CN106622198A - Composite nano-structured titanium dioxide photocatalyst and preparation method thereof - Google Patents
Composite nano-structured titanium dioxide photocatalyst and preparation method thereof Download PDFInfo
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- CN106622198A CN106622198A CN201611074933.0A CN201611074933A CN106622198A CN 106622198 A CN106622198 A CN 106622198A CN 201611074933 A CN201611074933 A CN 201611074933A CN 106622198 A CN106622198 A CN 106622198A
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- titanium dioxide
- anatase
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- rutile
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 239000011941 photocatalyst Substances 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 11
- 230000003287 optical effect Effects 0.000 claims description 11
- 239000002086 nanomaterial Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002096 quantum dot Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- IDIJOAIHTRIPRC-UHFFFAOYSA-J hexaaluminum;sodium;2,2,4,4,6,6,8,8,10,10,12,12-dodecaoxido-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane;iron(2+);triborate;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Fe+2].[Fe+2].[Fe+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-][Si]1([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O1 IDIJOAIHTRIPRC-UHFFFAOYSA-J 0.000 claims description 4
- 229910000246 schorl Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 20
- 239000001257 hydrogen Substances 0.000 abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 20
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 239000002253 acid Substances 0.000 abstract description 10
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000002073 nanorod Substances 0.000 abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000000243 solution Substances 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 18
- 239000007789 gas Substances 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000000376 reactant Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000007540 photo-reduction reaction Methods 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- 239000004575 stone Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a composite nano-structured titanium dioxide photocatalyst and a preparation method thereof. The composite nano-structured titanium dioxide photocatalyst is prepared by implementing self-assembled growth on anatase-phase titanium dioxide quantum dots on the surfaces of rutile-phase titanium dioxide one-dimensional nanorods, and then a heterojunction interface that anatase (112) crystal surfaces contact with rutile-phase (110) crystal surfaces can be formed. The preparation method is as follows: a hydrothermal method is adopted, hydrochloric acid, deionized water, absolute ethyl alcohol and butyl titanate are taken as raw materials, under different acid and temperature conditions, the anatase-phase titanium dioxide quantum dots and the rutile-phase titanium dioxide one-dimensional nanorods and mixtures of the anatase-phase titanium dioxide quantum dots and the rutile-phase titanium dioxide one-dimensional nanorods in different ratios are prepared. As preparation conditions are adjusted, self-assembled growth of the anatase-phase titanium dioxide quantum dots on the surfaces of the rutile-phase titanium dioxide one-dimensional nanorods (110) is achieved, the property of photocatalytic degradation on water to generate hydrogen by using the titanium dioxide catalyst can be greatly improved, and is prior to the hydrogen generation property of commercial photocatalytic P25. The preparation method disclosed by the invention is simple, controllable in preparation condition, low in production cost and green and environment friendly.
Description
Technical field
The present invention relates to a kind of composite nanostructure titanium dioxide optical catalyst and preparation method thereof, is mainly used in light and urges
Change decomposition water hydrogen making, belong to Photocatalitic Technique of Semiconductor and hydrogen as energy source field.
Background technology
The energy and environmental problem are always the greatest problem that the mankind are faced.In recent years, the exhausted and change of fossil fuel
Environmental problem caused by stone fuel combustion increasingly promotes people to look for the energy that is a kind of sustainable and cleaning.Hydrogen due to
Itself is a kind of high efficient energy sources, and the reactants water for generating can be reused, and become the optimal choosing of new cleaning fuel
Select.A large amount of productions of industrial hydrogen mostly come from fossil energy, and this method is both not environmentally or uneconomical.Therefore, study
Person is devoted to developing a kind of sustainable and economic product hydrogen means.Since 1972Fujishima and Honda are found that water in Ti02
On electrode can since the phenomenon of photocatalysis Decomposition, the characteristics of photochemical catalyzing is by its cleaning, low cost and environmental friendliness,
Have become a kind of new way of the utilization solar energy product hydrogen for having and having great prospects for development.
