CN113929135A - Nano porous Ti4O7Preparation method of (1) - Google Patents
Nano porous Ti4O7Preparation method of (1) Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 45
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910009848 Ti4O7 Inorganic materials 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 31
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 27
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 27
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- 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 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910010420 TinO2n-1 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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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
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- 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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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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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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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The invention belongs to the technical field of nano materials, and discloses nano porous Ti4O7By reacting SiO2Mixing the powder with polyethylene glycol, reacting with active organic titanate, adjusting viscosity with ethanol, drying, calcining, and acid washing to obtain nanometer porous Ti4O7(ii) a The invention controls SiO2Powder and polyethylene glycol solution ratio control synthesized Ti4O7Specific surface area of (2), synthesized nanoporous Ti4O7The specific surface area can reach 200-480 m2(ii)/g; in the calcining process, the original polyethylene glycol serves as a reducing agent, and no additional reducing agent is needed; the inventionThe raw materials needed by the preparation method are easy to obtain and low in price, the synthesis process is simple, hydrogen is avoided being used as a reducing agent, potential safety hazards are reduced, the specific surface area for development is large, the specific surface area is easy to control, and the synthesis process is simple Ti4O7Has important significance.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to nano porous Ti4O7The preparation method of (1).
Background
Magneli phase Ti4O7In a series of TinO2n-1Has the highest conductivity, excellent corrosion resistance and good photoelectric and thermoelectric properties, and is widely applied to lithium sulfurBatteries, metal-air batteries, fuel cells, and the like. However, Ti4O7Is generally above 800 ℃ resulting in synthesized Ti4O7Sintering is severe. Ti4O7The size of (A) is usually in the micron level, and the specific surface area is very small and is only 2-10 m2(ii) in terms of/g. Although the literature reports the use of gel sintering to prepare articles having specific surface areas in excess of 200m2Per g of Ti4O7However, this method is difficult to further increase the specific surface area, and Ti synthesized by this method4O7The specific surface area is difficult to control. In addition, the prior art also reports that Ti can be inhibited by introducing polydopamine in the preparation process4O7The crystal grains are coarsened, however, the method has higher cost and more complex process. Therefore, the research on Ti with large specific surface area, easy control of the specific surface area and simple synthesis process4O7Become highly desirable in the art.
Disclosure of Invention
Aiming at the existing Ti4O7Generally, the nano-porous Ti is in a micron level, has small specific surface area and is difficult to control, the preparation process is complex and the like, and the invention provides the nano-porous Ti4O7By controlling SiO2Ratio control of powder to polyethylene glycol solution4O7The specific surface area of the titanium oxide is reduced by using the original polyethylene glycol as a reducing agent in the calcining process, so that the production cost and the energy consumption are reduced, and the titanium oxide is nano-porous Ti which is suitable for application and popularization4O7The preparation method of (1).
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a nano-porous Ti4O7The preparation method comprises the following steps:
(1) mixing SiO2Mixing the powder with polyethylene glycol to obtain a first mixture;
(2) mixing the first mixture and active organic titanate to obtain a second mixture;
(3) mixing the second mixture with ethanol to obtain a gel;
(4) drying the obtained gel to obtain a crosslinking precursor;
(5) calcining the obtained cross-linked precursor in inert atmosphere, and then pickling to obtain the nano-porous Ti4O7。
Preferably, in the step (1), SiO2The particle size of the powder is less than or equal to 400nm, and the polyethylene glycol is a polyethylene glycol solution with the molecular weight of 200-600.
Preferably, in the step (2), the active organic titanate is one of tetraethyl titanate and tetrabutyl titanate.
Preferably, the polyethylene glycol is mixed with SiO2The mass ratio of the powder is 5: 1-30: 1, the mass ratio of the polyethylene glycol to the active organic titanate is 2: 1-5: 4, and the mass ratio of the polyethylene glycol to the ethanol is 6: 1-3: 2.
