CN108671907A - A kind of platinum/titanium oxide nanoflower composite material and preparation method and application - Google Patents
A kind of platinum/titanium oxide nanoflower composite material and preparation method and application Download PDFInfo
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- CN108671907A CN108671907A CN201810465518.0A CN201810465518A CN108671907A CN 108671907 A CN108671907 A CN 108671907A CN 201810465518 A CN201810465518 A CN 201810465518A CN 108671907 A CN108671907 A CN 108671907A
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- oxide nanoflower
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 124
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000002057 nanoflower Substances 0.000 title claims abstract description 65
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 229910003446 platinum oxide Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 238000000137 annealing Methods 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 4
- 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
- 230000007547 defect Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 238000003786 synthesis reaction 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
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 4
- -1 platinum ion Chemical class 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 230000001699 photocatalysis Effects 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 239000011157 advanced composite material Substances 0.000 description 6
- 239000013049 sediment 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
- 230000000694 effects Effects 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
- 238000000151 deposition Methods 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
- 238000001228 spectrum Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical group [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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
- 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—
-
- B01J35/39—
Abstract
The invention discloses a kind of preparation methods of platinum/titanium oxide nanoflower composite material, platinum prepared by the present invention/titanium oxide nanoflower composite material is combined by titanium oxide nanoflower and Pt nanoparticle, and wherein titanium oxide nanoflower provides bigger serface and is rich in a large amount of Lacking oxygens.Having reproducibility using Lacking oxygen makes Pt nanoparticle uniform deposition on titanium dioxide nano flower surface, has close interfacial contact between the two.Platinum/titanium oxide nanoflower composite material of the present invention is a kind of efficient, stable photoelectric conversion material, using the simple reduction method of a step, and reduction platinum ion process is not related to any reducing agent, the preparation method is simple to operate and friendly to environment, and reaction condition is mild, low energy consumption, use easy to spread.
Description
Technical field
The invention belongs to nano materials and photocatalysis technology field, are related to a kind of in titanium oxide nanoflower surface deposition platinum
Nano particle composite material and the preparation method and application thereof.
Background technology
As a kind of emerging advanced oxidation reduction technique, it has low, easy to operate, the nontoxic nothing of Energy in use for photocatalysis
The advantages that evil, non-secondary pollution, is developing and using solar energy, and photochemical catalyzing hydrogen producing is as new cleaning fuel etc.
It has broad application prospects.With the development of nanotechnology in recent years, semiconductor light-catalyst causes the very big of people
Pay attention to.
Traditional titanium dioxide optical catalyst is since its chemical stability is high, fast light corrosion, oxidation ability is strong, light-catalyzed reaction
Driving force is big, photocatalytic activity is high, and the chemical reaction that some absorb heat can be made accomplished by the titanium dioxide surface of light radiation
And acceleration, it is in addition nontoxic, at low cost, so the photocatalysis research of titanium dioxide is the most active.But titanium dioxide photoproduction carrier
It is compound serious, cause its quantum efficiency low, greatly limits the heavy industrialization of photocatalysis material of titanium dioxide
Using.
Carrier separation can be improved as co-catalyst by loading a small amount of small size nano platinum particle in titanium dioxide surface
Efficiency, to obtain high-activity photocatalyst, and the Pt nanoparticle deposited forms close boundary with carrier titanium oxide nanoflower
The separation of photo-generated carrier is improved in face, promotes the efficiency of Photocatalyzed Hydrogen Production.Experiment shows that prepared titanium oxide nanoflower is rich
The Lacking oxygen contained has reproducibility, and when being reacted with platinum ion, electric charge transfer occurs between the two, so utilizing titanium dioxide
The method that one step of Lacking oxygen reproducibility deposition Pt nanoparticle prepares advanced composite material (ACM), can be in Pt nanoparticle and titanium dioxide
Titanium forms close interface, and can also regulate and control the platinum amount of load and the size of platinum grain in this way, to improve light
It is catalyzed hydrogen generation efficiency.Compared with traditional method, the method is easy to operate, nontoxic, efficient and can the advantages such as large area production.
Invention content
Purpose of the present invention is in view of the above-mentioned problems, depositing small sized metallic platinum nanometer on titanium oxide nanoflower surface
Grain solves and compound inside titanium dioxide photoproduction carrier in the prior art seriously limits asking for its Photocatalyzed Hydrogen Production inefficiency
Topic.
