CN108786792A - A kind of metal/semiconductor composite photo-catalyst and its preparation and application - Google Patents
A kind of metal/semiconductor composite photo-catalyst and its preparation and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000004065 semiconductor Substances 0.000 title claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 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 74
- 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 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 12
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 53
- 235000019441 ethanol Nutrition 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000002077 nanosphere Substances 0.000 claims description 17
- 239000003643 water by type Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 39
- 238000000034 method Methods 0.000 abstract description 9
- 229910052697 platinum Inorganic materials 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 3
- 230000002745 absorbent Effects 0.000 abstract description 2
- 239000002250 absorbent Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000010453 quartz Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical group [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- 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
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of metal/semiconductor composite photo-catalyst and its preparation and application, and using silica as carrier, by sol-gal process, silica titanium dioxide core shell structure is prepared（SiO2@TiO2）, after the positive electrification in surface is carried out to it, Coulomb force self assembly is carried out with the metal platinum nano-particle of surface elecrtonegativity, obtains nano platinum particle in SiO2@TiO2Evenly distributed metal/semiconductor composite photo-catalyst SiO2@TiO2/Pt-SA.The method of the present invention is by optimizing nano platinum particle in SiO2@TiO2The space distribution situation on surface, can effectively improve SiO2@TiO2Activity and stability in photocatalysis Decomposition aquatic products hydrogen reactions of/the Pt-SA for the absorbent properties of visible light and its under ultraviolet-visible light illumination, this method is simple and effective easy, is conducive to construct efficient metal/semiconductors coupling catalysis material that solar energy conversion is responded, can be used for wide spectrum.
Description
Technical field
The invention belongs to field of photocatalytic material, and in particular to a kind of metal/semiconductor composite photo-catalyst and its preparation
With application.
Background technology
Photocatalysis technology provides a possible green approach to alleviate increasingly prominent energy crisis using solar energy,
Hydrogen Energy is converted solar energy into have obtained more and more studying concern.In common photochemical catalyst, titanium dioxide
（TiO2）Because it has many advantages, such as chemical stabilization, cheap and easy to get, become study at present most commonly used semiconductor light-catalyst it
One.But due to TiO2Wider energy gap（3.2 eV）And the high recombination rate of electrons and holes, it cannot be absorbed and utilized
Visible light, and individual TiO2Photocatalytic activity is relatively low.How TiO is improved2Absorbing properties and its photocatalytic activity be always
One of hot spot in terms of catalysis material research.
In the improvement TiO having proposed2In the strategy of performance, compound with metal component is a kind of effective method, not only
TiO can be expanded to a certain extent2Light abstraction width, be also used as electron acceptor, promote TiO2Middle electron-hole
To separation.Wherein, Pt metal not only has broadband optic response, high work function（5.65eV）, and for producing hydrogen
Reaction has lower reaction overpotential, therefore is often used as co-catalyst, improves the photocatalysis Decomposition aquatic products of semi-conducting material
Hydrogen performance.Currently used Pt metal and semiconductor TiO2Complex method, be that Pt metal is simply loaded or is deposited on TiO2Table
Face, the composite material obtained by above method, in liquid phase reactor, metal component Pt, which there are problems that easily leaching, to be lost in, from
And cause the stability of composite material not high.Such as Pt nano-particles are wrapped in inside semiconductor component, then can block its surface
Production hydrogen reactivity site, lead to not using its it is lower production hydrogen overpotential advantage.Therefore, there is wide spectrum to ring for exploitation
It answers, Pt metal-semiconductor TiO of high photocatalysis Decomposition aquatic products hydrogen activity and good stability2Composite material is high for structure
The stable photocatalysis Decomposition aquatic products hydrogen system of effect has important scientific research meaning and actual application value.
