CN110013841A - A kind of two dimension titanium dioxide nanosheet photocatalytic material and preparation method thereof - Google Patents
A kind of two dimension titanium dioxide nanosheet photocatalytic material and preparation method thereof Download PDFInfo
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- CN110013841A CN110013841A CN201910328363.0A CN201910328363A CN110013841A CN 110013841 A CN110013841 A CN 110013841A CN 201910328363 A CN201910328363 A CN 201910328363A CN 110013841 A CN110013841 A CN 110013841A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 55
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- 239000002135 nanosheet Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 40
- 239000002055 nanoplate Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 23
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 20
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 20
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000047 product Substances 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 241000790917 Dioxys <bee> Species 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000008367 deionised water Substances 0.000 abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 238000006303 photolysis reaction Methods 0.000 abstract description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- -1 structure and size 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
- 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—
-
- B01J35/40—
Abstract
The invention discloses a kind of two-dimentional titanium dioxide nanoplate catalysis materials and preparation method thereof.The two dimension titanium dioxide nanoplate catalysis material with a thickness of 3-10nm, length is 10~50 μm.It is uniformly dispersed the preparation method comprises the following steps: adding graphene oxide into dehydrated alcohol, obtains graphene dispersion solution；Four fourth rouge of metatitanic acid is added in graphene dispersion solution and is stirred evenly；Mixed solution is centrifuged, washed, is dried；Product is calcined to get unmodified titanium dioxide nanoplate, it is add to deionized water with ascorbic acid, is stirred evenly, heating reaction obtains brown head product, calcines up to titanium dioxide nanosheet photocatalytic material.The present invention passes through GO template first and prepares ultra-thin two-dimension TiO2, modified with reduction is then carried out to it by ascorbic acid, to introduce defect, realizes the raising of its photocatalysis performance, i.e., by ultra-thin two-dimension TiO2It is modified and significantly promotes it in the performance of photolysis water hydrogen.
Description
Technical field
The present invention relates to a kind of modified sheeted nanometer photocatalysis material of titanium dioxide and preparation method thereof, belong to photocatalysis skill
Art field.
Background technique
With the continuous improvement of people's living standards, petroleum, coal and natural gas etc. it is non-renewable natural resources it is more next
It is consumed more by the mankind.Meanwhile product is likely to bring to environment in the extraction, transport and conversion process of raw material
Negative effect.Therefore, energy shortage and environmental pollution phenomenon become the global problem that the mankind cope at present.Solving energy danger
In terms of machine, the efficient utilization of renewable energy is realized by modes such as the hydrogen manufacturing of photodegradation water, solar batteries.Semiconductor light is urged
Effect of the change technology in environment remediation field can not be ignored, and have proved to be noxious pollutant in degradation water body and atmospheric environment
Effective way.Titanium dioxide (TiO2) because of its high stability, non-toxic and low cost is considered as ideal semiconductor light
Catalysis material.
It is very big that research finds that the pattern of material, structure and size, composition, crystal face etc. characteristic can have its catalytic performance
It influences.It has successfully prepared such as at present: the TiO of rodlike, linear, flower-shaped, tubulose, sheet different structure2Nano material, and
It was found that performance has notable difference in terms of its each comfortable photocatalysis performance.However, untreated TiO2It is lower under full spectrum
Quantum efficiency and the problems such as compound higher photo-generated carrier, seriously limit it in the practical application of photocatalysis field.
Therefore, in order to increase TiO2The photocatalysis efficiency of nano material, controllable preparation have the TiO of bigger serface2Nanometer
Material is most important.
Summary of the invention
The technical problems to be solved by the present invention are: existing TiO2The catalytic activity of catalysis material is high, stability not
High technical problem.
To solve the above-mentioned problems, the present invention provides a kind of two-dimentional titanium dioxide nanoplate catalysis material, feature exists
In, the two dimension titanium dioxide nanoplate catalysis material with a thickness of 3-10nm, length is 10~50 μm.
