CN107020073A - A kind of preparation method of the photocatalyst material based on graphene - Google Patents
A kind of preparation method of the photocatalyst material based on graphene Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 45
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
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- 238000005286 illumination Methods 0.000 claims abstract description 23
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- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 12
- 238000002604 ultrasonography Methods 0.000 claims abstract description 7
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
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- 239000007788 liquid Substances 0.000 claims description 17
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- 238000007146 photocatalysis Methods 0.000 claims description 13
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- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- APIDIPGVBRXKEJ-UHFFFAOYSA-N acetic acid titanium Chemical compound [Ti].CC(O)=O.CC(O)=O APIDIPGVBRXKEJ-UHFFFAOYSA-N 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 229910017582 La2Ti2O7 Inorganic materials 0.000 abstract description 26
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 230000031700 light absorption Effects 0.000 abstract description 3
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
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- 239000003054 catalyst Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- 150000002603 lanthanum Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
-
- 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—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
Abstract
The present invention relates to a kind of preparation method of the photocatalyst material based on graphene, using lanthanum chloride, titanium source and graphene as raw material, lanthanium titanate material is obtained through precipitating aerated reaction ground rice heating aerated reaction, and ultrasound and illumination reaction are carried out with graphene, graphene lanthanium titanate material is obtained.The present invention utilizes La2Ti2O7The further reduced graphene of ability of the photo catalytic reduction in situ of nanometer, reduces the defect of grapheme material, while adding graphene and La2Ti2O7Nano material is directly contacted, and adds La2Ti2O7The efficiency of light absorption of nano material.
Description
Technical field
The invention belongs to photocatalyst technology field, it is related to a kind of preparation side of the photocatalyst material based on graphene
Method.
Background technology
Graphene has just turned into the dazzling nova of nanometer circle since being found from 2004 and causes the very big of researcher
Concern.Graphene (Graphene) is sp2Hydbridized carbon atoms it is tightly packed into individual layer bi-dimensional cellular shape lattice structure carbonaceous
Material, is the elementary cell for constituting other graphite materials, and its pattern is analogous to the lamellar structure of thin paper, and thickness in monolayer is only
0.335nm, is the most thin two-dimensional material found in the world at present.Graphene excellent combination property：Theoretical strength is 125GPa,
It is stronger than steel 100 times；Its modulus of elasticity can reach 1.0TPa, can be compared favourably with CNT；Its thermal conductivity is 5300W/ (m K),
Better than metal materials such as silver；Electron mobility is up to 2 × 105cm2/ (V s), electric conductivity exceedes current any high-temperature superconductor material
Material, but also with properties such as room-temperature quantum Hall effect.Therefore graphene often replaces other carbon Nano fillings as preferable
Filler prepares highly conductive, tough polymer matrix composite, and in solar cell, ultracapacitor, sensor, biological material
Expect, be electromagnetically shielded contour performance, have wide prospect in high application of function.