Invention content
The purpose of the present invention is to provide one kind/semiconductor compound photocatalyst and its preparation and application, it is intended to pass through
Optimize microstructure and improves Pt metal/semiconductor TiO2Activity and stabilization of the composite photocatalyst material in decomposing the reaction of aquatic products hydrogen
Property.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of metal/semiconductor composite photo-catalyst, includes the following steps：
（1）By SiO2Nanosphere is mixed with ethanol solution, and ultrasonic disperse is uniform, adds tetrabutyl titanate, stirs 15-25
Min obtains mixed solution；
Wherein, SiO2The amount ratio of nanosphere and tetrabutyl titanate is 0.1g: 0.08-0.12 mL；
（2）By polyvinylpyrrolidone（PVP）It is dissolved in EtOH-DI water mixed solution, stirs evenly, acquired solution adds
Enter into above-mentioned mixed solution, stir 1-1.5h, washing of precipitate, drying are obtained SiO by centrifugation2@TiO2Composite material；
Wherein, polyvinylpyrrolidone and SiO2The amount ratio of nanosphere is 0.28-0.32 g: 0.1 g；
（3）By SiO2@TiO2Composite material is mixed with ethyl alcohol, and ultrasonic disperse is uniform, adds 3- aminopropyl triethoxysilanes
（APTES）In, 55-65 DEG C of reaction 2-2.5 h is then centrifuged for, and by washing of precipitate, drying, obtains the SiO of the positive electrification in surface2@
TiO2-APTES；
Wherein, SiO2@TiO2The amount ratio of composite material and 3- aminopropyl triethoxysilanes is 0.1 g: 0.45-0.55
mL；
（4）By SiO2@TiO2- APTES, which is scattered in deionized water, obtains SiO2@TiO2- APTES solution, it is then that Pt colloids is molten
Liquid is added dropwise to SiO2@TiO2In-APTES solution, washing of precipitate, drying are obtained SiO by centrifugation2@TiO2/ Pt-SA is compound
Material, i.e., the described metal-semiconductor composite photo-catalyst.
Through the above steps（3）With（4）, Pt nano-particles may be implemented in SiO2@TiO2It is uniformly distributed on surface, and
Obtained composite material, the photochemical catalyzing H2-producing capacity with efficient stable.
Further, step（1）In, the SiO2The preparation method of nanosphere is：The ammonia for being 30% by 2 mL mass fractions
Water, 1 mL deionized waters, the mixing of 40 mL isopropanols, after stirring evenly, are added 2 mL tetraethyl orthosilicates, react 2- at room temperature
2.5 h obtain the SiO that average diameter is 400 nm2Nanosphere.
Step（2）In, the amount ratio of the polyvinylpyrrolidone and EtOH-DI water mixed solution is 0.28-
0.32 g : 21 mL。
Step（2）In, in the EtOH-DI water mixed solution, the volume ratio of ethyl alcohol and deionized water is 20: 1.
Step（4）In, the preparation method of the Pt colloidal solution is：By the citric acid of a concentration of 2.8 mmol/L of 26 mL
Three sodium solutions are added in the chloroplatinic acid aqueous solution of a concentration of 0.4 mmol/L of 50 mL, after being uniformly mixed, are added dropwise 5
The sodium borohydride solution of a concentration of 12 mmol/L of mL reacts 3.5-4.5 h, obtains Pt colloidal solution at room temperature.
Step（4）In, the SiO2@TiO2The amount ratio of-APTES and Pt colloidal solution is 0.05-0.1g: 21mL.
Step（2）,（3）In precipitation washed with ethyl alcohol, step（4）In precipitation be washed with deionized.
Step（2）,（3）,（4）In drying temperature be 55-65 DEG C.
SiO prepared by the present invention2@TiO2/ Pt-SA composite materials, which are used to decompose water under ultraviolet-visible light, generates hydrogen.Light
Catalytic decomposition aquatic products hydrogen reaction is as follows：
（1）By SiO2@TiO2/ Pt-SA compound material ultrasounds are scattered in deionized water, and lactic acid is then added, and are mixed equal
It is even, it is added in quartz reactor；
（2）It will be vacuumized inside quartz reactor；
（3）Use ultraviolet-visible light（320 nm ≤ λ ≤ 780 nm）System is irradiated above quartz reactor.
（4）Use the obtained hydrogen output of gas chromatographic analysis.
Using above technical scheme, by sol-gal process, titanium dioxide is prepared using silica as carrier in the present invention
Silicon titanium dioxide core shell structure（SiO2@TiO2）, after the positive electrification in surface is carried out to it, the metal platinum nanometer with surface elecrtonegativity
Particle carries out Coulomb force self assembly, obtains nano platinum particle in SiO2@TiO2Evenly distributed composite photo-catalyst
SiO2@TiO2/Pt-SA.The present invention passes through optimising and adjustment Pt nano-particles and TiO2Complex method and its microstructure, make Pt
With TiO2Between have stronger Coulomb interactions power, Pt nano-particles can be in TiO2Surface is uniformly distributed.In addition, Pt receives
TiO can also be absorbed and utilized in rice corpuscles2The scattering light of spherical shell realizes the good response to visible light, therefore the composite wood
Material embodies high photocatalytic activity and stability for decomposing the reaction of aquatic products hydrogen.