Preferably, the two-dimentional titanium dioxide nanoplate catalysis material surface has meso-hole structure.
It is highly preferred that the aperture of the meso-hole structure is 3~10nm.
The present invention also provides the preparation methods of above-mentioned two-dimentional titanium dioxide nanoplate catalysis material, which is characterized in that packet
Include following steps:
Step 1): adding graphene oxide into dehydrated alcohol and be uniformly dispersed, and obtains graphene dispersion solution；
Step 2): four fourth rouge of metatitanic acid being added in the graphene dispersion solution that step 1) obtains and is stirred evenly, purpose
It is to be made on butyl titanate uniform adsorption to graphene oxide using template；
Step 3): the mixed solution that step 2) is obtained is centrifuged, and resulting sediment is washed with dehydrated alcohol
Butyl titanate residual is removed, is then centrifuged again, collects product after resulting drying precipitate being centrifuged again；
Step 4): the product that step 3) is obtained is put into Muffle furnace and calcines to get unmodified titanium dioxide nanoplate；
Step 5): the unmodified titanium dioxide nanosheet photocatalytic material that step 4) is obtained is added to ascorbic acid
In ionized water, stir evenly；
Step 6): the solution that step 5) is obtained is transferred in water heating kettle, and heating reaction obtains brown head product；
Step 7): by the brown head product that step 6) obtains be placed under inert gas shielding and vacuum condition calcine to get
Titanium dioxide nanosheet photocatalytic material.
Preferably, the ratio of graphene oxide and dehydrated alcohol is (10-200) mg:(20-200 in the step 1)) mL,
Preferably 100mg:200mL.
Preferably, the step 1) specifically: graphene oxide and dehydrated alcohol are put into ultrasound 25- in Ultrasound Instrument
30min；The control power of Ultrasound Instrument is 400W, frequency 32kHz.
Preferably, the temperature stirred in the step 2) is 10~30 DEG C, revolving speed 500-700r/min, and mixing time is
12-18h。
Preferably, the revolving speed being centrifuged twice in the step 3) is 10000r/min, and centrifugation time is each 15min.
Preferably, the drying temperature in the step 3) is 60 DEG C；The temperature calcined in the step 4) is 500 DEG C, is risen
Warm rate is 2 DEG C/min, calcination time 2h.
Preferably, the quality of unmodified two dimension titanium dioxide nanoplate and ascorbic acid is 0.25-1 in the step 5):
1, the revolving speed of stirring is 500-700r/min, mixing time 30min；Heating temperature is 180 DEG C, when reaction in the step 6)
Between be 8-12h.
Preferably, the inert gas in the step 7) is nitrogen or argon gas, and vacuum degree is -0.08atm, and calcination temperature is
450 DEG C, calcination time 2-4h is down to room temperature after calcining.
The present invention passes through GO template first and prepares ultra-thin two-dimension TiO2, reduction is then carried out to it by ascorbic acid and is changed
Property, to introduce defect, realize the raising of its photocatalysis performance, i.e., by ultra-thin two-dimension TiO2It is modified and is significantly promoted
Its performance in photolysis water hydrogen.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention is using butyl titanate and graphene oxide as raw material, and ascorbic acid is reducing agent, in conjunction with template,
Hydro-thermal method and the modified two-dimentional titanium dioxide nanosheet photocatalytic material of high-temperature roasting processing preparation.Due to making using template
Modified two-dimentional titanium dioxide nanosheet photocatalytic material provided by the invention has the structure of two-dimensional nano piece, passes through ascorbic acid
Ultra-thin two-dimension TiO is modified as reducing agent2, improve ultra-thin two-dimension TiO2Material light under 500W medium pressure mercury lamp directional light photograph
It is catalyzed H2-producing capacity；
2, preparation process according to the present invention is simple mild and environmental-friendly, than traditional hydrogen or sodium borohydride nanometer
TiO2Method of modifying is safer.
