CN111821970A - Graphene/aluminum oxide/titanium dioxide heterojunction material and preparation method and application thereof - Google Patents
Graphene/aluminum oxide/titanium dioxide heterojunction material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 134
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 79
- 229910021389 graphene Inorganic materials 0.000 title claims description 74
- 239000004408 titanium dioxide Substances 0.000 title claims description 42
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 17
- 239000002121 nanofiber Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 7
- 239000000919 ceramic Substances 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 13
- 239000012498 ultrapure water Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000010041 electrostatic spinning Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 239000012084 conversion product Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 238000001523 electrospinning Methods 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- 239000002131 composite material Substances 0.000 description 23
- 238000003917 TEM image Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000004065 semiconductor Substances 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
- 241001089723 Metaphycus omega Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- -1 potassium ferricyanide Chemical compound 0.000 description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction 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
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- 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
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Abstract
The preparation method comprises the steps of dissolving polyvinylpyrrolidone in absolute ethyl alcohol to obtain an electrospinning precursor solution; adding a substance source of a ceramic material, a corresponding solvent and an auxiliary agent into the precursor liquid, then collecting the electrospun fiber under a certain condition, and roasting in air at 600 ℃ to obtain the ceramic nanofiber. Carrying out hydrothermal reaction on the obtained fiber and GO solution, and regulating and controlling the growth morphology of the heterostructure by adjusting the content of GO and utilizing the interaction of oxygen-containing functional groups of GO and heterojunction in a hydrothermal environment. The obtained material is used as a photo-anode in the traditional three-electrode system, and shows controllable and optimized photoelectric properties. The method does not involve complex chemical control, does not introduce a surfactant and does not involve time-consuming treatment procedures, belongs to a green, efficient and sustainable process, and can provide a new method for preparing the functional nano material with controllable morphology and optimized performance.
Description
Technical Field
The invention belongs to the technical field of titanium dioxide-based heterojunction composite material regulation and control, and particularly relates to a graphene/aluminum oxide/titanium dioxide heterojunction material as well as a preparation method and application thereof.
Background
Titanium dioxide-based semiconductor materials are of great interest in the fields of environmental protection and photocatalytic energy conversion. The titanium dioxide nanofiber prepared by the electrostatic spinning method has the unique properties of porosity, high specific surface area and the like, the characteristics are favorable for promoting the transfer of carriers and the electron transmission, but the application of the titanium dioxide nanofiber in the photoelectric field is limited by the narrow absorption range. Designing titanium dioxide-based heterostructures with controllable structures and morphologies is one of the effective strategies, however, most preparation technologies require addition of surfactants, and time-consuming and complex post-treatment procedures are required at the later stage. As a novel carbon nano material with excellent conductivity, the graphene not only can be compounded with a semiconductor material to optimize the electronic characteristics of the semiconductor material, but also can regulate and control the structure, growth morphology and performance of the material through the interaction between oxygen-containing functional groups and oxides of the graphene. In most of the existing preparation technologies, the means for regulating and controlling the morphology and the performance of the synthesized functional material is complex, and graphene is easy to agglomerate in the hybridization process and is difficult to control.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the technical problems, the invention provides a graphene/alumina/titanium dioxide heterojunction material and a preparation method and application thereof, wherein the graphene/alumina/titanium dioxide heterojunction material is synthesized under the condition of not adding any surfactant by combining electrostatic spinning and hydrothermal processes; the structure and growth morphology of the heterojunction are successfully regulated and controlled by changing the content of graphene in the hydrothermal process; the obtained material is used as a photo-anode in a three-electrode system, and shows controllably enhanced photoelectric characteristics under the irradiation of a xenon lamp light source.
