CN109772300A - MnO (MnO)x-CeO2Preparation method of-graphene aerogel catalyst material - Google Patents
MnO (MnO)x-CeO2Preparation method of-graphene aerogel catalyst material Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000004964 aerogel Substances 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000000017 hydrogel Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 150000002696 manganese Chemical class 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 9
- 238000006073 displacement reaction Methods 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000000703 Cerium Chemical class 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- -1 cerium salt Chemical class 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 229910016978 MnOx Inorganic materials 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 241000143437 Aciculosporium take Species 0.000 description 5
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000012814 acoustic material Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
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Abstract
The invention relates to MnOx‑CeO2-a method for preparing a graphene aerogel catalyst material. Through sol-gel process, hydrothermal or chemical reduction of RE oxide CeO2And transition metal oxide MnOxCompounding with graphene aerogel to finally prepare MnO with excellent and efficient catalytic performancex‑CeO2-a graphene aerogel composite. The load of the nano oxide particles improves the agglomeration among graphene sheets, and the graphene aerogel is used as a carrier, so that more catalytic active sites are provided for active components, the dispersity of the active oxide nanoparticles is improved, and the active components are in contact with reactants more fully. Such a catalyst materialThe material can effectively overcome the defects of single-component materials, thereby greatly improving the catalytic efficiency. Prepared MnOx‑CeO2The specific surface area of the/graphene aerogel catalyst material is 119-145 m2And the catalytic conversion rate of NO is 89-99%.
Description
Technical field
The invention belongs to the preparation process fields of nano-porous materials, are related to a kind of with hydrophobic, low-density, high-ratio surface
Accumulate and have the MnO of catalytic activityx-CeO2The preparation method of graphene aerogel catalyst material.
Background technique
Numerous studies prove that Mn-Ce oxide can provide electronics at low temperature, during the reaction the oxygen of different valence state
Compound can mutually convert, and be conducive to the progress of redox reaction.But due to oxide nano particles easily aggregately stacked,
And its specific surface area is smaller, catalytic efficiency is not high.Aerogel material is the manmade materials that known density is minimum in the world, is had
The title of " solid-state smog ".Other than extremely low apparent density, aeroge also has high porosity, extremely low thermal conductivity and big ratio
The features such as surface area.It is with a wide range of applications in many fields, such as heat-barrier material, acoustic material, optical device, super electricity
Container etc..However, the high porosity of aeroge makes this material very fragile, the mechanical property in actual application environment
Difference, this severely limits application of the aeroge in many fields.Graphene possesses higher mechanical strength and greatly theory
Specific surface area, a large amount of functional groups on surface and active site and good hydrophobicity, make it can be used as the materials such as adsorbent, catalyst
Material.But since there are strong pi-pi bonds, and graphene to be caused easily to reunite in aqueous solution for graphene film interlayer, actual specific surface
Product is much smaller than theoretical value.Three-dimensional grapheme aeroge inherits the excellent properties of graphene and aeroge, and surface has numerous again
Active site, therefore extensive attention is received in catalytic field.
Summary of the invention
A kind of MnO is provided the purpose of the present invention is improving the deficiencies in the prior artx-CeO2Graphene aerogel catalyst
The preparation method of material.
The present invention is based on graphene aerogel high porosity, bigger serface, high electron mobility, there is catalytic active site
Point and transition metal oxide MnOxWith rare earth oxide CeO2In advantages such as catalytic field activity with higher, by molten
Glue-gel process, hydrothermal reduction method or chemical reduction method, by rare earth oxide CeO2With transition metal oxide MnOxWith graphite
Alkene aeroge is compound, prepares the MnO with excellent, efficient catalytic performancex-CeO2/ graphene aerogel catalyst material.
The load of nano-oxide particles improves the reunion of graphene film interlayer, and graphene aerogel is as carrier, is active group
Divide and provide more active sites, and improve the dispersibility of activating oxide nanoparticle, makes active component more
Come into full contact with reactant.This catalyst material can effectively solve the defect of single component material, to greatly improve catalysis effect
Rate.Prepared MnOx-CeO2/ graphene aerogel catalyst material specific surface area is 119~145m2/ g, NO catalytic conversion
It is 89~99%.