As a kind of typical semiconductor light-catalyst, the titanium dioxide of nanostructured with its Stability Analysis of Structures, environmental friendliness,
It is readily available and is widely used in photocatalytic degradation organic matter and photocatalysis hydrogen production the characteristics of low price.P25 is current business
The preferable product of generally acknowledged photocatalysis efficiency of production.How photocatalysis hydrogen production efficiency is further improved, to meet the need of new forms of energy
Ask, be the problem in a very forward position.
The content of the invention
The purpose of the present invention be for existing titanium dioxide optical catalyst is inefficient or complicated process of preparation and propose one
Plant simple controllable, cost is relatively low, and the high titanium dioxide optical catalyst of photocatalysis efficiency and its preparation technology.
A kind of composite nanostructure titanium dioxide optical catalyst that the present invention is provided is anatase phase titanium dioxide quantum dot
Self-assembled growth forms anatase (112) crystal face and Rutile Type (110) on red schorl phase titanium dioxide monodimension nano stick surface
The heterojunction boundary that crystal face contacts, the wherein anatase quality accounting in compound phase is 6%～30%.Quality accounting optimum is
12%～15%.
Mainly by control acidity and temperature conditionss, a step hydro-thermal prepares anatase quantum dot to the preparation method of the present invention
The high efficiency photocatalyst of growth is independently filled in one-dimensional red schorl nanorod surfaces.
The concrete preparation process of the present invention is as follows：
1) precursor solution is configured, its component is：Concentration is 37% 10～15ml of concentrated hydrochloric acid, deionized water 135ml, dense
Spend the butyl titanate 10ml for 98%；
2) after hydrochloric acid and water stirring, 10ml butyl titanates are added dropwise and are sufficiently stirred for, by the presoma for stirring
Solution is poured in reactor, 180 DEG C of 10～20hrs of hydro-thermal reaction；
3) question response kettle is naturally cooled to after room temperature, and sample is taken out, cleaning powder to neutrality, drying, and grinding obtains
Titanium dioxide powder photocatalyst.
The preparation process of the optimal parameter of the present invention is as follows：
1st, precursor solution is configured, its component is：Concentrated hydrochloric acid 13ml (concentration is 37%), deionized water 135ml, metatitanic acid fourth
Ester (concentration is 98%) 10ml；
2nd, after hydrochloric acid and water stirring, 10ml butyl titanates are added dropwise and are sufficiently stirred for.By the presoma for stirring
Solution is poured in reactor, 180 DEG C of hydro-thermal reactions 12hrs；
3rd, question response kettle is naturally cooled to after room temperature, and sample is taken out, cleaning powder to neutrality, drying, and grinding obtains
Titanium dioxide powder photocatalyst.
The present invention has clear advantage, and method is simply controllable, and cost is relatively low, and photocatalysis efficiency is high.
Description of the drawings
Fig. 1 is the X ray diffracting spectrum of prepared titania powder.As a result the sharp titanium that sample is different proportion is shown
The mixed phase of ore deposit/Rutile Type.
Fig. 2 is prepared titania powder TEM figures.It can be seen that Anatase quantum dot is one-dimensional in rutile in figure
Nanorod surfaces self-organizing generate, define with anatase (112) crystal face and rutile (110) crystal face contact interface constituted it is different
Matter is tied.Wherein A is anatase TiO2, and R is Rutile Type TiO2.
Fig. 3 is corresponding anatase A (112) crystal faces and rutile R (110) crystal face matching simulation drawing.Wherein a, for sharp titanium
Ore deposit A (112) crystal face atomic arrangement figure, b, for rutile R (110) crystal face atomic arrangement figure, c is anatase (112) crystal face and gold
Red stone (110) crystal face matched atoms arrangement figure.Interface local area portion Ti atom site matchings can be seen, become quantum dot certainly
The nucleating point of assembling growth.