The technical scheme is as follows: the preparation method of the graphene/aluminum oxide/titanium dioxide heterojunction material comprises the following preparation steps: a. preparing a spinning solution: dissolving polyvinylpyrrolidone (PVP) in absolute ethyl alcohol, and magnetically stirring at room temperature for 20-28h to obtain a uniform and transparent solution with the mass fraction of the PVP being 10-20 wt%; sequentially adding a ceramic material source, a good solvent and an auxiliary agent into the solution, wherein the volume ratio of an ethanol solution of PVP to the good solvent to the auxiliary agent is (3-6):5:3, the ceramic material source is isopropyl titanate and aluminum acetylacetonate, the mass fraction of the aluminum acetylacetonate accounts for 10-50 wt% of the ceramic material source, and the volume ratio of isopropyl titanate to ethanol is (2-5):9, and stirring at room temperature to obtain a uniform spinning solution; b. preparing the spinning solution into nano fibers by using an electrostatic spinning device, and roasting the obtained fibers in a muffle furnace at 600 ℃ for 290min at the heating rate of 2.0 ℃/min to obtain ceramic nano fibers; c. graphene oxide with a concentration of 4.83mg/mL was synthesized using a modified Hummer's method: mixing and grinding graphite powder and sodium chloride in a mass ratio of 10:1-30:1, washing with water, adding 98 wt.% of concentrated sulfuric acid, and magnetically stirring for 20-25 h; under the ice bath condition, adding potassium permanganate into the solution according to the mass fraction of 20-30 wt.%, and controlling the temperature not to exceed 20 ℃; then, the temperature is increased to 35-45 ℃ and kept for 20-40min, and finally the temperature is increased to 85-95 ℃ and kept for 30-60 min; adding 18.2M omega ultrapure water to dilute the sulfuric acid concentration to 30-40 vol.%, finally heating to 100 ℃ and 110 ℃, and after 15-35min, adding distilled water and 30 vol.% hydrogen peroxide into the solution according to the volume ratio of (12-16) to 1, wherein the volume fractions of the total solution, which are respectively 60-70 vol.% and 3-5 vol.%, of the added distilled water and hydrogen peroxide; pickling the product obtained in the previous step with 5wt.% hydrochloric acid solution, and dialyzing the product in distilled water to obtain graphene oxide; d. mixing graphene oxide with ceramic nano fibers according to the mass fraction of 1-15 wt.%, performing ultrasonic dispersion in 18.2M omega ultrapure water, wherein the volume ratio of the graphene oxide to the ultrapure water is (1-37):1000, and performing hydrothermal reaction at 180 ℃ for 8 hours to obtain the graphene/alumina/titanium dioxide multi-component heterojunction material.
Preferably, the polyvinylpyrrolidone has a molecular weight of 1300000.
Preferably, Al is obtained by pyrolysis of the above-mentioned aluminum acetylacetonate and isopropyl titanate2O3The mass fraction is 10-30 wt.%.
Preferably, the good solvent is acetone, the auxiliary agent is acetic acid, and the volume ratio of the ethanol solution of the PVP to the amount of the acetone to the amount of the acetic acid is 9:10: 6.
Preferably, the electrostatic spinning device has a set voltage of 17.5kV, a distance between the metal needle and the filament collector of 12.5cm, a flow rate of 0.5mL/h, and an ambient humidity of not more than 50%.
The graphene/aluminum oxide/titanium dioxide heterojunction material with controllable morphology prepared by the preparation method.
The graphene/aluminum oxide/titanium dioxide heterojunction material is applied to preparation of photoelectron energy conversion products.
The graphene/aluminum oxide/titanium dioxide heterojunction material is applied to preparation of a traditional three-electrode system as a photo-anode.
Has the advantages that: the structural morphology of the graphene/aluminum oxide/titanium dioxide composite heterojunction prepared by the method is finely regulated and controlled by the content of graphene oxide. Through hydrothermal reaction, alumina crystal grains migrate to the surface of the titanium dioxide fiber and form a nano sheet. The graphene oxide can be used as an effective catalyst to successfully regulate the growth kinetics of an alumina heterojunction based on the surface of a titanium dioxide fiber, and the content of the graphene oxide is regulated to convert an alumina nanosheet into a nano-thorn, so that the active sites exposed on the surface of the fiber are increased, and a direct injection path is provided for photo-generated electrons. Under the synergistic effect between the graphene and the heterojunction, the composite material has controllable photoelectric characteristics under the irradiation of visible light, the maximum instantaneous photocurrent density of the composite material is 3.5 times that of pure alumina/titanium dioxide fibers, and the composite material has obvious advantages compared with the traditional single-component titanium dioxide fibers.
