CN108786792B - Metal/semiconductor composite photocatalyst and preparation and application thereof - Google Patents
Metal/semiconductor composite photocatalyst and preparation and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 239000004065 semiconductor Substances 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 148
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 72
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 71
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 71
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 71
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 71
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 29
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000002077 nanosphere Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 6
- 229940038773 trisodium citrate Drugs 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 42
- 239000002105 nanoparticle Substances 0.000 abstract description 12
- 229910052697 platinum Inorganic materials 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 230000004044 response Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
The invention discloses a metal/semiconductor composite photocatalyst, and preparation and application thereof2@TiO2) After the surface of the nano-platinum particle is positively charged, the nano-platinum particle and the surface electronegative metal platinum nano-particle are subjected to coulomb force self-assembly to obtain the platinum nano-particle in SiO2@TiO2Metal/semiconductor composite photocatalyst SiO uniformly distributed on surface2@TiO2The Pt-SA. The method of the invention optimizes the platinum nano-particles in SiO2@TiO2The spatial distribution of the surface can effectively improve SiO2@TiO2The Pt-SA has the absorption performance on visible light and the activity and stability in the reaction of generating hydrogen by photocatalytic decomposition under the illumination of ultraviolet-visible light.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to a metal/semiconductor composite photocatalyst as well as preparation and application thereof.
Background
The photocatalysis technology provides a possible green way for relieving the increasingly prominent energy crisis by utilizing solar energy, and the conversion of the solar energy into the hydrogen energy has been paid more and more research attention. Among the commonly used photocatalysts, titanium dioxide (TiO)2) The photocatalyst has the advantages of chemical stability, low price, easy obtaining and the like, and is one of the most widely researched semiconductor photocatalysts at present. However, due to TiO2Wide forbidden band width (3.2 eV) and electricityHigh recombination rate of the electrons and holes, which cannot absorb and utilize visible light, and TiO alone2The photocatalytic activity is low. How to improve TiO2The light absorption property and the photocatalytic activity thereof have been one of the hot spots in the research of photocatalytic materials.
Improvements in TiO have been proposed2In the performance strategy, the composition with metal components is an effective method, which not only can expand TiO to a certain extent2Can also be used as an electron acceptor to promote TiO2Separation of the medium electron-hole pairs. Among them, metal Pt not only has a wide-band optical response, a high work function (5.65 eV), but also has a low reaction overpotential for hydrogen production reaction, and thus is often used as a co-catalyst to improve the photocatalytic water decomposition hydrogen production performance of semiconductor materials. The metal Pt and the semiconductor TiO commonly used at present2The composite method of (1) is to simply load or deposit metal Pt on TiO2On the surface, in the composite material obtained by the method, the metal component Pt is easy to leach and run off in the liquid phase reaction, so that the stability of the composite material is not high. If the Pt nano-particles are wrapped in the semiconductor component, the active sites of the hydrogen production reaction on the surface of the semiconductor component can be shielded, so that the advantage of low hydrogen production overpotential cannot be utilized. Therefore, the development of a metal Pt-semiconductor TiO with wide spectral response, high photocatalytic water splitting hydrogen production activity and good stability2The composite material has important scientific research significance and practical application value for constructing a high-efficiency and stable hydrogen production system by photocatalytic water decomposition.
