CN113713814A - Au/SrTiO3/TiO2Hollow nano-sphere photocatalytic material, and preparation method and application thereof - Google Patents
Au/SrTiO3/TiO2Hollow nano-sphere photocatalytic material, and preparation method and application thereof Download PDFInfo
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- 239000002077 nanosphere Substances 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 68
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 53
- 229910002370 SrTiO3 Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 239000002131 composite material Substances 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 10
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- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- UJPWWRPNIRRCPJ-UHFFFAOYSA-L strontium;dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Sr+2] UJPWWRPNIRRCPJ-UHFFFAOYSA-L 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006303 photolysis reaction Methods 0.000 claims description 9
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 claims description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001338 self-assembly Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 150000004684 trihydrates Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 17
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000969 carrier Substances 0.000 description 6
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- 238000005215 recombination Methods 0.000 description 4
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- 238000000926 separation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000005684 electric field Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
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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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B01J35/39—
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- B01J35/50—
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- B01J35/51—
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- B01J35/61—
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- 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 relates to Au/SrTiO3/TiO2The invention relates to a nano hollow sphere photocatalytic material, a preparation method and application thereof, and SrTiO is subjected to hydrothermal method3With TiO2The nano hollow sphere is compounded, and finally Au/SrTiO nano particles are generated on the material by a light deposition method to prepare Au/SrTiO3/TiO2The hollow nano-sphere composite material. Wherein SrTiO3Nanoparticles in TiO2The hollow nanospheres are uniformly dispersed, regular in shape and adjustable in proportion, and the light of the material is remarkably improved after Au nanoparticles grow on the hollow nanospheresCatalytic hydrogen evolution efficiency. Au/SrTiO of the invention3/TiO2The nano hollow sphere photocatalytic material has good photocatalytic hydrogen evolution efficiency, and is irradiated by a 500W mercury lamp at room temperature, and Au/SrTiO3/TiO2The hydrogen generation rate of the hollow nanosphere photocatalytic material can reach 3.85h‑1The preparation method is simple, the cost is low, and the hydrogen evolution performance of the material is excellent.
Description
Technical Field
The invention relates to Au/SrTiO3/TiO2A hollow nanosphere photocatalytic material, a preparation method and application belong to the technical field of photocatalytic materials.
Background
With the exhaustion of natural resources and the emission of greenhouse gases, the global crisis of resource exhaustion occurs, and each country starts to develop sustainable energy respectively. Hydrogen energy is the cleanest energy, and semiconductor photocatalytic hydrogen production by water splitting starts to be widely researched by people. However, in the field of water photolysis, due to the fast recombination rate and the wide forbidden band of the photon-generated carriers, the mass application of water photolysis to hydrogen preparation is far from being achieved, and the efficiency of hydrogen preparation by water photolysis is very low.
Titanium dioxide (TiO)2) Has been a focus of research due to its low cost, eco-friendly and physico-chemical stability, but TiO2The fast recombination rate of the photon-generated carriers is high, and water is not easy to photolyze. And SrTiO3Is a favorable H2Evolution of the photocatalyst due to its conduction band edge ratio TiO2And more negative. SrTiO3Will be coupled TiO2A promising candidate for increasing photocatalytic activity because it can act as an electron donor and by shifting the fermi level of the composite to a more negative potential. In addition, Au, as a noble metal, has a Surface Plasmon Resonance (SPR) effect that absorbs visible lightLight strikes a photon and converts it into more energetic electrons. In addition, the Au nanoparticles can extract photogenerated electrons from the semiconductor on the interface Schottky junction and serve as an auxiliary catalyst to reduce the barrier of water splitting into hydrogen.
Most of the metal oxides are semiconductors, while Au has good conductivity and chemical stability, and can partially improve the separation efficiency of photogenerated carriers, so that Au and TiO are in contact with the photogenerated carriers2After the semiconductor is compounded, the material is a very promising water photolysis material.
Disclosure of Invention
Aiming at the problems, the invention provides Au/SrTiO3/TiO2The invention relates to a nano hollow sphere photocatalytic material, a preparation method and application thereof3With TiO2The composition of the hollow nanospheres and the light deposition of Au improve the separation efficiency of photon-generated carriers, thereby improving the water photolysis efficiency of the material. TiO 22The hollow nanospheres have larger specific surface area, and can improve the contact area of the material and water, thereby improving the water photolysis efficiency. And SrTiO3Conduction band edge ratio of TiO2More negative, in favor of H2Photocatalytic evolution of (c).