The present invention adopts the following technical scheme that：A kind of preparation method of platinum/titanium oxide nanoflower composite material, including with
Lower step：
Step 1：First isopropanol is added in diethylenetriamine, is stirred evenly, two (levulinic ketone group) metatitanic acids are added
Diisopropyl ester, isopropanol, diethylenetriamine, two (levulinic ketone group) metatitanic acid diisopropyl esters volume ratio be 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, washing,
It is dry.It will obtain product and stable annealing temperature is reached with the heating of 1~10 DEG C/min heating rates, annealing temperature is 425 DEG C, is moved back
The fiery time is 2 hours, obtains the oxygen-enriched vacancy titanium oxide nanoflower material of presoma.
Step 2：Platinum nanometer 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
0.297~0.5mL, the platinum acid chloride solution containing 2.97mg chloroplatinic acids, then water-bath, bath temperature are 80~100 DEG C, instead
It is 2~5 hours between seasonable, washs, it is dry, obtain platinum/titanium oxide nanoflower composite material.
Further, reaction temperature is 200 DEG C in step 1, and the reaction time is 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, and the reaction time is 2 hours.
A kind of platinum/titanium oxide nanoflower composite material, the titanium oxide nanoflower by Anatase titanium dioxide
Nanometer sheet forms, 2~9nm of titanium dioxide nanoplate thickness.The platinum of 2~4nm of grain size is carried on titanium dioxide nanoplate surface, shape
At heterojunction structure.
Prepared platinum/application of the titanium oxide nanoflower composite material as photochemical catalyst：Hydrogen production by water decomposition decomposes water
Oxygen processed, degradation of contaminant, biological antibiotic, photoelectric decomposition water, the related application field of other nano materials such as organic synthesis.
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 Pt nanoparticle to prepare the preparation side of advanced composite material (ACM)
Method.Titanium oxide nanoflower is self-assembly of by ultrathin nanometer piece, has 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 platinum ion occur redox reaction when, electric charge transfer occurs between the two, so utilizing titanium dioxide titanyl
The method that one step of vacancy reproducibility deposition Pt nanoparticle prepares advanced composite material (ACM), can obtain close noble metal platinum and two
TiOx nano spend interface, in addition, the Pt nanoparticle deposited have lower production hydrogen overpotential, higher catalytic activity with
And the photo-generated carrier separating property that reduced size is brought, therefore, platinum/titanium oxide nanoflower composite wood prepared by this method
Material, under analog light source, excellent Photocatalyzed Hydrogen Production performance at performance.And the amount of platinum load can also be controlled in this way
And the size of nano platinum particle, Photocatalyzed Hydrogen Production performance is improved, this material production cost is low, and preparation process is simple, is conducive to work
Industry metaplasia is produced；The present invention significantly improves Photocatalyzed Hydrogen Production efficiency while greatly reducing the production cost of photochemical catalyst, tool
Standby great application prospect.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram (SEM) of platinum prepared by embodiment 1/titanium oxide nanoflower composite material.
Fig. 2,3 be platinum prepared by embodiment 1/titanium oxide nanoflower composite material transmission electron microscope figure (TEM).
Fig. 4 is the X-ray diffractogram (XRD) of platinum prepared by embodiment 1/titanium oxide nanoflower composite material.
Fig. 5 is that photodissociation aquatic products hydrogen is bent when prepared platinum/titanium oxide nanoflower composite material is as photochemical catalyst in example 3
Line chart.
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, 425 DEG C of temperature anneal 2 hours, obtain presoma titanium oxide nanoflower material.
Step 2：Presoma titanium oxide nanoflower 100mg is taken to be added in 50mL deionized waters, addition contains 2.97mg
The platinum acid chloride solution 0.297mL of chloroplatinic acid.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, and after 60 DEG C of dryings 24 hours, it is multiple to obtain platinum/titanium oxide nanoflower
Condensation 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 platinum/titanium oxide nanoflower is 500~1000nm, is self-assembly of by ultra-thin titanium dioxide nanosheet, nanometer
Piece thickness is 2~9nm.
