CN110026171A - A kind of preparation method of high-efficient graphite alkenyl catalysis material - Google Patents
A kind of preparation method of high-efficient graphite alkenyl catalysis material Download PDFInfo
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- CN110026171A CN110026171A CN201910351123.2A CN201910351123A CN110026171A CN 110026171 A CN110026171 A CN 110026171A CN 201910351123 A CN201910351123 A CN 201910351123A CN 110026171 A CN110026171 A CN 110026171A
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 29
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- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012153 distilled water Substances 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 19
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 19
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- 238000005292 vacuum distillation Methods 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000007603 infrared drying Methods 0.000 claims abstract description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
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- 238000002604 ultrasonography Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 30
- 229920002125 Sokalan® Polymers 0.000 abstract description 22
- 239000004584 polyacrylic acid Substances 0.000 abstract description 22
- 239000004408 titanium dioxide Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 8
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/39—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a kind of high-efficient graphite alkenyl catalysis material, include the following steps: to enter two-dimensional graphene into distilled water, then ascorbic acid, stirs evenly, and obtains graphene suspension；Acrylic acid is added to graphene suspension, then low temperature ultrasonic reacts 2-4h, water-bath 2-6h, and vacuum distillation reaction 2-4h obtains band coating three-dimensional grapheme；Tetrabutyl titanate is added into dehydrated alcohol, ethyl cellulose is added and stirs to being completely dissolved, forms titanium liquid；Band coating three-dimensional grapheme is put into low temperature ultrasonic in titanium liquid and reacts 2-4h, flash baking is taken out and obtains the three-dimensional grapheme with titanium film；Three-dimensional grapheme with titanium film is put into constant temperature drying 2-4h in infrared drying case, Isothermal sinter 1-2h after nitrogen purging obtains graphene-based catalysis material.The present invention solves the problems, such as that existing catalysis material is easy to lose in water, and titanium dioxide is adhered on three-dimensional grapheme using ethyl cellulose and polyacrylic acid.
Description
Technical field
The invention belongs to photocatalysis fields, and in particular to a kind of high-efficient graphite alkenyl catalysis material.
Background technique
In the past 20 years, with the rapid development of our country's economy, all significantly to the exploitation of lake resource, using scale and speed
Reinforce, affects the natural evolution process in lake, serious destruction is caused to lake ecosystem.With Chinese society economy and
The fast development of urbanization process, Water Environment In Lakes pollution problem become increasingly conspicuous.According to national comprehensive planning of water resources evaluation at
Fruit, the representative Lakes in Nutrition status evaluation in 84, the whole nation the result shows that: whole year has 44 lakes in eutrophic state, accounts for evaluation
The 52.4% of lake sum, remaining lake is middle nutritional status.Lake variation and pollution control have become China environmental protection
Emphasis, increase pollution source apportionment and contained the impetus of pollution and the deterioration of the ecological environment to a certain extent, but according to country
The situation of economic development and future plan, lake pollution and degeneration allows of no optimist.
Currently, graphene photocatalysis technology is the hot spot studied for waste water control, pollution treatment principle is to utilize visible light
Restore the self-purification of water, natural light is unique light source, power device is not necessarily to, without adding chemical reagent or biological inoculum.But stone
The putting mode of black alkene photochemical catalyst is the bottleneck of current waste water control.It is existing mostly use graphene photocatalysis net carry out river or
The waste water control in lake loads multi-layer graphene photochemical catalyst by unique coating processes that is, using polypropylene fibre as substrate
At, it can be used for water body purification, air cleaning etc., be particularly suitable for the improvement of city black and odorous water, it can be to toxic organic in water body
Object is decomposed, deodorization, increases oxygen content of water, and strong with other Treatment process compatibility, material is environmentally protective, and can follow
Ring uses.But the catalysis material of current graphene photo-catalyst and the associativity of graphene be not strong, easily light is caused to urge
Change material in water a large amount of lost, reduces whole treatment effeciency.
