CN109794241A - A kind of cerium oxide selective coated load type palladium catalyst and preparation method thereof - Google Patents
A kind of cerium oxide selective coated load type palladium catalyst and preparation method thereof Download PDFInfo
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Abstract
A kind of cerium oxide selective coated load type palladium catalyst and preparation method thereof, is related to precious metal catalyst technical field, a kind of preparation method of cerium oxide selective coated load type palladium catalyst provided by the invention, comprising the following steps: by Pd/Al2O3Loaded catalyst, L-arginine, cerous nitrate and solvent mixing, are successively coated and are roasted, obtain cerium oxide selective coated load type palladium catalyst.The cerium oxide selective coated load type palladium catalyst being prepared using preparation method of the present invention not only has preferable low temperature active, also has more excellent high high-temp stability.
Description
Technical field
The present invention relates to noble metal carrier catalyst technical fields more particularly to a kind of cerium oxide selective coated to load
Type palladium catalyst and preparation method thereof.
Background technique
With the rapid development of our country's economy and the continuous improvement of people's trip requirements, Domestic Automotive Industry are swift and violent
Development, lead to vehicles number rapid growth, car ownership is continuously increased, so that China's moving source disposal of pollutants problem day
Benefit is prominent.Catalysis and purification technology is to reduce motor vehicle exhaust emission most efficient method at present, and precious metals pt, Rh, Pd are in car tail
Superior catalytic activity is shown in gas catalysis reaction, is the active component of automobile-use three-way catalyst.But Precious Metals Resources
Increasingly depleted, price is growing, and noble metal Decrement Technique is the huge challenge of automotive catalyst industry.The development of nano-catalytic
Greatly increase the catalytic efficiency of catalyst.But it since the thermal stability of noble metal nano catalyst is poor, was reacted in catalysis
Noble metal nano particles easily sintering deactivation in journey, seriously affects its industrial application.The operating temperature of present automotive catalyst can
Up to 800 DEG C or more, it is apparent that serious sintering deactivation can occur in use for noble metal nano particles, therefore improve
The thermal stability of noble metal catalyst is one of the main problem faced at present.
Currently, three-way catalyst is mainly support type three-way catalyst, the serious shadow of the thermal stability of noble metal nano particles
The catalytic activity of catalyst is rung, many researchers expand a system around how improving noble metal nano particles thermal stability
Column work, the more extensive method of research is to wrap up oxide noble metal nano particles to improve catalyst at present
High high-temp stability.Lu Junling etc. (science, 2012,335 (6073) 1205-1208) is using atomic layer deposition method to catalysis
Agent integrally carries out Al2O3The package of coating, when Al is enclosed in carry out 452O3After depositional packages, catalyst reacts 28h at 675 DEG C
Afterwards, the pattern of catalyst and activity can be effectively prevented catalyst and receive in high temperature application there is no substantially changeing
The case where rice corpuscles is sintered；Qin Yong etc. (Chem.Eur.J.2016,22,8438-8443) is using atomic layer deposition method to Al2O3Limit
The Pt nanoparticle in domain carries out ALD Al2O3Thin layer is modified to maximize metal-oxide interface, and catalyst is not only increased
Catalytic activity, stability have also obtained certain raising.But above-mentioned atomic layer deposition process needs specific instrument and equipment, and
Presoma needed for depositing is expensive, can not in high volume handle catalyst, therefore be not suitable for practical application.
Summary of the invention
The purpose of the present invention is to provide a kind of operating process simple, resistant to high temperatures to work well and lower-cost prepare oxygen
Change the method for cerium selective coated load type palladium catalyst.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of cerium oxide selective coated load type palladium catalyst, including following step
It is rapid:
By Pd/Al2O3Loaded catalyst, L-arginine, cerous nitrate and solvent mixing, are successively coated and are roasted, obtained
To cerium oxide selective coated load type palladium catalyst.
Preferably, the Pd/Al2O3The load capacity of Pd is 0.5wt%~5wt% in loaded catalyst.
Preferably, the Pd/Al2O3The molar ratio of Pd and the cerous nitrate in loaded catalyst are 1:(10~30).
