CN106861680A - A kind of Graphene Pt TiO2The preparation method of multiple elements design nano-tube material - Google Patents
A kind of Graphene Pt TiO2The preparation method of multiple elements design nano-tube material Download PDFInfo
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- CN106861680A CN106861680A CN201710156048.5A CN201710156048A CN106861680A CN 106861680 A CN106861680 A CN 106861680A CN 201710156048 A CN201710156048 A CN 201710156048A CN 106861680 A CN106861680 A CN 106861680A
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- 239000002071 nanotube Substances 0.000 title claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 31
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052786 argon Inorganic materials 0.000 claims abstract description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000004927 fusion Effects 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000010431 corundum Substances 0.000 claims abstract description 17
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000002955 isolation Methods 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 claims description 7
- -1 Compound titanate Chemical class 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 235000003642 hunger Nutrition 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 230000037351 starvation Effects 0.000 claims description 4
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 12
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000010792 warming Methods 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—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A kind of Graphene Pt TiO2The preparation method of multiple elements design nano-tube material, including：It is prepared by mixed material：By commercially available nano particle TiO2With NaOH raw materials in mass ratio 1：8 ratio is weighed, and is poured into corundum crucible；Graphene powder is weighed respectively again, the compound of platinum is placed in corundum crucible, fully mix, it is standby；High-temperature fusion：At room temperature, the above-mentioned corundum crucible equipped with mixed material is placed in the high-temperature vacuum furnace of isolation air, closes fire door；Argon flow amount valve is opened, is passed through argon gas to dispel the air in body of heater；400~500 DEG C, melting mixing raw material are risen to from room temperature with the programming rate of 5 DEG C/min；Cooling down high-temperature stove takes out corundum crucible to room temperature, closes argon gas, and raw material forms titanate mixing alkali fusion frit；Hydro-thermal process under extracting in boiling water, and normal pressure；Washing of precipitate；Calcining finished product.Low cost of the present invention, required time is short, and the length of the nanotube of preparation is greatly improved, stable in properties, and effectively improves the photocatalysis characteristic of the composite nano materials.
Description
【Technical field】
The invention belongs to preparation method of nano material, a kind of Graphene-Pt-TiO is specifically referred to2Multiple elements design nanometer tubing
The preparation method of material.
【Background technology】
TiO2A kind of important inorganic functional material, because its active height, good stability, non-secondary pollution, to people
Body is harmless and cheap, in the storage of solar energy and utilization, opto-electronic conversion, photochromic and photocatalytic degradation air and water
The field such as pollutant have wide application.
Since finding CNT by Iijima from 1991, attracted that people are studied nano-tube material is very big emerging
Interest.TiO2Nanotube (TNTs) is used as TiO2A kind of existence form of nano material.The titanium dioxide of tubular structure is because of its draw ratio
And the hollow duct of nanoscale, if smaller inorganic, organic, metal or magnetic nano-particle assembling can be loaded in pipe
Into composite nano materials, then TiO2The photoelectric properties and catalysis activity of nanotube will be much improved.Caliber is less than 10nm
Opening, hollow TiO2Nanotube also tends to show significant dimensional effect, and nanotube have than nanometer film it is bigger
Specific surface area, thus with adsorption capacity higher, substantially improve TiO2Photoelectricity, electromagnetism and catalytic performance, further widen
It is applied in fields such as sensor, hydrogen storage material, Solar use, photochemical catalysts.
TiO2The preparation method of nanotube, mainly there is two methods of hydro-thermal method and anodizing.Simple to operate, low cost
Honest and clean hydrothermal synthesis method is to prepare TiO at present2One of most common method of nanotube.Hydro-thermal method refers at high temperature by TiO2Receive
Rice grain with alkali lye (generally from cheap NaOH solution) react and obtains titanate, then by ion exchange and roasting
So as to prepare TiO2The method of nanotube.According to existing document report：TiO is prepared using gentle hydro-thermal method2The method of nanotube
It is exactly nothing more than by TiO in autoclave2Nano particle is mixed with the aqueous solution of NaOH, constant temperature a couple of days, is washed and is calcined
Titanate is precipitated, and TiO is finally obtained2Nanotube.
