CN108579738B - Gold nanoparticle/titanium dioxide nanoflower composite material and preparation method and application thereof - Google Patents
Gold nanoparticle/titanium dioxide nanoflower composite material and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 87
- 239000002057 nanoflower Substances 0.000 title claims abstract description 65
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- 239000010931 gold Substances 0.000 title claims abstract description 59
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 59
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000002135 nanosheet Substances 0.000 claims description 15
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 10
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
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- 238000000354 decomposition reaction Methods 0.000 description 11
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- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 2
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a gold nanoparticle/titanium dioxide nanoflower composite material. The gold nanoparticles are uniformly deposited on the surface of the titanium dioxide, and a close contact interface is formed between the gold nanoparticles and the titanium dioxide. The gold nanoparticle/titanium dioxide nanoflower composite material is an efficient and stable photoelectric conversion material, is prepared by a one-step simple reduction method, is simple in preparation process, easy to control reaction conditions, and is suitable for large-scale preparation and industrial production.
Description
Technical Field
The invention relates to a method for preparing a gold nanoparticle/titanium dioxide nanoflower composite material by depositing gold nanoparticles on the surface of a titanium dioxide nanoflower and application thereof, belonging to the technical field of nanomaterials and photocatalysis.
Background
Two major challenges that will be faced in the 21 st century of human beings in the process of walking the way of sustainable development are energy problems and environmental problems. Solar energy has the advantages of cleanness, low price, renewability and the like, and how to efficiently utilize the solar energy is one of the main means for solving the energy problem. The photocatalytic hydrogen production technology is mainly based on chemical conversion and storage of solar energy, and the solar energy excites a semiconductor to realize high-efficiency photolysis of water to prepare hydrogen. Semiconductor photocatalysts such as titanium dioxide, zinc oxide and the like draw great attention, but in practical application, most of the photocatalysts are wide-bandgap semiconductors, have narrow light absorption wavelength range and are limited in an ultraviolet region, and only account for 4% of the solar spectrum, so that the utilization efficiency of the solar spectrum is low, and the quantum efficiency is low. Therefore, the development of new efficient visible light catalysts has become one of the hottest research directions in catalyst research.
Titanium dioxide is used as a traditional photocatalyst, and has the advantages of high chemical stability, light corrosion resistance, strong oxidation capacity, large driving force of photocatalytic reaction, high photocatalytic activity and the like, so that the titanium dioxide is widely applied to the field of photocatalysis, but the forbidden band width of the titanium dioxide is 3.2eV, the light absorption is limited to an ultraviolet region, the light accounts for only 4% of the solar spectrum, the quantum efficiency is low, and the large-scale industrial application of the titanium dioxide photocatalytic material is limited to a great extent. It is noted that controlling the concentration of the defect state of titanium dioxide can also effectively broaden the light absorption range. For example, the light absorption range of titanium dioxide can be widened to the visible region by introducing an oxygen vacancy defect state into titanium dioxide. It must be noted, however, that the presence of a large number of oxygen vacancies inhibits the separation of their photo-generated electrons from holes, resulting in a reduction in photocatalytic activity. This is because the photo-generated electrons are bound to oxygen vacancies, which in turn results in poor mobility of the photo-generated electrons.
The carrier separation efficiency can be improved by loading a small amount of small-size gold nanoparticles on the surface of titanium dioxide as a co-catalyst, so that high-activity photocatalysis performance can be obtained, a compact interface is formed by the deposited gold nanoparticles and the carrier titanium dioxide nanoflower, the separation of photo-generated carriers is improved, the efficiency of photocatalytic hydrogen production is promoted, and the absorption range of the titanium dioxide in a visible light region can be greatly widened due to the existence of the gold nanoparticle plasma resonance effect. Gold nanoparticles are deposited on the surface of the oxygen-rich vacancy defect-state titanium dioxide, the light absorption performance of the titanium dioxide can be improved due to the existence of oxygen vacancies, and meanwhile, the separation of photo-generated electron holes can be inhibited due to the fact that a large number of oxygen vacancies are used as recombination centers of the electron holes. Therefore, the separation of photogenerated carriers of the titanium dioxide is promoted by depositing the noble metal on the surface of the titanium dioxide. Meanwhile, the light absorption range of the titanium dioxide can be effectively widened by the gold nanoparticles. In addition, due to the existence of the oxygen vacancy defect state on the surface of the titanium dioxide, the interface action between the noble metal nano particles and the titanium dioxide can be enhanced, the loss of carriers on the interface of the noble metal nano particles and the titanium dioxide can be reduced, and the efficient separation of the photon-generated carriers can be promoted. The method has the advantages of simple operation, no toxicity, high efficiency, large-area production and the like, and therefore, the method has the feasibility of industrialization.
