CN109052451A - A kind of cerium dioxide nano piece and its preparation method and application - Google Patents
A kind of cerium dioxide nano piece and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of cerium dioxide nano piece and its preparation method and application, the preparation method includes the following steps: that (1) precipitates cerous nitrate aqueous solution using alkaline solution, obtains cerium hydroxide nano piece presoma；(2) cerium hydroxide nano piece presoma obtained by dry, calcination steps (1), obtains cerium dioxide nano piece；Step (1) described alkaline solution includes sodium hydroxide solution and/or potassium hydroxide solution；The molar ratio of hydroxide ion and cerous nitrate in the cerous nitrate aqueous solution is (8-27) in the alkaline solution: 1.The obtained cerium dioxide nano piece of the present invention can be used as a variety of nano metal palladium/supporters, in the energy, environment and the great application prospect of catalytic field.The present invention has many advantages, such as without the high-temperature high-pressure apparatus of reactions such as hydro-thermal, does not add any organic modifier or organic solvent, environmental-friendly, reaction condition is mild, at low cost, is conducive to industrial amplification production.
Description
Technical field
The invention belongs to field of composite material preparation field, it is related to a kind of nanocomposite and preparation method thereof and uses
On the way more particularly to a kind of cerium dioxide nano piece and its preparation method and application.
Background technique
Ce4+/Ce3+Redox transformation and Lacking oxygen abundant, make nano ceric oxide as catalyst and catalysis
Agent carrier has a wide range of applications in the fields such as the energy, environment and catalysis.The catalytic activity of nano ceric oxide is exposed with it
Crystal face it is closely related, as catalyst and catalyst carrier, (100) of ceria, (110) crystal face have compared with (111) crystalline substance
The higher activity in face, therefore the nano ceric oxide for preparing exposure high activity crystal face is known as the hot spot studied.Preparation nanometer at present
The method of ceria mainly has the precipitation method, water (solvent) thermal method, sol-gal process, microemulsion method etc..
Liu Zien etc. has delivered preparation and the catalytic performance of entitled different types of structure noble metal-cerium dioxide nano material
Article (Science Bulletin, 2015 (24): 2288-2303), this article points out nano Ce O2It is a kind of unique rare earth oxygen
Compound has excellent catalytic activity, good thermal stability and chemical stability and electronics, Lacking oxygen transmission capacity, often
It is used as the carrier of noble metal catalyst to promote the catalytic performance of material.Noble metal-ceria (M-CeO2) composite catalyzing
Agent is widely used in CO catalysis oxidation, water-gas shift, NOxReduction and the fields such as solid-oxide fuel cell, to controlling
Reason environmental pollution and solution energy crisis are made that significant contribution.CeO2There is complicated interaction between noble metal, this
Kind interaction is to M-CeO2The catalytic performance of composite catalyst has a major impact, and the structure type of M-CeO2 and it is this mutually
There is close relationship between effect, different structure types will affect the stability of catalyst, activity and selectivity etc..
Yan Chunhua etc. has delivered entitled Shape-selective synthesis and oxygen storage
Article (the Journal of of behavior of ceria nanopolyhedra, nanorods, and nanocubes
Physical Chemistry B, 2005,109 (51): 24380-24385), this article is prepared for the exposure not isomorphous with hydro-thermal method
The ceria of the polyhedron in face, cube and nanorod structure.
101407330 B of CN proposes a kind of method for preparing nano ceric oxide nanometer rods, the dioxy of this method preparation
Change cerium specific surface area with higher and catalyzing carbon monoxide activity, but this method length reaction time, resulting ceria knot
Crystalline substance is poor.The study found that there are a large amount of defects, specific surface area with higher and more for laminated structure ceria surface
Active site shows higher catalytic activity.
105668606 A of CN is that raw material is made under 360 DEG C of high temperature with cerium nitrate hexahydrate, enuatrol, oleyl amine, trioctylamine etc.
For square cerium dioxide nano piece；Preparation process is using a large amount of oil-dissolving solvent and needs the equipment such as high temperature and pressure,
The problems such as that there are energy consumptions is high, seriously polluted, safety.
106186036 B of CN, for raw material, is prepared with cerium nitrate hexahydrate, sodium fluoborate, sodium hydroxide etc. by hydro-thermal reaction
The hexagon cerium dioxide nano piece of thickness 8-10nm, side length 50-60nm.But the cerium dioxide nano piece of this method preparation is not
Only thickness is high, and the reaction time is long, and energy consumption is high.
103991891 B of CN 101734706 A and CN is all made of the precipitation method and has prepared flake nano ceria, but
Resulting nanometer titanium dioxide cerium tablet thickness is larger, and specific surface area is low.
Noble metal nano particles (such as Platinum Nanoparticles, gold, palladium) have very extensive in fields such as the energy, environment, biologies
Using.Since the big specific surface area of metal nanoparticle and high surface can make metal nanoparticle be easy to happen reunion now
As greatly reducing the reactivity of metal nanoparticle, limiting its application.Surfactant is to noble metal nano particles
Modification can effectively improve the dispersibility of nano particle, but a large amount of surfactant molecule occupies metal nanoparticle
Active site reduce the activity of noble metal nano particles, simultaneously to hinder the interaction of substrate molecule and nano particle
It is very big to environmental hazard using a large amount of surfactant in preparation process.Using cerium dioxide nano piece as carrier, by noble metal
Nanoparticulate particles, which load on cerium dioxide nano piece carrier, can effectively inhibit the reunion of metal nanoparticle while improve
Its reactivity.
Therefore it is multiple that a kind of low preparation cost, the ultra-thin cerium dioxide nano piece of simple process synthesis and its noble metal nano are designed
The preparation method of condensation material has a very important significance and wide application prospect.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of cerium dioxide nano piece and its preparation
Method and purposes.The large specific surface area of the cerium dioxide nano piece, surface-active site is abundant, can effectively load your gold
Metal nano-particle, the preparation method simple process, easy to operate, environment optimization, reaction condition is mild, is conducive to industrialization and puts
Mass production.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the preparation method includes such as the present invention provides a kind of preparation method of cerium dioxide nano piece
Lower step:
(1) cerous nitrate aqueous solution is precipitated using alkaline solution, obtains cerium hydroxide nano piece presoma；
(2) cerium hydroxide nano piece presoma obtained by dry, calcination steps (1), obtains cerium dioxide nano piece.
Step (1) described alkaline solution includes sodium hydroxide solution and/or potassium hydroxide solution.
The molar ratio of hydroxide ion and cerous nitrate in the cerous nitrate aqueous solution is (8-27) in the alkaline solution: 1,
Such as it can be 8:1,9:1,10:1,11:1,12:1,13:1,14:1,15:1,16:1,17:1,18:1,19:1,20:1,21:
1,22:1,23:1,24:1,25:1,26:1 or 27:1, preferably (10-25): 1, further preferably (12-21): 1.