Summary of the invention
For the problems of the prior art, the present invention provides a kind of preparation method of high-efficient graphite alkenyl catalysis material,
Solve the problems, such as that existing catalysis material is easy to lose in water, it, will using ethyl cellulose and polyacrylic acid as adhesive
Titanium dioxide is adhered to three-dimensional grapheme, effectively promotes adhesiveness, and forms surface key during the sintering process and connect, and is formed and is stablized
Solidification effect.
To realize the above technical purpose, the technical scheme is that
A kind of preparation method of high-efficient graphite alkenyl catalysis material, includes the following steps:
Step 1, two-dimensional graphene will be entered into distilled water, then ascorbic acid, will be stirred evenly, it is suspended to obtain graphene
Liquid；
Step 2, acrylic acid is added to graphene suspension, then low temperature ultrasonic reacts 2-4h, and water-bath 2-6h subtracts
Distillation reaction 2-4h is pressed, band coating three-dimensional grapheme is obtained；
Step 3, tetrabutyl titanate is added into dehydrated alcohol, ethyl cellulose is added and stirs to being completely dissolved, is formed
Titanium liquid；
Step 4, band coating three-dimensional grapheme is put into low temperature ultrasonic in titanium liquid and reacts 2-4h, taken out flash baking and obtain
Three-dimensional grapheme with titanium film；
Step 5, the three-dimensional grapheme with titanium film is put into constant temperature drying 2-4h in infrared drying case, constant temperature after nitrogen purging
It is sintered 1-2h, obtains graphene-based catalysis material.
Concentration 5-10g/L of the two-dimensional graphene in distilled water in the step 1, the additional amount of the ascorbic acid are
The 300-900% of two-dimensional graphene quality, the mixing speed stirred evenly are 300-800r/min.
The additional amount of acrylic acid in the step 2 is graphene quality 100-150%, the temperature of the low temperature ultrasonic reaction
Degree is 5-10 DEG C, supersonic frequency 40-100kHz, and the temperature of the water-bath is 90-100 DEG C, the vacuum distillation reaction
Pressure be atmospheric pressure 60-70%, temperature be 100-120 DEG C.
Isopropanol is added while addition in acrylic acid in the step 2, and the additional amount of the isopropanol is acrylic acid matter
The 20-40% of amount.
Concentration of the tetrabutyl titanate in dehydrated alcohol in the step 3 is 100-200g/L, the ethyl cellulose
Additional amount be tetrabutyl titanate quality 40-60%, the speed of the stirring is 1000-2000r/min,.
The mass ratio of band coating three-dimensional grapheme in the step 4 and the tetrabutyl titanate in titanium liquid is 2:10-
200, the temperature of the low temperature ultrasonic reaction is 2-8 DEG C, supersonic frequency 100-200kHz, and the drying temperature is 100-110
℃。
The temperature of constant temperature drying in the step 5 is 180-220 DEG C, and humidity 30-50%, the nitrogen purging is blown
Sweeping speed is 100-200mL/min, and purge time 30-100min, the temperature of the Isothermal sinter is 300-350 DEG C.
Two-dimensional graphene is added into distilled water step 1, and ascorbic acid is then added, and it is suspended that graphene is formed after stirring
Liquid.
Acrylic acid is added into graphene suspension step 2, and acrylic acid can be dissolved in distilled water；Low temperature ultrasonic is anti-
Two-dimensional graphene should can be separated to the graphene of porous three dimensional structure with ascorbic acid, while the high-frequency of ultrasound can incite somebody to action
In polypropylene rapid dispersion to the porous three dimensional structure of graphene, good osmotic effect is formed, and be evenly distributed on graphite
On the bigger serface of alkene, it is capable of forming stable liquid film structure；Water-bath can promote the acrylic acid in graphene to carry out
Polymerization reaction obtains polyacrylic acid, and polyacrylic acid is evenly distributed in distilled water, and forms adherency liquid film on the surface of graphene；
Distilled water evaporative removal as lysate can be obtained the three-dimensional stone that polyacrylic acid liquid film is contained on surface by vacuum distillation reaction
Black alkene, and it is mingled with the distilled water being adsorbed in polyacrylic acid on a small quantity in the graphene.