With the quickening of global industry paces, curbing environmental pollution becomes extremely important, and some semi-conducting materials start
Applied to environmental pollution improvement and develop rapidly.Research has shown that many semiconductor oxide materials all have photocatalysis
Activity, under illumination condition, semiconductor oxide materials surface can effectively be obtained oxidation Decomposition organic matter, gone back by after activation
Original weight metal ion, killing bacterium and elimination peculiar smell.Because photocatalysis technology can at room temperature be reacted using solar energy, than
It is more economical, can by organic pollution permineralization Cheng Shui and inorganic ions, non-secondary pollution, so have traditional high temperature, often
Catalysis technique and the incomparable tempting glamour of adsorption technology are advised, is that a kind of green environment with broad prospect of application administers skill
Art.The semi-conducting material with photocatalytic activity having now been found that is in these semiconductor catalysis materials, and lanthanium titanate is a kind of new
Type catalysis material, energy gap is 3.8eV, belongs to the semi-conducting material of broad stopband.Lanthanium titanate is with perovskite structure
Lamellar compound.Some researchs in recent years find that the lanthanium titanate of this layer structure has good high-temperature stability, high
Chemical stability, higher photocatalysis efficiency makes it have in numerous areas such as photocatalysis, ion exchange, absorption and separation
Wide application prospect, and be expected in high-quantum efficiency photochemical catalyst of future generation turn into main flow.It is well known that, such as
Photo-generated carrier of the nano-photocatalyst of lanthanium titanate produced by after ultraviolet excitation easily occurs empty during transmission
Cave-electronics significantly reduces the quantum efficiency of material, causes undesirable photocatalysis effect to being combined phenomenon.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of photocatalysis performance is good
The preparation method for the photocatalyst material that good, efficiency of light absorption is improved.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of the photocatalyst material based on graphene, its preparation process is as follows：
Step 1, lanthanum chloride is added into absolute ethyl alcohol, then adds titanium source, continue to stir to formation colloidal sol；
Step 2, colloidal sol is put into aerated reaction 2-5h in reactor, then carries out sealing warming circulating aerated reaction 10-15h,
Filtration washing is carried out after natural cooling, mixed sediment is obtained；
Step 3, the mixed sediment of step 2 is put into absolute ethyl alcohol, sequentially adds dispersant and graphene powder, ultrasound
2-4h reactions obtain scattered precursor liquid；
Step 4, scattered precursor liquid is put into illumination reaction kettle and reacts 2-5h, filtering can obtain photocatalysis material after reaction terminates
Material.
The preparation formula of the photocatalyst material is as follows：
10-15 parts of lanthanum chloride, 11-18 parts of titanium source, 2-5 parts of dispersant, 3-7 parts of graphene powder.
The titanium source uses one kind in titanium chloride, acetic acid titanium, titanium sulfate.
The dispersant uses polyvinylpyrrolidone or 1-METHYLPYRROLIDONE.
Mixing speed in step 1 is 500-1500r/min.The step is used as dissolution solvent by absolute ethyl alcohol, can
Lanthanum chloride and titanium source are uniformly distributed in a solvent, while absolute ethyl alcohol can prevent titanium ion from agglomerating into.
Aerated reaction in step 2 is using ammonia and the mixture of carbon dioxide, the ammonia and carbon dioxide gas
The ratio of body is 1：0.3-1.8, the flow velocity of the aerated reaction is 10-15mL/min, and the aerated reaction temperature is 60-80
℃；Aerated reaction can be added into solution by ammonia and carbon dioxide using aerated reaction, lanthanum salt can not only be formed and sunk
Form sediment and titanium salt precipitation, while having good dispersion effect.
The aerating gas of sealing warming circulating aerated reaction in step 2 is nitrogen, and the flow velocity of the aerated reaction is 10-
15mL/min, the aerated reaction temperature is 100-130 DEG C, and the pressure is 1-5MPa；It is anti-using sealing warming circulating aeration
It should be able to ensure that the reaction between lanthanum salt and titanium salt forms lanthanium titanate, and lanthanium titanate good dispersion, Stability Analysis of Structures.
Washing methods is in step 2：First filtered using soaked in absolute ethyl alcohol, 2-3 cleaning then carried out using distilled water,
Secondary cleaning is finally carried out using ethanol, dried naturally after filtering.
Supersonic frequency in step 3 is 10-21kHz, and the ultrasonic temperature is 40-60 DEG C, and the ultrasonic reaction is water-bath
Thermostatic ultrasonic reacts；It ensure that absolute ethyl alcohol is not distributed using ultrasonic reaction, it is ensured that absolute ethyl alcohol film forming, formed well
Dispersiveness.
Illumination reaction kettle in step 4 uses UV illumination, and liquid electric is carried out while the illumination reaction kettle reaction
Solution backflow, the decomposition voltage is 4-7V, and the electrolysis flow velocity is 30-140mL/min；Can not only by the way of illumination reaction
Photochemical catalyst is enough excited, while the attachment structure of can also degrade dispersant, graphene and lanthanium titanate, while using liquid electrolytic
The mode of backflow can increase liquid active, increase photochemical catalyst excitating performance.