The present invention by by sodium hydroxide solution and/or potassium hydroxide solution composition alkaline solution and cerous nitrate aqueous solution
Mixing, wherein the molar ratio of hydroxide ion and cerous nitrate in cerous nitrate aqueous solution is (8-27) in alkaline solution: 1, it can obtain
To meet the present invention claims cerium hydroxide nano piece presoma.The cerium hydroxide nano piece presoma is dried, is roasted
Available cerium dioxide nano piece after burning processing, the cerium dioxide nano piece thickness being prepared are no more than 3nm, specific surface area
It is higher, it can achieve 182m2/ g, can be equal by the cerium dioxide nano composite material that the cerium dioxide nano piece is prepared
The even more noble metal catalysts of load, high catalytic efficiency.
Preferably, step (1) is described is deposited in the lower progress of non-oxidizing gas protection.
Preferably, the non-oxidizing gas include in nitrogen, helium or argon gas any one or at least two group
It closes, preferably nitrogen.
Preferably, the molar concentration of cerous nitrate is 0.01-0.1mol/L in step (1) the cerous nitrate aqueous solution, such as
Can be 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L,
0.08mol/L, 0.09mol/L or 0.1mol/L, preferably 0.02-0.08mol/L.
Preferably, step (1) described alkaline solution includes sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the molar concentration of hydroxide ion is 0.5-6mol/L in the alkaline solution, such as be can be
0.5mol/L、1mol/L、1.5mol/L、2mol/L、2.5mol/L、3mol/L、3.5mol/L、4mol/L、4.5mol/L、
5mol/L, 5.5mol/L or 6mol/L, preferably 1-5mol/L, further preferably 2-4mol/L.
Preferably, the alkaline solution is added in the cerous nitrate aqueous solution in a manner of being added dropwise.
Preferably, the speed of the dropwise addition is 10-20mL/h, such as can be 10mL/h, 12mL/h, 14mL/h, 16mL/
H, 18mL/h or 20mL/h, preferably 12-18mL/h.
Preferably, step (1) described precipitation process is also with stirring.
Preferably, the speed of the stirring be 600-1500r/min, such as can be 600r/min, 650r/min,
700r/min、750r/min、800r/min、850r/min、900r/min、950r/min、1000r/min、1050r/min、
1100r/min、1150r/min、1200r/min、1250r/min、1300r/min、1350r/min、1400r/min、1450r/
Min or 1500r/min, preferably 1200-1500r/min.
Preferably, the time of the stirring be 2-15h, such as can be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h,
11h, 12h, 13h, 14h or 15h, preferably 4-12h, further preferably 6-8h.
Preferably, washing of precipitate obtained by the step (1) is to neutrality.
Preferably, the temperature of step (1) described precipitating is 0-40 DEG C, such as can be 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20
DEG C, 25 DEG C, 30 DEG C, 35 DEG C or 40 DEG C, preferably 10-30 DEG C, further preferably 15-25 DEG C.
Preferably, step (2) drying includes freeze-drying, spray drying or drying drying, is preferably freeze-dried.
Preferably, the temperature of step (2) described roasting be 380-800 DEG C, such as can be 380 DEG C, 400 DEG C, 420 DEG C,
440 DEG C, 460 DEG C, 480 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 640 DEG C, 660 DEG C, 700 DEG C, 730 DEG C, 750 DEG C, 780 DEG C or 800
DEG C, preferably 400-780 DEG C, further preferably 420-750 DEG C.
Preferably, the time of step (2) described roasting be 0.5-4.2h, such as can be 0.5h, 1h, 1.5h, 2h,
2.5h, 3h, 3.5h, 4h or 4.2h, preferably 1-4h, further preferably 2-3h.
If the temperature of roasting is lower, it is unfavorable for improving the porosity of cerium dioxide nano piece, to influence subsequent expensive
Load of the metallic catalyst in cerium dioxide nano on piece.If the temperature of roasting is excessively high, the sheet knot of cerium dioxide nano piece
Structure will receive destruction, equally be unfavorable for noble metal catalyst in the load of cerium dioxide nano on piece.
Second aspect, the present invention also provides the cerium dioxide nanos that preparation method as described in relation to the first aspect is prepared
Piece.
Preferably, the cerium dioxide nano piece with a thickness of 0.8-3.2nm, such as can be 0.8nm, 1nm, 1.2nm,
1.4nm, 1.6nm, 1.8nm, 2nm, 2.4nm, 2.7nm, 3nm or 3.2nm, preferably 1-3nm, further preferably 1.2-
2.7nm。
Preferably, the equivalent diameter of the cerium dioxide nano piece be 150-1200nm, such as can be 150nm,
200nm、250nm、300nm、350nm、400nm、450nm、500nm、550nm、600nm、650nm、700nm、750nm、
800nm, 850nm, 900nm, 950nm, 1000nm, 1050nm, 1100nm, 1150nm or 1200nm, preferably 200-1000nm,
Further preferably 250-800nm.
Preferably, the cerium dioxide nano piece is covered with nanoscale hole hole.
The cerium dioxide nano piece large specific surface area that is prepared using the above method and it has been covered with nanoscale hole hole, and
The active site of gained cerium dioxide nano piece is more, can preferably load to noble metal.
Preferably, the aperture of the nanoscale hole hole be 1-6nm, such as can be 1nm, 2nm, 3nm, 4nm, 5nm or
6nm, preferably 2-5nm, further preferably 3-4nm.
The third aspect, the present invention also provides a kind of cerium dioxide nano composite material, the cerium dioxide nano is compound
Material includes cerium dioxide nano piece as described in respect of the second aspect of the invention.
Fourth aspect, the present invention also provides the preparation sides of the cerium dioxide nano composite material as described in the third aspect
Method, the preparation method include the following steps:
(I) cerium dioxide nano piece is prepared using the preparation method of the cerium dioxide nano piece；
(II) cerium dioxide nano piece obtained by step (I) is immersed in reducing solution, obtains ceria dispersion liquid；
(III) noble metal precursor liquid solution is added in step (II) the ceria dispersion liquid, obtains mixed liquor；
(IV) heating stirring step (III) mixed liquor, cooling, centrifuge separation washs drying, obtains the titanium dioxide
Cerium nanocomposite.
Preferably, the reducing solution includes no water glycol, the ethylene glycol solution of sodium hydroxide or potassium hydroxide
In ethylene glycol solution any one or at least two combination, it is typical but non-limiting combination include sodium hydroxide second two
The combination of the ethylene glycol solution of alcoholic solution and potassium hydroxide.