Fig. 2,3 be composite material prepared by embodiment 1 transmission electron microscope figure (TEM), as can be seen from the figure platinum
Nano particle is dispersed in titanium oxide nanoflower on piece, forms heterojunction structure, and Pt nanoparticle grain size is 2~4nm.
Fig. 4 is the X-ray diffractogram (XRD) of composite material prepared by embodiment 1, and material XRD spreads out as seen from the figure
Penetrate figure and standard Anatase TiO2Characteristic peak be consistent.
Under full spectrum, platinum prepared by the present embodiment/titanium oxide nanoflower composite material 50mg ultrasonic disperses is taken to exist
In 30% (v/v) methanol solution of 100mL, reaction unit is vacuumized, is placed under analog light source, one is sampled every half an hour
It is secondary, with gas chromatographic detection gas.To draw out the photocatalysis point under analog light source of platinum/titanium oxide nanoflower composite material
Solve aquatic products hydrogen curve graph (Fig. 5), as seen from the figure, platinum/titanium oxide nanoflower composite material photocatalysis under analog light source
Water is decomposed, shows preferably to produce hydrogen effect.Illumination 2.5 hours, hydrogen output 34.5mmol/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, 425 DEG C of temperature anneal 2 hours, obtain presoma titanium oxide nanoflower material.
Step 2：Presoma titanium oxide nanoflower 100mg is taken to be added in 50mL deionized waters, addition contains 5.95mg
The platinum acid chloride solution 0.595mL of chloroplatinic acid.It is 5 hours to keep 100 DEG C of solution bath temperature, reaction time.After reaction will
Sediment deionized water and absolute ethyl alcohol wash three times respectively, after 60 DEG C of dryings 24 hours, obtain platinum/titanium oxide nanoflower
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.Pt nanoparticle is dispersed in titanium oxide nanoflower on piece, forms hetero-junctions
Structure, Pt nanoparticle grain size are 2~4nm.Material XRD diffraction patterns and standard Anatase TiO2Characteristic peak be consistent.
Under full spectrum, platinum prepared by the present embodiment/titanium oxide nanoflower composite material 50mg ultrasonic disperses is taken to exist
In 30% (v/v) methanol solution of 100mL, reaction unit is vacuumized, is placed under analog light source, one is sampled every half an hour
It is secondary, with gas chromatographic detection gas.To draw out the photocatalysis point under analog light source of platinum/titanium oxide nanoflower composite material
Solve aquatic products hydrogen curve graph, as seen from the figure, platinum/titanium oxide nanoflower composite material photocatalysis Decomposition under analog light source
Water shows preferably to produce hydrogen effect.Illumination 2.5 hours, hydrogen output 30.4mmol/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,
425 DEG C of temperature anneals 2 hours, obtains presoma titanium oxide nanoflower material.
Step 2：Presoma titanium oxide nanoflower 100mg is taken to be added in 50mL deionized waters, addition contains 2.97mg
The platinum acid chloride solution 0.297mL of chloroplatinic acid.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, and after 60 DEG C of dryings 24 hours, it is multiple to obtain platinum/titanium oxide nanoflower
Condensation 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.Pt nanoparticle is dispersed in titanium oxide nanoflower on piece, forms heterogeneous junction
Structure, Pt nanoparticle grain size are 2~4nm.Material XRD diffraction patterns and standard Anatase TiO2Characteristic peak be consistent.
Under full spectrum, platinum prepared by the present embodiment/titanium oxide nanoflower composite material 50mg ultrasonic disperses is taken to exist
In 30% (v/v) methanol solution of 100mL, reaction unit is vacuumized, is placed under analog light source, one is sampled every half an hour
It is secondary, with gas chromatographic detection gas.To draw out the photocatalysis point under analog light source of platinum/titanium oxide nanoflower composite material
Solve aquatic products hydrogen curve graph, as seen from the figure, platinum/titanium oxide nanoflower composite material photocatalysis Decomposition under analog light source
Water shows preferably to produce hydrogen effect.Illumination 2.5 hours, hydrogen output 32.9mmol/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,
425 DEG C of temperature anneals 2 hours, obtains presoma titanium oxide nanoflower material.
Step 2：Presoma titanium oxide nanoflower 100mg is taken to be added in 50mL deionized waters, addition contains 5.95mg
The platinum acid chloride solution 0.595mL of chloroplatinic acid.It is 5 hours to keep 100 DEG C of solution bath temperature, reaction time.After reaction will
Sediment deionized water and absolute ethyl alcohol wash three times respectively, after 60 DEG C of dryings 24 hours, obtain platinum/titanium oxide nanoflower
Composite material.