Drawings
FIG. 1 is a schematic view of an electrospinning apparatus;
FIG. 2 is a schematic diagram of a hydrothermal reaction kettle apparatus;
FIG. 3 is a TEM image of electrospun alumina/titania fibers (alumina to titania mass ratio of 3: 7);
FIG. 4 is a TEM image of an alumina/titania composite heterojunction after hydrothermal treatment (alumina to titania mass ratio of 3: 7);
fig. 5 is a TEM image of a graphene/alumina/titania composite heterojunction (mass ratio of alumina to titania is 3:7, graphene oxide content is 1 wt.%);
fig. 6 is a TEM image of a graphene/alumina/titania composite heterojunction (alumina to titania mass ratio of 3:7, graphene oxide content of 5 wt.%);
fig. 7 is a TEM image of a graphene/alumina/titania composite heterojunction (alumina to titania mass ratio of 3:7, graphene oxide content of 10 wt.%);
fig. 8 is a TEM image of a graphene/alumina/titania composite heterojunction (alumina to titania mass ratio of 3:7, graphene oxide content of 15 wt.%);
fig. 9 is a TEM image of a graphene/alumina/titania composite heterojunction (mass ratio of alumina to titania is 1:9, graphene oxide content is 10 wt.%);
fig. 10 is a TEM image of a graphene/alumina/titania composite heterojunction (alumina to titania mass ratio of 2:8, graphene oxide content of 10 wt.%);
FIG. 11 is a schematic view of an electrochemical workstation apparatus;
fig. 12 shows the photoelectric characteristic parameters of the graphene/alumina/titania composite heterojunction. (the mass ratio of the alumina to the titanium dioxide is 3:7, a is the instantaneous photocurrent density, and b is the charge transfer resistance);
fig. 13 shows the photoelectric characteristic parameters of the graphene/alumina/titania composite heterojunction. (the mass ratio of the aluminum oxide to the titanium dioxide is 1:9 and 2:8 respectively, the content of the graphene oxide is 10 wt.%, a is the instantaneous photocurrent density, and b is the charge transfer resistance).
Detailed Description
Example 1:
a. and carrying out hydrothermal mixing on the alumina/titanium dioxide nano-fibers and the graphene oxide with different contents by adopting an electrostatic spinning and hydrothermal process to prepare the graphene/alumina/titanium dioxide heterojunction composite material.
First, an electrospinning solution was prepared. 0.6g of PVP is mixed with 4.5mL of absolute ethyl alcohol, the mixture is magnetically stirred for 24 hours at room temperature to obtain a uniform and transparent solution, 5mL of acetone, 1g of aluminum acetylacetonate, 3mL of acetic acid and 1.4011mL of isopropyl titanate are sequentially added into the solution, and the mixture is stirred at room temperature to be completely dissolved to obtain a uniform and transparent spinning solution. Under the conditions that the voltage is 17.5kV, the distance between the metal needle and the metal mesh is 12.5cm, the flow rate is 0.5mL/h and the spinning humidity is below 50%, collecting the PVP/aluminum acetylacetonate/isopropyl titanate fiber. And (3) roasting the fiber in a muffle furnace at 600 ℃ for 290min at the heating rate of 2.0 ℃/min to obtain the alumina/titanium dioxide nanofiber, wherein the mass ratio of alumina to titanium dioxide is 3: 7.
Secondly, a graphene oxide solution with the concentration of 4.83mg/mL is synthesized by using a modified Hummer's method. Mixing and grinding 1g of graphite powder and 0.05g of sodium chloride, washing with water, adding 23mL of 98 wt.% concentrated sulfuric acid, and magnetically stirring for 22 hours; under the ice bath condition, 6g of potassium permanganate is added into the solution, and the temperature is controlled not to exceed 20 ℃; subsequently, the temperature is raised to 40 ℃ and kept for 30min, and finally raised to 90 ℃ and kept for 45 min; after 46mL of 18.2 M.OMEGA.ultrapure water was added, the temperature of the solution was raised to 105 ℃. After 25min, 140mL of distilled water and 10mL of 30 vol.% hydrogen peroxide are added into the solution, and after acid washing with 5wt.% hydrochloric acid solution, the solution is dialyzed in distilled water for 3 days to obtain graphene oxide, and the graphene oxide concentration is diluted to 4.83mg/mL with ultrapure water.