Compared with prior art, the invention has the characteristics that：
1）The present invention utilizes La2Ti2O7The further reduced graphene of ability of the photo catalytic reduction in situ of nanometer, reduces graphene
The defect of material, while adding graphene and La2Ti2O7Nano material is directly contacted, and adds La2Ti2O7Nano material
Efficiency of light absorption；
2）Graphene-La prepared by the present invention2Ti2O7Nano composite material has the enhancing effect of obviously photocatalysis performance
Really, the performance advantage and application potential of graphene-based compound are shown.
Brief description of the drawings
Fig. 1 is graphene-La made from embodiment 12Ti2O7The ultravioletvisible absorption curve of nano composite material.
Fig. 2 be different condition under rhodamine B photocatalytic degradation surplus ratio with the time degradation curve.
Fig. 3 is graphene-La2Ti2O7Nano composite material and La2Ti2O7The UV-Vis absorption spectrums of nano material.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to
Following embodiments.
Embodiment 1：
A kind of preparation method of the photocatalyst material based on graphene, its preparation process is as follows：
Step 1, lanthanum chloride is added into absolute ethyl alcohol, then adds titanium source, continue to stir to formation colloidal sol；
Step 2, colloidal sol is put into aerated reaction 2h in reactor, then progress sealing warming circulating aerated reaction 10h, naturally cold
But filtration washing is carried out afterwards, obtains mixed sediment；
Step 3, the mixed sediment of step 2 is put into absolute ethyl alcohol, sequentially adds dispersant and graphene powder, ultrasound
2h reactions obtain scattered precursor liquid；
Step 4, scattered precursor liquid is put into illumination reaction kettle and reacts 2h, filtering can obtain photocatalysis material after reaction terminates
Material.
The preparation formula of the photocatalyst material is as follows：
10 parts of lanthanum chloride, 11 parts of titanium source, 2 parts of dispersant, 3 parts of graphene powder.
The titanium source uses titanium chloride.
The dispersant uses polyvinylpyrrolidone.
Mixing speed in step 1 is 500r/min.The step is used as dissolution solvent by absolute ethyl alcohol, can be by chlorination
Lanthanum is uniformly distributed in a solvent with titanium source, while absolute ethyl alcohol can prevent titanium ion from agglomerating into.
Aerated reaction in step 2 is using ammonia and the mixture of carbon dioxide, the ammonia and carbon dioxide gas
The ratio of body is 1：0.3, the flow velocity of the aerated reaction is 10mL/min, and the aerated reaction temperature is 60 DEG C.
The aerating gas of sealing warming circulating aerated reaction in step 2 is nitrogen, and the flow velocity of the aerated reaction is
10mL/min, the aerated reaction temperature is 100 DEG C, and the pressure is 1MPa.
Washing methods is in step 2：First filtered using soaked in absolute ethyl alcohol, 2 cleanings are then carried out using distilled water, most
Secondary cleaning is carried out using ethanol afterwards, dried naturally after filtering.
Supersonic frequency in step 3 is 10kHz, and the ultrasonic temperature is 40 DEG C, and the ultrasonic reaction is super for constant temperature water bath
Phonoresponse.
Illumination reaction kettle in step 4 uses UV illumination, and liquid electric is carried out while the illumination reaction kettle reaction
Solution backflow, the decomposition voltage is 4V, and the electrolysis flow velocity is 30mL/min.
Graphene-La2Ti2O7The research of photocatalysis performance is with rhodamine B（RhB）For target degradation product, in ultraviolet light
It is lower to carry out.Fig. 1 is graphene-La2Ti2O7The ultraviolet-ray visible absorbing light that RhB degrades during nano composite material photocatalyst
Spectrum.It can be seen that with the increase of ultraviolet lighting time, the intensity of RhB absorption spectrums significantly constantly weakens, this
Corresponding one phenomenon is graphene-La2Ti2O7Nano composite material is constantly degraded the process of rhodamine B, and when the time prolongs
When length is to 60min, RhB color disappears substantially, illustrates that RhB is completely degraded substantially.