Preferably, the molar ratio of the L-arginine and the cerous nitrate is (2.5~10): 1.
Preferably, the temperature of the cladding is 60~100 DEG C, time of the cladding is 8~for 24 hours.
Preferably, the temperature of the roasting is 500~900 DEG C, and the time of the roasting is 2~8h.
In the present invention, the solvent is preferably the mixed liquor of deionized water or/and ethyl alcohol；
Preferably, the Pd/Al2O3The preparation method of loaded catalyst, comprising the following steps:
By poly-vinyl alcohol solution, Na2PdCl4Solution and NaBH4Solution mixing, occurs reduction reaction, obtains containing Pd nanometers
The product system of particle；
By the product system containing Pd nanoparticle and carrier Al2O3Mixing, is impregnated, obtains Pd/Al2O3It is negative
Supported catalyst.
Preferably, the Na2PdCl4Na in solution2PdCl4Mass ratio with polyvinyl alcohol in poly-vinyl alcohol solution is
(2~3): (4~6)；
The Na2PdCl4Na in solution2PdCl4With NaBH4NaBH in solution4Molar ratio be 1:(4~6).
Preferably, the temperature of the dipping is 20~40 DEG C, and the time of the dipping is 10~20h.
The cerium oxide selective coated being prepared the present invention also provides the preparation method described in above-mentioned technical proposal is negative
Load type palladium catalyst, including Al2O3Be supported on the Al2O3Pd nano particle and CeO on carrier2；
The CeO2Selective coated is in Pd nano grain surface.
The present invention provides a kind of preparation methods of cerium oxide selective coated load type palladium catalyst, including following step
It is rapid: by Pd/Al2O3Loaded catalyst, L-arginine, cerous nitrate and solvent mixing, are successively coated and are roasted, obtain oxygen
Change cerium selective coated load type palladium catalyst.Cerium oxide in the present invention is a kind of active carrier material, with excellent
Hydrogen Energy power is stored, this is because it is there are two types of valence state, Ce under different conditions4+And Ce3+It can mutually convert.In oxygen-enriched item
Under part, extra oxygen is can be absorbed in cerium oxide；Under the conditions of dilute oxygen, oxygen can be discharged, is urged in selective coated load type palladium
The pollutant of vehicle exhaust can be effectively eliminated after agent.L-arginine is amphiprotic substance, and the both ends of molecule are respectively provided with
Guanidine radicals and carboxyl Liang Zhong functional group, wherein the amino in guanidine radicals has lone pair electrons, and Pd has electronics unoccupied orbital, and guanidine radicals can be with
Pd is coordinated；And carboxyl is soluble in water has elecrtonegativity, and Ce3+Ion has electropositive, and complexing can occur, and carries out carboxylic
Base and Ce3+The bonding of ion utilizes L-arginine induced oxidation cerium selective coated due to this special structure of L-arginine
Noble metal, not only can use cerium oxide selective coated noble metal expand noble metal-oxide interface to improve catalytic activity,
The anti-caking power of loaded catalyst can also be improved and then improve the thermal stability of noble metal carrier catalyst.
Detailed description of the invention
Fig. 1 is 1#, 2#, 3# catalyst sample at different temperatures to the three way activity of CO；
Fig. 2 is 1#, 2#, 3# catalyst sample at different temperatures to the three way activity of HC；
Fig. 3 is 1#, 2#, 3# catalyst sample at different temperatures to NOxThree way activity；
Fig. 4 is 4#, 5#, 6# catalyst sample at different temperatures to the three way activity of CO；
Fig. 5 is 4#, 5#, 6# catalyst sample at different temperatures to the three way activity of HC；
Fig. 6 is 4#, 5#, 6# catalyst sample at different temperatures to NOxThree way activity；
Fig. 7 is the XRD diagram of 1#, 2#, 3#, 4#, 4#, 6# catalyst sample；
Fig. 8 is that the TEM of 1# catalyst sample schemes；
Fig. 9 is that the TEM of 2# catalyst sample schemes；
Figure 10 is that the TEM of 3# catalyst sample schemes；
Figure 11 is that the TEM of 4# catalyst sample schemes；
Figure 12 is that the TEM of 5# catalyst sample schemes；
Figure 13 is that the TEM of 6# catalyst sample schemes.