The remarkable advantage of the present invention is：
（1）The present invention optimizes the microstructure of metal-semiconductor composite material by simple modification；
（2）The composite material SiO being randomly distributed in the platinum prepared by infusion process on silica@titanium dioxide surfaces2@
TiO2/ Pt-IM is compared, by optimizing nano platinum particle in SiO2@TiO2The space distribution situation on surface, can effectively improve
SiO2@TiO2The photocatalysis Decomposition aquatic products hydrogen of/Pt-SA for the absorbent properties of visible light and its under ultraviolet-visible light illumination is anti-
Activity in answering and stability.
（3）Prepared SiO2@TiO2/ Pt-SA composite photocatalyst materials have wide spectrum response, high photocatalysis Decomposition
Aquatic products hydrogen activity and good cyclical stability；
（4）The present invention is easy to operate, with obvious effects, has a extensive future.
Description of the drawings
Fig. 1 is SiO2@TiO2/ Pt-SA's（A,B）Transmission electron microscope figure and（C）Distribution diagram of element；
Fig. 2 is SiO2@TiO2The UV-Vis DRS figure of/Pt-SA；
Fig. 3 is SiO2@TiO2、SiO2@TiO2/ Pt-SA and SiO2@TiO2/ Pt-IM composite materials irradiate 2 h in ultraviolet-visible light
The activity figure of lower photocatalysis Decomposition aquatic products hydrogen；
Fig. 4 is SiO2@TiO2/ Pt-SA and SiO2@TiO2/ Pt-IM photocatalysis Decomposition aquatic products in the case where ultraviolet-visible light irradiates 10 h
The rate diagram of hydrogen.
Specific implementation mode
The present invention is further illustrated the present invention with the following example, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment 1
Metal/semiconductor composite photo-catalyst SiO2@TiO2The preparation of/Pt-SA
（1）By 2 mL ammonium hydroxide（Mass fraction 30%）, 1 mL deionized waters be added in 40 mL isopropanols, be mixed evenly
Afterwards, 2 mL tetraethyl orthosilicates are added, react 2 h at room temperature, obtain the SiO that average diameter is 400 nm2Nanosphere；
（2）Weigh the SiO of 0.1 g2Nanosphere is scattered in 2 mL ethanol solutions, and ultrasonic disperse is uniform, and 0.1 mL metatitanic acids are added
N-butyl stirs 20 min；
（3）By 0.3 g polyvinylpyrrolidones（PVP）It is dissolved in the solution containing 20 mL ethyl alcohol and 1 mL deionized waters, mixes
Conjunction stirs evenly, and obtained solution is added in above-mentioned solution, and 1 h is mixed at room temperature, and centrifugation obtains corresponding sample
Product, 60 DEG C of drying, obtain SiO after washing 2 times with ethyl alcohol2@TiO2Composite material；
（4）Weigh the SiO of 0.1 g2@TiO2Composite material is scattered in 50 mL ethyl alcohol, and ultrasonic disperse is uniform, and 0.5 mL is added
3- aminopropyl triethoxysilanes（APTES）In, it centrifuges after 60 DEG C of 2 h of reaction, is washed 2 times with ethyl alcohol, 60 DEG C of drying obtain
To the SiO of the positive electrification in surface2@TiO2-APTES；
（5）The citric acid three sodium solution of a concentration of 2.8 mmol/L of 26 mL is added to the chlorine of a concentration of 0.4 mmol/L of 50 mL
In platinic acid aqueous solution, after being uniformly mixed, the sodium borohydride solution of a concentration of 12 mmol/L of 5 mL is added dropwise, at room temperature
4 h are reacted, Pt colloidal solution is obtained；
（6）Weigh the SiO of 0.05 g2@TiO2- APTES samples, ultrasonic disperse is in 50 mL deionized waters, by the Pt of 21 mL
Colloidal solution is added dropwise to SiO2@TiO2It in-APTES solution, centrifuges, is washed with deionized later, 60 DEG C of drying obtain
To SiO2@TiO2/ Pt-SA composite materials.