Fig. 4 is the photochemical catalyzing hydrogen generation efficiency figure of prepared composite nanostructure titanium dioxide optical catalyst, and
Contrasted with pure anatase TiO2, pure rutile phase TiO2 nanometer powder and Douglas P25 commercialization TiO2 powder, said
Bright this anatase quantum dot modified rutile monodimension nano stick titanium dioxide optical catalyst has than commercial Douglas P25 titaniums
The higher photocatalytic activity of white powder.
Specific implementation method
Case explanation will be made to the specific embodiment of the present invention below, the implementation case is with the present invention as technical scheme
On the premise of implement, but protection scope of the present invention is not limited to following case study on implementation.
Case study on implementation 1
Raw material：Deionized water 135ml, concentration is 37% hydrochloric acid 10ml, and concentration is 98% butyl titanate 10ml.
Butyl titanate is added dropwise over after acid and water are sufficiently mixed, by magnetic agitation and is sufficiently mixed, obtain faint yellow
Settled solution.Then solution is poured in reactor, 180 DEG C of drying box hydro-thermal reaction 12 hours is put into after sealing.Question response kettle
The sediment that reaction is generated is poured out after cooling, deionized water is repeatedly rinsed to neutrality, and anatase gold is obtained after drying grinding
Red stone compound phase nano titanium dioxide powder.Anatase quality accounting in compound phase is 60.4%.Two that 20mg is prepared
(64mL deionized waters and 16mL methyl alcohol) adds reaction to hold in titanium dioxide powder and methanol solution that 80mL volumetric concentrations are 20%
In device, and instill the H of a certain amount of configuration2PtCl6·6H2The aqueous solution of O, the method deposited by photoreduction bears sample
The Pt atoms of load 1wt.% are on sample.Air before reaction, during halfhour nitrogen is led in container to exclude container.Reaction
When, container reactant has always magnetic stirrer dispersed to ensure catalyst.After a period of time, in taking reactor
Gas 1mL sends in gas chromatograph and detects, will measure retention time, the peak of retention time, peak area and the base peak of peak position
Area is contrasted, and the efficiency that photocatalysis hydrogen production is obtained after calculating is 577 μm of ol/h.
Case study on implementation 2
Raw material：Deionized water 135ml, concentration is 37% hydrochloric acid 11ml, and concentration is 98% butyl titanate 10ml.
Butyl titanate is added dropwise over after acid and water are sufficiently mixed, by magnetic agitation and is sufficiently mixed, obtain faint yellow
Settled solution.Then solution is poured in reactor, 180 DEG C of drying box hydro-thermal reaction 12 hours is put into after sealing.Question response kettle
The sediment that reaction is generated is poured out after cooling, deionized water is repeatedly rinsed to neutrality, and anatase gold is obtained after drying grinding
Red stone compound phase nano titanium dioxide powder.Anatase quality accounting in compound phase is 30.1%.Two that 20mg is prepared
(64mL deionized waters and 16mL methyl alcohol) adds reaction to hold in titanium dioxide powder and methanol solution that 80mL volumetric concentrations are 20%
In device, and instill the H of a certain amount of configuration2PtCl6·6H2The aqueous solution of O, the method deposited by photoreduction bears sample
The Pt atoms of load 1wt.% are on sample.Air before reaction, during halfhour nitrogen can be led in container to exclude container.Instead
At once, container reactant has always magnetic stirrer dispersed to ensure catalyst.After a period of time, in taking reactor
Gas 1mL send into gas chromatograph in detect, by measure retention time, peak area and the base peak of peak position retention time,
Peak area is contrasted, and the efficiency that photocatalysis hydrogen production is obtained after calculating is 1090 μm of ol/h.
Case study on implementation 3
Raw material：Deionized water 135ml, concentration is 37% hydrochloric acid 12ml, and concentration is 98% butyl titanate 10ml.