Graphene-La2Ti2O7The humidification of the photocatalytic activity of nano composite material, except the degraded of compound in itself
Experiment is outer, has also been following contrast experiment：（1）Added with graphene-La2Ti2O7Stirred at the dark of nano composite photo-catalyst
The photocatalytic degradation curve of the RhB solution of 60 minutes；（2）Without the photocatalytic degradation of the RhB solution of any catalyst
Curve；（3）Only add La2Ti2O7The photocatalytic degradation curve of the RhB solution of nano composite material photocatalyst；（4）Plus
The photocatalytic degradation curve of the RhB solution of P25 titanium dioxide photocatalysts.After this several groups of contrast tests are carried out, lead to
The surplus ratio versus time curve crossed after the rhodamine B photocatalytic degradation for calculating and having obtained such as Fig. 2.Without appoint
The blank RhB samples and addition graphene-La of what catalyst2Ti2O7The compound photochemical catalyst feelings that still no light is tested
Under condition, RhB solution is difficult to degrade.Other three samples are after degraded 20 minutes, graphene-La2Ti2O7Composite wood
The degradation rate for expecting photocatalytic degradation rhodamine B solution is 60%, and simple La2Ti2O7Nanometer sheet and P25 are less than 30%；
After light urges degraded 40 minutes, graphene-La2Ti2O7The degradation rate of the degraded rhodamine B of composite has exceeded 90%, its
His two kinds of materials are less than 60%；Finally after 60 minutes, it can be seen that graphene-La2Ti2O7Composite is by RhB
It is degradable, and the not degradable RhB of other two kinds of materials.Thus result is visible, graphene-La2Ti2O7Composite
With the obvious excellent photocatalytic degradation capability in other two kinds of materials.
Fig. 3 is graphene-La2Ti2O7Nano composite material and La2Ti2O7The UV-Vis absorption spectrums of nano material, from
It can be seen from the figure that, graphene-La2Ti2O7The Absorption edge of compound is relative to La2Ti2O7Nano material sample does not occur bright
The phenomenon of aobvious displacement, illustrates that the addition of graphene does not have influence on La2Ti2O7The energy gap of nanometer sheet, still, graphene
Add and cause La2Ti2O7The absorption intensity of the ultraviolet light of nanometer sheet is remarkably reinforced, and this phenomenon shows graphene-La2Ti2O7It is compound
Photochemical catalyst can utilize more ultraviolet lights.
Embodiment 2：
A kind of preparation method of the photocatalyst material based on graphene, its preparation process is as follows：
Step 1, lanthanum chloride is added into absolute ethyl alcohol, then adds titanium source, continue to stir to formation colloidal sol；
Step 2, colloidal sol is put into aerated reaction 5h in reactor, then progress sealing warming circulating aerated reaction 15h, naturally cold
But filtration washing is carried out afterwards, obtains mixed sediment；
Step 3, the mixed sediment of step 2 is put into absolute ethyl alcohol, sequentially adds dispersant and graphene powder, ultrasound
4h reactions obtain scattered precursor liquid；
Step 4, scattered precursor liquid is put into illumination reaction kettle and reacts 5h, filtering can obtain photocatalysis material after reaction terminates
Material.
The preparation formula of the photocatalyst material is as follows：
15 parts of lanthanum chloride, 18 parts of titanium source, 5 parts of dispersant, 7 parts of graphene powder.
The titanium source uses acetic acid titanium.
The dispersant uses 1-METHYLPYRROLIDONE.
Mixing speed in step 1 is 1500r/min.The step is used as dissolution solvent by absolute ethyl alcohol, can be by chlorine
Change lanthanum to be uniformly distributed in a solvent with titanium source, while absolute ethyl alcohol can prevent titanium ion from agglomerating into.
Aerated reaction in step 2 is using ammonia and the mixture of carbon dioxide, the ammonia and carbon dioxide gas
The ratio of body is 1：1.8, the flow velocity of the aerated reaction is 15mL/min, and the aerated reaction temperature is 80 DEG C.
The aerating gas of sealing warming circulating aerated reaction in step 2 is nitrogen, and the flow velocity of the aerated reaction is
15mL/min, the aerated reaction temperature is 130 DEG C, and the pressure is 5MPa.
Washing methods is in step 2：First filtered using soaked in absolute ethyl alcohol, 3 cleanings are then carried out using distilled water, most
Secondary cleaning is carried out using ethanol afterwards, dried naturally after filtering.