Hong Rui Peng etc. are using Anatase TiO2Nano-particle is with the NaOH aqueous solution in hydro-thermal process temperature higher
Degree (>190 DEG C) under synthetic reaction, through 500 DEG C of high-temperature calcinations one hour, caliber 5-15nm, length is obtained up to hundreds of nanometers extremely
Several microns of fascicular texture TiO2Nanotube.Beam is built certain density NaOH aqueous solution 50ml and commercially available TiO etc.2Powder
After grain is mixed according to a certain percentage, the white suspension for obtaining is fitted into the autoclave of polytetrafluoroethyllining lining, by high pressure
After kettle is put into heating furnace, 130 DEG C are warming up to, carry out the incubation water heating treatment of 2~3 days by a definite date.White depositions deionized water
Washing to neutrality, powder obtain TiO in 60 DEG C of drying2Nanotube.Ming-deng Wei etc. are by commercial reagent Na2CO3With it is sharp
Titanium ore TiO2 is with 1：3 ratio is mixed, and in 1000 DEG C of high temperature melting 2h, is melted block and is placed in 30ml autoclaves and 140
~170 DEG C are incubated 5~18 days.Again TiO is obtained after drying 4h at filtering, washing and 60 DEG C2Nanotube product.
Li Jing's tinkling of pieces of jade etc. uses alkali fusion-hydro-thermal method, by AgNO3TiO2 nanotubes are introduced, Ag-TiO is prepared for2Composite nano tube
Material, and its pattern and performance are studied.
Graphene (Graphene) is because only that one layer of atom (i.e. two dimension), the motion of electronics is limited in a plane
On, therefore have brand-new electrical properties.Graphene is the best material of electric conductivity, electronics movement velocity wherein in the world
The 1/300 of the light velocity is reached, considerably beyond movement velocity of the electronics in general conductor.Due to its high conductivity, high intensity,
The characteristics such as ultra-thin, develop the good and superpower tough new material of thin, light, draftability, in the manufacture of automobile, aircraft and satellite and newly
The development and application of energy industry, will play prior effect.In TiO2Increase Graphene in nano-tube material, to its composite wood
The optics of material, electrical properties and photocatalysis will produce large effect.
So far, Graphene doping TiO2Autoclave hydro-thermal method is more common in the preparation of nanometer tube composite materials.For
The further crystallinity for improving compound TNTs, obtains the more excellent TNTs of performance, it is necessary to carry out the operation of high-temperature calcination.
In this operation link, if not taking the heating measures of effectively isolation air, Graphene will inevitably generate the oxygen of carbon
Compound, this will produce considerable influence to the structure of composite graphite alkene-TNTs (GTNTs) and performance.So far, there is not yet using
Completely cut off the report that the high-temperature heating measure of air is used for Graphene-TNTs preparation methods.Relatively conventional preparation method is, in order to
Avoid oxycarbide from generating, high-temperature calcination operation no longer is carried out to Graphene-TNTs, this will influence the crystallinity of TNTs, and then
Directly affect the performance of TNTs.