Butyl titanate is added dropwise over after acid and water are sufficiently mixed, by magnetic agitation and is sufficiently mixed, obtain faint yellow
Settled solution.Then solution is poured in reactor, 180 DEG C of drying box hydro-thermal reaction 12 hours is put into after sealing.Question response kettle
The sediment that reaction is generated is poured out after cooling, deionized water is repeatedly rinsed to neutrality, and anatase gold is obtained after drying grinding
Red stone compound phase nano titanium dioxide powder.Anatase quality accounting in compound phase is 15.3%.Two that 20mg is prepared
(64mL deionized waters and 16mL methyl alcohol) adds reaction to hold in titanium dioxide powder and methanol solution that 80mL volumetric concentrations are 20%
In device, and instill the H of a certain amount of configuration2PtCl6·6H2The aqueous solution of O, the method deposited by photoreduction bears sample
The Pt atoms of load 1wt.% are on sample.Air before reaction, during halfhour nitrogen can be led in container to exclude container.Instead
At once, container reactant has always magnetic stirrer dispersed to ensure catalyst.After a period of time, in taking reactor
Gas 1mL send into gas chromatograph in detect, by measure retention time, peak area and the base peak of peak position retention time,
Peak area is contrasted, and the efficiency that photocatalysis hydrogen production is obtained after calculating is 1273 μm of ol/h.
Case study on implementation 4
Raw material：Deionized water 135ml, concentration is 37% hydrochloric acid 13ml, and concentration is 98% butyl titanate 10ml.
Butyl titanate is added dropwise over after acid and water are sufficiently mixed, by magnetic agitation and is sufficiently mixed, obtain faint yellow
Settled solution.Then solution is poured in reactor, 180 DEG C of drying box hydro-thermal reaction 12 hours is put into after sealing.Question response kettle
The sediment that reaction is generated is poured out after cooling, deionized water is repeatedly rinsed to neutrality, and anatase gold is obtained after drying grinding
Red stone compound phase nano titanium dioxide powder.Anatase quality accounting in compound phase is 12.0%.Two that 20mg is prepared
(64mL deionized waters and 16mL methyl alcohol) adds reaction to hold in titanium dioxide powder and methanol solution that 80mL volumetric concentrations are 20%
In device, and instill the H of a certain amount of configuration2PtCl6·6H2The aqueous solution of O, the method deposited by photoreduction bears sample
The Pt atoms of load 1wt.% are on sample.Air before reaction, during halfhour nitrogen can be led in container to exclude container.Instead
At once, container reactant has always magnetic stirrer dispersed to ensure catalyst.After a period of time, in taking reactor
Gas 1mL send into gas chromatograph in detect, by measure retention time, peak area and the base peak of peak position retention time,
Peak area is contrasted, and the efficiency that photocatalysis hydrogen production is obtained after calculating is 1488 μm of ol/h.
Case study on implementation 5
Raw material：Deionized water 135ml, concentration is 37% hydrochloric acid 15ml, and concentration is 98% butyl titanate 10ml.By acid
Butyl titanate is added dropwise over after being sufficiently mixed with water, by magnetic agitation and is sufficiently mixed, obtain faint yellow settled solution.Then
Solution is poured in reactor, 180 DEG C of drying box hydro-thermal reaction 12 hours is put into after sealing.By reaction life after the cooling of question response kettle
Into sediment pour out, deionized water is repeatedly rinsed to neutrality, and after drying grinding anatase rutile compound phase nanometer is obtained
Titania powder.Anatase quality accounting in compound phase is 5.6%.The titania powder that 20mg is prepared and 80mL
Volumetric concentration be 20% methanol solution in (64mL deionized waters and 16mL methyl alcohol) add in reaction vessel, and instill a certain amount of
The H of configuration2PtCl6·6H2The aqueous solution of O, by photoreduction deposit method make sample load 1wt.% Pt atoms in
On sample.Air before reaction, during halfhour nitrogen can be led in container to exclude container.During reaction, container reactant one
Directly there is magnetic stirrer dispersed to ensure catalyst.After a period of time, the gas 1mL taken in reactor sends into gas phase
Detect in chromatograph, retention time, the peak area contrast of retention time, peak area and the base peak of peak position will be measured, after calculating
The efficiency for obtaining photocatalysis hydrogen production is 843 μm of ol/h.