Detailed description of the invention
Fig. 1 is the two-dimentional titanium dioxide nanosheet photocatalytic material and unmodified two-dimentional titanium dioxide of embodiment 1-4 preparation
The x-ray diffraction pattern of titanium nanometer sheet；
Fig. 2 is the two-dimentional titanium dioxide nanosheet photocatalytic material and unmodified two-dimentional titanium dioxide of embodiment 1-4 preparation
The ultraviolet-visible diffuse reflectance spectrum of titanium nanometer sheet；
Fig. 3 is the scanning electron microscope (SEM) photograph of two-dimentional titanium dioxide nanosheet photocatalytic material prepared by embodiment 2 and embodiment 3
Comparison diagram；
Fig. 4 is the transmission electron microscope picture of two-dimentional titanium dioxide nanosheet photocatalytic material prepared by embodiment 2 and embodiment 3
Comparison diagram；
Fig. 5 is the two-dimentional titanium dioxide nanosheet photocatalytic material and unmodified two-dimentional titanium dioxide of embodiment 1-4 preparation
The data result figure of H2-producing capacity after titanium nanometer sheet photocatalysis.
Specific embodiment
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is cooperated to be described in detail below.
Embodiment 1
A kind of preparation method of two dimension titanium dioxide nanosheet photocatalytic material:
1) 100mg graphene oxide is added in 200mL dehydrated alcohol, control power be 400W, frequency be 32kHz into
Row ultrasonic treatment 30min obtains graphene dispersion solution so that graphene oxide is dispersed in ethanol solution；
2) four fourth rouge of the metatitanic acid of 2.47mmol is added in the graphene dispersion solution of step 1), controlled at 20
DEG C, revolving speed be to be stirred 15h under 600r/min, obtain mixed solution, the purpose is to make butyl titanate using template
On uniform adsorption to graphene oxide template；
3) the resulting mixed solution control revolving speed 10000r/min of step 2) is subjected to centrifugation 15min, resulting precipitating is used
Dehydrated alcohol is washed not to be had subject to butyl titanate into efflux, then again control revolving speed 10000r/min carry out from
Heart 15min will be centrifuged resulting precipitating again and be dried controlled at 60 DEG C, the product after collecting drying；
4) product after will be dry obtained by step 3) is put into Muffle furnace, is warming up to 500 DEG C of progress with the rate of 2 DEG C/min
Calcination processing 2h is to get unmodified two-dimentional titanium dioxide nanoplate；
5) the unmodified two-dimentional titanium dioxide nanoplate and ascorbic acid of step 4) are added in 35mL deionized water,
The mass ratio of the described unmodified two-dimentional titanium dioxide nanoplate and ascorbic acid is 1:1, in the case where revolving speed is 600r/min into
Row stirring 30min.
6) solution of step 5) is transferred in water heating kettle, reacts 12h at 180 DEG C of temperature, obtains brown ceramic powder；
7) brown ceramic powder of step 6) is placed in the tube furnace under inert gas shielding, and is adjusted by control vacuum pump
Vacuum degree is -0.08atm, in 450 DEG C of calcining at constant temperature 2h of temperature, is down to room temperature, obtains modified two-dimentional nano titania
Piece catalysis material.