Ethylene glycol solution has reproducibility, can restore completely the noble metal in noble metal precursor liquid solution.As excellent
Change technical solution, the addition energy of sodium ion and potassium ion in the ethylene glycol solution of sodium hydroxide and the ethylene glycol solution of potassium hydroxide
The generation of noble metal Cluster Phenomenon is enough avoided, to improve the catalytic performance of the cerium dioxide nano composite material of preparation.
Preferably, hydroxide ion rubs in the ethylene glycol solution of the sodium hydroxide or the ethylene glycol solution of potassium hydroxide
Your concentration is 0.8-1.2mol/L, such as can be 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L or 1.2mol/L, excellent
It is selected as 0.9-1.1mol/L.
Preferably, step (III) the noble metal precursor liquid solution includes platinum acid chloride solution, chlorauric acid solution, chloro-iridic acid
One of solution or potassium chloroplatinate solution or at least two combination, it is typical but non-limiting combination include platinum acid chloride solution
With the combination of chlorauric acid solution, the combination of chlorauric acid solution, Chloroiridic Acid solution and potassium chloroplatinate solution, platinum acid chloride solution, chlorine gold
The combination of acid solution, Chloroiridic Acid solution and potassium chloroplatinate solution.
Preferably, the mass fraction of precious metal element is 0.5-15wt% in the noble metal precursor liquid solution, such as can
Be 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%,
11wt% or 12wt%, preferably 1-12wt%, further preferably 3-10wt%.
Preferably, the mass ratio of precious metal element and the cerium dioxide nano piece is in the noble metal precursor liquid solution
1:(5-60), such as 1:5,1:10,1:15,1:20,1:25,1:30,1:35,1:40,1:45,1:50,1:55 or 1 be can be:
60, preferably 1:(10-50), further preferably 1:(20-40).The not beneficial mistake of precious metal element in noble metal precursor liquid solution
More, the noble metal partial size after otherwise restoring increases, and catalytic activity reduces.
Preferably, the temperature of step (IV) described heating be 100-210 DEG C, such as can be 100 DEG C, 110 DEG C, 120 DEG C,
130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C or 210 DEG C, preferably 120-200 DEG C, further
Preferably 150-180 DEG C.
Preferably, the time of step (IV) described stirring be 0.3-2.1h, such as can be 0.3h, 0.5h, 0.8h, 1h,
1.2h, 1.4h, 1.6h, 1.8h, 2h or 2.1h, preferably 0.5-2h, further preferably 0.8-1.6h.
As the preferred technical solution of the present invention, the preparation method includes the following steps:
It (a) is 0.5- by the molar concentration of hydroxide ion within the temperature range of 0-40 DEG C under non-oxidizing gas protection
The molar concentration that the sodium hydrate aqueous solution and/or potassium hydroxide aqueous solution of 6mol/L is added drop-wise to cerous nitrate is 0.01-0.1mol/
In the cerous nitrate aqueous solution of L, the molar ratio of the hydroxide ion and the cerous nitrate is (10-25): 1, the speed of the dropwise addition
Degree is 10-20mL/h, and cerous nitrate aqueous solution is stirred in precipitation process, and the time of the stirring is 2-15h, the speed of the stirring
For 600-1500r/min, washing is precipitated to neutrality, obtains cerium hydroxide nano piece presoma；
(b) cerium hydroxide nano piece presoma obtained by freeze-drying step (a), to freeze-drying under the conditions of 380-800 DEG C
Cerium hydroxide nano piece presoma afterwards is roasted, and the time of the roasting is 0.5-4.2h, obtains cerium dioxide nano piece；
(c) cerium dioxide nano piece is immersed in reducing solution, obtains ceria dispersion liquid；
(d) precious metal element mass fraction is added to step (c) institute for the noble metal precursor liquid solution of 0.5-15wt%
It states in ceria dispersion liquid, obtains mixed liquor, precious metal element and the ceria in the noble metal precursor liquid solution
The mass ratio of nanometer sheet is 1:(5-60)；
(e) under the conditions of 100-210 DEG C, whipping step (d) mixed liquor is cooling, and centrifuge separation is washed drying, obtained
The cerium dioxide nano composite material, the time of the stirring are 0.3-2.1h.
5th aspect, the present invention also provides the use that the cerium dioxide nano composite material is used for catalysis oxidation formaldehyde
On the way.
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, beneficial effects of the present invention are as follows:
The preparation method of cerium dioxide nano piece provided by the invention is simple, easy to operate, and prepared ceria is received
Rice piece with a thickness of 0.8-3.2nm, the equivalent diameter of the cerium dioxide nano piece is 150-1200nm, and the ceria is received
Rice piece is covered with the nanoscale hole hole that aperture is 1-6nm, is prepared by the cerium dioxide nano piece supported precious metal catalyst
Cerium dioxide nano composite material, large specific surface area is capable of providing more active sites, to improve catalytic efficiency.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture for the cerium hydroxide nano piece presoma that embodiment 8 is prepared；
Fig. 2 is the transmission electron microscope picture for the cerium dioxide nano piece that embodiment 8 is prepared；
Fig. 3 is the transmission electron microscope picture for the cerium dioxide nano piece that embodiment 9 is prepared；
Fig. 4 is the transmission electron microscope picture for the cerium dioxide nano composite material that embodiment 10 is prepared；
Fig. 5 is the transmission electron microscope picture for the cerium dioxide nano composite material that embodiment 11 is prepared.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Embodiment 1
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method includes as follows
Step:
(1) 20 DEG C under nitrogen protection, and the sodium hydrate aqueous solution that the molar concentration of hydroxide ion is 3mol/L is dripped
The molar concentration for being added to cerous nitrate is the hydroxide ion and the cerous nitrate in the cerous nitrate aqueous solution of 0.05mol/L
Molar ratio is 18:1, and the speed of the dropwise addition is 14mL/h, stirs cerous nitrate aqueous solution, the time of the stirring in precipitation process
For 9h, the speed of the stirring is 1000r/min, and washing is precipitated to neutrality, obtains cerium hydroxide nano piece presoma；
(2) cerium hydroxide nano piece presoma obtained by freeze-drying step (1), under the conditions of 600 DEG C to freeze-drying after
Cerium hydroxide nano piece presoma is roasted, and the time of the roasting is 2h, obtains cerium dioxide nano piece；
(3) cerium dioxide nano piece obtained by step (2) is immersed in the ethylene glycol solution of sodium hydroxide, obtains ceria
Dispersion liquid, the molar concentration of hydroxide ion is 1mol/L in the ethylene glycol solution of the sodium hydroxide；
(4) platinum acid chloride solution that precious metal element mass fraction is 6wt% is added to step (3) ceria point
In dispersion liquid, mixed liquor is obtained, the mass ratio of platinum element and the cerium dioxide nano piece is 1:30 in the platinum acid chloride solution；
Under the conditions of (5) 180 DEG C, whipping step (4) described mixed liquor is cooling, and drying is washed in centrifuge separation, obtains described
Cerium dioxide nano composite material, the time of the stirring are 1h.