Preferably, in the step (1), SiO2The mixing of the powder and the polyethylene glycol comprises ultrasonic dispersion and stirring which are sequentially carried out, wherein the ultrasonic dispersion time is 0.5-1 h, the ultrasonic frequency is 40-100 KHz, and the stirring time is 0.5-2 h.
Preferably, in the step (3), the specific steps of mixing the second mixture and ethanol are as follows: adding ethanol while stirring in an oil bath at the temperature of 70-90 ℃, wherein the stirring time is 7-10 h.
Preferably, in the step (4), the drying temperature is 80-120 ℃, and the drying time is 2-8 hours.
Preferably, in the step (5), the calcining temperature is 800-1050 ℃, and the heat preservation time is 3-6 h; the heating rate of heating to the calcining temperature is 3-8 ℃/min.
Preferably, in the step (5), the inert gas is argon, and the flow rate of the inert gas is 40-100 sccm.
Preferably, in the step (5), the acid used in the acid washing process is hydrofluoric acid, the mass fraction of the hydrofluoric acid is 4-8%, and the mass ratio of the volume of the hydrofluoric acid to the calcined product is 3 ml: 20 mg-3 ml: 100 mg.
According to the technical scheme, compared with the prior art, the invention has the beneficial effects that:
1. the nano-porous Ti of the invention4O7By controlling SiO2The ratio of the powder to the polyethylene glycol solution can control the synthesized Ti4O7The specific surface area of the material can reach 200-480 m2/g；
2. The method does not need an additional reducing agent, and the original polyethylene glycol serves as the reducing agent in the calcining process after the polyethylene glycol is crosslinked with the active organic titanate. The decomposition of the carbon-containing organic substance not only reduces to produce Ti4O7CO or CO CO being produced2At Ti4O7Generate pores in the Ti alloy, promote the nano-porous Ti4O7Synthesizing;
3. the method has the advantages of easily obtained raw materials, low price and simple synthesis process, and avoids using hydrogen as a reducing agent, thereby reducing potential safety hazard.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows a diagram of nanoporous Ti according to the present invention4O7A flow chart of a preparation method;
FIG. 2 shows a view of the nano-porous Ti obtained in example 1 of the present invention4O7XRD pattern of (a);
FIG. 3 shows a view of the nano-porous Ti obtained in example 1 of the present invention4O7SEM picture of (1);
FIG. 4 shows a view of the nano-porous Ti obtained in example 1 of the present invention4O7A TEM image of (B);
FIG. 5 shows a view of the nano-porous Ti obtained in example 1 of the present invention4O7A BET plot of (A);
FIG. 6 shows a diagram of a nano-porous Ti obtained in example 2 of the present invention4O7BET diagram (b).
Detailed Description
The invention provides a nano-porous Ti4O7The preparation method comprises the following steps:
(1) mixing SiO2Mixing the powder with polyethylene glycol to obtain a first mixture;
(2) mixing the first mixture and active organic titanate to obtain a second mixture;
(3) mixing the second mixture with ethanol to obtain a gel;
(4) drying the obtained gel to obtain a crosslinking precursor;
(5) calcining the obtained cross-linked precursor in inert atmosphere, and then pickling to obtain the nano-porous Ti4O7。
In the present invention, in the step (1), SiO2The particle size of the powder is preferably less than or equal to 400nm, and more preferably less than or equal to 300 nm; the polyethylene glycol is preferably a polyethylene glycol solution with the molecular weight of 200-600, and is further preferably a polyethylene glycol solution with the molecular weight of 300-500;
specifically, the SiO2The preparation steps of the powder are as follows: 30mL of absolute ethanol, 12mL of deionized water, and 5mL of 25% NH3·H2O and stirring at room temperature, then adding 2.5mL tetraethyl orthosilicate to the mixture and stirring vigorously, and finally centrifuging to separate out SiO2The ball is washed and dried to obtain SiO2Powder;
furthermore, the water absorption, solubility, water solubility, vapor pressure and other factors of the polyethylene glycol can be reduced along with the increase of the molecular weight of the polyethylene glycol, and the relative density, viscosity, freezing point and flash point can be improved along with the increase of the molecular weight of the polyethylene glycol.