Disclosure of Invention
The invention aims to solve the problems, provides a preparation method for preparing a novel composite material by utilizing titanium dioxide oxygen vacancies with reducibility to deposit gold nanoparticles in one step, and solves the problems of serious internal recombination of titanium dioxide photon-generated carriers, narrow light absorption range and the like in the prior art.
The invention adopts the following technical scheme: a preparation method of a gold nanoparticle/titanium dioxide nanoflower composite material comprises the following steps:
step 1: adding isopropanol into diethylenetriamine, uniformly stirring, adding diisopropyl di (acetylacetonate) titanate, wherein the volume ratio of the isopropanol to the diethylenetriamine to the diisopropyl di (acetylacetonate) titanate is 1260-2520: 1-10: 45-360, uniformly stirring, pouring into a reaction kettle, carrying out solvent heat treatment for 24-36 hours at 200-220 ℃, washing, drying, heating the obtained nano material to an annealing temperature at 1-10 ℃/min, wherein the annealing temperature is 425 ℃, and the annealing time is 2 hours, thus obtaining the precursor oxygen-rich vacancy titanium dioxide nano flower material.
Step 2: the gold nanoparticle is loaded by utilizing the reducibility of the oxygen vacancy defect of the titanium dioxide nanoflower prepared in the step 1, and the method specifically comprises the following steps: uniformly dispersing 100mg of titanium dioxide nanoflower into 50mL of deionized water, adding a chloroauric acid solution with the volume of 0.21-0.42 mL and containing 2.1mg of chloroauric acid, then carrying out water bath at the temperature of 80-100 ℃ for 2-5 hours, washing and drying to obtain the gold nanoparticle/titanium dioxide nanoflower composite material.
Further, in the step 1, the reaction temperature is 200 ℃, the reaction time is 24 hours, and the volume ratio of the isopropanol, the diethylenetriamine and the diisopropyl di (acetylacetonate) titanate is 1260:1: 45.
Further, the water bath temperature in step 2 was 80 ℃ and the reaction time was 2 hours.
The gold nanoparticle/titanium dioxide nanoflower composite material is characterized in that the titanium dioxide nanoflowers are composed of anatase-phase titanium dioxide nanosheets, and the thickness of each titanium dioxide nanosheet is 2-9 nm. Gold with the particle size of 2-9 nm is loaded on the surface of the titanium dioxide nanosheet to form a heterojunction structure.
The prepared gold nanoparticle/titanium dioxide nanoflower composite material is applied as a photocatalyst: the water decomposition hydrogen production, the water decomposition oxygen production, the pollutant degradation, the biological antibiosis, the photoelectric water decomposition, the organic matter synthesis and other nanometer material related application fields.
The invention has the beneficial effects that: the invention provides a preparation method for preparing a novel composite material by depositing small-size gold nanoparticles on the surface of a titanium dioxide nanoflower in one step by utilizing the reducibility of oxygen vacancies rich in the titanium dioxide nanoflower, wherein the titanium dioxide nanoflower is formed by self-assembly of ultrathin nanosheets and has a large specific surface area and a three-dimensional hierarchical structure. The nano material has a large number of active sites due to the special high specific surface area and three-dimensional structure, can rapidly transfer photoelectrons and simultaneously increase the multiple scattering performance of light, and further improves the photocatalytic hydrogen production efficiency. Meanwhile, the oxygen vacancies have reducibility, and when the oxygen vacancies react with gold nanoparticle ions, charge transfer occurs between the oxygen vacancies and the gold nanoparticle ions, so the method for preparing the novel composite material by depositing the gold nanoparticles by one step by using the reducibility of the titanium dioxide oxygen vacancies can obtain a compact interface between the noble metal gold nanoparticles and the titanium dioxide nanoflower, and in addition, the deposited gold nanoparticles have a very strong plasma resonance effect in a visible light region due to small size, so the gold nanoparticle/titanium dioxide nanoflower composite material prepared by the method has excellent photocatalytic hydrogen production performance under a simulated light source. And the method can also control the gold loading amount and the size of the gold nanoparticles, and improve the photocatalytic hydrogen production performance. The composite nano material has low production cost and simple preparation process, and is beneficial to industrial production; the invention greatly reduces the production cost of the photocatalyst, obviously improves the photocatalytic hydrogen production efficiency, and has great application prospect.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the gold nanoparticle/titanium dioxide nanoflower composite prepared in example 1.