The technical solution of the present invention is as follows: a kind of MnOx-CeO2The preparation method of graphene aerogel catalyst material, tool
Steps are as follows for body:
(1) graphene oxide GO is dispersed in deionized water during stirring, is uniformly mixing to obtain oxidation
Graphene aqueous solution；
(2) ammonium hydroxide is added dropwise in the graphene oxide water solution in step (1) and adjusts pH, stir at room temperature, be allowed to complete
Mixing, obtains mixed solution A；
(3) it disperses manganese salt and cerium salt in deionized water during stirring, obtains mixed solution after mixing evenly
B；
(4) B solution in step (3) is added drop-wise in the solution A in step (2), at room temperature stirring a period of time, and surpassed
Sound dispersion a period of time, obtain mixed dispersion liquid；
(5) dispersion liquid in step (4) is poured into and carries out hydro-thermal reaction in hydrothermal reaction kettle liner, obtain MnOx-CeO2-
Graphene hydrogel；
(6) by the MnO in step (5)x-CeO2Graphene hydrogel takes out out of furnace, is put into aging in deionized water, often
A deionized water, which is replaced, every a period of time carries out solvent displacement；
(7) the good sample of the solution replacement in step (6) is taken out, after freeze-drying, obtains MnOx-CeO2Graphene
Aerogel catalyst material.
Graphene oxide concentration in preferred steps (1) is 4~8mg/ml.
PH value in preferred steps (2) is 10~12.
Manganese salt described in preferred steps (3) is manganese nitrate or manganese chloride；The cerium salt is cerous nitrate or cerium chloride；Manganese
The molar ratio of Mn:Ce is 1:(0.25~4 in salt and cerium salt)；Manganese salt and cerium salt be always added quality and graphene oxide quality it
Than for (1~3): 1；Deionized water additional amount is equal with deionized water additional amount in step (1).
Speed of agitator in preferred steps (4) is 600~1000rpm, and the time is 2~4h；Supersonic frequency be 80~
120kHz, time are 20~50min.
In hydro-thermal reaction in preferred steps (5), hydrothermal temperature be 160~190 DEG C, the hydro-thermal reaction time be 11~
15h。
Ageing time in preferred steps (6) is 4~8h, and solvent replaces interval time as 10~14h, and displacement number is 4
~8 times.
The temperature that hydrogel is freeze-dried in preferred steps (7) is -50~-60 DEG C, time of freeze-drying is 24~
48h。
MnO produced by the present inventionx-CeO2The specific surface area of graphene aerogel catalyst material is 119~145g/cm3,
NO catalytic conversion is 89~99%.
The utility model has the advantages that
(1) by sol-gel technology, using hydrothermal reduction method or chemical reduction method, by rare earth oxide CeO2And mistake
Cross metal oxide MnO2It is compound with graphene aerogel, prepare the MnO with excellent, efficient catalytic performancex-CeO2Stone
Black alkene aerogel catalyst material.
(2) wherein, in MnOx-CeO2In graphene aerogel composite catalyst, active component nano-oxide
The load of grain is so that catalyst material not only catalytic activity with higher, but also can improve the reunion of graphene film interlayer.
(3) graphene aerogel is as carrier, specific surface area with higher, and provides more for active component
Active site, while the dispersibility of activating oxide nanoparticle is also improved, come into full contact with active component more instead
Answer object.
(4)MnOx-CeO2Graphene aerogel catalyst material can effectively solve the defect of single component material, thus greatly
Width improves catalytic efficiency.
Detailed description of the invention
Fig. 1 is MnO prepared in example 1x-CeO2The XRD diagram of graphene aerogel catalyst material.
Fig. 2 is MnO prepared in example 2x-CeO2The pictorial diagram of graphene aerogel catalyst material.
Specific embodiment
The present invention will be further explained below with reference to examples, but protection scope is not limited to this.
Example 1
In the deionized water that 40mg graphene oxide (GO) is dispersed in 10ml during stirring in beaker,
It obtains 4mg/ml graphene oxide water solution after mixing evenly at room temperature, ammonium hydroxide is added dropwise into graphene oxide water solution and makes pH
Reach 10, stir at room temperature, is allowed to be thoroughly mixed, obtains mixed solution A.Take another beaker that the deionized water of 10ml is added,
(molar ratio of Mn:Ce is 1:1, manganese salt and cerium salt to the cerium nitrate hexahydrate of the manganese nitrate of addition 12mg and 28mg in deionized water
Total quality and the mass ratio of graphene oxide of being added is 1:1), mixed solution B is obtained after mixing evenly.B solution is added drop-wise to A
In solution, revolving speed is 1000rpm at room temperature, stirs 2h, and frequency is 120kHz ultrasonic disperse 50min, obtains mixed dispersion liquid.