Isopropanol not only can make molecular weight distribution small range relatively narrow as molecular weight regulator, and there are also reduce viscosity, move
Walk the effect of reaction heat.The boiling point of isopropanol is 82-83 DEG C simultaneously, and gaseous state, while the reaction are formed during water-bath
Polyacrylic acid is polymerized in system, so isopropanol promotes quickly remove while reaction, it will not be to subsequent reactions shape
At influence.
Tetrabutyl titanate is added into dehydrated alcohol and forms dissolution and dispersion by step 3, and ethyl cellulose shape is then added
At dispersion dissolution can be formed in ethanol, together since ethyl cellulose has good dissolubility in dehydrated alcohol
When be dispersed to tetrabutyl titanate surface, form package system；Since the content of ethyl cellulose is less than tetrabutyl titanate, so second
Base cellulose is merely able to form half package system, obtains the finely dispersed titanium alcohol liquid of tetrabutyl titanate.
Three-dimensional grapheme with polyacrylic acid liquid film is added into titanium liquid step 4, using polyacrylic acid in dehydrated alcohol
Dissolubility, form the secondary dissolution of liquid film, the cosolvency based on polyacrylic acid and ethyl cellulose can be by tetrabutyl titanate
Uniform adhesion forms good film on three-dimensional grapheme surface, and drying obtains with polyacrylic acid and ethyl cellulose being compound
Adhesive, using tetrabutyl titanate as the three-dimensional grapheme of film layer.
Three-dimensional grapheme with titanium film is put into constant temperature drying in infrared drying case by step 5, I has one in air at this time
The water absorbing properties of quantitative vapor, polyacrylic acid absorb moisture in the stage that begins to warm up, and convert nanometer for tetrabutyl titanate
The curing performance of titanium dioxide, polyacrylic acid and ethyl cellulose solves the agglomeration traits of nano-titanium dioxide, with temperature
Rising, the moisture in polyacrylic acid is gradually lost, and forms stable polyacrylic acid high-molecular compound；The mode of nitrogen purging
Steam-laden air is removed, the environment of nitrogen system is formed, the butyl ester for also generating reaction removes；In a nitrogen environment into
Row Isothermal sinter, polyacrylic acid and ethyl cellulose are formed in the temperature and are decomposed, and nano-titanium dioxide is set in graphite
Alkene surface, while temperature at this time can convert nano-titanium dioxide to anatase titanium dioxide, and have part titanium dioxide to be converted into gold
Red stone-type can guarantee rutile type nano titanic oxide and anatase titanium dioxide shape due to the high thermal conductivity of graphene
At inside and outside wrong system, the Photocatalytic Degradation Property of titanium dioxide is greatly improved.
From the above, it can be seen that the present invention has following advantages:
1. the present invention solves the problems, such as that existing catalysis material is easy to lose in water, ethyl cellulose and polypropylene are utilized
Acid is used as adhesive, and titanium dioxide is adhered to three-dimensional grapheme, effectively promotes adhesiveness, and form table during the sintering process
Face key connects, and forms stable solidification effect.
2. the present invention is using dehydrated alcohol to polyacrylic acid, tetrabutyl titanate and solubility of ethylcellulose, Neng Goubao
Card tetrabutyl titanate rearranging on the surface of graphene, formed be with polyacrylic acid and ethyl cellulose adherency main body surface
Film.
3. tetrabutyl titanate is hydrolyzed to form titanium dioxide using the steam in air by the present invention, while utilizing ethyl cellulose
The solidification of element and polyacrylic acid, prevents Aggregation of Nanometer Titanium Dioxide, solves the agglomeration traits of titanium dioxide.
Specific embodiment
The present invention will be described in detail in conjunction with the embodiments, but does not do any restriction to claim of the invention.