In the present invention, in the step (2), the active organic titanate is preferably one of tetraethyl titanate and tetrabutyl titanate, and more preferably tetrabutyl titanate.
In the invention, the polyethylene glycol and SiO2The mass ratio of the powder is preferably 5: 1-30: 1, and more preferably 6: 1-16: 1; the mass ratio of the polyethylene glycol to the active organic titanate is preferably 2: 1-5: 4, and further preferably 2: 4-3: 4; the mass ratio of the polyethylene glycol to the ethanol is preferably 6: 1-3: 2, and more preferably 3: 1-4: 2;
further, the invention controls SiO2The addition amount of the powder can be controlled to synthesize Ti4O7The specific surface area of the alloy can reach 200-480 m2The amount of the synthesized Ti can be controlled by controlling the addition amount of the polyethylene glycol4O7The purity of (2); after the polyethylene glycol and the active organic titanate are crosslinked, the original polyethylene glycol serves as a reducing agent in the calcining process, and the addition amount of the polyethylene glycol meets the requirement of controlling the synthesized Ti4O7The specific surface area of (A) also meets the requirement that the polyethylene glycol is used as a reducing agent.
In the present invention, in the step (1), SiO2The mixing of the powder and the polyethylene glycol comprises ultrasonic dispersion and stirring which are sequentially carried out, wherein the ultrasonic dispersion time is preferably 0.5-1 h, and more preferably 40 min; the ultrasonic frequency is preferably 40-100 KHz, and further preferably 60-80 KHz; the stirring time is preferably 0.5 to 2 hours, and more preferably 1 hour.
In the present invention, in the step (3), the specific steps of mixing the second mixture and ethanol are as follows: adding ethanol while stirring in an oil bath at the temperature of 70-90 ℃, wherein the stirring time is 7-10 h;
further, the second mixture and the ethanol are mixed under the condition that the ambient humidity is less than 50%, so that the cross-linking effect of the precursor can be prevented from being influenced by more water vapor.
In the invention, in the step (4), the drying temperature is preferably 80-120 ℃, and more preferably 90-100 ℃; the drying time is preferably 2 to 8 hours, and more preferably 5 to 7 hours.
In the invention, in the step (5), the calcination temperature is preferably 800-1050 ℃, and more preferably 850-1000 ℃; the heat preservation time is preferably 3-6 h, and further preferably 4-5 h; the heating rate for heating to the calcination temperature is preferably 3 to 8 ℃/min, and more preferably 5 to 7 ℃/min.
In the present invention, in the step (5), the inert gas is preferably argon; the flow rate of the inert gas is preferably 40-100 sccm, and more preferably 50-80 sccm;
further, the inert gas is continuously introduced, specifically: and (3) ventilating for 0.5-1 h before starting the temperature raising program, and continuously ventilating after the temperature is raised until the reaction is finished and the temperature is reduced to the room temperature.