Dispersion liquid is poured into hydrothermal reaction kettle liner, in 160 DEG C of hydro-thermal reaction 15h, obtains MnOx-CeO2Graphene hydrogel.Deng
After hydrothermal reaction kettle temperature is fallen, hydrogel is taken out out of furnace, aging 4h is put into deionized water, replaces one every 10h
Secondary deionized water carries out solvent displacement, and replaces 8 times.The sample replaced is taken out, is freeze-dried at -50 DEG C and takes afterwards for 24 hours
Out, MnO is obtainedx-CeO2Graphene aerogel catalyst material.Prepared MnOx-CeO2Graphene aerogel catalyst material
Material specific surface area is 145m2/ g, NO catalytic conversion are 99%.
Fig. 1 is MnOx-CeO2The XRD diagram of graphene aerogel catalyst material, it can be seen that MnO occurx、CeO2With
And the characteristic peak of graphene.
Example 2
In the deionized water that 50mg graphene oxide (GO) is dispersed in 10ml during stirring in beaker,
It obtains 5mg/ml graphene oxide water solution after mixing evenly at room temperature, ammonium hydroxide is added dropwise into graphene oxide water solution and makes pH
Reach 10, stir at room temperature, is allowed to be thoroughly mixed, obtains mixed solution A.Take another beaker that the deionized water of 10ml is added,
(molar ratio of Mn:Ce is 1:2, manganese salt and cerium to the cerium nitrate hexahydrate of the tetrahydrate manganese chloride of addition 9mg and 41mg in deionized water
It is 1:1 that quality and the mass ratio of graphene oxide, which is always added, in salt), mixed solution B is obtained after mixing evenly.B solution is added dropwise
Into solution A, revolving speed is 900rpm at room temperature, stirs 2.5h, and frequency is 110kHz ultrasonic disperse 40min, obtains mixing point
Dispersion liquid.Dispersion liquid is poured into hydrothermal reaction kettle liner, in 165 DEG C of hydro-thermal reaction 14h, obtains MnOx-CeO2Graphene water-setting
Glue.After equal hydrothermal reaction kettles temperature is fallen, hydrogel is taken out out of furnace, aging 5h is put into deionized water, more every 11h
It changes a deionized water and carries out solvent displacement, and replace 7 times.The sample replaced is taken out, is freeze-dried 30h at -50 DEG C
After take out, obtain MnOx-CeO2Graphene aerogel catalyst material.Prepared MnOx-CeO2Graphene aerogel catalysis
Agent material specific surface area is 139m2/ g, NO catalytic conversion are 98%.
Fig. 2 is prepared MnOx-CeO2The pictorial diagram of graphene aerogel catalyst material, it can be seen that formation finishes
The complete graphene aerogel composite material of structure.
Example 3
In the deionized water that 60mg graphene oxide (GO) is dispersed in 10ml during stirring in beaker,
It obtains 6mg/ml graphene oxide water solution after mixing evenly at room temperature, ammonium hydroxide is added dropwise into graphene oxide water solution and makes pH
Reach 11, stir at room temperature, is allowed to be thoroughly mixed, obtains mixed solution A.Take another beaker that the deionized water of 10ml is added,
(molar ratio of Mn:Ce is 1:4, manganese salt and cerium salt to the cerium chloride seven-hydrate of the manganese nitrate of addition 14mg and 106mg in deionized water
Total quality and the mass ratio of graphene oxide of being added is 2:1), mixed solution B is obtained after mixing evenly.B solution is added drop-wise to A
In solution, revolving speed is 800rpm at room temperature, stirs 3h, and frequency is 100kHz ultrasonic disperse 35min, obtains mixed dispersion liquid.
Dispersion liquid is poured into hydrothermal reaction kettle liner, in 170 DEG C of hydro-thermal reaction 13h, obtains MnOx-CeO2Graphene hydrogel.Deng
After hydrothermal reaction kettle temperature is fallen, hydrogel is taken out out of furnace, aging 6h is put into deionized water, replaces one every 12h
Secondary deionized water carries out solvent displacement, and replaces 6 times.The sample replaced is taken out, is taken after being freeze-dried 36h at -55 DEG C
Out, MnO is obtainedx-CeO2Graphene aerogel catalyst material.Prepared MnOx-CeO2Graphene aerogel catalyst material
Material specific surface area is 134m2/ g, NO catalytic conversion are 98%.