Thirdly, 16mg of the fiber was mixed with 0.034mL, 0.174mL, 0.368mL, 0.584mL of the graphene oxide solution, respectively, with the graphene oxide content of 1 wt.%, 5wt.%, 10 wt.%, 15 wt.%, respectively; and then carrying out ultrasonic dispersion in 18.2M omega ultrapure water, adding the ultrapure water into the reactor respectively in the volume of 19.966mL, 19.826mL, 19.632mL and 19.416mL, and then carrying out hydrothermal treatment for 8 hours at 180 ℃ to obtain the graphene/alumina/titanium dioxide heterojunction composite material. As shown in fig. 1-8, as GO content increases, the morphology of the alumina heterojunction structure evolves from nanosheets to nano-spines, eventually gradually decreasing. The TEM chart shows that the growth of the alumina heterojunction is regulated and controlled by introducing the graphene as a catalyst, and the heterojunction composite material with controllable morphology is successfully synthesized.
b. And (3) testing photoelectric characteristics:
the prepared sample was mixed with titanium dioxide particles (P25) with absolute ethanol as solvent to give a suspension with a concentration of 4mg/mL, wherein the mass fraction of P25 was 95 wt.%. Dripping 10 μ L of suspension on fluorine-doped tin oxide glass (FTO) for 6 times, and calcining at 450 deg.C for 151min in a nitrogen-filled tube furnace at a temperature rise rate of 2.8 deg.C/min. Taking the prepared sample as an anode of a traditional three-electrode system, adopting 0.2M sodium sulfate as an electrolyte, applying a constant voltage of 0.5V, and recording generated photocurrent by using an electrochemical workstation shown in figure 11 under the irradiation of a xenon lamp light source; 2.5mM potassium ferricyanide/potassium ferrocyanide in a volume ratio of 1:1 was dissolved in 0.1M potassium chloride solution, which was used as an electrolyte, and impedance values were recorded using an electrochemical workstation as shown in FIG. 11. As shown in fig. 12, the graphene/alumina/titania heterostructure with multi-spine branches coupled with graphene oxide in an amount of 10 wt.% produced a maximum instantaneous photocurrent density 3.5 times that of the pure alumina/titania fiber, while the impedance value decreased from 71.9 Ω to 33.6 Ω.
c. Compared with the prior art
The resulting material was compared to other titania-based materials for photocurrent density under visible light, as shown in the following table.
Example 2:
a. and carrying out hydrothermal mixing on the alumina/titanium dioxide nano-fiber and graphene oxide with the content of 10 wt.% by adopting an electrostatic spinning and hydrothermal process to prepare the graphene/alumina/titanium dioxide heterojunction composite material.
First, an electrospinning solution was prepared. 0.6g of PVP is mixed with 4.5mL of absolute ethyl alcohol, the mixture is magnetically stirred for 24 hours at room temperature to obtain a uniform and transparent solution, 5mL of acetone, aluminum acetylacetonate, 3mL of acetic acid and 2.5mL of isopropyl titanate are sequentially added into the solution, and the mixture is stirred at room temperature to be completely dissolved to obtain a uniform and transparent spinning solution. Wherein the mass of the added aluminum acetylacetonate is 0.4625g and 1.0407g respectively. Under the conditions that the voltage is 17.5kV, the distance between the metal needle and the metal mesh is 12.5cm, the flow rate is 0.5mL/h and the spinning humidity is below 50%, collecting the PVP/aluminum acetylacetonate/isopropyl titanate fiber. And roasting the fiber in a muffle furnace at 600 ℃ for 290min at the heating rate of 2.0 ℃/min to obtain the alumina/titanium dioxide nanofiber, wherein the mass ratio of alumina to titanium dioxide is respectively 1:9 and 2: 8.