It will be seen from figure 1 that Pt nano-particles are evenly distributed on SiO2@TiO2Surface.Figure it is seen that SiO2@
TiO2/ Pt-SA in visible light region there is apparent absorb to respond.
Comparative example 1
SiO2@TiO2The preparation of/Pt-IM
（1）By 2 mL ammonium hydroxide（Mass fraction 30%）, 1 mL deionized waters be added in 40 mL isopropanols, be mixed evenly
Afterwards, 2 mL tetraethyl orthosilicates are added, react 2 h at room temperature, obtain the SiO that average diameter is 400 nm2Nanosphere；
（2）Weigh the SiO of 0.1 g2Nanosphere is scattered in 2 mL ethanol solutions, and ultrasonic disperse is uniform, and 0.1 mL metatitanic acids are added
N-butyl stirs 20 min；
（3）By 0.3 g polyvinylpyrrolidones（PVP）It is dissolved in the solution containing 20 mL ethyl alcohol and 1 mL deionized waters, mixes
Conjunction stirs evenly, and obtained solution is added in above-mentioned solution, and 1 h is mixed at room temperature, and centrifugation obtains corresponding sample
Product are washed 2 times with ethyl alcohol, and rear 60 DEG C of drying obtain SiO2@TiO2Composite material；
（4）The citric acid three sodium solution of a concentration of 2.8 mmol/L of 26 mL is added to the chlorine of a concentration of 0.4 mmol/L of 50 mL
In platinic acid aqueous solution, after being uniformly mixed, the sodium borohydride solution of a concentration of 12 mmol/L of 5 mL is added dropwise, at room temperature
4 h are reacted, Pt colloidal solution is obtained；
（5）Weigh the SiO of 0.05 g2@TiO2Sample, ultrasonic disperse are molten by the Pt colloids of 21 mL in 50 mL deionized waters
Liquid is added to SiO2@TiO2In solution, after getting rid of most solutions by rotary evaporation, 60 DEG C of drying of sample obtain
To SiO2@TiO2/ Pt-IM composite materials.
Application examples 1
SiO2@TiO2Composite material, SiO2@TiO2/ Pt-SA composite materials, SiO2@TiO2The photocatalysis of/Pt-IM composite materials point
Solve the experiment of aquatic products hydrogen
With SiO2@TiO2Composite material, SiO2@TiO2/ Pt-SA composite materials and SiO2@TiO2/ Pt-IM composite materials are tried
It tests：
The above-mentioned composite materials of 50 mg are distinguished into ultrasonic disperse in 72 mL deionized waters, 8 mL lactic acid are then added, mixing is stirred
It mixes uniformly, is added in quartz reactor.It will be vacuumized inside quartz reactor, use ultraviolet-visible light（320 nm ≤ λ
≤ 780 nm）System is irradiated above quartz reactor, light application time is 2 h.Use the obtained hydrogen of gas chromatographic analysis
Yield.
As shown in figure 3, SiO2@TiO2、SiO2@TiO2/ Pt-SA and SiO2@TiO2/ Pt-IM irradiates 2 in ultraviolet-visible light
Under conditions of h, hydrogen output is respectively 0.098 mmol/g, 5.79 mmol/g and 2.56 mmol/g.
Application examples 2
SiO2@TiO2The rate comparison of/Pt-SA composite material photocatalysis Decomposition aquatic products hydrogen is tested
With SiO2@TiO2/ Pt-SA composite materials and SiO2@TiO2/ Pt-IM composite materials are tested：
The above-mentioned composite material of 50 mg is distinguished into ultrasonic disperse in 72 mL deionized waters, 8 mL lactic acid are then added, mix
It stirs evenly, is added in quartz reactor.It will be vacuumized inside quartz reactor, use ultraviolet-visible light（320 nm ≤
λ ≤ 780 nm）System, 10 h of continuous illumination are irradiated above quartz reactor.Using every small obtained by gas chromatographic analysis
When hydrogen output, and calculate its hydrogen-producing speed.
As shown in figure 4, in 10 h of illumination, SiO2@TiO2It is left that the hydrogen-producing speed of/Pt-SA is maintained at 2.6 mmol/g h
The right side, and SiO2@TiO21.3 mmol/g hs of the hydrogen-producing speed of/Pt-IM by are gradually lowered to 1.0 mmol/g h.