Embodiment 2
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method includes as follows
Step:
(1) 25 DEG C under protection of argon gas, and the sodium hydrate aqueous solution that the molar concentration of hydroxide ion is 4mol/L is dripped
The molar concentration for being added to cerous nitrate is the hydroxide ion and the cerous nitrate in the cerous nitrate aqueous solution of 0.06mol/L
Molar ratio is 12:1, and the speed of the dropwise addition is 16mL/h, stirs cerous nitrate aqueous solution, the time of the stirring in precipitation process
For 12h, the speed of the stirring is 1200r/min, and washing is precipitated to neutrality, obtains cerium hydroxide nano piece presoma；
(2) cerium hydroxide nano piece presoma obtained by freeze-drying step (1), under the conditions of 420 DEG C to freeze-drying after
Cerium hydroxide nano piece presoma is roasted, and the time of the roasting is 3h, obtains cerium dioxide nano piece；
(3) cerium dioxide nano piece obtained by step (2) is immersed in the ethylene glycol solution of potassium hydroxide, obtains ceria
Dispersion liquid, the molar concentration of hydroxide ion is 0.9mol/L in the ethylene glycol solution of the potassium hydroxide；
(4) chlorauric acid solution that precious metal element mass fraction is 10wt% is added to step (3) described ceria
In dispersion liquid, mixed liquor is obtained, the mass ratio of gold element and the cerium dioxide nano piece is 1:40 in the chlorauric acid solution；
Under the conditions of (5) 200 DEG C, whipping step (4) described mixed liquor is cooling, and drying is washed in centrifuge separation, obtains described
Cerium dioxide nano composite material, the time of the stirring are 2h.
Embodiment 3
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method includes as follows
Step:
(1) 15 DEG C under helium protection, the potassium hydroxide aqueous solution that the molar concentration of hydroxide ion is 2mol/L is dripped
The molar concentration for being added to cerous nitrate is the hydroxide ion and the cerous nitrate in the cerous nitrate aqueous solution of 0.02mol/L
Molar ratio is 10:1, and the speed of the dropwise addition is 12mL/h, stirs cerous nitrate aqueous solution, the time of the stirring in precipitation process
For 6h, the speed of the stirring is 800r/min, and washing is precipitated to neutrality, obtains cerium hydroxide nano piece presoma；
(2) cerium hydroxide nano piece presoma obtained by freeze-drying step (1), under the conditions of 400 DEG C to freeze-drying after
Cerium hydroxide nano piece presoma is roasted, and the time of the roasting is 1h, obtains cerium dioxide nano piece；
(3) cerium dioxide nano piece obtained by step (2) is immersed without in water glycol, obtaining ceria dispersion liquid；
(4) Chloroiridic Acid solution that precious metal element mass fraction is 3wt% is added to step (3) ceria point
In dispersion liquid, mixed liquor is obtained, the mass ratio of iridium and the cerium dioxide nano piece is 1:20 in the Chloroiridic Acid solution；
Under the conditions of (5) 150 DEG C, whipping step (4) described mixed liquor is cooling, and drying is washed in centrifuge separation, obtains described
Cerium dioxide nano composite material, the time of the stirring are 1h.
Embodiment 4
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method includes as follows
Step:
(1) 30 DEG C under protection of argon gas, the potassium hydroxide and hydroxide for being 5mol/L by the molar concentration of hydroxide ion
The mixed aqueous solution of sodium be added drop-wise to cerous nitrate molar concentration be 0.08mol/L cerous nitrate aqueous solution in, the hydroxyl from
The sub molar ratio with the cerous nitrate is 21:1, and the speed of the dropwise addition is 18mL/h, and stirring cerous nitrate is water-soluble in precipitation process
Liquid, the time of the stirring are 12h, and the speed of the stirring is 1300r/min, and washing is precipitated to neutrality, obtains cerium hydroxide
Nanometer sheet presoma；
(2) cerium hydroxide nano piece presoma obtained by freeze-drying step (1), under the conditions of 750 DEG C to freeze-drying after
Cerium hydroxide nano piece presoma is roasted, and the time of the roasting is 4h, obtains cerium dioxide nano piece；
(3) cerium dioxide nano piece obtained by step (2) is immersed in the ethylene glycol solution of sodium hydroxide, obtains titanium dioxide
Cerium dispersion liquid, the molar concentration of hydroxide ion is 1.1mol/L in the ethylene glycol solution of the sodium hydroxide；
(4) the potassium chloroplatinate solution that precious metal element mass fraction is 12wt% is added to step (3) described titanium dioxide
In cerium dispersion liquid, mixed liquor is obtained, platinum element and the mass ratio of the cerium dioxide nano piece are in the potassium chloroplatinate solution
1:50；
Under the conditions of (5) 200 DEG C, whipping step (4) described mixed liquor is cooling, and drying is washed in centrifuge separation, obtains described
Cerium dioxide nano composite material, the time of the stirring are 2h.
Embodiment 5
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method includes as follows
Step:
(1) 10 DEG C under nitrogen protection, the potassium hydroxide and hydroxide for being 1mol/L by the molar concentration of hydroxide ion
The mixed aqueous solution of sodium be added drop-wise to cerous nitrate molar concentration be 0.02mol/L cerous nitrate aqueous solution in, the hydroxyl from
The sub molar ratio with the cerous nitrate is 25:1, and the speed of the dropwise addition is 12mL/h, and stirring cerous nitrate is water-soluble in precipitation process
Liquid, the time of the stirring are 6h, and the speed of the stirring is 800r/min, and washing is precipitated to neutrality, obtains cerium hydroxide and receive
Rice piece presoma；
(2) cerium hydroxide nano piece presoma obtained by freeze-drying step (1), under the conditions of 780 DEG C to freeze-drying after
Cerium hydroxide nano piece presoma is roasted, and the time of the roasting is 1h, obtains cerium dioxide nano piece；
(3) cerium dioxide nano piece obtained by step (2) is immersed in the ethylene glycol solution of sodium hydroxide, obtains titanium dioxide
Cerium dispersion liquid, the molar concentration of hydroxide ion is 1.2mol/L in the ethylene glycol solution of the sodium hydroxide；
(4) mixed solution of chloroplatinic acid and gold chloride that precious metal element mass fraction is 1wt% is added to step (3)
In the ceria dispersion liquid, mixed liquor is obtained, precious metal element and the cerium dioxide nano piece in the mixed solution
Mass ratio be 1:10；
Under the conditions of (5) 120 DEG C, whipping step (4) described mixed liquor is cooling, and drying is washed in centrifuge separation, obtains described
Cerium dioxide nano composite material, the time of the stirring are 0.5h.