Example 4
In the deionized water that 70mg graphene oxide (GO) is dispersed in 10ml during stirring in beaker,
It obtains 7mg/ml graphene oxide water solution after mixing evenly at room temperature, ammonium hydroxide is added dropwise into graphene oxide water solution and makes pH
Reach 11, stir at room temperature, is allowed to be thoroughly mixed, obtains mixed solution A.Take another beaker that the deionized water of 10ml is added,
(molar ratio of Mn:Ce is 1:0.5, manganese salt to the cerium nitrate hexahydrate of the tetrahydrate manganese chloride of addition 67mg and 73mg in deionized water
The mass ratio that quality and graphene oxide are always added with cerium salt is 2:1), mixed solution B is obtained after mixing evenly.By B solution
It is added drop-wise in solution A, revolving speed is 700rpm at room temperature, stirs 3.5h, and frequency is 90kHz ultrasonic disperse 30min, is mixed
Dispersion liquid.Dispersion liquid is poured into hydrothermal reaction kettle liner, in 180 DEG C of hydro-thermal reaction 12h, obtains MnOx-CeO2Graphene water
Gel.After equal hydrothermal reaction kettles temperature is fallen, hydrogel is taken out out of furnace, aging 7h is put into deionized water, every 13h
It replaces a deionized water and carries out solvent displacement, and replace 5 times.The sample replaced is taken out, is freeze-dried at -55 DEG C
It is taken out after 42h, obtains MnOx-CeO2Graphene aerogel catalyst material.Prepared MnOx-CeO2Graphene aerogel
Catalyst material specific surface area is 128m2/ g, NO catalytic conversion are 93%.
Example 5
In the deionized water that 80mg graphene oxide (GO) is dispersed in 10ml during stirring in beaker,
It obtains 8mg/ml graphene oxide water solution after mixing evenly at room temperature, ammonium hydroxide is added dropwise into graphene oxide water solution and makes pH
Reach 12, stir at room temperature, is allowed to be thoroughly mixed, obtains mixed solution A.Take another beaker that the deionized water of 10ml is added,
In deionized water be added 148mg manganese nitrate and 92mg cerium nitrate hexahydrate (molar ratio of Mn:Ce be 1:0.25, manganese salt and
It is 3:1 that quality and the mass ratio of graphene oxide, which is always added, in cerium salt), mixed solution B is obtained after mixing evenly.B solution is dripped
It is added in solution A, revolving speed is 600rpm at room temperature, stirs 4h, and frequency is 80kHz ultrasonic disperse 20min, obtains mixing dispersion
Liquid.Dispersion liquid is poured into hydrothermal reaction kettle liner, in 190 DEG C of hydro-thermal reaction 11h, obtains MnOx-CeO2Graphene hydrogel.
After equal hydrothermal reaction kettles temperature is fallen, hydrogel is taken out out of furnace, aging 8h is put into deionized water, is replaced every 14h
Deionized water carries out solvent displacement, and replaces 4 times.The sample replaced is taken out, after being freeze-dried 48h at -60 DEG C
It takes out, obtains MnOx-CeO2Graphene aerogel catalyst material.Prepared MnOx-CeO2Graphene aerogel catalyst
Material specific surface area is 119m2/ g, NO catalytic conversion are 89%.
Claims (9)
1. a kind of MnOx-CeO2The preparation method of graphene aerogel catalyst material, the specific steps of which are as follows:
(1) graphene oxide GO is dispersed in deionized water during stirring, is uniformly mixing to obtain graphite oxide
Aqueous solution；
(2) ammonium hydroxide is added dropwise in the graphene oxide water solution in step (1) and adjusts pH, stir at room temperature, be allowed to be thoroughly mixed,
Obtain mixed solution A；
(3) it disperses manganese salt and cerium salt in deionized water during stirring, obtains mixed solution B after mixing evenly；
(4) B solution in step (3) is added drop-wise in the solution A in step (2), at room temperature stirring a period of time, and ultrasound point
A period of time is dissipated, mixed dispersion liquid is obtained；
(5) dispersion liquid in step (4) is poured into and carries out hydro-thermal reaction in hydrothermal reaction kettle liner, obtain MnOx-CeO2Graphite
Alkene hydrogel；
(6) by the MnO in step (5)x-CeO2Graphene hydrogel takes out out of furnace, is put into aging in deionized water, Mei Geyi
The section time replaces a deionized water and carries out solvent displacement；
(7) the good sample of the solution replacement in step (6) is taken out, after freeze-drying, obtains MnOx-CeO2Graphene airsetting
Glue catalyst material.