Disclosure of Invention
The invention aims to provide a genus/semiconductor composite photocatalyst and preparation and application thereof, and aims to improve the metal Pt/semiconductor TiO by optimizing a microstructure2The activity and stability of the composite photocatalytic material in the hydrogen production decomposition reaction are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a metal/semiconductor composite photocatalyst comprises the following steps:
(1) mixing SiO2Mixing the nanospheres with an ethanol solution, uniformly dispersing by ultrasonic, adding n-butyl titanate, and stirring for 15-25 min to obtain a mixed solution;
wherein, SiO2The dosage ratio of the nanospheres to the n-butyl titanate is 0.1g to 0.08-0.12 mL;
(2) dissolving polyvinylpyrrolidone (PVP) in ethanol-deionized water mixed solution, stirring, adding the obtained solution into the mixed solution, stirring for 1-1.5h, centrifuging, washing the precipitate, and drying to obtain SiO2@TiO2A composite material;
wherein, polyvinylpyrrolidone and SiO2The dosage ratio of the nanospheres is 0.28-0.32 g to 0.1 g;
(3) mixing SiO2@TiO2Mixing the composite material with ethanol, ultrasonically dispersing uniformly, adding 3-Aminopropyltriethoxysilane (APTES), reacting at 55-65 deg.C for 2-2.5 h, centrifuging, washing precipitate, and oven drying to obtain SiO with positive electrochemical surface2@TiO2-APTES；
Wherein, SiO2@TiO2The dosage ratio of the composite material to the 3-aminopropyl triethoxysilane is 0.1 g: 0.45-0.55 mL;
(4) mixing SiO2@TiO2Dispersing APTES in deionized water to obtain SiO2@TiO2APTES solution, then Pt colloid solution is added dropwise to SiO2@TiO2Centrifuging in APTES solution, washing and drying the precipitate to obtain SiO2@TiO2the/Pt-SA composite material is the metal-semiconductor composite photocatalyst.
Through the steps (3) and (4), Pt nano particles can be prepared in SiO2@TiO2The surface of the composite material is uniformly distributed, and the obtained composite material has high-efficiency and stable hydrogen production performance by photocatalytic water decomposition.
Further, in the step (1), the SiO2The preparation method of the nanosphere comprises the following steps: mixing 2 mL of ammonia water with the mass fraction of 30%, 1mL of deionized water and 40 mL of isopropanol, stirring uniformly, adding 2 mL of tetraethyl orthosilicate, and reacting at room temperature for 2-2.5 h to obtain the productSiO with an average diameter of 400 nm2Nanospheres.
In the step (2), the dosage ratio of the polyvinylpyrrolidone to the ethanol-deionized water mixed solution is 0.28-0.32 g: 21 mL.
In the step (2), the volume ratio of ethanol to deionized water in the ethanol-deionized water mixed solution is 20: 1.
In the step (4), the preparation method of the Pt colloid solution comprises the following steps: adding 26 mL of trisodium citrate solution with the concentration of 2.8 mmol/L into 50 mL of chloroplatinic acid aqueous solution with the concentration of 0.4 mmol/L, stirring and mixing uniformly, dropwise adding 5 mL of sodium borohydride solution with the concentration of 12 mmol/L, and reacting for 3.5-4.5 h at room temperature to obtain a Pt colloidal solution.
In the step (4), the SiO2@TiO2The dosage ratio of APTES to Pt colloidal solution is 0.05-0.1 g: 21 mL.
And (3) washing the precipitates in the steps (2) and (3) with ethanol, and washing the precipitates in the step (4) with deionized water.
The drying temperature in the steps (2), (3) and (4) is 55-65 ℃.
SiO prepared by the invention2@TiO2the/Pt-SA composite material is used for decomposing water under ultraviolet-visible light to generate hydrogen. The reaction for decomposing hydrogen by photocatalysis comprises the following specific steps:
(1) mixing SiO2@TiO2Ultrasonically dispersing the Pt-SA composite material in deionized water, then adding lactic acid, uniformly mixing and stirring, and adding into a quartz reactor;
(2) vacuumizing the inside of the quartz reactor;
(3) ultraviolet-visible light (lambda is more than or equal to 320 nm and less than or equal to 780 nm) is used for irradiating the system from the upper part of the quartz reactor.
(4) The hydrogen yield obtained was analyzed using gas chromatography.
According to the technical scheme, the silicon dioxide @ titanium dioxide core-shell Structure (SiO) is prepared by taking silicon dioxide as a carrier through a sol-gel method2@TiO2) After being positively charged, the surface of the material is negatively chargedThe electric metal platinum nano particles are subjected to coulomb force self-assembly to obtain the platinum nano particles in SiO2@TiO2Composite photocatalyst SiO uniformly distributed on surface2@TiO2The Pt-SA. The invention optimizes Pt nano particles and TiO by regulation2The composite method and microstructure thereof are adopted to ensure that Pt and TiO are mixed2Has stronger coulomb interaction force between them, and the Pt nano-particle can be in TiO2The surface is uniformly distributed. In addition, the Pt nano particles can absorb and utilize TiO2The scattered light of the spherical shell realizes good response to visible light, so that the composite material has high photocatalytic activity and stability for hydrogen decomposition reaction of water.