Embodiment 1
A kind of preparation method of high-efficient graphite alkenyl catalysis material, includes the following steps:
Step 1, two-dimensional graphene will be entered into distilled water, then ascorbic acid, will be stirred evenly, it is suspended to obtain graphene
Liquid；
Step 2, acrylic acid is added to graphene suspension, then low temperature ultrasonic reacts 2h, water-bath 2h, and decompression is steamed
Reaction 2h is evaporated, band coating three-dimensional grapheme is obtained；
Step 3, tetrabutyl titanate is added into dehydrated alcohol, ethyl cellulose is added and stirs to being completely dissolved, is formed
Titanium liquid；
Step 4, band coating three-dimensional grapheme is put into low temperature ultrasonic in titanium liquid and reacts 2h, taken out flash baking and obtain band
The three-dimensional grapheme of titanium film；
Step 5, the three-dimensional grapheme with titanium film is put into constant temperature drying 2h in infrared drying case, constant temperature is burnt after nitrogen purging
1-2h is tied, graphene-based catalysis material is obtained.
Concentration 5g/L of the two-dimensional graphene in distilled water in the step 1, the additional amount of the ascorbic acid is two
The 300% of graphene quality is tieed up, the mixing speed stirred evenly is 300r/min.
The additional amount of acrylic acid in the step 2 is graphene quality 100%, and the temperature of the low temperature ultrasonic reaction is
5 DEG C, supersonic frequency 40kHz, the temperature of the water-bath is 90 DEG C, and the pressure of the vacuum distillation reaction is atmospheric pressure
60%, temperature is 100 DEG C.
Concentration of the tetrabutyl titanate in dehydrated alcohol in the step 3 is 100g/L, and the ethyl cellulose adds
Entering amount is tetrabutyl titanate quality 40%, the speed of the stirring is 1000r/min,.
The mass ratio of band coating three-dimensional grapheme in the step 4 and the tetrabutyl titanate in titanium liquid is 2:10, institute
The temperature for stating low temperature ultrasonic reaction is 2 DEG C, supersonic frequency 100kHz, and the drying temperature is 100 DEG C.
The temperature of constant temperature drying in the step 5 is 180 DEG C, humidity 30%, the purging speed of the nitrogen purging
For 100mL/min, purge time 30min, the temperature of the Isothermal sinter is 300 DEG C.
Embodiment 2
A kind of preparation method of high-efficient graphite alkenyl catalysis material, includes the following steps:
Step 1, two-dimensional graphene will be entered into distilled water, then ascorbic acid, will be stirred evenly, it is suspended to obtain graphene
Liquid；
Step 2, acrylic acid is added to graphene suspension, then low temperature ultrasonic reacts 4h, water-bath 6h, and decompression is steamed
Reaction 4h is evaporated, band coating three-dimensional grapheme is obtained；
Step 3, tetrabutyl titanate is added into dehydrated alcohol, ethyl cellulose is added and stirs to being completely dissolved, is formed
Titanium liquid；
Step 4, band coating three-dimensional grapheme is put into low temperature ultrasonic in titanium liquid and reacts 4h, taken out flash baking and obtain band
The three-dimensional grapheme of titanium film；
Step 5, the three-dimensional grapheme with titanium film is put into constant temperature drying 4h in infrared drying case, constant temperature is burnt after nitrogen purging
2h is tied, graphene-based catalysis material is obtained.
Concentration 10g/L of the two-dimensional graphene in distilled water in the step 1, the additional amount of the ascorbic acid is two
The 900% of graphene quality is tieed up, the mixing speed stirred evenly is 800r/min.
The additional amount of acrylic acid in the step 2 is graphene quality 150%, and the temperature of the low temperature ultrasonic reaction is
10 DEG C, supersonic frequency 100kHz, the temperature of the water-bath is 100 DEG C, and the pressure of the vacuum distillation reaction is atmosphere
The 70% of pressure, temperature are 120 DEG C.
Concentration of the tetrabutyl titanate in dehydrated alcohol in the step 3 is 200g/L, and the ethyl cellulose adds
Entering amount is tetrabutyl titanate quality 60%, the speed of the stirring is 2000r/min,.