The technical scheme of the invention is as follows:
Au/SrTiO3/TiO2The hollow nanosphere composite photocatalytic material is a composite hollow nanosphere material consisting of strontium titanate and titanium dioxide, and Au nanoparticles are deposited on the surface of the material by a light deposition method.
According to the invention, the composite hollow nanosphere is preferably of a three-dimensional structure and has a diameter of 450-500 nm.
According to the invention, the Au/SrTiO is preferable3/TiO2The hollow nano-sphere photocatalytic material is prepared from isopropyl titanate, sodium fluoride, polyvinylpyrrolidone, strontium hydroxide octahydrate and chloroauric acid trihydrate through two steps of hydrothermal treatment, calcination and light deposition.
Further preferably, the Au/SrTiO3/TiO2The molar ratio of Sr to Ti in the hollow nanospheres is 1:8, 1:4, 2:4 or 3: 4.
The Au/SrTiO3/TiO2The preparation method of the hollow nanosphere photocatalytic material comprises the following steps:
(1) with isopropyl titanate (C)12H28O4Ti) as raw material, adding ammonia water and deionized water into mixed solution of ethanol and acetonitrile, and preparing amorphous TiO by self-assembly2A precursor;
(2) TiO prepared in the step (1)2Mixing the precursor with sodium fluoride (NaF), dispersing in deionized water, adding polyvinylpyrrolidone (PVP), transferring into a polytetrafluoroethylene autoclave for hydrothermal treatment, placing the obtained material in a tubular furnace for calcination treatment to obtain TiO2A hollow nanosphere; preferably, the TiO is2The mass ratio of the precursor to the polyvinylpyrrolidone (PVP) to the sodium fluoride (NaF) is 450:60: 19.
(3) TiO prepared in the step (2)2Hollow nanosphere and strontium hydroxide octahydrate (Sr (OH)2·8H2O), dispersing in deionized water, transferring into a polytetrafluoroethylene autoclave, preserving heat at 180 ℃ for 18h, naturally cooling to room temperature, taking out the mixed solution, centrifugally washing with 0.1M hydrochloric acid and deionized water for multiple times, and vacuum drying the obtained washed matter at 60 ℃ to obtain SrTiO3/TiO2A hollow nanosphere; preferably, the TiO is2Hollow nanosphere and strontium hydroxide octahydrate (Sr (OH)2·8H2O) in a mass ratio of 25: 18.
(4) SrTiO prepared in the step (3)3/TiO2Chloroauric acid trihydrate (HAuCl) is added into the hollow nanospheres4·3H2O), dispersing in deionized water, and carrying out light deposition to obtain Au/SrTiO3/TiO2The nano hollow sphere composite photocatalytic material; preferably, the Au/SrTiO3/TiO2The Au content in the hollow nanosphere composite photocatalytic material is 5 wt.%.
Further, the above Au/SrTiO3/TiO2The preparation method of the hollow nanosphere photocatalytic material comprises the following specific steps:
(1) with isopropyl titanate (C)12H28O4Ti) as raw material, adding a small amount of ammonia water and deionized water into a mixed solution of ethanol and acetonitrile, and preparing amorphous TiO by a self-assembly mode2A precursor;
(2) TiO prepared in the step (1)2Dispersing 1.5g of precursor in 30mL of deionized water, adding 0.0631g of sodium fluoride (NaF), stirring for 1h, adding 0.2g of polyvinylpyrrolidone (PVP), stirring until the mixture is completely dissolved, transferring the mixture into a polytetrafluoroethylene autoclave, preserving the heat for 3h at 110 ℃, centrifuging the solution for 5min by using a 1mmol/L NaOH solution and deionized water, pouring out the supernatant, repeating the operation for 3-5 times, and collecting the bottom precipitate; then drying the washings at 60 ℃ in vacuum for 24 h; placing the obtained material in a high-temperature furnace for calcination treatment at the calcination speed of 1 ℃/min and the calcination temperature of 350 ℃ for 2h to obtain TiO2A hollow nanosphere;
(3) 0.1g of TiO prepared in the step (2)2Strontium hydroxide octahydrate (Sr (OH)) with molar ratios of the hollow nanospheres to Sr and Ti of 1:8, 1:4, 2:4 or 3:4 respectively2·8H2O), dispersing in 30mL of deionized water, transferring into a polytetrafluoroethylene autoclave, preserving heat for 18h at 180 ℃, naturally cooling to room temperature, centrifuging the precipitate for 5min by using 0.1mol/L HCl solution and deionized water, pouring out supernatant, repeating the operation for 3-5 times, and collecting bottom precipitate; the washings were then dried under vacuum at 60 ℃ for 24 h.