The invention has the following remarkable advantages:
(1) the invention optimizes the microstructure of the metal-semiconductor composite material by a simple surface modification method;
(2) and composite material SiO prepared by impregnation method and having platinum randomly distributed on the surface of silicon dioxide @ titanium dioxide2@TiO2Compared with Pt-IM, by optimizing platinum nano particles in SiO2@TiO2The spatial distribution of the surface can effectively improve SiO2@TiO2The Pt-SA has the absorption performance on visible light and the activity and stability in the reaction of generating hydrogen by photocatalytic decomposition under the illumination of ultraviolet-visible light.
(3) Prepared SiO2@TiO2The Pt-SA composite photocatalytic material has wide spectral response, high activity of photocatalytic decomposition of water to produce hydrogen and good cycle stability;
(4) the method is simple to operate, obvious in effect and wide in application prospect.
Drawings
FIG. 1 is SiO2@TiO2(A, B) transmission electron microscopy picture and (C) elemental distribution map of/Pt-SA;
FIG. 2 is SiO2@TiO2UV-visible diffuse reflectance plot of/Pt-SA;
FIG. 3 is SiO2@TiO2、SiO2@TiO2Pt-SA and SiO2@TiO2/Pt-IAn activity diagram of photocatalytic decomposition of water to produce hydrogen of the M composite material under ultraviolet-visible light irradiation for 2 hours;
FIG. 4 is SiO2@TiO2Pt-SA and SiO2@TiO2A Pt-IM rate chart of photocatalytic water decomposition hydrogen production under ultraviolet-visible light irradiation for 10 h.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
Metal/semiconductor composite photocatalyst SiO2@TiO2Preparation of Pt-SA
(1) Adding 2 mL of ammonia water (mass fraction of 30%) and 1mL of deionized water into 40 mL of isopropanol, uniformly mixing and stirring, adding 2 mL of tetraethyl orthosilicate, and reacting at room temperature for 2 hours to obtain SiO with the average diameter of 400 nm2Nanospheres;
(2) 0.1g of SiO are weighed2The nanospheres are dispersed in 2 mL of ethanol solution, uniformly dispersed by ultrasonic, added with 0.1 mL of n-butyl titanate and stirred for 20 min;
(3) dissolving 0.3 g of polyvinylpyrrolidone (PVP) in a solution containing 20 mL of ethanol and 1mL of deionized water, uniformly mixing and stirring, adding the obtained solution into the solution, mixing and stirring for 1 h at room temperature, centrifuging to obtain a corresponding sample, washing for 2 times by using ethanol, and drying at 60 ℃ to obtain SiO2@TiO2A composite material;
(4) 0.1g of SiO are weighed2@TiO2Dispersing the composite material in 50 mL of ethanol, performing ultrasonic dispersion uniformly, adding the dispersed material into 0.5 mL of 3-Aminopropyltriethoxysilane (APTES), reacting for 2 h at 60 ℃, centrifuging, washing for 2 times by using ethanol, and drying at 60 ℃ to obtain SiO with a positive electrochemical surface2@TiO2-APTES；
(5) Adding 26 mL of trisodium citrate solution with the concentration of 2.8 mmol/L into 50 mL of chloroplatinic acid aqueous solution with the concentration of 0.4 mmol/L, stirring and mixing uniformly, dropwise adding 5 mL of sodium borohydride solution with the concentration of 12 mmol/L, and reacting for 4 hours at room temperature to obtain Pt colloidal solution;
(6) 0.05 g of SiO are weighed2@TiO2-APTES sample, ultrasonically dispersed in 50 mL deionized water, 21mL of Pt colloidal solution, added dropwise to SiO2@TiO2The solution of-APTES is centrifuged, washed by deionized water and dried at 60 ℃ to obtain SiO2@TiO2a/Pt-SA composite material.
