CN108579738A - A kind of gold nano grain/titanium oxide nanoflower composite material and preparation method and application - Google Patents
A kind of gold nano grain/titanium oxide nanoflower composite material and preparation method and application Download PDFInfo
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- CN108579738A CN108579738A CN201810462437.5A CN201810462437A CN108579738A CN 108579738 A CN108579738 A CN 108579738A CN 201810462437 A CN201810462437 A CN 201810462437A CN 108579738 A CN108579738 A CN 108579738A
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- titanium oxide
- gold nano
- nano grain
- composite material
- oxide nanoflower
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 128
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000010931 gold Substances 0.000 title claims abstract description 59
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 59
- 239000002057 nanoflower Substances 0.000 title claims abstract description 58
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 125000000468 ketone group Chemical group 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 230000007547 defect Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 239000002086 nanomaterial Substances 0.000 claims description 5
- 239000002055 nanoplate Substances 0.000 claims description 5
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical class Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 4
- 235000013339 cereals Nutrition 0.000 description 48
- 239000000243 solution Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000011157 advanced composite material Substances 0.000 description 6
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of gold nano grain/titanium oxide nanoflower composite material, gold nano grain prepared by the present invention/titanium oxide nanoflower composite material is combined by titanium oxide nanoflower and gold nano grain, and wherein titanium oxide nanoflower provides bigger serface and is rich in a large amount of Lacking oxygens.Gold nano grain uniform deposition forms close contact interface between the two in titanium dioxide surface.Gold nano grain/titanium oxide nanoflower composite material of the present invention is efficient, the stable photoelectric conversion material of one kind, is prepared using the simple reduction method of a step, and preparation process is simple, easy control of reaction conditions, is suitable for extensive preparation and industrialized production.
Description
Technical field
The present invention relates to one kind preparing gold nano grain/titanium dioxide in titanium oxide nanoflower surface deposition gold nano grain
The method of titanium nano flower composite material and application belong to nano material and photocatalysis technology field.
Background technology
It is exactly energy problem and environment that the 21 century mankind, which challenge greatly during walking sustainable development path by face two,
Problem.Solar energy has many advantages, such as cleaning, cheap, renewable, the master that will be solution energy problem how to efficiently use solar energy
Want one of means.Photocatalyzed Hydrogen Production technology exactly with the chemical conversion of solar energy and is stored as core, passes through solar energy excitation half
Conductor realizes that high efficiency photodegradation water prepares hydrogen.Semiconductor light-catalyst such as titanium dioxide, zinc oxide etc. causes people's
Greatly pay attention to, but most of these photochemical catalysts are wide band gap semiconducter in practical applications, the absorbing wavelength range of light is narrow
It is narrow, it is limited in ultra-violet (UV) band, only accounts for the 4% of solar spectrum, low to the utilization ratio of solar spectrum, quantum efficiency is low.Therefore,
It develops new and effective visible light catalyst and has been increasingly becoming one of research direction most popular in catalyst research.
Titanium dioxide is as traditional photochemical catalyst, since its chemical stability is high, fast light corrosion, oxidation ability is strong, light
It is catalyzed the advantages that reacting driving force is big and photocatalytic activity is high, titanium dioxide is caused to be widely used in photocatalysis field, but two
Titanium oxide energy gap 3.2eV, light absorption are only limitted to ultraviolet region, this part light only accounts for the 4% of solar spectrum, and its quantum is imitated
Rate is low, greatly limits the heavy industrialization application of photocatalysis material of titanium dioxide.It is worth noting that, control
The concentration of titanium dioxide defect state, it is possibility to have widen its light abstraction width to effect.For example Lacking oxygen is introduced in titanium dioxide
The light abstraction width of titanium dioxide can be widened visible region by the mode of defect state.However it must be noted that a large amount of oxygen
The presence in vacancy can inhibit the separation in its light induced electron and hole, and photocatalytic activity is caused to reduce.This is because light induced electron meeting
It is strapped on Lacking oxygen, and then causes the transfer ability of light induced electron weaker.