Case study on implementation 6
Raw material：Deionized water 135ml, concentration is 37% hydrochloric acid 18ml, and concentration is 98% butyl titanate 10ml.By acid
Butyl titanate is added dropwise over after being sufficiently mixed with water, by magnetic agitation and is sufficiently mixed, obtain faint yellow settled solution.Then
Solution is poured in reactor, 180 DEG C of drying box hydro-thermal reaction 12 hours is put into after sealing.By reaction life after the cooling of question response kettle
Into sediment pour out, deionized water is repeatedly rinsed to neutrality, and after drying grinding anatase rutile compound phase nanometer is obtained
Titania powder.Anatase quality accounting in compound phase is 3.1%.The titania powder that 20mg is prepared and 80mL
Volumetric concentration be 20% methanol solution in (64mL deionized waters and 16mL methyl alcohol) add in reaction vessel, and instill a certain amount of
The H of configuration2PtCl6·6H2The aqueous solution of O, by photoreduction deposit method make sample load 1wt.% Pt atoms in
On sample.Air before reaction, during halfhour nitrogen can be led in container to exclude container.During reaction, container reactant one
Directly there is magnetic stirrer dispersed to ensure catalyst.After a period of time, the gas 1mL taken in reactor sends into gas phase
Detect in chromatograph, retention time, the peak area contrast of retention time, peak area and the base peak of peak position will be measured, after calculating
The efficiency for obtaining photocatalysis hydrogen production is 808 μm of ol/h.
Contrast case 1：
Raw material：Deionized water 135ml, concentration is 37% hydrochloric acid 0ml, and concentration is 98% butyl titanate 10ml.By acid
Butyl titanate is added dropwise over after being sufficiently mixed with water, by magnetic agitation and is sufficiently mixed, obtain faint yellow settled solution.Then
Solution is poured in reactor, 180 DEG C of drying box hydro-thermal reaction 12 hours is put into after sealing.By reaction life after the cooling of question response kettle
Into sediment pour out, deionized water is repeatedly rinsed to neutrality, and after drying grinding pure anatase-phase nano titanium dioxide is obtained
Powder.Anatase quality accounting in compound phase is 100%.The titania powder that 20mg is prepared and 80mL volumetric concentrations
Add in reaction vessel for (64mL deionized waters and 16mL methyl alcohol) in 20% methanol solution, and instill a certain amount of configuration
H2PtCl6·6H2The aqueous solution of O, the method deposited by photoreduction makes sample load the Pt atoms of 1wt.% in sample
On.Air before reaction, during halfhour nitrogen can be led in container to exclude container.During reaction, container reactant has always
Magnetic stirrer is dispersed to ensure catalyst.After a period of time, the gas 1mL taken in reactor sends into gas-chromatography
Detect in instrument, retention time, the peak area contrast of retention time, peak area and the base peak of peak position will be measured, obtain after calculating
The efficiency of photocatalysis hydrogen production is 230 μm of ol/h.