The shortcoming of the preparation prior art of Graphene-platinum-TNTs (Graphene-Pt-TNTs, GATNTs) material：1st, make
With the isopressor equipment of autoclave or heating using microwave operation is carried out, in commercial process is carried out, will increased
The input of equipment, improves production cost.2nd, nanotube more long is prepared using conventional high-tension reactor or microwave heating technique,
Required hydrothermal temperature higher and hydro-thermal time more long in unit interval.3rd, in conventional autoclave or microwave
Heating is carried out in hydro-thermal reaction, and the crystallization degree of the doped chemical platinum participation nanotube of composite nano tube is not high, there is doping unit
Plain platinum easily comes off problem.4th, the preparation method of current document report Graphene-TNTs composites, is more common in autoclave
Hydro-thermal method etc..In order to further improve the crystallinity of compound TNTs, obtain the more excellent TNTs of performance and forged, it is necessary to carry out high temperature
The operation of burning.If not taking the heating measures of effectively isolation air, Graphene will inevitably generate the oxide of carbon, this
To the structure of composite graphite alkene-TNTs considerable influence will be produced with performance.So far, there is not yet using the heating of isolation air
Measure is used for the report about Graphene-TNTs preparation methods.Relatively conventional preparation method is, in order to avoid oxycarbide is given birth to
Into, high-temperature calcination operation no longer is carried out to Graphene-TNTs, this will influence the crystallinity of TNTs, and then directly affect TNTs's
Performance.5th, so far, the preparation technology for being proposed using patent number ZL200910111090.0, is simply prepared for compound Ag-
TiO2Nanotube.Inventor's Li Jing's tinkling of pieces of jade etc. still has three patent applications to disclose, respectively：Pt-TiO under a kind of normal pressure2Nanometer
Pipe technology of preparing, patent publication No. is CN104689815A；Pt-TiO under a kind of normal pressure2Nanotube technology of preparing, patent is disclosed
Number be CN104722294A.Ag-Pt-TiO under a kind of normal pressure2Nanotube technology of preparing, patent publication No. is
CN201610415206.X.In above-mentioned four patent specifications, there is not yet GMTNTs material preparation process under normal pressure.
【The content of the invention】
The technical problems to be solved by the invention are to provide a kind of Graphene-Pt-TiO2Multiple elements design nano-tube material
(GATNTs) preparation method, the method is to take preparation GATNTs materials under the conditions of isolation air, constant pressure hydro-thermal, low cost,
The length of the nanotube of preparation is greatly improved, and required time is short, and obtained composite nano tube is stable in properties, and effectively improves
The photocatalysis characteristic of the composite nano materials.
What the present invention was realized in：
A kind of Graphene-Pt-TiO2The preparation method of multiple elements design nano-tube material (GATNTs), comprises the following steps：
Step one：It is prepared by mixed material：
By commercially available nano particle TiO2With NaOH raw materials in mass ratio 1：8 ratio is weighed, and is poured into corundum crucible；Again
It is that the graphene powder of 0.01~10.0wt%, the compound of platinum are placed in the corundum crucible to weigh mass percent respectively,
Fully mix, it is standby；Metal ion Pt in the compound of wherein described platinum3+It is 0.01~5.0%；
Step 2：High-temperature fusion：
At room temperature, the above-mentioned corundum crucible equipped with mixed material is placed in the high-temperature vacuum furnace of isolation air, is closed
Fire door；
Argon flow amount valve is opened, 30~120min of argon gas is passed through, to dispel the air in body of heater；
400~500 DEG C, melting mixing raw material 30min~60min are risen to from room temperature with the programming rate of 5 DEG C/min；
Cooling down high-temperature stove takes out corundum crucible to room temperature, closes argon gas, and raw material forms the titanium containing Graphene, platinum ion
Hydrochlorate mixing alkali fusion frit；
Step 3：Extracting in boiling water：
Above-mentioned mixing titanate alkali fusion frit is put into polytetrafluoroethylplastic plastic beaker, appropriate boiling distillated water is added
Dissolving, distilled water addition need to ensure that the concentration of NaOH in solution is not less than 10mol/L, be operated through the hydro-thermal process, mixed with titanium
Hydrochlorate alkali fusion frit becomes mixing titanate precipitation；
Step 4：Hydro-thermal process under normal pressure：
Cup lid on mixing titanate precipitation polytetrafluoroethylplastic plastic beaker cover is will be equipped with, is placed in drier；Above-mentioned drying
Device is placed in 110~130 DEG C of baking oven inside holdings and carries out hydro-thermal reaction in 2~5 days；After hydrothermal treatment, mixing titanate precipitation is
Generation compound titanate nanotube；
Step 5：Washing of precipitate：
Take out plastic beaker and be cooled to room temperature, originally water washing mixed with titanium silicate nanometer pipe is precipitated to weakly acidic pH；Continue to make
It is 2%HNO with volume ratio3Wash to the Na in nanotube+By H+Substitution so that mixing titanate nanotube is to generating mixed with titanium
Sour nanotube；Distill water washing mixed with titanium acid nanotube to weakly acidic pH；
Step 6：Calcining：
Mixing titanate radical nanopipe sediment is transferred in glass beaker, glass beaker is placed in the vacuum with argon gas device
In high temperature furnace, high temperature furnace fire door is closed, 60~120min of argon gas is passed through, to dispel the air in body of heater；
500 DEG C are risen to from room temperature with the programming rate of 5 DEG C/min, is calcined 2 hours, in temperature-rise period, stove must not be opened
Door, must not close argon gas, to ensure starvation in stove, it is to avoid the simple substance carbon atom of Graphene is oxidized to graphene oxide,
Or generation CO, CO2；Mixing titanate radical nanopipe becomes Graphene-Pt-TiO2Multiple elements design nanotube (GATNTs))；
Step 7：Finished product：
Lead to argon gas in high-temperature vacuum furnace, naturally cool to room temperature, close argon flow amount valve, take out multiple elements design nanotube
Grinding finished product.