Fig. 2 and 3 are Transmission Electron Micrographs (TEMs) of the gold nanoparticle/titanium dioxide nanoflower composite prepared in example 1.
Fig. 4 is a graph of hydrogen production by hydrolysis of gold nanoparticle/titanium dioxide nanoflower composite as photocatalyst in example 5.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following examples. The following examples are intended to illustrate the present invention, but not to limit the present invention, and any modifications and changes made within the spirit of the present invention and the scope of the claims fall within the scope of the present invention.
Example 1:
step 1: to 31.5mL of isopropyl alcohol was added 0.025mL of diethylenetriamine (EDTA), and the mixture was stirred for 10 min. To the solution was added 1.125mL of diisopropyl di (acetylacetonate) titanate. Stirring was continued for 10 min. The obtained mixed solution was poured into a reaction vessel and solvent-heat treated at 200 ℃ for 24 hours. And after the reaction is finished, washing the precipitate for three times by using deionized water and absolute ethyl alcohol respectively, placing the washed precipitate in a 60 ℃ oven, drying the washed precipitate for 24 hours, finally placing the reactant in a muffle furnace, and annealing the reactant at the temperature of 425 ℃ for 2 hours at the heating speed of 1 ℃/min to obtain the precursor titanium dioxide nanoflower material.
Step 2: 100mg of precursor titanium dioxide nanoflower is added into 50mL of deionized water, and 0.21mL of chloroauric acid solution containing 2.1mg of chloroauric acid is added. The temperature of the solution water bath was kept at 80 ℃ and the reaction time was 2 hours. And after the reaction is finished, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and drying at 60 ℃ for 24 hours to obtain the gold nanoparticle/titanium dioxide nanoflower composite material.
FIG. 1 is a Scanning Electron Microscope (SEM) image of the composite material prepared in example 1, from which it can be clearly seen that the size of the gold nanoparticle/titanium dioxide nanoflower is 500-1000 nm, the gold nanoparticle/titanium dioxide nanoflower is formed by self-assembly of ultrathin titanium dioxide nanosheets, and the thickness of the nanosheets is 2-9 nm.
Fig. 2 and 3 are Transmission Electron Micrographs (TEM) of the composite material prepared in example 1, from which it can be seen that the gold nanoparticles are uniformly dispersed on the titanium dioxide nanoflowers to form a heterojunction, and the particle size of the gold nanoparticles is 2 to 9 nm.
Under a full spectrum, 50mg of the gold nanoparticle/titanium dioxide nanoflower composite material prepared in the embodiment is ultrasonically dispersed in 100mL of 30% (v/v) methanol solution, a reaction device is vacuumized and placed under a simulated light source, samples are taken once every half hour, and gas is detected by gas chromatography. Thereby drawing a hydrogen curve graph of the gold nanoparticle/titanium dioxide nanoflower composite material in the photocatalytic decomposition of water under a simulated light source. As shown in FIG. 4, the composite material can be used for photocatalytic decomposition of water under a simulated light source, and shows a good hydrogen production effect. The light irradiation was carried out for 2.5 hours, and the hydrogen production was 20.14 mmol/g.
Example 2:
step 1: to 31.5mL of isopropyl alcohol was added 0.025mL of diethylenetriamine (EDTA), and the mixture was stirred for 10 min. To the solution was added 1.125mL of diisopropyl di (acetylacetonate) titanate. Stirring was continued for 10 min. The obtained mixed solution was poured into a reaction vessel and solvent-heat treated at 200 ℃ for 24 hours. And after the reaction is finished, washing the precipitate for three times by using deionized water and absolute ethyl alcohol respectively, placing the washed precipitate in a 60 ℃ oven, drying the washed precipitate for 24 hours, finally placing the reactant in a muffle furnace, raising the temperature at the speed of 1 ℃/min, and annealing the reactant for 2 hours at 425 ℃ to obtain the precursor titanium dioxide nanoflower material.
Step 2: 100mg of precursor titanium dioxide nanoflower is added into 50mL of deionized water, and 0.42mL of chloroauric acid solution containing 4.2mg of chloroauric acid is added. The temperature of the solution water bath is kept at 100 ℃, and the reaction time is 5 hours. And after the reaction is finished, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and drying at 60 ℃ for 24 hours to obtain the gold nanoparticle/titanium dioxide nanoflower composite material.