(4) Then, a sample (0.01 g) was dropped into 200. mu.L of chloroauric acid trihydrate, and light deposition was carried out.
Further, amorphous TiO in the step (1)2The preparation method of the precursor comprises the following steps:
adding 150mL of ethanol and 100mL of acetonitrile into a 500mL measuring cylinder, adding 0.38g of ammonia water and 0.91g of deionized water, and then violently stirring;
② isopropyl titanate (C)12H28O4Ti) is quickly injected into the step I, and the mixed solution is vigorously stirred for 6 hours;
thirdly, centrifuging the solution obtained in the second step for 5min by using absolute ethyl alcohol and deionized water, pouring out supernatant, repeating the operation for 3-5 times, and collecting bottom sediment; the precipitate was then dried under vacuum at 60 ℃ for 24 h.
The invention also comprises Au/SrTiO prepared by the invention3/TiO2The application of the hollow nano-sphere photocatalytic material in photolysis of water.
Compared with the prior art, the invention has the following advantages:
1. the composite material of the present invention and TiO2Compared with the material, the separation efficiency of the photon-generated carriers is improved.
2. The invention adopts an etching method to obtain the hollow sphere structure, and has good specific surface area compared with the traditional spherical semiconductor nano material.
3. Au/SrTiO obtained by the invention3/TiO2Hollow nano-ball photocatalytic material and hollow-ball-structured TiO2Has a large specific surface area, and SrTiO3With TiO2The internal electric field between the recombination interfaces can provide a huge driving force, effectively reduces the binding energy of excitons and separates photogenerated electrons from holes, and the Au, which is a noble metal, has a Surface Plasmon Resonance (SPR) effect and can absorb incident photons of visible light and convert the incident photons into more high-energy electrons.
Drawings
FIG. 1 is an SEM image of a precursor in step (1) of example 1 of the present invention.
FIG. 2 shows TiO in step (1) of example 1 of the present invention2TEM images of the hollow nanospheres.
Figure 3 is an XRD pattern of example 2 of the invention.
FIG. 4 shows SrTiO prepared in example 2 of the present invention3/TiO2SEM image of hollow nanosphere photocatalytic material.
FIG. 5 is a graph showing the comparison of the hydrogen production amount in examples 1, 2, 3 and 4 of the present invention using a 500W mercury lamp as a light source.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. The examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1: Au/SrTiO3/TiO2Hollow nano-sphere photocatalytic material and preparation method and application thereof
(1)TiO2Synthesis of hollow nanospheres
Mixing 150mL of ethanol and 100mL of acetonitrile, adding 0.38g of ammonia water and 0.91g of deionized water into a 500mL beaker, injecting 5mL of isopropyl titanate under vigorous stirring, vigorously stirring for 6h, collecting precipitates, centrifuging with absolute ethanol and deionized water respectively, and vacuum-drying at 60 ℃ for 12 h. Taking 1.5g of dried precursor, dispersing in 30mL of deionized water, adding 0.0631g of sodium fluoride (NaF), stirring for 1h, adding 0.2g of polyvinylpyrrolidone (PVP), stirring until the PVP is completely dissolved, transferring into a polytetrafluoroethylene high-pressure kettle, preserving heat for 18h at 110 ℃, cooling, centrifuging the precipitate for 5min by using a 1mmol/L NaOH solution and deionized water, respectively centrifuging for 3 times, and collecting the bottom precipitate; the washings were then dried under vacuum at 60 ℃ for 24 h. Placing the obtained material in a high-temperature furnace for calcination treatment at the calcination speed of 1 ℃/min and the calcination temperature of 350 ℃ for 2h to obtain TiO2The hollow nanospheres.