As can be seen from FIG. 1, Pt nanoparticles are uniformly distributed in SiO2@TiO2A surface. As can be seen from FIG. 2, SiO2@TiO2the/Pt-SA has obvious absorption response in a visible light region.
Comparative example 1
SiO2@TiO2Preparation of Pt-IM
(1) Adding 2 mL of ammonia water (mass fraction of 30%) and 1mL of deionized water into 40 mL of isopropanol, uniformly mixing and stirring, adding 2 mL of tetraethyl orthosilicate, and reacting at room temperature for 2 hours to obtain SiO with the average diameter of 400 nm2Nanospheres;
(2) 0.1g of SiO are weighed2The nanospheres are dispersed in 2 mL of ethanol solution, uniformly dispersed by ultrasonic, added with 0.1 mL of n-butyl titanate and stirred for 20 min;
(3) dissolving 0.3 g of polyvinylpyrrolidone (PVP) in a solution containing 20 mL of ethanol and 1mL of deionized water, uniformly mixing and stirring, adding the obtained solution into the solution, mixing and stirring for 1 h at room temperature, centrifuging to obtain a corresponding sample, washing for 2 times by using ethanol, and drying at 60 ℃ to obtain SiO2@TiO2A composite material;
(4) adding 26 mL of trisodium citrate solution with the concentration of 2.8 mmol/L into 50 mL of chloroplatinic acid aqueous solution with the concentration of 0.4 mmol/L, stirring and mixing uniformly, dropwise adding 5 mL of sodium borohydride solution with the concentration of 12 mmol/L, and reacting for 4 hours at room temperature to obtain Pt colloidal solution;
(5) 0.05 g of SiO are weighed2@TiO2The sample was ultrasonically dispersed in 50 mL of deionized water, and 21mL of Pt colloidal solution was added to SiO2@TiO2Removing most of the solution from the solution by rotary evaporationThen, the sample is dried at 60 ℃ to obtain SiO2@TiO2A Pt-IM composite material.
Application example 1
SiO2@TiO2Composite material and SiO2@TiO2Pt-SA composite material, SiO2@TiO2Photocatalytic decomposition water hydrogen production test of Pt-IM composite material
With SiO2@TiO2Composite material and SiO2@TiO2Pt-SA composite material and SiO2@TiO2The Pt/IM composite was tested:
respectively ultrasonically dispersing 50 mg of the composite material in 72 mL of deionized water, then adding 8 mL of lactic acid, uniformly mixing and stirring, and adding into a quartz reactor. Vacuumizing the interior of the quartz reactor, and irradiating the system from the upper part of the quartz reactor by using ultraviolet-visible light (lambda is more than or equal to 320 nm and less than or equal to 780 nm) for 2 hours. The hydrogen yield obtained was analyzed using gas chromatography.
As shown in FIG. 3, SiO2@TiO2、SiO2@TiO2Pt-SA and SiO2@TiO2The hydrogen production of Pt-IM under the irradiation of UV-visible light for 2 h is 0.098 mmol/g, 5.79 mmol/g and 2.56 mmol/g respectively.
Application example 2
SiO2@TiO2Comparison test of rate of photocatalytic water decomposition and hydrogen production of Pt-SA composite material
With SiO2@TiO2Pt-SA composite material and SiO2@TiO2The Pt/IM composite was tested:
respectively ultrasonically dispersing 50 mg of the composite material in 72 mL of deionized water, then adding 8 mL of lactic acid, uniformly mixing and stirring, and adding into a quartz reactor. Vacuumizing the interior of the quartz reactor, and irradiating the system from the upper part of the quartz reactor by using ultraviolet-visible light (lambda is more than or equal to 320 nm and less than or equal to 780 nm) for 10 hours continuously. The hydrogen production amount per hour obtained was analyzed using gas chromatography, and the hydrogen production rate thereof was calculated.
As shown in FIG. 4, in 10 h of illumination, SiO2@TiO2The hydrogen production rate of Pt-SA is kept to be about 2.6 mmol/g h, and SiO is kept2@TiO2The hydrogen production rate of the Pt-IM is gradually reduced from the initial 1.3 mmol/g h to 1.0 mmol/g h.