Carrier separation can be improved as co-catalyst by loading a small amount of small size gold nanoparticle in titanium dioxide surface
Efficiency, to obtain high activity photocatalysis performance, and the gold nano grain deposited is formed closely with carrier titanium oxide nanoflower
The separation of photo-generated carrier is improved at interface, promotes the efficiency of Photocatalyzed Hydrogen Production, and since gold nanoparticle plasma resonance is imitated
There should be the absorption region that can greatly widen titanium dioxide in visible region.It is heavy in oxygen-enriched vacancy defect state titanium dioxide surface
Product gold nano grain, the presence of titanium dioxide Lacking oxygen can improve its absorbing properties, while notice that a large amount of oxygen is empty again
Complex centre of the position as electron hole, can inhibit the separation of its photo-generate electron-hole.So by heavy in titanium dioxide surface
The separation of its photo-generated carrier of product noble metal promoted.Gold nano grain can also effectively widen the light absorption model of titanium dioxide simultaneously
It encloses.Further, since the presence of titanium dioxide surface Lacking oxygen defect state, can enhance noble metal nano particles and titanium dioxide it
Between interface interaction, reduce carrier in the loss at the two interface, promote its photo-generated carrier to efficiently separate.The method has operation
Simply, nontoxic, efficient and can with large area produce etc. advantages, therefore, the feasibility with industrialization.
Invention content
Purpose of the present invention is in view of the above-mentioned problems, offer is a kind of to have one step of reproducibility deposition using titanium dioxide Lacking oxygen
Gold nano grain prepares the preparation method of advanced composite material (ACM), solves multiple inside titanium dioxide photoproduction carrier in the prior art
Close the problems such as serious and light abstraction width is narrow.
The present invention uses following technical scheme：A kind of preparation side of gold nano grain/titanium oxide nanoflower composite material
Method includes the following steps：
Step 1：First isopropanol is added in diethylenetriamine, is stirred evenly, two (levulinic ketone group) metatitanic acids are added
The volume ratio of diisopropyl ester, isopropanol, diethylenetriamine and two (levulinic ketone group) metatitanic acid diisopropyl esters is 1260~2520:1
~10:45~360, it stirs evenly, pours into reaction kettle, under the conditions of 200~220 DEG C, solvent heat treatment 24~36 hours is washed
It washs, it is dry, nano material will be obtained, annealing temperature is warming up to 1~10 DEG C/min, annealing temperature is 425 DEG C, annealing time 2
Hour, obtain the oxygen-enriched vacancy titanium oxide nanoflower material of presoma.
Step 2：Gold nano is realized using the reproducibility of the Lacking oxygen defect of titanium oxide nanoflower prepared by step 1
The load of grain, specially：100mg titanium oxide nanoflowers are dispersed in 50mL deionized waters, adding volume is
Then 0.21~0.42mL, the chlorauric acid solution containing 2.1mg gold chlorides carry out water-bath, bath temperature is 80~100 DEG C, instead
It is 2~5 hours between seasonable, washs, it is dry, obtain gold nano grain/titanium oxide nanoflower composite material.
Further, in step 1 reaction temperature be 200 DEG C, the reaction time be 24 hours, isopropanol, diethylenetriamine and
The volume ratio of two (levulinic ketone group) metatitanic acid diisopropyl esters is 1260:1:45.
Further, bath temperature is 80 DEG C in step 2, and the reaction time is 2 hours.
A kind of gold nano grain/titanium oxide nanoflower composite material, the titanium oxide nanoflower is by Anatase
Titanium dioxide nanoplate forms, 2~9nm of titanium dioxide nanoplate thickness.The gold of 2~9nm of grain size is carried on nano titania
Piece surface forms heterojunction structure.
Prepared gold nano grain/application of the titanium oxide nanoflower composite material as photochemical catalyst：The water system of decomposition
Hydrogen decomposes water oxygen, degradation of contaminant, biological antibiotic, photoelectric decomposition water, the related application of other nano materials such as organic synthesis
Field.