Embodiment 6
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method includes as follows
Step:
(1) 0 DEG C under nitrogen protection, and the potassium hydroxide aqueous solution that the molar concentration of hydroxide ion is 0.5mol/L is dripped
The molar concentration for being added to cerous nitrate is the hydroxide ion and the cerous nitrate in the cerous nitrate aqueous solution of 0.01mol/L
Molar ratio is 8:1, and the speed of the dropwise addition is 10mL/h, stirs cerous nitrate aqueous solution, the time of the stirring in precipitation process
For 2h, the speed of the stirring is 600r/min, and washing is precipitated to neutrality, obtains cerium hydroxide nano piece presoma；
(2) it is freeze-dried cerium hydroxide nano piece presoma obtained by step (1), after drying under the conditions of 380 DEG C to drying
Cerium hydroxide nano piece presoma is roasted, and the time of the roasting is 4.2h, obtains cerium dioxide nano piece；
(3) cerium dioxide nano piece obtained by step (2) is immersed in the ethylene glycol solution of sodium hydroxide, obtains titanium dioxide
Cerium dispersion liquid, the molar concentration of hydroxide ion is 0.8mol/L in the ethylene glycol solution of the sodium hydroxide；
(4) platinum acid chloride solution that precious metal element mass fraction is 0.5wt% is added to step (3) described ceria
In dispersion liquid, mixed liquor is obtained, the mass ratio of platinum element and the cerium dioxide nano piece is 1:5 in the platinum acid chloride solution；
Under the conditions of (5) 100 DEG C, whipping step (4) described mixed liquor is cooling, and drying is washed in centrifuge separation, obtains described
Cerium dioxide nano composite material, the time of the stirring are 2.1h.
Embodiment 7
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method includes as follows
Step:
(1) 40 DEG C under nitrogen protection, and the sodium hydrate aqueous solution that the molar concentration of hydroxide ion is 6mol/L is dripped
The molar concentration for being added to cerous nitrate is in the cerous nitrate aqueous solution of 0.1mol/L, and the hydroxide ion rubs with the cerous nitrate
You are than being 20mL/h for the speed of 27:1, the dropwise addition, and stirring cerous nitrate aqueous solution, the time of the stirring are in precipitation process
15h, the speed of the stirring are 1500r/min, and washing is precipitated to neutrality, obtains cerium hydroxide nano piece presoma；
(2) cerium hydroxide nano piece presoma obtained by freeze-drying step (1), under the conditions of 800 DEG C to spray drying after
Cerium hydroxide nano piece presoma is roasted, and the time of the roasting is 0.5h, obtains cerium dioxide nano piece；
(3) cerium dioxide nano piece obtained by step (2) is immersed in no water glycol, obtains ceria dispersion liquid；
(4) platinum acid chloride solution that precious metal element mass fraction is 15wt% is added to step (3) described ceria
In dispersion liquid, mixed liquor is obtained, the mass ratio of platinum element and the cerium dioxide nano piece is 1:60 in the platinum acid chloride solution；
Under the conditions of (5) 210 DEG C, whipping step (4) described mixed liquor is cooling, and drying is washed in centrifuge separation, obtains described
Cerium dioxide nano composite material, the time of the stirring are 0.3h.
Embodiment 8
A kind of preparation method of cerium dioxide nano piece is present embodiments provided, the preparation method includes the following steps:
(1) 25 DEG C under nitrogen protection, the sodium hydroxide water for being 1.25mol/L by the molar concentration of 20mL hydroxide ion
The molar concentration that solution is added drop-wise to 30mL cerous nitrate is in the cerous nitrate aqueous solution of 0.033mol/L, and the speed of the dropwise addition is
20mL/h stirs cerous nitrate aqueous solution in precipitation process, and the time of the stirring is 6h, and the speed of the stirring is 1500r/
Min, washing are precipitated to neutrality, obtain cerium hydroxide nano piece presoma, the transmission electricity of gained cerium hydroxide nano piece presoma
Mirror figure is as shown in Figure 1；
(2) cerium hydroxide nano piece presoma obtained by freeze-drying step (1), under the conditions of 600 DEG C to freeze-drying after
Cerium hydroxide nano piece presoma is roasted, and the time of the roasting is 2h, obtains cerium dioxide nano piece, gained titanium dioxide
The transmission electron microscope picture of cerium nanometer sheet is as shown in Figure 2.
As shown in Figure 1, the cerium hydroxide nano piece presoma stacking that step (1) is prepared is serious, as shown in Figure 2, has
The cerium dioxide nano piece pattern that the cerium dioxide nano piece that embodiment 8 provides is prepared is uniform, structural integrity.
Embodiment 9
A kind of preparation method of cerium dioxide nano piece is present embodiments provided, the preparation method includes the following steps:
(1) 25 DEG C under nitrogen protection, and the molar concentration of 20mL hydroxide ion is water-soluble for the sodium hydroxide of 2mol/L
The molar concentration that drop is added to 80mL cerous nitrate is in the cerous nitrate aqueous solution of 0.025mol/L, and the speed of the dropwise addition is
20mL/h stirs cerous nitrate aqueous solution in precipitation process, and the time of the stirring is 8h, and the speed of the stirring is 1500r/
Min, washing are precipitated to neutrality, obtain cerium hydroxide nano piece presoma；
(2) cerium hydroxide nano piece presoma obtained by freeze-drying step (1), under the conditions of 600 DEG C to freeze-drying after
Cerium hydroxide nano piece presoma is roasted, and the time of the roasting is 2h, obtains cerium dioxide nano piece, gained titanium dioxide
The transmission electron microscope picture of cerium nanometer sheet is as shown in Figure 3.
From the figure 3, it may be seen that the cerium dioxide nano piece pattern that the cerium dioxide nano piece for having embodiment 9 to provide is prepared is equal
One, structural integrity.
Embodiment 10
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method includes as follows
Step:
(1) 8 gained cerium dioxide nano piece of 30mg embodiment is immersed in the ethylene glycol solution of sodium hydroxide, obtains two
Cerium oxide dispersion, the molar concentration of hydroxide ion is 1mol/L in the ethylene glycol solution of the sodium hydroxide；
(2) platinum acid chloride solution is added in ceria dispersion liquid obtained by step (1), obtains mixed liquor, the chlorine platinum
The mass ratio of platinum element and the cerium dioxide nano piece is 1:30 in acid solution；
Under the conditions of (3) 180 DEG C, whipping step (2) described mixed liquor is cooling, and drying is washed in centrifuge separation, obtains described
Cerium dioxide nano composite material, the time of the stirring are 2h, the transmission electron microscope picture of gained cerium dioxide nano composite material
As shown in Figure 4.