Embodiment 2
Metal/semiconductor composite photo-catalyst SiO2@TiO2The preparation of/Pt-SA
（1）By 2 mL ammonium hydroxide（Mass fraction 30%）, 1 mL deionized waters be added in 40 mL isopropanols, be mixed evenly
Afterwards, 2 mL tetraethyl orthosilicates are added, react 2 h at room temperature, obtain the SiO that average diameter is 400 nm2Nanosphere；
（2）Weigh the SiO of 0.1 g2Nanosphere is scattered in 2 mL ethanol solutions, and ultrasonic disperse is uniform, and 0.08 mL titaniums are added
Sour N-butyl stirs 15 min；
（3）By 0.28 g polyvinylpyrrolidones（PVP）It is dissolved in the solution containing 20 mL ethyl alcohol and 1 mL deionized waters,
It is mixed evenly, obtained solution is added in above-mentioned solution, 1.5 h are mixed at room temperature, centrifugation obtains corresponding
Sample, after washing 2 times with ethyl alcohol 55 DEG C drying, obtain SiO2@TiO2Composite material；
（4）Weigh the SiO of 0.1 g2@TiO2Composite material is scattered in 50 mL ethyl alcohol, and ultrasonic disperse is uniform, is added 0.45
The 3- aminopropyl triethoxysilanes of mL（APTES）In, it centrifuges, is washed 2 times with ethyl alcohol, 55 DEG C of bakings after 55 DEG C of 2.5 h of reaction
It is dry, obtain the SiO of the positive electrification in surface2@TiO2-APTES；
（5）The citric acid three sodium solution of a concentration of 2.8 mmol/L of 26 mL is added to the chlorine of a concentration of 0.4 mmol/L of 50 mL
In platinic acid aqueous solution, after being uniformly mixed, the sodium borohydride solution of a concentration of 12 mmol/L of 5 mL is added dropwise, at room temperature
4 h are reacted, Pt colloidal solution is obtained；
（6）Weigh the SiO of 0.1 g2@TiO2- APTES samples, ultrasonic disperse is in 50 mL deionized waters, by the Pt glue of 21 mL
Liquid solution is added dropwise to SiO2@TiO2It in-APTES solution, centrifuges, is washed with deionized later, 55 DEG C of drying obtain
SiO2@TiO2/ Pt-SA composite materials.
Embodiment 3
Metal/semiconductor composite photo-catalyst SiO2@TiO2The preparation of/Pt-SA
（1）By 2 mL ammonium hydroxide（Mass fraction 30%）, 1 mL deionized waters be added in 40 mL isopropanols, be mixed evenly
Afterwards, 2 mL tetraethyl orthosilicates are added, react 2 h at room temperature, obtain the SiO that average diameter is 400 nm2Nanosphere；
（2）Weigh the SiO of 0.1 g2Nanosphere is scattered in 2 mL ethanol solutions, and ultrasonic disperse is uniform, and 0.12 mL titaniums are added
Sour N-butyl stirs 25 min；
（3）By 0.32 g polyvinylpyrrolidones（PVP）It is dissolved in the solution containing 20 mL ethyl alcohol and 1 mL deionized waters,
It is mixed evenly, obtained solution is added in above-mentioned solution, 1 h is mixed at room temperature, centrifugation obtains corresponding
Sample, 65 DEG C of drying, obtain SiO after washing 2 times with ethyl alcohol2@TiO2Composite material；
（4）Weigh the SiO of 0.1 g2@TiO2Composite material is scattered in 50 mL ethyl alcohol, and ultrasonic disperse is uniform, is added 0.55
The 3- aminopropyl triethoxysilanes of mL（APTES）In, it centrifuges, is washed 2 times with ethyl alcohol, 65 DEG C of drying after 65 DEG C of 2 h of reaction,
Obtain the SiO of the positive electrification in surface2@TiO2-APTES；
（5）The citric acid three sodium solution of a concentration of 2.8 mmol/L of 26 mL is added to the chlorine of a concentration of 0.4 mmol/L of 50 mL
In platinic acid aqueous solution, after being uniformly mixed, the sodium borohydride solution of a concentration of 12 mmol/L of 5 mL is added dropwise, at room temperature
4 h are reacted, Pt colloidal solution is obtained；
（6）Weigh the SiO of 0.075 g2@TiO2- APTES samples, ultrasonic disperse is in 50 mL deionized waters, by the Pt of 21 mL
Colloidal solution is added dropwise to SiO2@TiO2It in-APTES solution, centrifuges, is washed with deionized later, 65 DEG C of drying obtain
To SiO2@TiO2/ Pt-SA composite materials.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (10)