Embodiment 2
A kind of preparation method of two dimension titanium dioxide nanosheet photocatalytic material:
1) 100mg graphene oxide is added in 200mL dehydrated alcohol, control power be 400W, frequency be 32kHz into
Row ultrasonic treatment 30min obtains graphene dispersion solution so that graphene oxide is dispersed in ethanol solution；
2) four fourth rouge of the metatitanic acid of 2.47mmol is added in the graphene dispersion solution of step 1), controlled at 20
DEG C, revolving speed be to be stirred 15h under 600r/min, obtain mixed solution, the purpose is to make butyl titanate using template
On uniform adsorption to graphene oxide template；
3) the resulting mixed solution control revolving speed 10000r/min of step 2) is subjected to centrifugation 15min, resulting precipitating is used
Dehydrated alcohol is washed not to be had subject to butyl titanate into efflux, then again control revolving speed 10000r/min carry out from
Heart 15min will be centrifuged resulting precipitating again and be dried controlled at 60 DEG C, the product after collecting drying；
4) product after will be dry obtained by step 3) is put into Muffle furnace, is warming up to 500 DEG C of progress with the rate of 2 DEG C/min
Calcination processing 2h is to get unmodified two-dimentional titanium dioxide nanoplate；
5) the unmodified two-dimentional titanium dioxide nanoplate and ascorbic acid of step 4) are added in 35mL deionized water,
The mass ratio of the described unmodified two-dimentional titanium dioxide nanoplate and ascorbic acid is 1:2, in the case where revolving speed is 600r/min into
Row stirring 30min.
6) solution of step 5) is transferred in water heating kettle, reacts 12h at 180 DEG C of temperature, obtains brown ceramic powder；
7) brown ceramic powder of step 6) is placed in the tube furnace under inert gas shielding, and is adjusted by control vacuum pump
Vacuum degree is -0.08atm, in 450 DEG C of calcining at constant temperature 2h of temperature, is down to room temperature, obtains modified two-dimentional nano titania
Piece catalysis material.
Embodiment 3
A kind of preparation method of two dimension titanium dioxide nanosheet photocatalytic material:
1) 100mg graphene oxide is added in 200mL dehydrated alcohol, control power be 400W, frequency be 32kHz into
Row ultrasonic treatment 30min obtains graphene dispersion solution so that graphene oxide is dispersed in ethanol solution；
2) four fourth rouge of the metatitanic acid of 2.47mmol is added in the graphene dispersion solution of step 1), controlled at 20
DEG C, revolving speed be to be stirred 15h under 600r/min, obtain mixed solution, the purpose is to make butyl titanate using template
On uniform adsorption to graphene oxide template；
3) the resulting mixed solution control revolving speed 10000r/min of step 2) is subjected to centrifugation 15min, resulting precipitating is used
Dehydrated alcohol is washed not to be had subject to butyl titanate into efflux, then again control revolving speed 10000r/min carry out from
Heart 15min will be centrifuged resulting precipitating again and be dried controlled at 60 DEG C, the product after collecting drying；
4) product after will be dry obtained by step 3) is put into Muffle furnace, is warming up to 500 DEG C of progress with the rate of 2 DEG C/min
Calcination processing 2h is to get unmodified two-dimentional titanium dioxide nanoplate；
5) the unmodified two-dimentional titanium dioxide nanoplate and ascorbic acid of step 4) are added in 35mL deionized water,
The mass ratio of the described unmodified two-dimentional titanium dioxide nanoplate and ascorbic acid is 1:3, in the case where revolving speed is 600r/min into
Row stirring 30min.
6) solution of step 5) is transferred in water heating kettle, reacts 12h at 180 DEG C of temperature, obtains brown ceramic powder；
7) brown ceramic powder of step 6) is placed in the tube furnace under inert gas shielding, and is adjusted by control vacuum pump
Vacuum degree is -0.08atm, in 450 DEG C of calcining at constant temperature 2h of temperature, is down to room temperature, obtains modified two-dimentional nano titania
Piece catalysis material.