Through characterization, which is nanometer flower structure, and size is 200~500nm nm, by ultra-thin titanium dioxide nanosheet
It is self-assembly of, nanometer sheet thickness is 2~9nm.Pt nanoparticle is dispersed in titanium oxide nanoflower on piece, is formed heterogeneous
Junction structure, Pt nanoparticle grain size are 2~4nm.Material XRD diffraction patterns and standard Anatase TiO2Characteristic peak be consistent.
Under full spectrum, platinum prepared by the present embodiment/titanium oxide nanoflower composite material 50mg ultrasonic disperses is taken to exist
In 30% (v/v) methanol solution of 100mL, reaction unit is vacuumized, is placed under analog light source, one is sampled every half an hour
It is secondary, with gas chromatographic detection gas.To draw out the photocatalysis point under analog light source of platinum/titanium oxide nanoflower composite material
Solve aquatic products hydrogen curve graph, as seen from the figure, platinum/titanium oxide nanoflower composite material photocatalysis Decomposition under analog light source
Water shows preferably to produce hydrogen effect.Illumination 2.5 hours, hydrogen output 29.8mmol/g.
Claims (5)
1. a kind of preparation method of platinum/titanium oxide nanoflower composite material, which is characterized in that include the following steps：
Step 1：First isopropanol is added in diethylenetriamine, is stirred evenly, it is different to add two (levulinic ketone group) metatitanic acids two
Propyl ester, isopropanol, diethylenetriamine, two (levulinic ketone group) metatitanic acid diisopropyl esters volume ratio be 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 product and stable annealing temperature is reached with the heating of 1~10 DEG C/min heating rates, annealing temperature is 425 DEG C, annealing
Time is 2 hours, obtains the oxygen-enriched vacancy titanium oxide nanoflower material of presoma.
Step 2：Pt nanoparticle 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 0.297~
0.5mL, the platinum acid chloride solution containing 2.97mg chloroplatinic acids, then water-bath, bath temperature are 80~100 DEG C, the reaction time
It is 2~5 hours, washs, it is dry, obtain platinum/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, the reaction time is 2 hours.
4. the platinum that method as described in claim 1 is prepared/titanium oxide nanoflower composite material, which is characterized in that described
Titanium oxide nanoflower is made of the titanium dioxide nanoplate of Anatase, 2~9nm of titanium dioxide nanoplate thickness.Grain size 2~
The platinum of 4nm is carried on titanium dioxide nanoplate surface, forms heterojunction structure.
5. the platinum that method as described in claim 1 is prepared/titanium oxide nanoflower composite material is answered as photochemical catalyst
With, which is characterized in that including：Hydrogen production by water decomposition, decomposition water oxygen, degradation of contaminant, biological antibiotic, photoelectric decomposition water are organic
Object synthesis etc..
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| CN109289845A (en) * | 2018-10-30 | 2019-02-01 | 中国科学院宁波城市环境观测研究站 | A kind of titanium dioxide composite noble metal catalyst and its preparation method and application |
| CN109331816A (en) * | 2018-11-06 | 2019-02-15 | 郑州大学 | A kind of preparation method of metal/oxide hybridized nanometer system photochemical catalyst |
| CN109331816B (en) * | 2018-11-06 | 2021-09-21 | 郑州大学 | Preparation method of metal/oxide hybrid nano-system photocatalyst |
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| CN113976110A (en) * | 2021-11-25 | 2022-01-28 | 浙江理工大学 | Catalyst for photocatalytic hydrogen production in alcohol-water system and preparation method thereof |
| CN113976110B (en) * | 2021-11-25 | 2023-01-03 | 浙江理工大学 | Catalyst for photocatalytic hydrogen production in alcohol-water system and preparation method thereof |
| CN114471543A (en) * | 2022-02-23 | 2022-05-13 | 北京工业大学 | Method for preparing platinum-based noble metal catalyst by wet process |
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