TiO obtained in this example2SEM pictures of the precursors are shown in figure 1.
TiO obtained in this example2A TEM picture of the hollow nanosphere photocatalytic material is shown in fig. 2.
(2)SrTiO3/TiO2Synthesis of hollow nano-ball photocatalytic material
0.1g of TiO prepared in the step (2)2Hollow nanospheres with 0.0416g of strontium hydroxide octahydrate (Sr (OH))2·8H2O), dispersing in 30mL of deionized water, transferring into a polytetrafluoroethylene autoclave, preserving heat for 18h at 180 ℃, centrifuging the precipitate for 5min by using 0.1mol/L HCl solution and deionized water, pouring out supernatant, repeating the operation for 4 times, and collecting bottom precipitate;the washings were then dried under vacuum at 60 ℃ for 24 h.
SrTiO obtained in this example3/TiO2The XRD diffraction pattern of the hollow nanosphere photocatalytic material is shown in figure 3.
(3)Au/SrTiO3/TiO2Hydrogen evolution test of hollow nanosphere photocatalytic material
Taking the Au/SrTiO obtained in the step (2)3/TiO210mg of hollow nanosphere photocatalytic material was dispersed in an aqueous solution (30mL) containing methanol (20 vol%) as a sacrificial reagent, and 200. mu.L of chloroauric acid trihydrate was added dropwise. The gas formed in the interval of 60min was quantitatively analyzed by on-line gas chromatography using a 500W mercury lamp as a simulated light source.
Example 2 Au/SrTiO3/TiO2Preparation method and application of hollow nanosphere photocatalytic material
(1)TiO2Synthesis of hollow nanospheres
The procedure is as in example 1.
(2)SrTiO3/TiO2Synthesis of hollow nano-ball photocatalytic material
0.1g of TiO prepared in the step (2)2Hollow nanospheres with 0.0832g of strontium hydroxide octahydrate (Sr (OH))2·8H2O), dispersing in 30mL of deionized water, transferring into a polytetrafluoroethylene autoclave, preserving heat for 18h at 180 ℃, centrifuging the precipitate for 5min by using 0.1mol/L HCl solution and deionized water, pouring out supernatant, repeating the operation for 5 times, and collecting bottom precipitate; the washings were then dried under vacuum at 60 ℃ for 24 h.
SrTiO obtained in this example3/TiO2An SEM picture of the hollow nanosphere photocatalytic material is shown in fig. 4.
(3)Au/SrTiO3/TiO2Hydrogen evolution test of hollow nanosphere photocatalytic material
The procedure is as in example 1.
Example 3: Au/SrTiO3/TiO2Preparation method and application of hollow nanosphere photocatalytic material
(1)TiO2Of hollow nanospheresSynthesis of
The procedure is as in example 1.
(2)SrTiO3/TiO2Synthesis of hollow nano-ball photocatalytic material
0.1g of TiO prepared in the step (2)2Hollow nanospheres with 0.1663g of strontium hydroxide octahydrate (Sr (OH))2·8H2O), dispersing in 30mL of deionized water, transferring into a polytetrafluoroethylene autoclave, preserving heat for 18h at 180 ℃, centrifuging the precipitate for 5min by using 0.1mol/L HCl solution and deionized water, pouring out supernatant, repeating the operation for 3 times, and collecting bottom precipitate; the washings were then dried under vacuum at 60 ℃ for 24 h.
(3)Au/SrTiO3/TiO2Hydrogen evolution test of hollow nanosphere photocatalytic material
The procedure is as in example 1.
Example 4: Au/SrTiO3/TiO2Preparation method and application of hollow nanosphere photocatalytic material
(1)TiO2Synthesis of hollow nanospheres
The procedure is as in example 1.
(2)SrTiO3/TiO2Synthesis of hollow nano-ball photocatalytic material
0.1g of TiO prepared in the step (2)2Hollow nanospheres with 0.2625g of strontium hydroxide octahydrate (Sr (OH))2·8H2O), dispersing in 30mL of deionized water, transferring into a polytetrafluoroethylene autoclave, preserving heat for 18h at 180 ℃, centrifuging the precipitate for 5min by using 0.1mol/L HCl solution and deionized water, pouring out supernatant, repeating the operation for 5 times, and collecting bottom precipitate; the washings were then dried under vacuum at 60 ℃ for 24 h.