Example 2
Metal/semiconductor composite photocatalyst SiO2@TiO2Preparation of Pt-SA
(1) Adding 2 mL of ammonia water (mass fraction of 30%) and 1mL of deionized water into 40 mL of isopropanol, uniformly mixing and stirring, adding 2 mL of tetraethyl orthosilicate, and reacting at room temperature for 2 hours to obtain SiO with the average diameter of 400 nm2Nanospheres;
(2) 0.1g of SiO are weighed2The nanospheres are dispersed in 2 mL of ethanol solution, uniformly dispersed by ultrasonic, added with 0.08 mL of n-butyl titanate and stirred for 15 min;
(3) dissolving 0.28 g of polyvinylpyrrolidone (PVP) in a solution containing 20 mL of ethanol and 1mL of deionized water, uniformly mixing and stirring, adding the obtained solution into the solution, mixing and stirring at room temperature for 1.5h, centrifuging to obtain a corresponding sample, washing for 2 times by using ethanol, and drying at 55 ℃ to obtain SiO2@TiO2A composite material;
(4) 0.1g of SiO are weighed2@TiO2Dispersing the composite material in 50 mL of ethanol, performing ultrasonic dispersion uniformly, adding the dispersed material into 0.45 mL of 3-Aminopropyltriethoxysilane (APTES), reacting at 55 ℃ for 2.5 h, centrifuging, washing with ethanol for 2 times, and drying at 55 ℃ to obtain SiO with a positive electrochemical surface2@TiO2-APTES；
(5) Adding 26 mL of trisodium citrate solution with the concentration of 2.8 mmol/L into 50 mL of chloroplatinic acid aqueous solution with the concentration of 0.4 mmol/L, stirring and mixing uniformly, dropwise adding 5 mL of sodium borohydride solution with the concentration of 12 mmol/L, and reacting for 4 hours at room temperature to obtain Pt colloidal solution;
(6) 0.1g of SiO are weighed2@TiO2-APTES sample, ultrasonically dispersed in 50 mL deionized water, 21mL of Pt colloidal solution, added dropwise to SiO2@TiO2The solution of-APTES is centrifuged, washed by deionized water and dried at 55 ℃ to obtain SiO2@TiO2a/Pt-SA composite material.
Example 3
Metal/semiconductor composite photocatalyst SiO2@TiO2Preparation of Pt-SA
(1) Adding 2 mL of ammonia water (mass fraction of 30%) and 1mL of deionized water into 40 mL of isopropanol, uniformly mixing and stirring, adding 2 mL of tetraethyl orthosilicate, and reacting at room temperature for 2 hours to obtain SiO with the average diameter of 400 nm2Nanospheres;
(2) 0.1g of SiO are weighed2The nanospheres are dispersed in 2 mL of ethanol solution, uniformly dispersed by ultrasonic, added with 0.12 mL of n-butyl titanate and stirred for 25 min;
(3) dissolving 0.32 g of polyvinylpyrrolidone (PVP) in a solution containing 20 mL of ethanol and 1mL of deionized water, uniformly mixing and stirring, adding the obtained solution into the solution, mixing and stirring for 1 h at room temperature, centrifuging to obtain a corresponding sample, washing for 2 times by using ethanol, and drying at 65 ℃ to obtain SiO2@TiO2A composite material;
(4) 0.1g of SiO are weighed2@TiO2Dispersing the composite material in 50 mL of ethanol, performing ultrasonic dispersion uniformly, adding the dispersed material into 0.55 mL of 3-Aminopropyltriethoxysilane (APTES), reacting at 65 ℃ for 2 h, centrifuging, washing with ethanol for 2 times, and drying at 65 ℃ to obtain SiO with a positive electrochemical surface2@TiO2-APTES；
(5) Adding 26 mL of trisodium citrate solution with the concentration of 2.8 mmol/L into 50 mL of chloroplatinic acid aqueous solution with the concentration of 0.4 mmol/L, stirring and mixing uniformly, dropwise adding 5 mL of sodium borohydride solution with the concentration of 12 mmol/L, and reacting for 4 hours at room temperature to obtain Pt colloidal solution;