Embodiment 4
A kind of preparation method of two dimension titanium dioxide nanosheet photocatalytic material:
1) 100mg graphene oxide is added in 200mL dehydrated alcohol, control power be 400W, frequency be 32kHz into
Row ultrasonic treatment 30min obtains graphene dispersion solution so that graphene oxide is dispersed in ethanol solution；
2) four fourth rouge of the metatitanic acid of 2.47mmol is added in the graphene dispersion solution of step 1), controlled at 20
DEG C, revolving speed be to be stirred 15h under 600r/min, obtain mixed solution, the purpose is to make butyl titanate using template
On uniform adsorption to graphene oxide template；
3) the resulting mixed solution control revolving speed 10000r/min of step 2) is subjected to centrifugation 15min, resulting precipitating is used
Dehydrated alcohol is washed not to be had subject to butyl titanate into efflux, then again control revolving speed 10000r/min carry out from
Heart 15min will be centrifuged resulting precipitating again and be dried controlled at 60 DEG C, the product after collecting drying；
4) product after will be dry obtained by step 3) is put into Muffle furnace, is warming up to 500 DEG C of progress with the rate of 2 DEG C/min
Calcination processing 2h is to get unmodified two-dimentional titanium dioxide nanoplate；
5) the unmodified two-dimentional titanium dioxide nanoplate and ascorbic acid of step 4) are added in 35mL deionized water,
The mass ratio of the described unmodified two-dimentional titanium dioxide nanoplate and ascorbic acid is 1:1, in the case where revolving speed is 600r/min into
Row stirring 30min.
6) solution of step 5) is transferred in water heating kettle, reacts 12h at 180 DEG C of temperature, obtains brown ceramic powder；
7) brown ceramic powder of step 6) is placed in the tube furnace under inert gas shielding, and is adjusted by control vacuum pump
Vacuum degree is -0.08atm, in 450 DEG C of calcining at constant temperature 2h of temperature, is down to room temperature, obtains modified ultra-thin two-dimension TiO2。
As seen from Figure 1, the two-dimentional titanium dioxide nanosheet photocatalytic material of embodiment 1-4 preparation lives through hydro-thermal and high temperature
Crystal form does not change after roasting, and diffraction maximum is mainly Detitanium-ore-type TiO2(JCPDS21-1272).But it can be seen that experience
TiO after ascorbic acid reduction and high-temperature roasting2Its crystallinity is all improved in varying degrees, and crystalline raising is conducive to light
Raw carrier mobility reacts to surface, to improve photocatalysis performance.
From Figure 2 it can be seen that the two-dimentional titanium dioxide nanosheet photocatalytic material and unmodified titanium dioxide of embodiment 1-4 preparation
Titanium nanometer sheet has different degrees of absorption to light, it can be seen that improves two-dimentional dioxy after the reduction of experience ascorbic acid and high-temperature roasting
Change titanium nanosheet photocatalytic material light absorpting ability, there are enough energy to carry out light-catalyzed reaction under ultraviolet light conditions.
As seen from Figure 3, the two-dimentional titanium dioxide nanosheet photocatalytic material that prepared by embodiment 2 and embodiment 3 is two-dimensional slice
Shape structure.
From fig. 4, it can be seen that the sheet knot of two-dimentional titanium dioxide nanosheet photocatalytic material prepared by embodiment 2 and embodiment 3
Structure is by TiO2Particle packing composition.
As seen from Figure 5, to the two-dimentional titanium dioxide nanosheet photocatalytic material and unmodified two dimension of embodiment 1-4 preparation
Titanium dioxide nanoplate has carried out Photocatalyzed Hydrogen Production performance test.Under 500W medium pressure mercury lamp, the 30mL of Xiang Han 3mL methanol go from
The modified two-dimentional titanium dioxide nanosheet photocatalytic material of 10mg and unmodified two-dimentional titanium dioxide are separately added into sub- water
Nanometer sheet.It is produced by modified two-dimentional titanium dioxide nanosheet photocatalytic material than unmodified two-dimentional titanium dioxide nanoplate
The mass ratio that hydrogen performance improves several times to more than ten times, especially when unmodified two-dimentional titanium dioxide nanoplate and ascorbic acid
When 1:2, i.e., the Photocatalyzed Hydrogen Production effect of modified two-dimentional titanium dioxide nanosheet photocatalytic material for preparing of embodiment 2 is most
It is good, there is high photocatalytic activity.