and secondly, synthesizing a graphene oxide solution with the concentration of 4.83mg/mL by using an improved Hummer's method, namely mixing and grinding 1g of graphite powder and 0.05g of sodium chloride, washing with water, adding 23mL of 98 wt.% concentrated sulfuric acid, and magnetically stirring for 22 hours. Under the ice bath condition, 6g of potassium permanganate is added into the solution, and the temperature is controlled not to exceed 20 ℃; subsequently, the temperature is raised to 40 ℃ and kept for 30min, and finally raised to 90 ℃ and kept for 45 min; after 46mL of 18.2 M.OMEGA.ultrapure water was added, the temperature of the solution was raised to 105 ℃. After 25min, 140mL of distilled water and 10mL of 30 vol.% hydrogen peroxide are added into the solution, and after acid washing with 5wt.% hydrochloric acid solution, the solution is dialyzed in distilled water for 3 days to obtain graphene oxide, and the graphene oxide concentration is diluted to 4.83mg/mL with ultrapure water.
Thirdly, mixing 16mg of fiber with 0.368mL of graphene oxide solution, controlling the content of graphene oxide to be 10 wt.%, then performing ultrasonic dispersion in 19.632 mL18.2M omega ultrapure water, and performing hydrothermal treatment for 8 hours at 180 ℃ to obtain the graphene/alumina/titanium dioxide heterojunction composite material. As shown in fig. 9, alumina is epitaxially grown on the surface of the titanium dioxide fiber, and exhibits a nanosheet morphology. The TEM chart shows that the growth of an alumina heterojunction can be regulated and controlled by changing the content of alumina under the condition that graphene is used as a catalyst, and the heterojunction composite material with controllable morphology is successfully synthesized.
b. And (3) testing photoelectric characteristics:
the prepared sample was mixed with titanium dioxide particles (P25) with absolute ethanol as solvent, resulting in a suspension with a concentration of 4mg/mL, wherein the mass fraction of P25 was 95 wt.%. Dripping 10 μ L of suspension on fluorine-doped tin oxide glass (FTO) for 6 times, and calcining at 450 deg.C for 151min in a nitrogen-filled tube furnace at a temperature rise rate of 2.8 deg.C/min. The photoelectric performance of a sample is tested by using a traditional three-electrode system, 0.2M sodium sulfate is used as an electrolyte, a constant voltage of 0.5V is applied, and under the irradiation of a xenon lamp light source, the generated photocurrent is recorded by using an electrochemical workstation shown in figure 11; 2.5mM potassium ferricyanide/potassium ferrocyanide in a volume ratio of 1:1 was dissolved in 0.1M potassium chloride solution, which was used as an electrolyte, and impedance values were recorded using an electrochemical workstation as shown in FIG. 11. As shown in fig. 13, under the condition of coupling with 10 wt.% GO, the increase of the alumina multi-spine branches on the surface of the heterojunction composite material increases the photoelectric characteristics thereof with the increase of the alumina content, and when the mass ratio of alumina to titania is increased to 3:7, the graphene/alumina/titania heterostructure with multi-spine branches (example 1) has the best photoelectric performance, and the successful regulation of the morphology realizes the controllable photoelectric characteristics thereof.
Compared with the prior art, the invention has the advantages that:
1. the method does not involve the use of any surfactant in the process of preparing the heterostructure with controllable morphology and optimized photoelectric characteristics, does not involve complex chemical control means, does not need post-treatment and other procedures, and is green and efficient;
2. according to the preparation method, the graphene is used as a catalyst to regulate the growth kinetics of the heterojunction, so that the composite material with controllable morphology is prepared, the controllability is strong, and a new method can be provided for preparing the functional nano material with controllable morphology and applied to the field of photoelectricity;
3. according to the invention, the interaction between the oxygen-containing functional group on the graphene oxide and the oxide in the hydrothermal process is utilized to successfully and finely regulate and control the structure, the growth morphology and the photoelectric characteristic of the composite material, and a new means is provided for researching the composition and the regulation rule of the heterostructure.