(6) 0.075 g of SiO are weighed out2@TiO2-APTES sample, ultrasonically dispersed in 50 mL deionized water, 21mL of Pt colloidal solution, added dropwise to SiO2@TiO2The solution of-APTES is centrifuged, washed by deionized water and dried at 65 ℃ to obtain SiO2@TiO2a/Pt-SA composite material.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A preparation method of a metal/semiconductor composite photocatalyst is characterized by comprising the following steps: which comprises the following steps:
(1) mixing SiO2Mixing the nanospheres with an ethanol solution, uniformly dispersing by ultrasonic, adding n-butyl titanate, and stirring for 15-25 min to obtain a mixed solution;
wherein, SiO2The dosage ratio of the nanospheres to the n-butyl titanate is 0.1g to 0.08-0.12 mL;
(2) dissolving polyvinylpyrrolidone in ethanol-deionized water mixed solution, stirring well, adding the obtained solution into the mixed solution, stirring for 1-1.5h, centrifuging, washing the precipitate, and drying to obtain SiO2@TiO2A composite material;
wherein, polyvinylpyrrolidone and SiO2The dosage ratio of the nanospheres is 0.28-0.32 g to 0.1 g;
(3) mixing SiO2@TiO2Mixing the composite material with ethanol, performing ultrasonic dispersion uniformly, adding the mixture into 3-aminopropyltriethoxysilane, reacting for 2-2.5 h at 55-65 ℃, centrifuging, washing and drying the precipitate to obtain SiO with a positive surface2@TiO2-APTES；
Wherein, SiO2@TiO2The dosage ratio of the composite material to the 3-aminopropyl triethoxysilane is 0.1 g: 0.45-0.55 mL;
(4) mixing SiO2@TiO2Dispersing APTES in deionized water to obtain SiO2@TiO2APTES solution, then Pt colloid solution is added dropwise to SiO2@TiO2Centrifuging in APTES solution, washing and drying the precipitate to obtain SiO2@TiO2The Pt-SA composite material is the metal-semiconductor composite photocatalyst;
the SiO2@TiO2The dosage ratio of APTES to Pt colloidal solution is 0.05-0.1 g: 21 mL;
the preparation method of the Pt colloid solution comprises the following steps: adding 26 mL of trisodium citrate solution with the concentration of 2.8 mmol/L into 50 mL of chloroplatinic acid aqueous solution with the concentration of 0.4 mmol/L, stirring and mixing uniformly, dropwise adding 5 mL of sodium borohydride solution with the concentration of 12 mmol/L, and reacting for 3.5-4.5 h at room temperature to obtain a Pt colloidal solution.
2. The method for preparing a metal/semiconductor composite photocatalyst according to claim 1, wherein: in the step (1), the SiO2The preparation method of the nanosphere comprises the following steps: mixing 2 mL of ammonia water with the mass fraction of 30%, 1mL of deionized water and 40 mL of isopropanol, stirring uniformly, adding 2 mL of tetraethyl orthosilicate, and reacting at room temperature for 2-2.5 h to obtain SiO2Nanospheres.
3. The method for preparing a metal/semiconductor composite photocatalyst according to claim 1, wherein: in the step (2), the dosage ratio of the polyvinylpyrrolidone to the ethanol-deionized water mixed solution is 0.28-0.32 g: 21 mL.
4. The method for preparing a metal/semiconductor composite photocatalyst according to claim 1, wherein: in the step (2), the volume ratio of ethanol to deionized water in the ethanol-deionized water mixed solution is 20: 1.
5. The method for preparing a metal/semiconductor composite photocatalyst according to claim 1, wherein: and (3) washing the precipitates in the steps (2) and (3) with ethanol, and washing the precipitates in the step (4) with deionized water.
6. The method for preparing a metal/semiconductor composite photocatalyst according to claim 1, wherein: the drying temperature in the steps (2), (3) and (4) is 55-65 ℃.
7. A metal/semiconductor composite photocatalyst obtained by the production process according to any one of claims 1 to 6.
8. The use of the metal/semiconductor composite photocatalyst according to claim 7 in photocatalytic decomposition of water to produce hydrogen.
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