Claims (10)
1. a kind of two dimension titanium dioxide nanoplate catalysis material, which is characterized in that the two dimension titanium dioxide nanoplate is catalyzed material
Material with a thickness of 3-10nm, length is 10~50 μm.
2. two dimension titanium dioxide nanoplate catalysis material as described in claim 1, which is characterized in that the two dimension titanium dioxide
Nanometer sheet catalysis material surface has meso-hole structure.
3. two dimension titanium dioxide nanoplate catalysis material as claimed in claim 2, which is characterized in that the hole of the meso-hole structure
Diameter is 3~10nm.
4. the preparation method of two-dimentional titanium dioxide nanoplate catalysis material described in a kind of claim 1-3 any one, special
Sign is, comprising the following steps:
Step 1): adding graphene oxide into dehydrated alcohol and be uniformly dispersed, and obtains graphene dispersion solution；
Step 2): four fourth rouge of metatitanic acid is added in the graphene dispersion solution that step 1) obtains and is stirred evenly；
Step 3): the mixed solution that step 2) is obtained is centrifuged, and resulting sediment carries out washing removal with dehydrated alcohol
Butyl titanate residual, is then centrifuged again, collects product after being centrifuged again resulting drying precipitate；
Step 4): the product that step 3) is obtained is put into Muffle furnace and calcines to get unmodified titanium dioxide nanoplate；
Step 5): unmodified titanium dioxide nanosheet photocatalytic material and ascorbic acid that step 4) obtains are added to deionization
In water, stir evenly；
Step 6): the solution that step 5) is obtained is transferred in water heating kettle, and heating reaction obtains brown head product；
Step 7): the brown head product that step 6) obtains is placed under inert gas shielding and vacuum condition and is calcined to get dioxy
Change titanium nanosheet photocatalytic material.
5. the preparation method of two dimension titanium dioxide nanoplate catalysis material as claimed in claim 4, which is characterized in that the step
It is rapid 1) in the ratio of graphene oxide and dehydrated alcohol be (10-200) mg:(20-200) mL；Step 1) specifically: stone will be aoxidized
Black alkene and dehydrated alcohol are put into ultrasound 25-30min in Ultrasound Instrument；The control power of Ultrasound Instrument is 400W, frequency 32kHz.
6. the preparation method of two dimension titanium dioxide nanoplate catalysis material as claimed in claim 4, which is characterized in that the step
Rapid 2) the middle temperature stirred is 10~30 DEG C, revolving speed 500-700r/min, mixing time 12-18h.
7. the preparation method of two dimension titanium dioxide nanoplate catalysis material as claimed in claim 4, which is characterized in that the step
It is rapid 3) in the revolving speed that is centrifuged twice be 10000r/min, centrifugation time is each 15min.
8. the preparation method of two dimension titanium dioxide nanoplate catalysis material as claimed in claim 4, which is characterized in that the step
It is rapid 3) in drying temperature be 60 DEG C；The temperature calcined in the step 4) is 500 DEG C, and heating rate is 2 DEG C/min, when calcining
Between be 2h.
9. the preparation method of two dimension titanium dioxide nanoplate catalysis material as claimed in claim 4, which is characterized in that the step
It is rapid 5) in the mass ratio of unmodified two-dimentional titanium dioxide nanoplate and ascorbic acid be 0.25-1:1, the revolving speed of stirring is 500-
700r/min, mixing time 30min；Heating temperature is 180 DEG C in the step 6), reaction time 8-12h.
10. the preparation method of two dimension titanium dioxide nanoplate catalysis material as claimed in claim 4, which is characterized in that described
Inert gas in step 7) is nitrogen or argon gas, and vacuum degree is -0.08atm, and calcination temperature is 450 DEG C, calcination time 2-
4h is down to room temperature after calcining.
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