Supersonic frequency in step 3 is 21kHz, and the ultrasonic temperature is 60 DEG C, and the ultrasonic reaction is super for constant temperature water bath
Phonoresponse.
Illumination reaction kettle in step 4 uses UV illumination, and liquid electric is carried out while the illumination reaction kettle reaction
Solution backflow, the decomposition voltage is 7V, and the electrolysis flow velocity is 140mL/min.
Embodiment 3：
A kind of preparation method of the photocatalyst material based on graphene, its preparation process is as follows：
Step 1, lanthanum chloride is added into absolute ethyl alcohol, then adds titanium source, continue to stir to formation colloidal sol；
Step 2, colloidal sol is put into aerated reaction 4h in reactor, then progress sealing warming circulating aerated reaction 13h, naturally cold
But filtration washing is carried out afterwards, obtains mixed sediment；
Step 3, the mixed sediment of step 2 is put into absolute ethyl alcohol, sequentially adds dispersant and graphene powder, ultrasound
3h reactions obtain scattered precursor liquid；
Step 4, scattered precursor liquid is put into illumination reaction kettle and reacts 3h, filtering can obtain photocatalysis material after reaction terminates
Material.
The preparation formula of the photocatalyst material is as follows：
13 parts of lanthanum chloride, 16 parts of titanium source, 4 parts of dispersant, 5 parts of graphene powder.
The titanium source uses titanium sulfate.
The dispersant uses polyvinylpyrrolidone.
Mixing speed in step 1 is 1100r/min.The step is used as dissolution solvent by absolute ethyl alcohol, can be by chlorine
Change lanthanum to be uniformly distributed in a solvent with titanium source, while absolute ethyl alcohol can prevent titanium ion from agglomerating into.
Aerated reaction in step 2 is using ammonia and the mixture of carbon dioxide, the ammonia and carbon dioxide gas
The ratio of body is 1：1.3, the flow velocity of the aerated reaction is 13mL/min, and the aerated reaction temperature is 70 DEG C.
The aerating gas of sealing warming circulating aerated reaction in step 2 is nitrogen, and the flow velocity of the aerated reaction is
13mL/min, the aerated reaction temperature is 120 DEG C, and the pressure is 3MPa.
Washing methods is in step 2：First filtered using soaked in absolute ethyl alcohol, 2 cleanings are then carried out using distilled water, most
Secondary cleaning is carried out using ethanol afterwards, dried naturally after filtering.
Supersonic frequency in step 3 is 14kHz, and the ultrasonic temperature is 50 DEG C, and the ultrasonic reaction is super for constant temperature water bath
Phonoresponse.
Illumination reaction kettle in step 4 uses UV illumination, and liquid electric is carried out while the illumination reaction kettle reaction
Solution backflow, the decomposition voltage is 5V, and the electrolysis flow velocity is 120mL/min.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel are according to the announcement of the present invention, and not departing from improvement and modification that scope made all should be the present invention's
Within protection domain.
Claims (10)
1. a kind of preparation method of the photocatalyst material based on graphene, it is characterised in that its preparation process is as follows：
Step 1, lanthanum chloride is added into absolute ethyl alcohol, then adds titanium source, continue to stir to formation colloidal sol；
Step 2, colloidal sol is put into aerated reaction 2-5h in reactor, then carries out sealing warming circulating aerated reaction 10-15h,
Filtration washing is carried out after natural cooling, mixed sediment is obtained；
Step 3, the mixed sediment of step 2 is put into absolute ethyl alcohol, sequentially adds dispersant and graphene powder, ultrasound
2-4h reactions obtain scattered precursor liquid；
Step 4, scattered precursor liquid is put into illumination reaction kettle and reacts 2-5h, filtering can obtain photocatalysis material after reaction terminates
Material.
2. a kind of preparation method of photocatalyst material based on graphene according to claim 1, it is characterised in that institute
The preparation formula for stating photocatalyst material is as follows：
10-15 parts of lanthanum chloride, 11-18 parts of titanium source, 2-5 parts of dispersant, 3-7 parts of graphene powder.