The beneficial effects of the present invention are：The present invention provides a kind of going back for Lacking oxygen being rich in using titanium oxide nanoflower
Originality, on titanium oxide nanoflower surface, one step deposits small size gold nano grain to prepare the preparation side of advanced composite material (ACM)
Method, titanium oxide nanoflower are self-assembly of by ultrathin nanometer piece, have bigger serface and three-dimensional hierarchical structure.The nanometer
Material causes it to possess a large amount of active sites due to having distinguishingly high-specific surface area and three-dimensional structure, can be with fast transfer light
Electronics and the Multiple Scattering performance for increasing light simultaneously, and then improve Photocatalyzed Hydrogen Production efficiency.At the same time Lacking oxygen has
Reproducibility, and with gold nano grain ion occur redox reaction when, electric charge transfer occurs between the two, so utilizing two
The method that one step of titanium oxide Lacking oxygen reproducibility deposition gold nano grain prepares advanced composite material (ACM), can obtain your close gold
Belong to gold nano grain and titanium oxide nanoflower boundary, in addition, the gold nano grain deposited causes made since size is small
Standby gold nano grain has very strong plasma resonance effect in visible region, therefore, gold nano grain prepared by this method/
Titanium oxide nanoflower composite material shows excellent Photocatalyzed Hydrogen Production performance under analog light source.And in this way
The amount of gold load and the size of gold nano grain can also be controlled, Photocatalyzed Hydrogen Production performance is improved.This composite nano materials is given birth to
Produce at low cost, preparation process is simple, is conducive to industrialized production；While the present invention greatly reduces the production cost of photochemical catalyst
Photocatalyzed Hydrogen Production efficiency is significantly improved, has great application prospect.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram of gold nano grain prepared by embodiment 1/titanium oxide nanoflower composite material
(SEM)。
Fig. 2,3 be gold nano grain prepared by embodiment 1/titanium oxide nanoflower composite material transmission electron microscope
Scheme (TEM).
Fig. 4 be gold nano grain in example 5/titanium oxide nanoflower composite material as photochemical catalyst when photodissociation aquatic products hydrogen
Curve graph.
Specific implementation mode：
With reference to embodiment, the invention will be further described.Following embodiment is used for illustrating the present invention, without
It is to limit the invention, in the protection domain of spirit and claims of the present invention, any is repaiied to what the present invention made
Change and change, both falls within protection scope of the present invention.
Embodiment 1：
Step 1：Diethylenetriamine (EDTA) 0.025mL is added in 31.5mL isopropanols, stirs 10min.Again toward solution
In add two (levulinic ketone group) metatitanic acid diisopropyl ester 1.125mL.Continue to stir 10min.Gained mixed solution is poured into instead
It answers in kettle, the solvent heat treatment 24 hours under the conditions of 200 DEG C.After reaction by sediment deionized water and absolute ethyl alcohol point
It does not wash three times, is placed in 60 DEG C of baking ovens, it is 24 hours dry, finally reactant is placed in Muffle furnace, 1 DEG C of heating rate/
Min anneals 2 hours at 425 DEG C of temperature, obtains presoma titanium oxide nanoflower material.
Step 2：It takes presoma titanium oxide nanoflower 100mg to be added in 50mL deionized waters, is added and contains 2.1mg chlorine
The chlorauric acid solution 0.21mL of auric acid.It is 2 hours to keep 80 DEG C of solution bath temperature, reaction time.It after reaction will precipitation
Object deionized water and absolute ethyl alcohol wash three times respectively, after 60 DEG C of dryings 24 hours, obtain gold nano grain/titanium dioxide and receive
Popped rice composite material.
Fig. 1 is the scanning electron microscope diagram (SEM) of composite material prepared by embodiment 1, can be clearly from figure
The size for going out gold nano grain/titanium oxide nanoflower is 500~1000nm, by ultra-thin titanium dioxide nanosheet self assembly shape
At nanometer sheet thickness is 2~9nm.
Fig. 2,3 be composite material prepared by embodiment 1 transmission electron microscope figure (TEM), it is as can be seen from the figure golden
Nano particle is dispersed in titanium oxide nanoflower on piece, forms hetero-junctions, and gold nano grain grain size is 2~9nm.
Under full spectrum, gold nano grain prepared by the present embodiment/titanium oxide nanoflower composite material 50mg ultrasounds are taken
It is dispersed in 30% (v/v) methanol solution 100mL, reaction unit is vacuumized, is placed under analog light source, is sampled every half an hour
Once, with gas chromatographic detection gas.To draw out gold nano grain/titanium oxide nanoflower composite material in analog light source
Lower photocatalysis Decomposition aquatic products hydrogen curve graph.As shown in figure 4, composite material photochemical catalyzing under analog light source, shows
Preferable production hydrogen effect.Illumination 2.5 hours, hydrogen output 20.14mmol/g.
Embodiment 2：
Step 1：Diethylenetriamine (EDTA) 0.025mL is added in 31.5mL isopropanols, stirs 10min.Again toward solution
In add two (levulinic ketone group) metatitanic acid diisopropyl ester 1.125mL.Continue to stir 10min.Gained mixed solution is poured into instead
It answers in kettle, the solvent heat treatment 24 hours under the conditions of 200 DEG C.After reaction by sediment deionized water and absolute ethyl alcohol point
It does not wash three times, is placed in 60 DEG C of baking ovens, it is 24 hours dry, finally reactant is placed in Muffle furnace, 1 DEG C of heating rate/
Min anneals 2 hours at 425 DEG C, obtains presoma titanium oxide nanoflower material.