Further, in the high-temperature fusion step of the step 2, wherein being risen to from room temperature with the programming rate of 5 DEG C/min
500~800 DEG C, by prepared mixed crystal type nanometer pipe.
The advantage of the invention is that：1st, in the preparation technology, using the high-temperature operation measure of isolation air, effectively protect
Graphene crystal structure its distinctive high conductivity, high intensity, ultra-thin have been demonstrate,proved to characteristics such as the high penetrations of light.Graphene is still
TiO is participated in simple substance carbon C-shaped state2Nanotube crystal structure, it is to avoid physical and chemical performance of the generation graphene oxide to nanotube
Influence；2nd, compared with autoclave preparation technology, composite nano tube, equipment requirement reduction are prepared in atmospheric conditions；3、
Nanotube preparation efficiency is improved, that is, reduce hydro-thermal time, hydrothermal temperature, and nanotube length increases；4th, Graphene and noble metal platinum
The doping of ion and addition opportunity, can arbitrarily be adjusted according to material performance requirement；5th, the preparation technology is combined to this and receives
The specific surface area of rice material increases by 2~4 times；6th, directly to participate in titanate nanocrystalline for the Graphene and noble metal platinum ion of doping
Crystal is constituted.Doped chemical is difficult for drop-off, larger on its photoelectric characteristic and photocatalysis characteristic influence.
【Brief description of the drawings】
The invention will be further described in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is process chart of the invention.
【Specific embodiment】
As shown in figure 1, a kind of Graphene-Pt-TiO2The preparation method of multiple elements design nano-tube material, including following step
Suddenly：
Step one：It is prepared by mixed material：
By commercially available nano particle TiO2With NaOH raw materials in mass ratio 1：8 ratio is weighed, and is poured into corundum crucible；Again
It is that the graphene powder of 0.01~10.0wt%, the compound of platinum are placed in the corundum crucible to weigh mass percent respectively,
Fully mix, it is standby；Metal ion Pt in the compound of wherein described platinum3+It is 0.01~5.0%；
Step 2：High-temperature fusion：
At room temperature, the above-mentioned corundum crucible equipped with mixed material is placed in the high-temperature vacuum furnace of isolation air, is closed
Fire door；
Argon flow amount valve is opened, 30~120min of argon gas is passed through, to dispel the air in body of heater；
400~500 DEG C are risen to from room temperature with the programming rate of 5 DEG C/min, in temperature-rise period, fire door must not be opened, no
Argon gas must be closed, to ensure starvation in stove, it is to avoid the simple substance carbon atoms of Graphene are into graphene oxide, or generate
CO、CO2, melting mixing raw material 30min~60min；
Cooling down high-temperature stove takes out corundum crucible to room temperature, closes argon gas, and raw material forms the titanium containing Graphene, platinum ion
Hydrochlorate mixing alkali fusion frit；
Note：The titanate through melting, hydro-thermal process and calcining after, TiO2It is intrinsic that the crystal formation of nanotube retains raw material
Crystal formation, i.e. TiO2Crystal formation raw material be Detitanium-ore-type, then nanotube be Detitanium-ore-type；Rutile-type raw material, nanotube is golden red
Stone crystal formation；Mixed crystal type raw material, then the crystal formation of nanotube is mixed type；
Mixed crystal nano-tube material is prepared if desired, then above-mentioned corundum crucible is placed in the high temperature of higher 500~800 DEG C
Melting 30min~60min takes out crucible in stove, is cooled to room temperature and forms titanate alkali fusion frit；The titanate hydrothermal treatment
And after calcining, regardless of raw material crystal formation type, TiO2Nanotube crystal formation will all be changed into mixed crystal type；Reason is 500~800
DEG C high-temperature fusion treatment, the raw material of single anatase crystal will structure be brilliant again is mixed crystal type, this photoelectric characteristic to material
Influence.