The mass ratio of band coating three-dimensional grapheme in the step 4 and the tetrabutyl titanate in titanium liquid is 2:200, institute
The temperature for stating low temperature ultrasonic reaction is 8 DEG C, supersonic frequency 200kHz, and the drying temperature is 110 DEG C.
The temperature of constant temperature drying in the step 5 is 220 DEG C, humidity 50%, the purging speed of the nitrogen purging
For 200mL/min, purge time 100min, the temperature of the Isothermal sinter is 350 DEG C.
Embodiment 3
A kind of preparation method of high-efficient graphite alkenyl catalysis material, includes the following steps:
Step 1, two-dimensional graphene will be entered into distilled water, then ascorbic acid, will be stirred evenly, it is suspended to obtain graphene
Liquid；
Step 2, acrylic acid is added to graphene suspension, then low temperature ultrasonic reacts 3h, water-bath 4h, and decompression is steamed
Reaction 3h is evaporated, band coating three-dimensional grapheme is obtained；
Step 3, tetrabutyl titanate is added into dehydrated alcohol, ethyl cellulose is added and stirs to being completely dissolved, is formed
Titanium liquid；
Step 4, band coating three-dimensional grapheme is put into low temperature ultrasonic in titanium liquid and reacts 3h, taken out flash baking and obtain band
The three-dimensional grapheme of titanium film；
Step 5, the three-dimensional grapheme with titanium film is put into constant temperature drying 3h in infrared drying case, constant temperature is burnt after nitrogen purging
2h is tied, graphene-based catalysis material is obtained.
Concentration 8g/L of the two-dimensional graphene in distilled water in the step 1, the additional amount of the ascorbic acid is two
The 600% of graphene quality is tieed up, the mixing speed stirred evenly is 500r/min.
The additional amount of acrylic acid in the step 2 is graphene quality 130%, and the temperature of the low temperature ultrasonic reaction is
8 DEG C, supersonic frequency 80kHz, the temperature of the water-bath is 95 DEG C, and the pressure of the vacuum distillation reaction is atmospheric pressure
65%, temperature is 110 DEG C.
Isopropanol is added while addition in acrylic acid in the step 2, and the additional amount of the isopropanol is acrylic acid matter
The 30% of amount.
Concentration of the tetrabutyl titanate in dehydrated alcohol in the step 3 is 150g/L, and the ethyl cellulose adds
Entering amount is tetrabutyl titanate quality 50%, the speed of the stirring is 1500r/min,.
The mass ratio of band coating three-dimensional grapheme in the step 4 and the tetrabutyl titanate in titanium liquid is 2:100, institute
The temperature for stating low temperature ultrasonic reaction is 6 DEG C, supersonic frequency 150kHz, and the drying temperature is 105 DEG C.
The temperature of constant temperature drying in the step 5 is 200 DEG C, humidity 40%, the purging speed of the nitrogen purging
For 150mL/min, purge time 80min, the temperature of the Isothermal sinter is 330 DEG C.
Embodiment 4
A kind of preparation method of high-efficient graphite alkenyl catalysis material, includes the following steps:
Step 1, two-dimensional graphene will be entered into distilled water, then ascorbic acid, will be stirred evenly, it is suspended to obtain graphene
Liquid；
Step 2, acrylic acid and isopropanol are added to graphene suspension, then low temperature ultrasonic reacts 2h, water-bath
2h, vacuum distillation reaction 2h, obtains band coating three-dimensional grapheme；
Step 3, tetrabutyl titanate is added into dehydrated alcohol, ethyl cellulose is added and stirs to being completely dissolved, is formed
Titanium liquid；
Step 4, band coating three-dimensional grapheme is put into low temperature ultrasonic in titanium liquid and reacts 2h, taken out flash baking and obtain band
The three-dimensional grapheme of titanium film；
Step 5, the three-dimensional grapheme with titanium film is put into constant temperature drying 2h in infrared drying case, constant temperature is burnt after nitrogen purging
1h is tied, graphene-based catalysis material is obtained.