The product is characterized by having a nanoflower structure, the size of the nanoflower structure is 500-1000 nm, the nanoflower structure is formed by self-assembling ultrathin titanium dioxide nanosheets, and the thickness of the nanosheets is 2-9 nm. Gold nanoparticles are uniformly dispersedAnd forming a heterojunction structure on the titanium dioxide nano flower chip, wherein the particle size of the gold nano particles is 2-9 nm. The material XRD diffraction pattern and standard anatase phase TiO2The characteristic peaks of (a) coincide.
Under a full spectrum, 50mg of the gold nanoparticle/titanium dioxide nanoflower composite material prepared in the embodiment is ultrasonically dispersed in 100mL of 30% (v/v) methanol solution, a reaction device is vacuumized and placed under a simulated light source, samples are taken once every half hour, and gas is detected by gas chromatography. Thereby drawing a hydrogen curve graph of the gold nanoparticle/titanium dioxide nanoflower composite material in the photocatalytic decomposition of water under a simulated light source. The composite material can be used for photocatalytic decomposition of water under a simulated light source, and shows a good hydrogen production effect. The light irradiation was carried out for 2.5 hours, and the hydrogen production amount was 19.89 mmol/g.
Example 3:
step 1: to 31.5mL of isopropyl alcohol was added 0.125mL of diethylenetriamine (EDTA), and the mixture was stirred for 10 min. To the solution was added 4.5mL of diisopropyl di (acetylacetonate) titanate. Stirring was continued for 10 min. The resulting mixed solution was poured into a reaction vessel and subjected to solvothermal treatment at 220 ℃ for 36 hours. And after the reaction is finished, washing the precipitate for three times by using deionized water and absolute ethyl alcohol respectively, placing the washed precipitate in a 60 ℃ oven, drying the washed precipitate for 24 hours, finally placing the reactant in a muffle furnace, raising the temperature at a speed of 10 ℃/min, and annealing the reactant for 2 hours at 425 ℃ to obtain the precursor titanium dioxide nanoflower material.
Step 2: 100mg of precursor titanium dioxide nanoflower is added into 50mL of deionized water, and 0.21mL of chloroauric acid solution containing 2.1mg of chloroauric acid is added. The temperature of the solution water bath was kept at 80 ℃ and the reaction time was 2 hours. And after the reaction is finished, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and drying at 60 ℃ for 24 hours to obtain the gold nanoparticle/titanium dioxide nanoflower composite material.
The product is characterized by having a nanoflower structure, the size of the nanoflower structure is 200-500 nm, the nanoflower structure is formed by self-assembling ultrathin titanium dioxide nanosheets, and the thickness of the nanosheets is 2-9 nm. The gold nanoparticles are uniformly dispersed on the titanium dioxide nanoflower to form a heterojunction structure, and the particle size of the gold nanoparticles is 2-9 nm. The material XRD diffraction pattern and standard anatase phase TiO2The characteristic peaks of (a) coincide.
Under a full spectrum, 50mg of the gold nanoparticle/titanium dioxide nanoflower composite material prepared in the embodiment is ultrasonically dispersed in 100mL of 30% (v/v) methanol solution, a reaction device is vacuumized and placed under a simulated light source, samples are taken once every half hour, and gas is detected by gas chromatography. Thereby drawing a hydrogen curve graph of the gold nanoparticle/titanium dioxide nanoflower composite material in the photocatalytic decomposition of water under a simulated light source. The composite material can be used for photocatalytic decomposition of water under a simulated light source, and shows a good hydrogen production effect. The light irradiation was carried out for 2.5 hours, and the hydrogen production amount was 19.66 mmol/g.
Example 4:
step 1: to 31.5mL of isopropyl alcohol was added 0.125mL of diethylenetriamine (EDTA), and the mixture was stirred for 10 min. To the solution was added 4.5mL of diisopropyl di (acetylacetonate) titanate. Stirring was continued for 10 min. The resulting mixed solution was poured into a reaction vessel and subjected to solvothermal treatment at 220 ℃ for 36 hours. And after the reaction is finished, washing the precipitate for three times by using deionized water and absolute ethyl alcohol respectively, placing the washed precipitate in a 60 ℃ oven, drying the washed precipitate for 24 hours, finally placing the reactant in a muffle furnace, raising the temperature at a speed of 10 ℃/min, and annealing the reactant for 2 hours at 425 ℃ to obtain the precursor titanium dioxide nanoflower material.