In the invention, in the step (5), the acid used in the acid cleaning process is preferably hydrofluoric acid, the mass fraction of the hydrofluoric acid is preferably 4-8%, and the mass ratio of the volume of the hydrofluoric acid to the calcined product is preferably 3 ml: 20 mg-3 ml: 100 mg.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
SiO2Powder preparation: 30mL of absolute ethanol, 12mL of deionized water, and 5mL of 25% NH3·H2O mixing and stirring at room temperature, then adding 2.5mL tetraethyl orthosilicate and stirring and mixing strongly, and finally centrifuging to separate out SiO2The ball is washed and dried to obtain SiO2Powder;
nanoporous Ti4O7The preparation of (1): first 300mgSiO2Adding the powder into 5g of polyethylene glycol solution, performing ultrasonic dispersion for 1h, adding 9g of tetrabutyl titanate after stirring for 1h, adding 1.8g of ethanol while stirring under the conditions that the temperature is controlled to be 75 ℃ and the ambient humidity is less than 50% in an oil bath to reduce the viscosity of the mixture, and after continuously stirring for 8h, drying the obtained gel at 80 ℃ for 5h to obtain a crosslinking precursor; transferring the precursor into a graphite boat, then placing the graphite boat into a tubular furnace for calcination, continuously introducing argon at the flow rate of 50sccm, introducing the argon for 1h, then heating the graphite boat from room temperature to 900 ℃ at the speed of 5 ℃/min, preserving the heat for 4h, then cooling the graphite boat to the room temperature, and ensuring that the inert gas is continuously introduced until the reaction is finished and the temperature is reduced to the room temperature in the process; calcining 400mgAdding 30ml of hydrofluoric acid with the mass fraction of 5% into the powder for acid cleaning, and obtaining the nano-porous Ti after centrifugal washing and drying4O7。
From FIGS. 3 and 4, it can be seen that nanoporous Ti synthesized in example 14O7The particle size of (A) is in nanometer level; from FIG. 5, it can be seen that nanoporous Ti synthesized in example 14O7Has a specific surface area of 223m2(ii) in terms of/g. Upon detection, nanoporous Ti as synthesized in example 14O7The purity reaches more than 88 percent.
Example 2
SiO2The powder was prepared as in example 1;
nanoporous Ti4O7The preparation of (1): the difference from example 1 is that 800mgSiO was added2The powder was otherwise the same as in example 1.
From FIG. 6, it can be seen that nanoporous Ti synthesized in example 24O7Has a specific surface area of 480m2(ii) in terms of/g. Through detection, the nano-porous Ti synthesized in example 24O7The purity reaches more than 85 percent.
Example 3
SiO2The powder was prepared as in example 1;
nanoporous Ti4O7The preparation of (1): the difference from example 1 is that 6g of polyethylene glycol solution is added, and the other is the same as example 1.
Through detection, the nano-porous Ti synthesized in example 34O7Has a specific surface area of 243m2The purity of the product is more than 80 percent, and the residual amorphous carbon in the product is increased.
Example 4
SiO2The powder was prepared as in example 1;
nanoporous Ti4O7The preparation of (1): firstly, 800mgSiO2Adding the powder into 5.5g polyethylene glycol solution, ultrasonically dispersing for 0.5h, stirring for 2h, adding 9.5g tetraethyl titanate, stirring while controlling the temperature at 90 deg.C and the ambient humidity less than 50% in an oil bath, adding 1.8g ethanol to reduce the viscosity of the mixture, continuously stirring for 9h,drying the obtained gel at 120 ℃ for 5h to obtain a crosslinking precursor; and transferring the precursor into a graphite boat, then placing the graphite boat into a tubular furnace for calcination, continuously introducing argon at the flow rate of 70sccm, introducing the argon for 1h, then heating the graphite boat from room temperature to 900 ℃ at the speed of 5 ℃/min, preserving the temperature for 4h, then cooling the graphite boat to the room temperature, and ensuring that the inert gas is continuously introduced until the reaction is finished and the temperature is reduced to the room temperature in the process. Adding 30ml of hydrofluoric acid with the mass fraction of 7% into 400mg of calcined powder for acid cleaning, and centrifugally washing and drying to obtain the nano-porous Ti4O7。
Through detection, the nano-porous Ti synthesized in example 44O7Has a specific surface area of 470m2The purity of the product is more than 86 percent per gram.