Claims (8)
1. The preparation method of the graphene/aluminum oxide/titanium dioxide heterojunction material is characterized by comprising the following preparation steps: a. preparing a spinning solution: dissolving polyvinylpyrrolidone (PVP) in absolute ethyl alcohol, and magnetically stirring at room temperature for 20-28h to obtain a uniform and transparent solution with the mass fraction of the PVP being 10-20 wt%; sequentially adding a ceramic material source, a good solvent and an auxiliary agent into the solution, wherein the volume ratio of an ethanol solution of PVP to the good solvent to the auxiliary agent is (3-6):5:3, the ceramic material source is isopropyl titanate and aluminum acetylacetonate, the mass fraction of the aluminum acetylacetonate accounts for 10-50 wt% of the ceramic material source, and the volume ratio of isopropyl titanate to ethanol is (2-5):9, and stirring at room temperature to obtain a uniform spinning solution; b. preparing the spinning solution into nano fibers by using an electrostatic spinning device, and roasting the obtained fibers in a muffle furnace at 600 ℃ for 290min at the heating rate of 2.0 ℃/min to obtain ceramic nano fibers; c. graphene oxide with a concentration of 4.83mg/mL was synthesized using a modified Hummer's method: mixing and grinding graphite powder and sodium chloride in a mass ratio of 10:1-30:1, washing with water, adding 98 wt.% of concentrated sulfuric acid, and magnetically stirring for 20-25 h; under the ice bath condition, adding potassium permanganate into the solution according to the mass fraction of 20-30 wt.%, and controlling the temperature not to exceed 20 ℃; then, the temperature is increased to 35-45 ℃ and kept for 20-40min, and finally the temperature is increased to 85-95 ℃ and kept for 30-60 min; adding 18.2M omega ultrapure water to dilute the sulfuric acid concentration to 30-40 vol.%, finally heating to 100 ℃ and 110 ℃, and after 15-35min, adding distilled water and 30 vol.% hydrogen peroxide into the solution according to the volume ratio of (12-16) to 1, wherein the volume fractions of the total solution, which are respectively 60-70 vol.% and 3-5 vol.%, of the added distilled water and hydrogen peroxide; pickling the product obtained in the previous step with 5wt.% hydrochloric acid solution, and dialyzing the product in distilled water to obtain graphene oxide; d. mixing graphene oxide with ceramic nano fibers according to the mass fraction of 1-15 wt.%, performing ultrasonic dispersion in 18.2M omega ultrapure water, wherein the volume ratio of the graphene oxide to the ultrapure water is (1-37):1000, and performing hydrothermal reaction at 180 ℃ for 8 hours to obtain the graphene/alumina/titanium dioxide multi-component heterojunction material.
2. The method for preparing the graphene/alumina/titanium dioxide heterojunction material according to claim 1, wherein the molecular weight of the polyvinylpyrrolidone is 1300000.
3. The method for preparing the graphene/alumina/titanium dioxide heterojunction material according to claim 1, wherein Al is obtained after the aluminum acetylacetonate and isopropyl titanate are decomposed at high temperature2O3The mass fraction is 10-30 wt.%.
4. The method for preparing the graphene/alumina/titanium dioxide heterojunction material as claimed in claim 1, wherein the good solvent is acetone, the auxiliary agent is acetic acid, and the volume ratio of the ethanol solution of PVP to the amount of acetone to the amount of acetic acid is 9:10: 6.
5. The method for preparing the graphene/alumina/titanium dioxide heterojunction material according to claim 1, wherein the set voltage of the electrostatic spinning device is 17.5kV, the distance between the metal needle and the filament collector is 12.5cm, the flow rate is 0.5mL/h, and the ambient humidity is not more than 50%.
6. The graphene/aluminum oxide/titanium dioxide heterojunction material with controllable morphology prepared by the preparation method of any one of claims 1 to 5.
7. The use of the graphene/alumina/titania heterojunction material of claim 6 in the preparation of optoelectronic energy conversion products.
8. Use according to claim 7, characterized in that the graphene/alumina/titania heterojunction material is used as a photo-anode in the preparation of a conventional three-electrode system.
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