2. preparation method according to claim 1, it is characterised in that graphene oxide concentration in step (1) is 4~
8mg/ml。
3. preparation method according to claim 1, it is characterised in that the pH value in step (2) is 10~12.
4. preparation method according to claim 1, it is characterised in that manganese salt described in step (3) is manganese nitrate or chlorination
Manganese；The cerium salt is cerous nitrate or cerium chloride；The molar ratio of Mn:Ce is 1:(0.25~4 in manganese salt and cerium salt)；Manganese salt and cerium
It is (1~3) that quality and the mass ratio of graphene oxide, which is always added, in salt: 1；Deionization in deionized water additional amount and step (1)
Water additional amount is equal.
5. preparation method according to claim 1, it is characterised in that speed of agitator in step (4) is 600~
1000rpm, time are 2~4h；Supersonic frequency is 80~120kHz, and the time is 20~50min.
6. preparation method according to claim 1, it is characterised in that in the hydro-thermal reaction in step (5), hydro-thermal reaction temperature
Degree is 160~190 DEG C, and the hydro-thermal reaction time is 11~15h.
7. preparation method according to claim 1, it is characterised in that the ageing time in step (6) is 4~8h, and solvent is set
Changing interval time is 10~14h, and displacement number is 4~8 times.
8. preparation method according to claim 1, it is characterised in that in step (7) hydrogel be freeze-dried temperature be-
50~-60 DEG C, the time of freeze-drying is 24~48h.
9. preparation method according to claim 1, it is characterised in that MnO obtainedx-CeO2Graphene aerogel catalyst
The specific surface area of material is 119~145g/cm3, NO catalytic conversion is 89~99%.
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| CN113198477A (en) * | 2021-04-27 | 2021-08-03 | 南京工业大学 | Co3O4Preparation method of-NiO-graphene aerogel catalyst material |
| CN113838679A (en) * | 2021-07-29 | 2021-12-24 | 北京化工大学 | CeO (CeO)2Composite MnOxPreparation and application of electrode material |
| CN113842923A (en) * | 2021-11-02 | 2021-12-28 | 北京科技大学 | Nanowire aerogel denitration catalyst with high sulfur resistance and preparation method thereof |
| CN114250096A (en) * | 2021-11-30 | 2022-03-29 | 盘锦北方沥青股份有限公司 | Complex ester type nano refrigerator oil and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102592841A (en) * | 2012-03-21 | 2012-07-18 | 南京邮电大学 | Preparation method for manganese dioxide three-dimensional graphene composite material with controllable appearance |
| WO2013132259A1 (en) * | 2012-03-09 | 2013-09-12 | Bio Nano Consulting | Graphene and graphene oxide aerogels/xerogels for co2 capture |
| CN104098089A (en) * | 2014-07-25 | 2014-10-15 | 西南民族大学 | Preparation method for doped graphene foams |
| CN104190409A (en) * | 2014-08-19 | 2014-12-10 | 南京师范大学 | Graphene-loaded titanium-based core-shell-structured low-temperature SCR sulfur-resisting catalyst and preparation method thereof |
| CN105562029A (en) * | 2015-12-23 | 2016-05-11 | 浙江天蓝环保技术股份有限公司 | Formation and preparation technique for low-temperature SCR (selective catalytic reduction) monolithic catalyst with high active component ratio |
| CN105749894A (en) * | 2016-04-10 | 2016-07-13 | 南昌航空大学 | Preparation method of three-dimensional graphene-titanium dioxide compound photocatalyst |
| CN106622046A (en) * | 2016-11-14 | 2017-05-10 | 江苏大学 | Ag/CeO2/graphene aerogel and preparation method and application thereof |
| CN107099692A (en) * | 2016-02-20 | 2017-08-29 | 金承黎 | A kind of fibre-reinforced aerogel-metallic composite and preparation method thereof |
| CN107416802A (en) * | 2017-09-11 | 2017-12-01 | 长沙小新新能源科技有限公司 | A kind of porous graphene cerium-carrying composite nano germicide and preparation method thereof |