Further, nanoporous Ti synthesized from example 1 and example 24O7It can be seen that by controlling SiO2The amount of the powder can be controlled to synthesize the nano-porous Ti4O7The specific surface area of the material; nanoporous Ti synthesized from examples 1 and 34O7It can be known that the amount of polyethylene glycol solution has little influence on the surface area, and in a reasonable addition range, the increase of the amount of polyethylene glycol solution can increase the residual amorphous carbon in the product and reduce the purity of the synthetic material; the invention controls SiO2The addition amounts of the powder and the polyethylene glycol solution can be controlled to synthesize the nano-porous Ti4O7The specific surface area and the purity of the titanium oxide are improved, the original polyethylene glycol is used as a reducing agent in the calcining process, no additional reducing agent is needed, the process is simple, the environment is friendly, the titanium oxide is suitable for large-scale production, the specific surface area for development is large, the specific surface area is easy to control, and the synthesis process is simple4O7Has important significance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. Nano porous Ti4O7The preparation method is characterized by comprising the following steps:
(1) mixing SiO2Mixing the powder with polyethylene glycol to obtain a first mixture;
(2) mixing the first mixture and active organic titanate to obtain a second mixture;
(3) mixing the second mixture with ethanol to obtain a gel;
(4) drying the obtained gel to obtain a crosslinking precursor;
(5) calcining the obtained cross-linked precursor in inert atmosphere, and then pickling to obtain the nano-porous Ti4O7。
2. Nanoporous Ti according to claim 14O7Characterized in that, in the step (1), SiO2The particle size of the powder is less than or equal to 400nm, and the polyethylene glycol is a polyethylene glycol solution with the molecular weight of 200-600.
3. Nanoporous Ti according to claim 24O7The preparation method of (2) is characterized in that, in the step (2), the active organic titanate is one of tetraethyl titanate and tetrabutyl titanate.
4. Nanoporous Ti according to claim 34O7Characterized in that the polyethylene glycol and SiO are mixed2The mass ratio of the powder is 5: 1-30: 1, the mass ratio of the polyethylene glycol to the active organic titanate is 2: 1-5: 4, and the mass ratio of the polyethylene glycol to the ethanol is 6: 1-3: 2.
5. Nanoporous Ti according to claim 14O7Characterized in that, in the step (1), SiO2The mixing of the powder and the polyethylene glycol comprises ultrasonic dispersion and stirring which are sequentially carried out, wherein the ultrasonic dispersion time is 0.5-1 h, the ultrasonic frequency is 40-100 KHz, and the stirring time is 0.5-2 h.
6. Nanoporous Ti according to claim 54O7The preparation method of (2), wherein in the step (3), the specific step of mixing the second mixture with ethanol is: adding ethanol while stirring in an oil bath at the temperature of 70-90 ℃, wherein the stirring time is 7-10 h.
7. Nanoporous Ti according to claim 54O7The preparation method is characterized in that in the step (4), the drying temperature is 80-120 ℃, and the drying time is 2-8 hours.
8. Nanoporous Ti according to claim 14O7The preparation method is characterized in that in the step (5), the calcining temperature is 800-1050 ℃, and the heat preservation time is 3-6 h; the heating rate of heating to the calcining temperature is 3-8 ℃/min.
9. Nanoporous Ti according to claim 84O7The preparation method is characterized in that in the step (5), the inert gas is argon, and the flow rate of the inert gas is 40-100 sccm.
10. Nanoporous Ti according to claim 14O7The preparation method is characterized in that in the step (5), the acid used in the acid cleaning process is hydrofluoric acid, the mass fraction of the hydrofluoric acid is 4-8%, and the mass ratio of the volume of the hydrofluoric acid to the calcined product is 3 ml: 20 mg-3 ml: 100 mg.
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| AO CHEN: "Facile preparation of ultrafine Ti4O7 nanoparticle-embedded porous carbon for high areal capacity lithium–sulfur batteries" * |
| QUAN PANG: "Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries" * |
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| CN114797860B (en) * | 2022-03-14 | 2023-06-09 | 重庆大学 | Ti with transition metal loaded on surface 4 O 7 Preparation method and application thereof |
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