Step 3：Extracting in boiling water：
Above-mentioned mixing titanate alkali fusion frit is put into polytetrafluoroethylplastic plastic beaker, appropriate boiling distillated water is added
Dissolving, distilled water addition need to ensure that the concentration of NaOH in solution is not less than 10mol/L, be operated through the hydro-thermal process, mixed with titanium
Hydrochlorate alkali fusion frit becomes mixing titanate precipitation；
Step 4：Hydro-thermal process under normal pressure：
Cup lid on mixing titanate precipitation polytetrafluoroethylplastic plastic beaker cover is will be equipped with, is placed in drier；Above-mentioned drying
Device is placed in 110~130 DEG C of baking oven inside holdings and carries out hydro-thermal reaction in 2~5 days；Period, in hydro-thermal operating process, drier must not be made
The aqueous solution is evaporated in interior plastic beaker；Must not in order to check that the situation of water level in beaker arbitrarily opens drier lid, in order to avoid
Change inside it counter-balanced pressure；After hydrothermal treatment, mixing titanate precipitation has generated compound titanate nanotube；
Step 5：Washing of precipitate：
Take out plastic beaker and be cooled to room temperature, originally water washing mixed with titanium silicate nanometer pipe is precipitated to weakly acidic pH；Continue to make
It is 2%HNO with volume ratio3Wash to the Na in nanotube+By H+Substitution so that mixing titanate nanotube is to generating mixed with titanium
Sour nanotube；Distill water washing mixed with titanium acid nanotube to weakly acidic pH；
Step 6：Calcining：
Mixing titanate radical nanopipe sediment is transferred in glass beaker, glass beaker is placed in the vacuum with argon gas device
In high temperature furnace, high temperature furnace fire door is closed, 60~120min of argon gas is passed through, to dispel the air in body of heater；
500 DEG C are risen to from room temperature with the programming rate of 5 DEG C/min, is calcined 2 hours, in temperature-rise period, stove must not be opened
Door, must not close argon gas, to ensure starvation in stove, it is to avoid the simple substance carbon atom of Graphene is oxidized to graphene oxide,
Or generation CO, CO2；Mixing titanate radical nanopipe becomes Graphene-Pt-TiO2Multiple elements design nanotube (GATNTs))；
Step 7：Finished product：
Lead to argon gas in high-temperature vacuum furnace, naturally cool to room temperature, close argon flow amount valve, take out multiple elements design nanotube
Grinding finished product.
Preferable implementation use-case of the invention is the foregoing is only, is not intended to limit the scope of the present invention.It is all
Within the spirit and principles in the present invention, any modification, equivalent and improvement for being made etc., should be included in of the invention
Within protection domain.