(3)Au/SrTiO3/TiO2Hydrogen evolution test of hollow nanosphere photocatalytic material
The procedure is as in example 1.
Test example:
Au/SrTiO prepared by the invention3/TiO2The hollow nanosphere photocatalytic material is respectively subjected to photocatalytic hydrogen evolution, the test result is shown in figure 5, as can be seen from figure 5,the hydrogen evolution products for all photocatalysts increased linearly with time under simulated solar irradiation, indicating good stability for all samples. By separately reacting TiO2Hollow nanosphere, SrTiO3/TiO2The hollow nanospheres, examples 1, 2, 3 and 4 were subjected to hydrogen evolution test, and it was found that example 1(2.186mmol g)-1h-1) Example 2(2.95 mmoleg)-1h-1) Example 3(1.6983 mmoleg)-1h-1) Example 4(0.8152 mmoleg)-1h-1) Comparative TiO2Hollow nanosphere (0.0325 mmoleg)-1h-1)、SrTiO3/TiO2Hollow nanosphere (0.0374 mmoleg)-1h-1) All have higher hydrogen yield because of the special SrTiO3/TiO2The shape of the hollow sphere and an Internal Electric Field (IEF) in the heterostructure can effectively separate photo-generated electrons from holes, and Au, which is used as a noble metal, has a Surface Plasmon Resonance (SPR) effect and can effectively inhibit the recombination of the photo-generated electrons and the holes. The hydrogen evolution performance of example 2 was found to be best by comparison, reaching 2.95 mmoleg-1h-1The description is given in Sr: ti is 1: maximum separation of photo-generated electrons from holes at condition 4. The results show that the strategy for constructing the heterostructure is effective for promoting the photocatalytic hydrogen evolution activity.
When the Au nano particles are added, the hydrogen evolution performance of the material is remarkably improved, which shows that the introduction of Au can remarkably improve the optical property of the material, and the Au nano particles can convert solar energy into chemical energy on the surface of the material by utilizing sufficient light through plasma resonance energy transfer.
Claims (10)
1. Au/SrTiO3/TiO2The hollow nanosphere composite photocatalytic material is characterized in that the photocatalytic material is a composite hollow nanosphere material consisting of strontium titanate and titanium dioxide, and Au nanoparticles are deposited on the surface of the material by a light deposition method.
2. The Au/SrTiO of claim 13/TiO2The hollow nanosphere composite photocatalytic material is characterized in that the composite hollow nanosphere is of a three-dimensional structure, and the diameter of the composite hollow nanosphere is 450-500 nm.
3. The Au/SrTiO of claim 13/TiO2The nano hollow sphere composite photocatalytic material is characterized in that the Au/SrTiO composite photocatalytic material3/TiO2The hollow nano-sphere photocatalytic material is prepared from isopropyl titanate, sodium fluoride, polyvinylpyrrolidone, strontium hydroxide octahydrate and chloroauric acid trihydrate through two steps of hydrothermal treatment, calcination and light deposition.
4. The Au/SrTiO of claim 13/TiO2The nano hollow sphere composite photocatalytic material is characterized in that the Au/SrTiO composite photocatalytic material3/TiO2The molar ratio of Sr to Ti in the hollow nanospheres is 1:8, 1:4, 2:4 or 3: 4.
5. The Au/SrTiO of any one of claims 1 to 43/TiO2The preparation method of the hollow nanosphere photocatalytic material comprises the following steps:
(1) with isopropyl titanate (C)12H28O4Ti) as raw material, adding ammonia water and deionized water into mixed solution of ethanol and acetonitrile, and preparing amorphous TiO by self-assembly2A precursor;
(2) TiO prepared in the step (1)2Mixing the precursor with sodium fluoride (NaF), dispersing in deionized water, adding polyvinylpyrrolidone (PVP), transferring into a polytetrafluoroethylene autoclave for hydrothermal treatment, placing the obtained material in a tubular furnace for calcination treatment to obtain TiO2A hollow nanosphere;
(3) TiO prepared in the step (2)2Hollow nanosphere and strontium hydroxide octahydrate (Sr (OH)2·8H2O), dispersing in deionized water, transferring into a polytetrafluoroethylene autoclave, preserving heat at 180 ℃ for 18h, naturally cooling to room temperature, taking out the mixed solution, centrifugally washing with 0.1M hydrochloric acid and deionized water for multiple times, vacuum-drying the obtained washings at 60 ℃,to obtain SrTiO3/TiO2A hollow nanosphere;
(4) SrTiO prepared in the step (3)3/TiO2Chloroauric acid trihydrate (HAuCl) is added into the hollow nanospheres4·3H2O), dispersing in deionized water, and carrying out light deposition to obtain Au/SrTiO3/TiO2The nano hollow sphere composite photocatalytic material.