As shown in Figure 4, there are two that the preparation method of the cerium dioxide nano composite material of the offer of embodiment 10 is prepared
Cerium oxide nano composite material pattern is uniform, structural integrity, and noble metal platinum of the partial size no more than 3nm is equably supported on embodiment
The 8 cerium dioxide nano on pieces being prepared.
Embodiment 11
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method includes as follows
Step:
(1) 8 gained cerium dioxide nano piece of 30mg embodiment is immersed in the ethylene glycol solution of sodium hydroxide, obtains two
Cerium oxide dispersion, the molar concentration of hydroxide ion is 1mol/L in the ethylene glycol solution of the sodium hydroxide；
(2) chlorauric acid solution is added in ceria dispersion liquid obtained by step (1), obtains mixed liquor, the chlorine platinum
The mass ratio of platinum element and the cerium dioxide nano piece is 1:30 in acid solution；
Under the conditions of (3) 140 DEG C, whipping step (2) described mixed liquor is cooling, and drying is washed in centrifuge separation, obtains described
Cerium dioxide nano composite material, the time of the stirring are 2h, the transmission electron microscope picture of gained cerium dioxide nano composite material
As shown in Figure 5.
As shown in Figure 5, there are two that the preparation method of the cerium dioxide nano composite material of the offer of embodiment 11 is prepared
Cerium oxide nano composite material pattern is uniform, structural integrity, and noble metal gold of the partial size no more than 5nm is supported on the preparation of embodiment 8
Obtained cerium dioxide nano on piece.But your gold loaded in partial size ratio Fig. 4 of the noble metal gold of cerium dioxide nano piece load
The partial size for belonging to platinum is big.
Embodiment 12
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method removes step
(2) temperature of the roasting is 350 DEG C outer, remaining is same as Example 3.
Embodiment 13
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method removes step
(2) temperature of the roasting is 840 DEG C outer, remaining is same as Example 3.
Embodiment 14
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method removes step
(4) mass ratio of platinum element and the cerium dioxide nano piece is outside 1:3 in the platinum acid chloride solution, remaining with embodiment 3
It is identical.
Embodiment 15
A kind of preparation method of cerium dioxide nano composite material is present embodiments provided, the preparation method removes step
(4) mass ratio of platinum element and the cerium dioxide nano piece is outside 1:65 in the platinum acid chloride solution, remaining with embodiment 3
It is identical.
Comparative example 1
This comparative example provides a kind of preparation method of cerium dioxide nano composite material, and the preparation method removes step
(1) molar ratio of the hydroxide ion and the cerous nitrate is outside 5:1, remaining is same as Example 3.
Comparative example 2
This comparative example provides a kind of preparation method of cerium dioxide nano composite material, and the preparation method removes step
(1) molar ratio of the hydroxide ion and the cerous nitrate is outside 30:1, remaining is same as Example 3.
The cerium dioxide nano composite wood that embodiment 1-7,10-15 provided by the invention and comparative example 1-2 are prepared
The thickness and specific surface area of material are measured, and measurement result is as shown in table 1:
Table 1
As shown in Table 1, the thickness for the cerium dioxide nano composite material that embodiment 1-7,10-11 is prepared is no more than
2.5nm, specific surface area are more than 150m2/g。
In embodiment 12, the temperature of step (2) described roasting is lower, is 350 DEG C, the titanium dioxide that embodiment 12 is prepared
Cerium nanocomposite with a thickness of 2.8nm, higher than the thickness for the cerium dioxide nano composite material that embodiment 3 is prepared
1.8nm, the specific surface area for the cerium dioxide nano composite material that embodiment 12 is prepared are 146m2/ g makes lower than embodiment 3
The specific surface area 182m of standby obtained cerium dioxide nano composite material2/ g, therefore the roasting of cerium hydroxide nano piece presoma
The lower thickness for being unfavorable for reducing cerium dioxide nano composite material of temperature, and be unfavorable for improving cerium dioxide nano composite material
Specific surface area.
In embodiment 13, the temperature of step (2) described roasting is higher, is 840 DEG C, the titanium dioxide that embodiment 13 is prepared
Cerium nanocomposite with a thickness of 5.2nm, higher than the thickness for the cerium dioxide nano composite material that embodiment 3 is prepared
1.8nm, the specific surface area for the cerium dioxide nano composite material that embodiment 13 is prepared are 121m2/ g makes lower than embodiment 3
The specific surface area 182m of standby obtained cerium dioxide nano composite material2/ g, therefore the roasting of cerium hydroxide nano piece presoma
The higher thickness for being unfavorable for reducing cerium dioxide nano composite material of temperature, and be unfavorable for improving cerium dioxide nano composite material
Specific surface area.
In embodiment 14, the mass ratio of platinum element and the cerium dioxide nano piece in step (4) described platinum acid chloride solution
For 1:3, the cerium dioxide nano composite material being prepared with a thickness of 2.7nm, the titanium dioxide being prepared higher than embodiment 3
The specific surface area of the thickness 1.8nm of cerium nanocomposite, the cerium dioxide nano composite material that embodiment 14 is prepared is
146m2/ g, lower than the specific surface area 182m for the cerium dioxide nano composite material that embodiment 3 is prepared2/ g, therefore chloroplatinic acid
The higher thickness for being unfavorable for reducing cerium dioxide nano composite material of the content of platinum element in solution, and be unfavorable for improving titanium dioxide
The specific surface area of cerium nanocomposite.
In embodiment 15, the mass ratio of platinum element and the cerium dioxide nano piece in step (4) described platinum acid chloride solution
For 1:65, the cerium dioxide nano composite material being prepared with a thickness of 2.7nm, the dioxy being prepared higher than embodiment 3
Change the thickness 1.8nm of cerium nanocomposite, the specific surface area for the cerium dioxide nano composite material that embodiment 15 is prepared
For 144m2/ g, lower than the specific surface area 182m for the cerium dioxide nano composite material that embodiment 3 is prepared2/ g, therefore chlorine platinum
The lower thickness for being also unfavorable for reducing cerium dioxide nano composite material of the content of platinum element in acid solution, and it is unfavorable for raising two
The specific surface area of cerium oxide nano composite material.