1. a kind of preparation method of metal/semiconductor composite photo-catalyst, it is characterised in that：It includes the following steps：
（1）By SiO2Nanosphere is mixed with ethanol solution, and ultrasonic disperse is uniform, adds tetrabutyl titanate, stirs 15-25 min,
Obtain mixed solution；
Wherein, SiO2The amount ratio of nanosphere and tetrabutyl titanate is 0.1g: 0.08-0.12 mL；
（2）Polyvinylpyrrolidone is dissolved in EtOH-DI water mixed solution, is stirred evenly, acquired solution is added to
In above-mentioned mixed solution, 1-1.5h is stirred, washing of precipitate, drying are obtained SiO by centrifugation2@TiO2Composite material；
Wherein, polyvinylpyrrolidone and SiO2The amount ratio of nanosphere is 0.28-0.32 g: 0.1 g；
（3）By SiO2@TiO2Composite material is mixed with ethyl alcohol, and ultrasonic disperse is uniform, adds 3- aminopropyl triethoxysilanes
In, 55-65 DEG C of reaction 2-2.5 h is then centrifuged for, and by washing of precipitate, drying, obtains the SiO of the positive electrification in surface2@TiO2-
APTES；
Wherein, SiO2@TiO2The amount ratio of composite material and 3- aminopropyl triethoxysilanes is 0.1 g: 0.45-0.55
mL；
（4）By SiO2@TiO2- APTES, which is scattered in deionized water, obtains SiO2@TiO2- APTES solution, it is then that Pt colloids is molten
Liquid is added dropwise to SiO2@TiO2In-APTES solution, washing of precipitate, drying are obtained SiO by centrifugation2@TiO2/ Pt-SA is compound
Material, i.e., the described metal-semiconductor composite photo-catalyst.
2. a kind of preparation method of metal/semiconductor composite photo-catalyst according to claim 1, it is characterised in that：Step
Suddenly（1）In, the SiO2The preparation method of nanosphere is：It is 30% ammonium hydroxide, 1 mL deionized waters, 40 by 2 mL mass fractions
ML isopropanols mix, and after stirring evenly, 2 mL tetraethyl orthosilicates are added, reacts 2-2.5 h at room temperature, obtains SiO2Nanometer
Ball.
3. a kind of preparation method of metal/semiconductor composite photo-catalyst according to claim 1, it is characterised in that：Step
Suddenly（2）In, the amount ratio of the polyvinylpyrrolidone and EtOH-DI water mixed solution is 0.28-0.32 g: 21
mL。
4. a kind of preparation method of metal/semiconductor composite photo-catalyst according to claim 1, it is characterised in that：Step
Suddenly（2）In, in the EtOH-DI water mixed solution, the volume ratio of ethyl alcohol and deionized water is 20: 1.
5. a kind of preparation method of metal/semiconductor composite photo-catalyst according to claim 1, it is characterised in that：Step
Suddenly（4）In, the preparation method of the Pt colloidal solution is：The citric acid three sodium solution of a concentration of 2.8 mmol/L of 26 mL is added
Enter into the chloroplatinic acid aqueous solution of a concentration of 0.4 mmol/L of 50 mL, after being uniformly mixed, 5 mL a concentration of 12 are added dropwise
The sodium borohydride solution of mmol/L reacts 3.5-4.5 h, obtains Pt colloidal solution at room temperature.
6. a kind of preparation method of metal/semiconductor composite photo-catalyst according to claim 1, it is characterised in that：Step
Suddenly（4）In, the SiO2@TiO2The amount ratio of-APTES and Pt colloidal solution is 0.05-0.1g: 21mL.
7. a kind of preparation method of metal/semiconductor composite photo-catalyst according to claim 1, it is characterised in that：Step
Suddenly（2）,（3）In precipitation washed with ethyl alcohol, step（4）In precipitation be washed with deionized.
8. a kind of preparation method of metal/semiconductor composite photo-catalyst according to claim 1, it is characterised in that：Step
Suddenly（2）,（3）（4）In drying temperature be 55-65 DEG C.
9. the metal/semiconductor composite photo-catalyst obtained according to any preparation methods of claim 1-8.
10. application of the metal/semiconductor composite photo-catalyst according to claim 9 in photocatalysis Decomposition aquatic products hydrogen.
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