Concentration 5g/L of the two-dimensional graphene in distilled water in the step 1, the additional amount of the ascorbic acid is two
The 300% of graphene quality is tieed up, the mixing speed stirred evenly is 300r/min.
The additional amount of acrylic acid in the step 2 is graphene quality 100%, and the temperature of the low temperature ultrasonic reaction is
5 DEG C, supersonic frequency 40kHz, the temperature of the water-bath is 90 DEG C, and the pressure of the vacuum distillation reaction is atmospheric pressure
60%, temperature is 100 DEG C；The additional amount of the isopropanol is the 20% of acrylic acid quality.
Concentration of the tetrabutyl titanate in dehydrated alcohol in the step 3 is 100g/L, and the ethyl cellulose adds
Entering amount is tetrabutyl titanate quality 40%, the speed of the stirring is 1000r/min,.
The mass ratio of band coating three-dimensional grapheme in the step 4 and the tetrabutyl titanate in titanium liquid is 2:10, institute
The temperature for stating low temperature ultrasonic reaction is 2 DEG C, supersonic frequency 100kHz, and the drying temperature is 100 DEG C.
The temperature of constant temperature drying in the step 5 is 180 DEG C, humidity 30%, the purging speed of the nitrogen purging
For 100mL/min, purge time 30min, the temperature of the Isothermal sinter is 300 DEG C.
Embodiment 5
A kind of preparation method of high-efficient graphite alkenyl catalysis material, includes the following steps:
Step 1, two-dimensional graphene will be entered into distilled water, then ascorbic acid, will be stirred evenly, it is suspended to obtain graphene
Liquid；
Step 2, acrylic acid and isopropanol are added to graphene suspension, then low temperature ultrasonic reacts 4h, water-bath
6h, vacuum distillation reaction 4h, obtains band coating three-dimensional grapheme；
Step 3, tetrabutyl titanate is added into dehydrated alcohol, ethyl cellulose is added and stirs to being completely dissolved, is formed
Titanium liquid；
Step 4, band coating three-dimensional grapheme is put into low temperature ultrasonic in titanium liquid and reacts 4h, taken out flash baking and obtain band
The three-dimensional grapheme of titanium film；
Step 5, the three-dimensional grapheme with titanium film is put into constant temperature drying 4h in infrared drying case, constant temperature is burnt after nitrogen purging
2h is tied, graphene-based catalysis material is obtained.
Concentration 10g/L of the two-dimensional graphene in distilled water in the step 1, the additional amount of the ascorbic acid is two
The 900% of graphene quality is tieed up, the mixing speed stirred evenly is 800r/min.
The additional amount of acrylic acid in the step 2 is graphene quality 150%, and the temperature of the low temperature ultrasonic reaction is
10 DEG C, supersonic frequency 100kHz, the temperature of the water-bath is 100 DEG C, and the pressure of the vacuum distillation reaction is atmosphere
The 70% of pressure, temperature are 120 DEG C；The additional amount of the isopropanol is the 40% of acrylic acid quality.
Concentration of the tetrabutyl titanate in dehydrated alcohol in the step 3 is 200g/L, and the ethyl cellulose adds
Entering amount is tetrabutyl titanate quality 60%, the speed of the stirring is 2000r/min,.
The mass ratio of band coating three-dimensional grapheme in the step 4 and the tetrabutyl titanate in titanium liquid is 2:200, institute
The temperature for stating low temperature ultrasonic reaction is 8 DEG C, supersonic frequency 200kHz, and the drying temperature is 110 DEG C.
The temperature of constant temperature drying in the step 5 is 220 DEG C, humidity 50%, the purging speed of the nitrogen purging
For 200mL/min, purge time 100min, the temperature of the Isothermal sinter is 350 DEG C.