| CN108147931A (en) * | 2018-01-18 | 2018-06-12 | 南方科技大学 | Burning rate catalyst and preparation method thereof |
| CN108905910A (en) * | 2018-07-05 | 2018-11-30 | 平顶山学院 | A kind of three-dimensional redox graphene/MnO2Composite material and preparation method |
| CN109331604A (en) * | 2018-11-16 | 2019-02-15 | 成都新柯力化工科技有限公司 | A kind of lamellar graphite alkenyl titanium dioxide air cleaning filter material and preparation method |
-
2019
- 2019-02-25 CN CN201910136202.1A patent/CN109772300A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013132259A1 (en) * | 2012-03-09 | 2013-09-12 | Bio Nano Consulting | Graphene and graphene oxide aerogels/xerogels for co2 capture |
| CN102592841A (en) * | 2012-03-21 | 2012-07-18 | 南京邮电大学 | Preparation method for manganese dioxide three-dimensional graphene composite material with controllable appearance |
| CN104098089A (en) * | 2014-07-25 | 2014-10-15 | 西南民族大学 | Preparation method for doped graphene foams |
| CN104190409A (en) * | 2014-08-19 | 2014-12-10 | 南京师范大学 | Graphene-loaded titanium-based core-shell-structured low-temperature SCR sulfur-resisting catalyst and preparation method thereof |
| CN105562029A (en) * | 2015-12-23 | 2016-05-11 | 浙江天蓝环保技术股份有限公司 | Formation and preparation technique for low-temperature SCR (selective catalytic reduction) monolithic catalyst with high active component ratio |
| CN107099692A (en) * | 2016-02-20 | 2017-08-29 | 金承黎 | A kind of fibre-reinforced aerogel-metallic composite and preparation method thereof |
| CN105749894A (en) * | 2016-04-10 | 2016-07-13 | 南昌航空大学 | Preparation method of three-dimensional graphene-titanium dioxide compound photocatalyst |
| CN106622046A (en) * | 2016-11-14 | 2017-05-10 | 江苏大学 | Ag/CeO2/graphene aerogel and preparation method and application thereof |
| CN107416802A (en) * | 2017-09-11 | 2017-12-01 | 长沙小新新能源科技有限公司 | A kind of porous graphene cerium-carrying composite nano germicide and preparation method thereof |
| CN108147931A (en) * | 2018-01-18 | 2018-06-12 | 南方科技大学 | Burning rate catalyst and preparation method thereof |
| CN108905910A (en) * | 2018-07-05 | 2018-11-30 | 平顶山学院 | A kind of three-dimensional redox graphene/MnO2Composite material and preparation method |
| CN109331604A (en) * | 2018-11-16 | 2019-02-15 | 成都新柯力化工科技有限公司 | A kind of lamellar graphite alkenyl titanium dioxide air cleaning filter material and preparation method |
Non-Patent Citations (5)
| Title |
|---|
| HUANWEN WANG ET AL.: "One-step preparationofsingle-crystalline Fe2O3 particles/graphenecomposite hydrogels ashighperformanceanode materials forsupercapacitors", 《NANO ENERGY》 * |
| 唐熠: "纳米MnO2石墨烯气凝胶复合材料的制备及其超级电容特性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 焦金珍: "石墨烯负载金属氧化物催化剂的制备及其低温NH3-SCR性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 胡明江等: "MnOx-CeO2/ACF型催化剂低温去除柴油机NOx研究", 《燃烧科学与技术》 * |
| 黄利华等: "MnOx的掺杂对CeO2/AC催化剂NH3选择性催化还原NOx性能的影响", 《功能材料》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111804296A (en) * | 2020-07-10 | 2020-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ozone catalyst for removing peculiar smell, product and application thereof |
| CN111804296B (en) * | 2020-07-10 | 2023-03-31 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ozone catalyst for removing peculiar smell, product and application thereof |
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| CN113838679A (en) * | 2021-07-29 | 2021-12-24 | 北京化工大学 | CeO (CeO)2Composite MnOxPreparation and application of electrode material |
| CN113842923A (en) * | 2021-11-02 | 2021-12-28 | 北京科技大学 | Nanowire aerogel denitration catalyst with high sulfur resistance and preparation method thereof |
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