Step 2：It takes presoma titanium oxide nanoflower 100mg to be added in 50mL deionized waters, matter is added and contains 4.2mg
The chlorauric acid solution 0.42mL of gold chloride.It is 5 hours to keep 100 DEG C of solution bath temperature, reaction time.It will sink after reaction
Starch deionized water and absolute ethyl alcohol wash three times respectively, after 60 DEG C of dryings 24 hours, obtain gold nano grain/titanium dioxide
Nano flower composite material.
Through characterization, which is nanometer flower structure, and size is 500~1000nm, certainly by ultra-thin titanium dioxide nanosheet
Assembling is formed, and nanometer sheet thickness is 2~9nm.Gold nano grain is dispersed in titanium oxide nanoflower on piece, forms hetero-junctions
Structure, gold nano grain grain size are 2~9nm.Material XRD diffraction patterns and standard Anatase TiO2Characteristic peak be consistent.
Under full spectrum, gold nano grain prepared by the present embodiment/titanium oxide nanoflower composite material 50mg ultrasounds are taken
It is dispersed in 30% (v/v) methanol solution 100mL, reaction unit is vacuumized, is placed under analog light source, is sampled every half an hour
Once, with gas chromatographic detection gas.To draw out gold nano grain/titanium oxide nanoflower composite material in analog light source
Lower photocatalysis Decomposition aquatic products hydrogen curve graph.Composite material photochemical catalyzing under analog light source shows preferably to produce hydrogen
Effect.Illumination 2.5 hours, hydrogen output 19.89mmol/g.
Embodiment 3：
Step 1：Diethylenetriamine (EDTA) 0.125mL is added in 31.5mL isopropanols, stirs 10min.Again toward solution
In add two (levulinic ketone group) metatitanic acid diisopropyl ester 4.5mL.Continue to stir 10min.Gained mixed solution is poured into reaction
In kettle, the solvent heat treatment 36 hours under the conditions of 220 DEG C.Sediment deionized water and absolute ethyl alcohol are distinguished after reaction
Washing three times, is placed in 60 DEG C of baking ovens, 24 hours dry, finally reactant is placed in Muffle furnace, 10 DEG C/min of heating rate,
It anneals 2 hours at 425 DEG C, obtains presoma titanium oxide nanoflower material.
Step 2：It takes presoma titanium oxide nanoflower 100mg to be added in 50mL deionized waters, matter is added and contains 2.1mg
The chlorauric acid solution 0.21mL of gold chloride.It is 2 hours to keep 80 DEG C of solution bath temperature, reaction time.It will sink after reaction
Starch deionized water and absolute ethyl alcohol wash three times respectively, after 60 DEG C of dryings 24 hours, obtain gold nano grain/titanium dioxide
Nano flower composite material.
Through characterization, which is nanometer flower structure, and size is 200~500nm, by ultra-thin titanium dioxide nanosheet from group
Dress is formed, and nanometer sheet thickness is 2~9nm.Gold nano grain is dispersed in titanium oxide nanoflower on piece, forms heterogeneous junction
Structure, gold nano grain grain size are 2~9nm.Material XRD diffraction patterns and standard Anatase TiO2Characteristic peak be consistent.
Under full spectrum, gold nano grain prepared by the present embodiment/titanium oxide nanoflower composite material 50mg ultrasounds are taken
It is dispersed in 30% (v/v) methanol solution 100mL, reaction unit is vacuumized, is placed under analog light source, is sampled every half an hour
Once, with gas chromatographic detection gas.To draw out gold nano grain/titanium oxide nanoflower composite material in analog light source
Lower photocatalysis Decomposition aquatic products hydrogen curve graph.Composite material photochemical catalyzing under analog light source shows preferably to produce hydrogen
Effect.Illumination 2.5 hours, hydrogen output 19.66mmol/g.
