution that step 2 prepares, add 50 milliliters of chloroforms;
Carry out solvent heat treatment in step 4, the solution that step 3 is prepared, temperature is 240 ℃, and the time is 10 hours;
After step 5, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 6, product under vacuum condition 80 ℃ dry 6 hours down, promptly obtain white titania powder.
The SEM figure of this titania powder sees Fig. 2.
Embodiment 6
The preparation of graduation knot nanometer structure titanium dioxide.Preparation process is:
Step 3, in the solution that step 2 prepares, add 20 milliliters of toluene;
Carry out solvent heat treatment in step 4, the solution that step 3 is prepared, temperature is 180 ℃, and the time is 10 hours;
After step 5, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 6, product under vacuum condition 80 ℃ dry 6 hours down, can obtain white titania powder.
The SEM figure of this titania powder sees Fig. 2.
Embodiment 7
The preparation of graduation nanostructured zinc oxide.Preparation process is:
Carry out solvent heat treatment in step 3, the solution that step 2 is prepared, temperature is 120 ℃, and the time is 12 hours;
After step 4, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 5, product under vacuum condition 80 ℃ dry 6 hours down, 400 ℃ of following thermal treatment subsequently 2 hours, the white zinc oxide powder of the nanostructure that promptly obtains classifying.
The SEM figure of this Zinc oxide powder sees Fig. 3 a.
Embodiment 8
The preparation of graduation nanostructure tricobalt tetroxide.Preparation process is:
Carry out solvent heat treatment in step 3, the solution that step 2 is prepared, temperature is 150 ℃, and the time is 12 hours;
After step 4, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 5, product under vacuum condition 80 ℃ dry 6 hours down, 400 ℃ of following thermal treatment subsequently 3 hours, the red-purple cobaltosic oxide powder of the nanostructure that promptly obtains classifying.
The SEM figure of this cobaltosic oxide powder sees Fig. 3 b.
Embodiment 9
The preparation of graduation nanostructure nickel oxide.Preparation process is:
Carry out solvent heat treatment in step 3, the solution that step 2 is prepared, temperature is 150 ℃, and the time is 12 hours;
After step 4, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 5, product under vacuum condition 80 ℃ dry 6 hours down, 500 ℃ of following thermal treatment subsequently 1 hour, the nickel oxide powder of the nanostructure that promptly obtains classifying.
The SEM figure of this nickel oxide powder sees Fig. 3 e.
The preparation of graduation nanostructure cupric oxide.Preparation process is:
Carry out solvent heat treatment in step 3, the solution that step 2 is prepared, temperature is 150 ℃, and the time is 12 hours;
After step 4, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 5, product under vacuum condition 80 ℃ dry 6 hours down, 400 ℃ of following thermal treatment subsequently 1 hour, the cupric oxide powder of the nanostructure that promptly obtains classifying.
The SEM figure of this cupric oxide powder sees Fig. 3 d.
Embodiment 11
The preparation of graduation nanostructure cupric oxide.Preparation process is:
Carry out solvent heat treatment in step 3, the solution that step 2 is prepared, temperature is 150 ℃, and the time is 12 hours;
After step 4, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 5, product under vacuum condition 80 ℃ dry 6 hours down, 200 ℃ of following thermal treatment subsequently 5 hours, the cupric oxide powder of the nanostructure that promptly obtains classifying.
The SEM figure of this cupric oxide powder sees Fig. 3 d.
Embodiment 12
The preparation of graduation nanostructure Vanadium Pentoxide in FLAKES.Preparation process is:
Carry out solvent heat treatment in step 3, the solution that step 2 is prepared, temperature is 120 ℃, and the time is 12 hours;
After step 4, reaction finish, solid product is filtered, and with distilled water or ethanol drip washing product repeatedly;
Step 5, product under vacuum condition 80 ℃ dry 6 hours down, 400 ℃ of following thermal treatment subsequently 1 hour, the vanadium pentoxide powder of the nanostructure that promptly obtains classifying.
The SEM figure of this vanadium pentoxide powder sees Fig. 3 c.
Claims (6)
1, have the preparation method of the transition metal oxide of graduation nanostructure, it is characterized in that the preparation method is the two-phase solvent soft interface method, its preparation process is:
Step 1, the pH value that adds nitric acid, sulfuric acid, hydrochloric acid or ammoniacal liquor regulator solution in distilled water are 1～9;
Step 2, add transition metal salt or transition metal oxide in the solution of step 1, the content that makes transition metal ion in its solution is 0.001～1 mol;
Step 3, adding and the immiscible organic solvent of water in the solution that step 2 prepares, the volume ratio of organic solvent and water is 1: 1～1: 100;
Step 4, mixed solution is carried out solvent heat treatment, treatment temp is 100～240 ℃, and the time is 4～96 hours;
After step 5, step 4 finish, filter, and the solid product that filtration is obtained is with distilled water or repeatedly drip washing of ethanol, product is 30～100 ℃ of following vacuum-dryings, in 200～500 ℃ of following thermal treatments 0～5 hour, promptly obtain the transition metal oxide that it has the graduation nanostructure accordingly again;
The transition metal oxide that wherein has the graduation nanostructure is meant titanium dioxide, cupric oxide, zinc oxide, nickel oxide, tricobalt tetroxide, Vanadium Pentoxide in FLAKES.
2. preparation method according to claim 1 is characterized in that: the described transition metal salt of step 2 is the muriate of its metal, sulfide, nitrate, vitriol, phosphatic one or more combination.
3. preparation method according to claim 1 is characterized in that: the content of transition metal ion is 0.02～0.5 mol in the described solution of step 2.
4. preparation method according to claim 1 is characterized in that: step 3 described with the immiscible organic solvent of water be toluene, propyl carbinol, tetracol phenixin, chloroform, hexanaphthene, pentamethylene, ethylene dichloride, methylene dichloride, ethyl acetate, ether, normal heptane, normal hexane, methylethylketone, octane-iso, pentane, tetrachloroethane, dipropyl ether or trichloroethane.
5. preparation method according to claim 1 is characterized in that: the volume ratio of described organic solvent of step 3 and water is 1: 1～1: 12.5.
6, preparation method according to claim 1 is characterized in that: mixed solution solvent heat treatment temperature is 100～200 ℃ in the step 4, and the time is 10～36 hours.
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