In comparative example 1, the molar ratio of hydroxide ion and the cerous nitrate in cerous nitrate aqueous solution is 5:1 in alkaline solution,
The additive amount of hydroxide ion will be lower than the additive amount of hydroxide ion in embodiment 3.The ceria that comparative example 1 is prepared
Nanocomposite with a thickness of 3.1nm, higher than the thickness for the cerium dioxide nano composite material that embodiment 3 is prepared
1.8nm, the specific surface area for the cerium dioxide nano composite material that comparative example 1 is prepared are 133m2/ g makes lower than embodiment 3
The specific surface area 182m of standby obtained cerium dioxide nano composite material2/ g, therefore, when the additive amount of hydroxide ion is lower not
Conducive to the thickness of reduction cerium dioxide nano composite material, and it is unfavorable for improving the specific surface of cerium dioxide nano composite material
Product.
In comparative example 2, the molar ratio of hydroxide ion and the cerous nitrate in cerous nitrate aqueous solution is 30:1 in alkaline solution,
The additive amount of hydroxide ion will be lower than the additive amount of hydroxide ion in embodiment 3.The ceria that comparative example 1 is prepared
Nanocomposite with a thickness of 3.2nm, higher than the thickness for the cerium dioxide nano composite material that embodiment 3 is prepared
1.8nm, the specific surface area for the cerium dioxide nano composite material that comparative example 1 is prepared are 132m2/ g makes lower than embodiment 3
The specific surface area 182m of standby obtained cerium dioxide nano composite material2/ g, therefore, when the additive amount of hydroxide ion is higher not
Conducive to the thickness of reduction cerium dioxide nano composite material, and it is unfavorable for improving the specific surface of cerium dioxide nano composite material
Product.
To sum up, simple, easy to operate, the prepared titanium dioxide of the preparation method of cerium dioxide nano piece provided by the invention
The thickness of cerium nanometer sheet is lower, and the cerium dioxide nano piece is covered with the nanoscale hole hole that aperture is 1-6nm, by the titanium dioxide
The thickness for the cerium dioxide nano composite material that cerium nanometer sheet supported precious metal catalyst is prepared is no more than 2.5nm, gained
The specific surface area of cerium dioxide nano composite material is higher than 150m2/ g can uniformly load more noble metals, and then improve
Catalytic efficiency, while the dosage of metallic cerium can be reduced, reduce the production cost of cerium dioxide nano composite material.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of preparation method of cerium dioxide nano piece, which is characterized in that the preparation method includes the following steps:
(1) cerous nitrate aqueous solution is precipitated using alkaline solution, obtains cerium hydroxide nano piece presoma；
(2) cerium hydroxide nano piece presoma obtained by dry, calcination steps (1), obtains cerium dioxide nano piece；
Step (1) described alkaline solution includes sodium hydroxide solution and/or potassium hydroxide solution；
The molar ratio of hydroxide ion and cerous nitrate in the cerous nitrate aqueous solution is (8-27) in the alkaline solution: 1.
2. preparation method according to claim 1, which is characterized in that step (1) is described to be deposited in non-oxidizing gas guarantor
Shield is lower to be carried out；
Preferably, the non-oxidizing gas include in nitrogen, argon gas or helium any one or at least two combination, it is excellent
It is selected as nitrogen；
Preferably, the molar concentration of cerous nitrate is 0.01-0.1mol/L in step (1) the cerous nitrate aqueous solution, preferably
0.02-0.08mol/L；
Preferably, the molar concentration of hydroxide ion is 0.5-6mol/L, preferably 1- in step (1) described alkaline solution
5mol/L, further preferably 2-4mol/L；
Preferably, the molar ratio of the hydroxide ion and the cerous nitrate is (10-25): 1, further preferably (12-21):
1；
Preferably, the alkaline solution is added in the cerous nitrate aqueous solution in a manner of being added dropwise；
Preferably, the speed of the dropwise addition is 10-20mL/min, preferably 12-18mL/min；
Preferably, the process of step (1) described precipitating is also with stirring；
Preferably, the speed of the stirring is 600-1500r/min, preferably 1200-1500r/min；
Preferably, the time of the stirring is 2-15h, preferably 4-12h, further preferably 6-8h；
Preferably, washing of precipitate obtained by the step (1) is to neutrality；
Preferably, the temperature of step (1) described precipitating is 0-40 DEG C, preferably 10-30 DEG C, further preferably 15-25 DEG C.
3. preparation method according to claim 1 or 2, which is characterized in that step (2) drying include freeze-drying,
Spray drying or drying drying, are preferably freeze-dried；
Preferably, the temperature of step (2) described roasting is 380-800 DEG C, preferably 400-780 DEG C, further preferably 420-
750℃；
Preferably, the time of step (2) described roasting is 0.5-4.2h, preferably 1-4h, further preferably 2-3h.
4. a kind of cerium dioxide nano piece that preparation method as described in any one of claims 1-3 is prepared.
5. cerium dioxide nano piece according to claim 4, which is characterized in that the cerium dioxide nano piece with a thickness of
0.8-3.2nm, preferably 1-3nm, further preferably 1.2-2.7nm；
Preferably, the equivalent diameter of the cerium dioxide nano piece be 150-1200nm, preferably 200-1000nm, further it is excellent
It is selected as 250-800nm；
Preferably, the cerium dioxide nano piece is covered with nanoscale hole hole；
Preferably, the aperture of the nanoscale hole hole is 1-6nm, preferably 2-5nm, further preferably 3-4nm.
6. a kind of cerium dioxide nano composite material, which is characterized in that received comprising ceria as described in claim 4 or 5
Rice piece.
7. a kind of preparation method of cerium dioxide nano composite material as claimed in claim 6, which is characterized in that the preparation
Method includes the following steps:
(I) cerium dioxide nano piece is prepared using preparation method as described in any one of claims 1-3；
(II) cerium dioxide nano piece obtained by step (I) is immersed in reducing solution, obtains ceria dispersion liquid；
(III) noble metal precursor liquid solution is added in step (II) the ceria dispersion liquid, obtains mixed liquor；
(IV) heating stirring step (III) mixed liquor, cooling, centrifuge separation washs drying, obtains the ceria and receive
Nano composite material.