Claims (2)
1. a kind of Graphene-Pt-TiO2The preparation method of multiple elements design nano-tube material, it is characterised in that：Comprise the following steps：
Step one：It is prepared by mixed material：
By commercially available nano particle TiO2With NaOH raw materials in mass ratio 1：8 ratio is weighed, and is poured into corundum crucible；Distinguish again
It is that the graphene powder of 0.01~10.0wt%, the compound of platinum are placed in the corundum crucible to weigh mass percent, fully
Mix, it is standby；Metal ion Pt in the compound of wherein described platinum3+It is 0.01~5.0%；
Step 2：High-temperature fusion：
At room temperature, the above-mentioned corundum crucible equipped with mixed material is placed in the high-temperature vacuum furnace of isolation air, closes fire door；
Argon flow amount valve is opened, 30~120min of argon gas is passed through, to dispel the air in body of heater；
400~500 DEG C, melting mixing raw material 30min~60min are risen to from room temperature with the programming rate of 5 DEG C/min；
Cooling down high-temperature stove takes out corundum crucible to room temperature, closes argon gas, and raw material forms the titanate containing Graphene, platinum ion
Mixing alkali fusion frit；
Step 3：Extracting in boiling water：
Above-mentioned mixing titanate alkali fusion frit is put into polytetrafluoroethylplastic plastic beaker, adds appropriate boiling distillated water molten
Solution, distilled water addition need to ensure that the concentration of NaOH in solution is not less than 10mol/L, be operated through the hydro-thermal process, mix metatitanic acid
Salt alkali fusion frit becomes mixing titanate precipitation；
Step 4：Hydro-thermal process under normal pressure：
Cup lid on mixing titanate precipitation polytetrafluoroethylplastic plastic beaker cover is will be equipped with, is placed in drier；Above-mentioned drier is put
Hydro-thermal reaction is carried out in 110~130 DEG C of baking oven inside holdings within 2~5 days；After hydrothermal treatment, mixing titanate precipitation has been generated
Compound titanate nanotube；
Step 5：Washing of precipitate：
Take out plastic beaker and be cooled to room temperature, originally water washing mixed with titanium silicate nanometer pipe is precipitated to weakly acidic pH；It is continuing with body
Product is than being 2%HNO3Wash to the Na in nanotube+By H+Substitution so that mixing titanate nanotube is received to mixing metatitanic acid is generated
Mitron；Distill water washing mixed with titanium acid nanotube to weakly acidic pH；
Step 6：Calcining：
Mixing titanate radical nanopipe sediment is transferred in glass beaker, glass beaker is placed in the vacuum high-temperature with argon gas device
In stove, high temperature furnace fire door is closed, 60~120min of argon gas is passed through, to dispel the air in body of heater；
500 DEG C are risen to from room temperature with the programming rate of 5 DEG C/min, is calcined 2 hours, in temperature-rise period, fire door must not be opened, no
Argon gas must be closed, to ensure starvation in stove, it is to avoid the simple substance carbon atom of Graphene is oxidized to graphene oxide, Huo Zhesheng
Into CO, CO2；Mixing titanate radical nanopipe becomes Graphene-Pt-TiO2Multiple elements design nanotube；
Step 7：Finished product：
Lead to argon gas in high-temperature vacuum furnace, naturally cool to room temperature, close argon flow amount valve, take out the grinding of multiple elements design nanotube
Finished product.
2. a kind of Graphene-Pt-TiO as claimed in claim 12The preparation method of multiple elements design nano-tube material, its feature exists
In：In the high-temperature fusion step of the step 2, wherein 500~800 DEG C are risen to from room temperature with the programming rate of 5 DEG C/min, will
Mixed crystal type nanometer pipe is obtained.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100849220B1 (en) * | 2007-04-16 | 2008-07-31 | 요업기술원 | Method for preparaing high density titania nanotubes and nanowires that are selp-arrayed on a substrate |
| CN102496700A (en) * | 2011-12-20 | 2012-06-13 | 中国科学院新疆理化技术研究所 | Graphene-titanium dioxide nanotube composite material and preparation method thereof |
| CN104722294A (en) * | 2015-02-15 | 2015-06-24 | 福建工程学院 | Preparation technology of Pt-TiO2 nano-tube under normal pressure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100849220B1 (en) * | 2007-04-16 | 2008-07-31 | 요업기술원 | Method for preparaing high density titania nanotubes and nanowires that are selp-arrayed on a substrate |
| CN102496700A (en) * | 2011-12-20 | 2012-06-13 | 中国科学院新疆理化技术研究所 | Graphene-titanium dioxide nanotube composite material and preparation method thereof |
| CN104722294A (en) * | 2015-02-15 | 2015-06-24 | 福建工程学院 | Preparation technology of Pt-TiO2 nano-tube under normal pressure |
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Application publication date: 20170620 |