Embodiment 6
A kind of preparation method of high-efficient graphite alkenyl catalysis material, includes the following steps:
Step 1, two-dimensional graphene will be entered into distilled water, then ascorbic acid, will be stirred evenly, it is suspended to obtain graphene
Liquid；
Step 2, acrylic acid and isopropanol are added to graphene suspension, then low temperature ultrasonic reacts 3h, water-bath
4h, vacuum distillation reaction 3h, obtains band coating three-dimensional grapheme；
Step 3, tetrabutyl titanate is added into dehydrated alcohol, ethyl cellulose is added and stirs to being completely dissolved, is formed
Titanium liquid；
Step 4, band coating three-dimensional grapheme is put into low temperature ultrasonic in titanium liquid and reacts 3h, taken out flash baking and obtain band
The three-dimensional grapheme of titanium film；
Step 5, the three-dimensional grapheme with titanium film is put into constant temperature drying 3h in infrared drying case, constant temperature is burnt after nitrogen purging
1h is tied, graphene-based catalysis material is obtained.
Concentration 10g/L of the two-dimensional graphene in distilled water in the step 1, the additional amount of the ascorbic acid is two
The 700% of graphene quality is tieed up, the mixing speed stirred evenly is 600r/min.
The additional amount of acrylic acid in the step 2 is graphene quality 140%, and the temperature of the low temperature ultrasonic reaction is
5 DEG C, supersonic frequency 80kHz, the temperature of the water-bath is 100 DEG C, and the pressure of the vacuum distillation reaction is atmospheric pressure
65%, temperature be 115 DEG C；The additional amount of the isopropanol is the 30% of acrylic acid quality.
Concentration of the tetrabutyl titanate in dehydrated alcohol in the step 3 is 180g/L, and the ethyl cellulose adds
Entering amount is tetrabutyl titanate quality 50%, the speed of the stirring is 1600r/min,.
The mass ratio of band coating three-dimensional grapheme in the step 4 and the tetrabutyl titanate in titanium liquid is 2:150, institute
The temperature for stating low temperature ultrasonic reaction is 6 DEG C, supersonic frequency 150kHz, and the drying temperature is 105 DEG C.
The temperature of constant temperature drying in the step 5 is 210 DEG C, humidity 40%, the purging speed of the nitrogen purging
For 150mL/min, purge time 80min, the temperature of the Isothermal sinter is 330 DEG C.
Performance detection
Comparative example uses commercially available graphene photo-catalyst.
Above-mentioned test is tested according to the national standard of photocatalysis field, and specific national standard is as follows:
GB/T23761-2009 (photocatalysis air-cleaning material performance test method)
GB/T23762-2009 (catalysis material water solution system purifies test method)
GB/T23763-2009 (evaluation of photocatalysis antibacterial material and product anti-microbial property)
GB/T23764-2009 (photocatalytic self-cleaning material performance test method)
In detection process, in antibiotic property detection, embodiment 1-6 all has good antibacterial effect, and is using 100 days
After distilled water flushing impregnates, it is still 99.99% that photocatalysis antibacterial performance, which is basically unchanged, and the graphene light in comparative example is urged
Agent photocatalysis antibacterial performance after long-time distilled water immersion by 99.99% drops to 87%；It is real in automatically cleaning detection process
It is almost unchanged to apply 1-6 performance after 100 days distilled water flushings impregnate, and the contact angle of comparative example is by original 90.3 °
It is raised to 123.1 °.
Pond water quality compares (mg/L) before and after the processing
Graphene photo-catalyst prepared by embodiment 1 is put into bad V class pond surface, launched graphene photo-catalyst
Specific surface area is the 30% of pond area.
In conclusion the invention has the following advantages that
1. the present invention solves the problems, such as that existing catalysis material is easy to lose in water, ethyl cellulose and polypropylene are utilized
Acid is used as adhesive, and titanium dioxide is adhered to three-dimensional grapheme, effectively promotes adhesiveness, and form table during the sintering process
Face key connects, and forms stable solidification effect.