3. a kind of preparation method of photocatalyst material based on graphene according to claim 2, it is characterised in that institute
Titanium source is stated using one kind in titanium chloride, acetic acid titanium, titanium sulfate.
4. a kind of preparation method of photocatalyst material based on graphene according to claim 2, it is characterised in that institute
Dispersant is stated using polyvinylpyrrolidone or 1-METHYLPYRROLIDONE.
5. a kind of preparation method of photocatalyst material based on graphene according to claim 1, it is characterised in that step
Mixing speed in rapid 1 is 500-1500r/min.
6. a kind of preparation method of photocatalyst material based on graphene according to claim 1, it is characterised in that step
Aerated reaction in rapid 2 is using ammonia and the mixture of carbon dioxide, and the ratio of the ammonia and carbon dioxide is
1：0.3-1.8, the flow velocity of the aerated reaction is 10-15mL/min, and the aerated reaction temperature is 60-80 DEG C.
7. a kind of preparation method of photocatalyst material based on graphene according to claim 1, it is characterised in that step
The aerating gas of sealing warming circulating aerated reaction in rapid 2 is nitrogen, and the flow velocity of the aerated reaction is 10-15mL/min,
The aerated reaction temperature is 100-130 DEG C, and the pressure is 1-5MPa.
8. a kind of preparation method of photocatalyst material based on graphene according to claim 1, it is characterised in that step
Washing methods is in rapid 2：First filtered using soaked in absolute ethyl alcohol, 2-3 cleaning is then carried out using distilled water, finally using second
Alcohol carries out secondary cleaning, is dried naturally after filtering.
9. a kind of preparation method of photocatalyst material based on graphene according to claim 1, it is characterised in that step
Supersonic frequency in rapid 3 is 10-21kHz, and the ultrasonic temperature is 40-60 DEG C, and the ultrasonic reaction is that constant temperature water bath ultrasound is anti-
Should.
10. a kind of preparation method of photocatalyst material based on graphene according to claim 1, it is characterised in that
Illumination reaction kettle in step 4 uses UV illumination, and liquid electrolytic backflow, institute are carried out while the illumination reaction kettle reaction
Decomposition voltage is stated for 4-7V, the electrolysis flow velocity is 30-140mL/min.
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| CN108187653A (en) * | 2018-01-11 | 2018-06-22 | 绍兴文理学院 | Preparation method of graphene-based photocatalytic material |
| CN108246278A (en) * | 2018-01-08 | 2018-07-06 | 沈阳理工大学 | A kind of preparation method of environmental purification function type expanded vermiculite particle |
| CN109248676A (en) * | 2018-09-19 | 2019-01-22 | 福州大学 | A kind of photocatalytic synthesis is at PbTiO3The method of/RGO composite material |
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| CN108000971A (en) * | 2017-11-30 | 2018-05-08 | 朱明君 | A kind of air filter cloth of graphene-containing material and bamboo fiber |
| CN108126682A (en) * | 2017-12-20 | 2018-06-08 | 河北燕园众欣石墨烯科技有限公司 | A kind of graphene hydridization photochemical catalyst hydrogel |
| CN108126682B (en) * | 2017-12-20 | 2020-11-20 | 河北燕园众欣石墨烯科技有限公司 | Graphene hybrid photocatalyst hydrogel |
| CN108246278A (en) * | 2018-01-08 | 2018-07-06 | 沈阳理工大学 | A kind of preparation method of environmental purification function type expanded vermiculite particle |
| CN108246278B (en) * | 2018-01-08 | 2020-11-17 | 沈阳理工大学 | Preparation method of environment purification functional expanded vermiculite particles |
| CN108187653A (en) * | 2018-01-11 | 2018-06-22 | 绍兴文理学院 | Preparation method of graphene-based photocatalytic material |
| CN109248676A (en) * | 2018-09-19 | 2019-01-22 | 福州大学 | A kind of photocatalytic synthesis is at PbTiO3The method of/RGO composite material |
| CN109248676B (en) * | 2018-09-19 | 2020-04-17 | 福州大学 | Photocatalytic synthesis of PbTiO3Method for preparing/RGO composite material |
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