Step 2: 100mg of precursor titanium dioxide nanoflower is added into 50mL of deionized water, and 0.42mL of chloroauric acid solution containing 4.2mg of chloroauric acid is added. The temperature of the solution water bath is kept at 100 ℃, and the reaction time is 5 hours. And after the reaction is finished, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and drying at 60 ℃ for 24 hours to obtain the gold nanoparticle/titanium dioxide nanoflower composite material.
The product is characterized by having a nanoflower structure, the size of the nanoflower structure is 200-500 nm, the nanoflower structure is formed by self-assembling ultrathin titanium dioxide nanosheets, and the thickness of the nanosheets is 2-9 nm. The gold nanoparticles are uniformly dispersed on the titanium dioxide nanoflower to form a heterojunction structure, and the particle size of the gold nanoparticles is 2-9 nm. The material XRD diffraction pattern and standard anatase phase TiO2The characteristic peaks of (a) coincide.
Under a full spectrum, 50mg of the gold nanoparticle/titanium dioxide nanoflower composite material prepared in the embodiment is ultrasonically dispersed in 100mL of 30% (v/v) methanol solution, a reaction device is vacuumized and placed under a simulated light source, samples are taken once every half hour, and gas is detected by gas chromatography. Thereby drawing a hydrogen curve graph of the gold nanoparticle/titanium dioxide nanoflower composite material in the photocatalytic decomposition of water under a simulated light source. The composite material can be used for photocatalytic decomposition of water under a simulated light source, and shows a good hydrogen production effect. The light irradiation was carried out for 2.5 hours, and the hydrogen production amount was 19.57 mmol/g.
Claims (4)
1. A preparation method of a gold nanoparticle/titanium dioxide nanoflower composite material is characterized by comprising the following steps:
step 1: adding isopropanol into diethylenetriamine, uniformly stirring, adding diisopropyl di (acetylacetonate) titanate, wherein the volume ratio of the isopropanol to the diethylenetriamine to the diisopropyl di (acetylacetonate) titanate is 1260-2520: 1-10: 45-360, uniformly stirring, pouring into a reaction kettle, and stirring for 200-220oUnder the condition of C, carrying out heat treatment on the solvent for 24-36 hours, washing and drying; 1-10% of the obtained nano materialoC/min heating to annealing temperature of 425oC, annealing for 2 hours to obtain a precursor oxygen-rich vacancy titanium dioxide nanoflower material;
step 2: the gold nanoparticle is loaded by utilizing the reducibility of the oxygen vacancy defect of the titanium dioxide nanoflower prepared in the step 1, and the method specifically comprises the following steps: uniformly dispersing 100mg of titanium dioxide nanoflowers into 50mL of deionized water, adding a chloroauric acid solution with the volume of 0.21-0.42 mL and containing 2.1mg of chloroauric acid, and then carrying out water bath at the temperature of 80-100 DEGoC, reacting for 2-5 hours, washing and drying to obtain the gold nanoparticle/titanium dioxide nanoflower composite material; the titanium dioxide nanoflower is composed of anatase-phase titanium dioxide nanosheets, and the thickness of each titanium dioxide nanosheet is 2-9 nm; gold with the particle size of 2-9 nm is loaded on the surface of the titanium dioxide nanosheet to form a heterojunction structure.
2. The method of claim 1, wherein the reaction temperature in step 1 is 200%oC, reaction timeFor 24 hours, the volume ratio of isopropanol, diethylenetriamine and diisopropyl di (acetylacetonate) titanate is 1260:1: 45.
3. The method of claim 1, wherein the water bath temperature in step 2 is 80 deg.foAnd C, the reaction time is 2 hours.
4. The method as claimed in claim 1, wherein the application of the prepared gold nanoparticle/titanium dioxide nanoflower composite material as a photocatalyst comprises: the water is decomposed to produce hydrogen, the water is decomposed to produce oxygen, pollutants are degraded, the water is biologically and biologically antibacterial, and the water is decomposed by photoelectricity to synthesize organic matters.
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| "Hierarchical spheres assembled from large ultrathin anatase TiO2 nanosheets for photocatalytic hydrogen evolution from water splitting";Zixuan Ding et al.;《International Journal of Hydrogen Energy》;20180614;第43卷;第13190-13199页 * |
| "Oxygen vacancies mediated in-situ growth of noble-metal (Ag, Au, Pt) nanoparticles on 3D TiO2 hierarchical spheres for efficient photocatalytic hydrogen evolution from water splitting";Haihua Hu et al.;《International Journal of Hydrogen Energy》;20191126;第45卷;第629-639页 * |
| "TiO2分级纳米球的制备、异质结设计及其光催化性能的研究";丁子轩;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20190115;B014-627 * |
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