Contrast case 2：
Raw material：Deionized water 135ml, concentration is 37% hydrochloric acid 20ml, and concentration is 98% butyl titanate 10ml.By acid
Butyl titanate is added dropwise over after being sufficiently mixed with water, by magnetic agitation and is sufficiently mixed, obtain faint yellow settled solution.Then
Solution is poured in reactor, 180 DEG C of drying box hydro-thermal reaction 12 hours is put into after sealing.By reaction life after the cooling of question response kettle
Into sediment pour out, deionized water is repeatedly rinsed to neutrality, and after drying grinding pure rutile phase nano-titanium dioxide is obtained
Powder.Anatase quality accounting in compound phase is 0%.The titania powder and 80mL volumetric concentrations that 20mg is prepared be
(64mL deionized waters and 16mL methyl alcohol) is added in reaction vessel in 20% methanol solution, and instills a certain amount of configuration
H2PtCl6·6H2The aqueous solution of O, the method deposited by photoreduction makes sample load the Pt atoms of 1wt.% in sample
On.Air before reaction, during halfhour nitrogen can be led in container to exclude container.During reaction, container reactant has always
Magnetic stirrer is dispersed to ensure catalyst.After a period of time, the gas 1mL taken in reactor sends into gas-chromatography
Detect in instrument, retention time, the peak area contrast of retention time, peak area and the base peak of peak position will be measured, obtain after calculating
The efficiency of photocatalysis hydrogen production is 769 μm of ol/h.
Contrast case 3：
Raw material：Commercially available Douglas P25 powder 20mg, XRD analysis its anatase quality accounting in compound phase
For 85.9%.By in powder 20mg and methanol solution that 80mL volumetric concentrations are 20% (64mL deionized waters and 16mL methyl alcohol)
In adding reaction vessel, and instill the H of a certain amount of configuration2PtCl6·6H2The aqueous solution of O, the side deposited by photoreduction
Method makes the Pt atoms of sample load 1wt.% on sample.Before reaction, halfhour nitrogen can be led in container to exclude container
In air.During reaction, container reactant has always magnetic stirrer dispersed to ensure catalyst.For a period of time
Afterwards, take the gas 1mL in reactor and send into detection in gas chromatograph, retention time, peak area and the standard of peak position will be measured
The retention time at peak, peak area contrast, the efficiency that photocatalysis hydrogen production is obtained after calculating is 1201 μm of ol/h.
Claims (4)
1. a kind of composite nanostructure titanium dioxide optical catalyst, it is characterised in that：Anatase phase titanium dioxide quantum dot is from group
Dress is grown in red schorl phase titanium dioxide monodimension nano stick surface, forms anatase (112) crystal face and Rutile Type (110) crystal face
The heterojunction boundary for contacting, the wherein anatase quality accounting in compound phase is 6%～30%.
2. a kind of composite nanostructure titanium dioxide optical catalyst, it is characterised in that：Anatase phase titanium dioxide quantum dot is from group
Dress is grown in red schorl phase titanium dioxide monodimension nano stick surface, forms anatase (112) crystal face and Rutile Type (110) crystal face
The heterojunction boundary for contacting, the wherein anatase quality accounting in compound phase is 12%～15%.
3. a kind of preparation method of composite nanostructure titanium dioxide optical catalyst, it is characterised in that concrete preparation process is as follows：
1) precursor solution is configured, its component is：Concentration is 37% concentrated hydrochloric acid 10-15ml, deionized water 135ml, and concentration is
98% butyl titanate 10ml；
2) after hydrochloric acid and water stirring, 10ml butyl titanates are added dropwise and are sufficiently stirred for, by the precursor solution for stirring
In pouring reactor into, 180 DEG C of 10～20hrs of hydro-thermal reaction；
3) question response kettle is naturally cooled to after room temperature, and sample is taken out, cleaning powder to neutrality, drying, and grinding obtains dioxy
Change titanium powder photochemical catalyst.
4. a kind of preparation method of composite nanostructure titanium dioxide optical catalyst according to claim 3, its feature exists
It is as follows in concrete preparation process：
1) precursor solution is configured, its component is：Concentration is 37% concentrated hydrochloric acid 13ml, deionized water 135ml, and concentration is 98%
Butyl titanate 10ml, corresponding solution pH value be 0.41；
2) after hydrochloric acid and water stirring, 10ml butyl titanates are added dropwise and are sufficiently stirred for, by the precursor solution for stirring
In pouring reactor into, 180 DEG C of hydro-thermal reactions 12hrs.
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