2. the present invention is using dehydrated alcohol to polyacrylic acid, tetrabutyl titanate and solubility of ethylcellulose, Neng Goubao
Card tetrabutyl titanate rearranging on the surface of graphene, formed be with polyacrylic acid and ethyl cellulose adherency main body surface
Film.
3. tetrabutyl titanate is hydrolyzed to form titanium dioxide using the steam in air by the present invention, while utilizing ethyl cellulose
The solidification of element and polyacrylic acid, prevents Aggregation of Nanometer Titanium Dioxide, solves the agglomeration traits of titanium dioxide.
It is understood that being merely to illustrate the present invention above with respect to specific descriptions of the invention and being not limited to this
Technical solution described in inventive embodiments.Those skilled in the art should understand that still can be carried out to the present invention
Modification or equivalent replacement, to reach identical technical effect；As long as meet use needs, all protection scope of the present invention it
It is interior.
Claims (7)
1. a kind of preparation method of high-efficient graphite alkenyl catalysis material, characterized by the following steps:
Step 1, two-dimensional graphene will be entered into distilled water, then ascorbic acid, will be stirred evenly, and obtain graphene suspension；
Step 2, acrylic acid is added to graphene suspension, then low temperature ultrasonic reacts 2-4h, water-bath 2-6h, and decompression is steamed
Reaction 2-4h is evaporated, band coating three-dimensional grapheme is obtained；
Step 3, tetrabutyl titanate is added into dehydrated alcohol, ethyl cellulose is added and stirs to being completely dissolved, forms titanium liquid；
Step 4, band coating three-dimensional grapheme is put into low temperature ultrasonic in titanium liquid and reacts 2-4h, taken out flash baking and obtain band titanium
The three-dimensional grapheme of film；
Step 5, the three-dimensional grapheme with titanium film is put into constant temperature drying 2-4h in infrared drying case, Isothermal sinter after nitrogen purging
1-2h obtains graphene-based catalysis material.
2. the preparation method of high-efficient graphite alkenyl catalysis material according to claim 1, it is characterised in that: the step
Concentration 5-10g/L of the two-dimensional graphene in distilled water in 1, the additional amount of the ascorbic acid is two-dimensional graphene quality
300-900%, the mixing speed stirred evenly are 300-800r/min.
3. the preparation method of high-efficient graphite alkenyl catalysis material according to claim 1, it is characterised in that: the step
The additional amount of acrylic acid in 2 is graphene quality 100-150%, and the temperature of the low temperature ultrasonic reaction is 5-10 DEG C, ultrasound
Frequency is 40-100kHz, and the temperature of the water-bath is 90-100 DEG C, and the pressure of the vacuum distillation reaction is atmospheric pressure
60-70%, temperature are 100-120 DEG C.
4. the preparation method of high-efficient graphite alkenyl catalysis material according to claim 1, it is characterised in that: the step
Isopropanol is added while addition in acrylic acid in 2, and the additional amount of the isopropanol is the 20-40% of acrylic acid quality.
5. the preparation method of high-efficient graphite alkenyl catalysis material according to claim 1, it is characterised in that: the step
Concentration of the tetrabutyl titanate in dehydrated alcohol in 3 is 100-200g/L, the additional amount of the ethyl cellulose be metatitanic acid just
The 40-60% of butyl ester quality, the speed of the stirring are 1000-2000r/min,.
6. the preparation method of high-efficient graphite alkenyl catalysis material according to claim 1, it is characterised in that: the step
The mass ratio of band coating three-dimensional grapheme in 4 and the tetrabutyl titanate in titanium liquid is 2:10-200, and the low temperature ultrasonic is anti-
The temperature answered is 2-8 DEG C, supersonic frequency 100-200kHz, and the drying temperature is 100-110 DEG C.
7. the preparation method of high-efficient graphite alkenyl catalysis material according to claim 1, it is characterised in that: the step
The temperature of constant temperature drying in 5 is 180-220 DEG C, and humidity 30-50%, the purging speed of the nitrogen purging is 100-
200mL/min, purge time 30-100min, the temperature of the Isothermal sinter are 300-350 DEG C.
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