Embodiment 4：
Step 1：Diethylenetriamine (EDTA) 0.125mL is added in 31.5mL isopropanols, stirs 10min.Again toward solution
In add two (levulinic ketone group) metatitanic acid diisopropyl ester 4.5mL.Continue to stir 10min.Gained mixed solution is poured into reaction
In kettle, the solvent heat treatment 36 hours under the conditions of 220 DEG C.Sediment deionized water and absolute ethyl alcohol are distinguished after reaction
Washing three times, is placed in 60 DEG C of baking ovens, 24 hours dry, finally reactant is placed in Muffle furnace, 10 DEG C/min of heating rate,
It anneals 2 hours at 425 DEG C, obtains presoma titanium oxide nanoflower material.
Step 2：It takes presoma titanium oxide nanoflower 100mg to be added in 50mL deionized waters, matter is added and contains 4.2mg
The chlorauric acid solution 0.42mL of gold chloride.It is 5 hours to keep 100 DEG C of solution bath temperature, reaction time.It will sink after reaction
Starch deionized water and absolute ethyl alcohol wash three times respectively, after 60 DEG C of dryings 24 hours, obtain gold nano grain/titanium dioxide
Nano flower composite material.
Through characterization, which is nanometer flower structure, and size is 200~500nm, by ultra-thin titanium dioxide nanosheet from group
Dress is formed, and nanometer sheet thickness is 2~9nm.Gold nano grain is dispersed in titanium oxide nanoflower on piece, forms heterogeneous junction
Structure, gold nano grain grain size are 2~9nm.Material XRD diffraction patterns and standard Anatase TiO2Characteristic peak be consistent.
Under full spectrum, gold nano grain prepared by the present embodiment/titanium oxide nanoflower composite material 50mg ultrasounds are taken
It is dispersed in 30% (v/v) methanol solution 100mL, reaction unit is vacuumized, is placed under analog light source, is sampled every half an hour
Once, with gas chromatographic detection gas.To draw out gold nano grain/titanium oxide nanoflower composite material in analog light source
Lower photocatalysis Decomposition aquatic products hydrogen curve graph.Composite material photochemical catalyzing under analog light source shows preferably to produce hydrogen
Effect.Illumination 2.5 hours, hydrogen output 19.57mmol/g.
Claims (5)
1. a kind of preparation method of gold nano grain/titanium oxide nanoflower composite material, which is characterized in that including following step
Suddenly：
Step 1：First isopropanol is added in diethylenetriamine, is stirred evenly, it is different to add two (levulinic ketone group) metatitanic acids two
The volume ratio of propyl ester, isopropanol, diethylenetriamine and two (levulinic ketone group) metatitanic acid diisopropyl esters is 1260~2520:1~10:
45~360, it stirs evenly, pours into reaction kettle, under the conditions of 200~220 DEG C, solvent heat treatment 24~36 hours is washed, and is done
It is dry；It will obtain nano material and annealing temperature is warming up to 1~10 DEG C/min, annealing temperature is 425 DEG C, and annealing time is 2 hours,
Obtain the oxygen-enriched vacancy titanium oxide nanoflower material of presoma.
Step 2：Gold nano grain is realized using the reproducibility of the Lacking oxygen defect of titanium oxide nanoflower prepared by step 1
Load, specially：100mg titanium oxide nanoflowers are dispersed in 50mL deionized waters, add volume be 0.21~
Then 0.42mL, the chlorauric acid solution containing 2.1mg gold chlorides carry out water-bath, bath temperature is 80~100 DEG C, the reaction time
It is 2~5 hours, washs, it is dry, obtain gold nano grain/titanium oxide nanoflower composite material.
2. according to the method described in claim 1, it is characterized in that, in step 1 reaction temperature be 200 DEG C, the reaction time 24
Hour, the volume ratio of isopropanol, diethylenetriamine and two (levulinic ketone group) metatitanic acid diisopropyl esters is 1260:1:45.
3. according to the method described in claim 1, it is characterized in that, bath temperature is 80 DEG C in step 2, the reaction time is 2 small
When.
4. the gold nano grain that method as described in claim 1 is prepared/titanium oxide nanoflower composite material, feature exist
In the titanium oxide nanoflower is made of the titanium dioxide nanoplate of Anatase, 2~9nm of titanium dioxide nanoplate thickness.
The gold of 2~9nm of grain size is carried on titanium dioxide nanoplate surface, forms heterojunction structure.
5. the gold nano grain that method as described in claim 1 is prepared/titanium oxide nanoflower composite material is urged as light
The application of agent, which is characterized in that including：Hydrogen production by water decomposition decomposes water oxygen, degradation of contaminant, biological antibiotic, photoelectric decomposition
Water, organic synthesis etc..
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