6. The method according to claim 5, wherein the TiO compound of claim 2 is used2The mass ratio of the precursor to the polyvinylpyrrolidone (PVP) to the sodium fluoride (NaF) is 450:60: 19; TiO in the step (3)2Hollow nanosphere and strontium hydroxide octahydrate (Sr (OH)2·8H2O) in a mass ratio of 25: 18; in the step (4), Au/SrTiO3/TiO2The Au content in the hollow nanosphere composite photocatalytic material is 5 wt.%.
7. The method according to claim 5, wherein the Au/SrTiO is3/TiO2The preparation method of the hollow nanosphere photocatalytic material comprises the following specific steps:
(1) with isopropyl titanate (C)12H28O4Ti) as raw material, adding a small amount of ammonia water and deionized water into a mixed solution of ethanol and acetonitrile, and preparing amorphous TiO by a self-assembly mode2A precursor;
(2) TiO prepared in the step (1)2Dispersing 1.5g of precursor in 30mL of deionized water, adding 0.0631g of sodium fluoride (NaF), stirring for 1h, adding 0.2g of polyvinylpyrrolidone (PVP), stirring until the mixture is completely dissolved, transferring the mixture into a polytetrafluoroethylene autoclave, preserving the heat for 3h at 110 ℃, centrifuging the solution for 5min by using a 1mmol/L NaOH solution and deionized water, pouring out the supernatant, repeating the operation for 3-5 times, and collecting the bottom precipitate; then drying the washings at 60 ℃ in vacuum for 24 h; placing the obtained material in a high-temperature furnace for calcination treatment at the calcination speed of 1 ℃/min and the calcination temperature of 350 ℃ for 2h to obtain TiO2A hollow nanosphere;
(3) will step with0.1g of TiO prepared in step (2)2Strontium hydroxide octahydrate (Sr (OH)) with molar ratios of the hollow nanospheres to Sr and Ti of 1:8, 1:4, 2:4 or 3:4 respectively2·8H2O), dispersing in 30mL of deionized water, transferring into a polytetrafluoroethylene autoclave, preserving heat for 18h at 180 ℃, naturally cooling to room temperature, centrifuging the precipitate for 5min by using 0.1mol/L HCl solution and deionized water, pouring out supernatant, repeating the operation for 3-5 times, and collecting bottom precipitate; the washings were then dried under vacuum at 60 ℃ for 24 h.
(4) Then, a sample (0.01 g) was dropped into 200. mu.L of chloroauric acid trihydrate, and light deposition was carried out.
8. The method according to claim 1, wherein the amorphous TiO in the step (1)2The preparation method of the precursor comprises the following steps:
adding 150mL of ethanol and 100mL of acetonitrile into a 500mL measuring cylinder, adding 0.38g of ammonia water and 0.91g of deionized water, and then violently stirring;
② isopropyl titanate (C)12H28O4Ti) is quickly injected into the step I, and the mixed solution is vigorously stirred for 6 hours;
thirdly, centrifuging the solution obtained in the second step for 5min by using absolute ethyl alcohol and deionized water, pouring out supernatant, repeating the operation for 3-5 times, and collecting bottom sediment; the precipitate was then dried under vacuum at 60 ℃ for 24 h.
9. The Au/SrTiO of any one of claims 1 to 43/TiO2The application of the hollow nano-sphere photocatalytic material in photolysis of water.
10. Au/SrTiO obtained by the production method according to any one of claims 5 to 83/TiO2The application of the hollow nano-sphere photocatalytic material in photolysis of water.
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| CN114632513A (en) * | 2022-03-23 | 2022-06-17 | 海南大学 | Preparation method and application of monoatomic Au-loaded strontium titanate/titanium dioxide composite photocatalyst |
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