8. preparation method according to claim 7, which is characterized in that the reducing solution includes no water glycol, hydrogen
In the ethylene glycol solution of sodium oxide molybdena or the ethylene glycol solution of potassium hydroxide any one or at least two combination；
Preferably, in the ethylene glycol solution of the sodium hydroxide or the ethylene glycol solution of potassium hydroxide hydroxide ion it is mole dense
Degree is 0.8-1.2mol/L, preferably 0.9-1.1mol/L；
Preferably, step (III) the noble metal precursor liquid solution includes platinum acid chloride solution, chlorauric acid solution, Chloroiridic Acid solution
One of potassium chloroplatinate solution or at least two combination；
Preferably, the mass fraction of precious metal element is 0.5-15wt%, preferably 1- in the noble metal precursor liquid solution
12wt%, further preferably 3-10wt%；
Preferably, the mass ratio of precious metal element and the cerium dioxide nano piece is 1 in the noble metal precursor liquid solution:
(5-60), preferably 1:(10-50), further preferably 1:(20-40)；
Preferably, the temperature of step (IV) described heating is 100-210 DEG C, preferably 120-200 DEG C, further preferably 150-
180℃；
Preferably, the time of step (IV) described stirring is 0.3-2.1h, preferably 0.5-2h, further preferably 0.8-
1.6h。
9. preparation method according to claim 7 or 8, which is characterized in that the preparation method includes the following steps:
It (a) is 0.5- by the molar concentration of hydroxide ion within the temperature range of 0-40 DEG C under non-oxidizing gas protection
The molar concentration that the sodium hydrate aqueous solution and/or potassium hydroxide aqueous solution of 6mol/L is added drop-wise to cerous nitrate is 0.01-0.1mol/
In the cerous nitrate aqueous solution of L, the molar ratio of the hydroxide ion and the cerous nitrate is (10-25): 1, the speed of the dropwise addition
Degree is 10-20mL/min, and cerous nitrate aqueous solution is stirred in precipitation process, and the time of the stirring is 2-15h, the speed of the stirring
Degree is 600-1500r/min, and washing is precipitated to neutrality, obtains cerium hydroxide nano piece presoma；
(b) cerium hydroxide nano piece presoma obtained by freeze-drying step (a), under the conditions of 380-800 DEG C to freeze-drying after
Cerium hydroxide nano piece presoma is roasted, and the time of the roasting is 0.5-4.2h, obtains cerium dioxide nano piece；
(c) cerium dioxide nano piece is immersed in ethylene glycol solution, obtains ceria dispersion liquid；
(d) the noble metal precursor liquid solution that precious metal element mass fraction is 0.5-15wt% is added to step (c) described two
In cerium oxide dispersion, mixed liquor is obtained, precious metal element and the cerium dioxide nano in the noble metal precursor liquid solution
The mass ratio of piece is 1:(5-60)；
(e) under the conditions of 100-210 DEG C, whipping step (d) mixed liquor is cooling, and drying is washed in centrifuge separation, obtains described
Cerium dioxide nano composite material, the time of the stirring are 0.3-2.1h.
10. a kind of cerium dioxide nano composite material as claimed in claim 6 or such as described in any item systems of claim 7-9
The cerium dioxide nano composite material that Preparation Method is prepared is used for the purposes of catalysis oxidation formaldehyde.
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| CN114875658A (en) * | 2022-05-12 | 2022-08-09 | 广东宜纳新材料科技有限公司 | Nano silicon dioxide fiber loaded cerium dioxide and preparation method thereof |
| CN115725318A (en) * | 2022-11-29 | 2023-03-03 | 浙江大学 | Method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on decommissioned polyolefin with two-dimensional nanosheets |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792456A (en) * | 2005-12-23 | 2006-06-28 | 天津化工研究设计院 | Preparing method for nanometer cerium oxide catalyst material, and its use |
| CN101407330A (en) * | 2008-10-30 | 2009-04-15 | 上海大学 | Method of preparing cerium oxide nano-rod |
| CN101873999A (en) * | 2008-07-16 | 2010-10-27 | 纽维尔 | High purity cerium oxide powder, preparation method thereof, and CMP slurry containing the same |
| CN103991891A (en) * | 2014-05-08 | 2014-08-20 | 华东理工大学 | Preparation method of flaky nano-cerium oxide |
| CN104828852A (en) * | 2008-02-12 | 2015-08-12 | 圣戈本陶瓷及塑料股份有限公司 | Ceria material and method of forming same |
-
2018
- 2018-11-07 CN CN201811317889.0A patent/CN109052451B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792456A (en) * | 2005-12-23 | 2006-06-28 | 天津化工研究设计院 | Preparing method for nanometer cerium oxide catalyst material, and its use |
| CN104828852A (en) * | 2008-02-12 | 2015-08-12 | 圣戈本陶瓷及塑料股份有限公司 | Ceria material and method of forming same |
| CN101873999A (en) * | 2008-07-16 | 2010-10-27 | 纽维尔 | High purity cerium oxide powder, preparation method thereof, and CMP slurry containing the same |
| CN101407330A (en) * | 2008-10-30 | 2009-04-15 | 上海大学 | Method of preparing cerium oxide nano-rod |
| CN103991891A (en) * | 2014-05-08 | 2014-08-20 | 华东理工大学 | Preparation method of flaky nano-cerium oxide |
Non-Patent Citations (1)
| Title |
|---|
| GUOQING ZHANG等: "Green synthesis and catalytic performance of nanoscale CeO2 sheets", 《RSC ADV.》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999802A (en) * | 2019-04-15 | 2019-07-12 | 西安交通大学 | A kind of monatomic platinum based catalyst of high stability and preparation method thereof and the application in volatility oxygen-containing hydrocarbon low temperature purification |
| CN110745856A (en) * | 2019-11-27 | 2020-02-04 | 云南大学 | Preparation method of nano-granular cerium oxide composite ruthenium platinum palladium oxide |
| CN110745856B (en) * | 2019-11-27 | 2022-06-14 | 云南大学 | Preparation method of nano-granular cerium oxide composite ruthenium platinum palladium oxide |
| CN111715208A (en) * | 2020-04-07 | 2020-09-29 | 盐城师范学院 | CeO (CeO)2Preparation method of composite photocatalytic material and application of composite photocatalytic material in photocatalytic hydrogen production |
| CN112299469A (en) * | 2020-09-22 | 2021-02-02 | 江汉大学 | Cerium dioxide and preparation method and application thereof |
| CN112299469B (en) * | 2020-09-22 | 2023-03-14 | 江汉大学 | Cerium dioxide and preparation method and application thereof |
| CN113772710A (en) * | 2021-10-11 | 2021-12-10 | 陕西科技大学 | Preparation method and application of cerium dioxide nanowire |
| CN114875658A (en) * | 2022-05-12 | 2022-08-09 | 广东宜纳新材料科技有限公司 | Nano silicon dioxide fiber loaded cerium dioxide and preparation method thereof |
| CN114875658B (en) * | 2022-05-12 | 2023-11-24 | 广东宜纳新材料科技有限公司 | Nanometer silicon dioxide fiber-loaded cerium dioxide and preparation method thereof |
| CN115725318A (en) * | 2022-11-29 | 2023-03-03 | 浙江大学 | Method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on decommissioned polyolefin with two-dimensional nanosheets |
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