Specific embodiment
The present invention provides a kind of preparation methods of cerium oxide selective coated load type palladium catalyst, including following step
It is rapid:
By Pd/Al2O3Loaded catalyst, L-arginine, cerous nitrate and solvent mixing, are successively coated and are roasted, obtained
To cerium oxide selective coated load type palladium catalyst.
In the present invention, if without specified otherwise, all raw material components are commercial product well known to those skilled in the art.
The present invention is by Pd/Al2O3Loaded catalyst, L-arginine, cerous nitrate and solvent mixing, successively carry out cladding and
Roasting, obtains cerium oxide selective coated load type palladium catalyst.In the present invention, the Pd/Al2O3In loaded catalyst
The load capacity of Pd is preferably 0.5wt%~5wt%, more preferably 1.0wt%~3.0wt%, and most preferably 1.5wt%~
2.5wt%.
In the present invention, the Pd/Al2O3The preparation method of loaded catalyst preferably includes following steps:
By poly-vinyl alcohol solution, Na2PdCl4Solution and NaBH4Solution mixing, occurs reduction reaction, obtains containing Pd nanometers
The product system of particle；
By the product system containing Pd nanoparticle and carrier Al2O3Mixing, is impregnated, obtains Pd/Al2O3It is negative
Supported catalyst.
The present invention is by poly-vinyl alcohol solution, Na2PdCl4Solution and NaBH4Solution mixing, occurs reduction reaction, is contained
The product system of Pd nanoparticle.In the present invention, the concentration of the poly-vinyl alcohol solution is preferably 1.5~2.5g/L, more excellent
It is selected as 1.8~2.2g/L；In the present invention, the solvent of the poly-vinyl alcohol solution is preferably deionized water.In the present invention, institute
State Na2PdCl4The concentration of solution is preferably 0.008~0.012mol/L, more preferably 0.009~0.011mol/L；In the present invention
In, the Na2PdCl4The solvent of solution is preferably deionized water.In the present invention, the NaBH4The concentration of solution is preferably
1.5~2.5g/L, more preferably 1.8~2.2g/L；The NaBH4The solvent of solution is preferably deionized water.
In the present invention, the Na2PdCl4Na in solution2PdCl4With the quality of polyvinyl alcohol in poly-vinyl alcohol solution
Than preferably (2~3): (4~6), more preferably (2.2~2.8): (4.5~5.5), most preferably (2.4~2.6): (4.8~
5.2)；The Na2PdCl4Na in solution2PdCl4With NaBH4NaBH in solution4Molar ratio be preferably 1:(4~6), more preferably
For 1:(4.5~5.5), most preferably 1:(4.8~5.2).
In the present invention, the mixing preferably carries out under conditions of ice-water bath and stirring；The present invention does not have the stirring
There is any special restriction, is carried out using whipping process well known to those skilled in the art.
In the present invention, the poly-vinyl alcohol solution, Na2PdCl4Solution and NaBH4Solution mixing is preferably by polyethylene
Alcoholic solution and Na2PdCl4After solution is stirred 15~25min, under agitation, add rapidly into obtained mixed system
Enter NaBH4Solution.In the present invention, the NaBH4The adding manner of solution is preferably using well known to those skilled in the art fast
The mode that speed is toppled over is added.
In the present invention, the mixing preferably carries out under conditions of ice-water bath；In the present invention, in poly-vinyl alcohol solution
And Na2PdCl4NaBH is rapidly joined in the mixed liquor of solution4The reduction reaction can be rapidly completed after solution, i.e., in polyethylene
Alcoholic solution and Na2PdCl4NaBH is rapidly joined in the mixed liquor of solution4After solution can rapid examination generated into product system greatly
The Pd particle of amount.
After obtaining the product system containing Pd nanoparticle, the present invention by the product system containing Pd nanoparticle with
Carrier Al2O3Mixing, is impregnated, obtains Pd/Al2O3Loaded catalyst；The present invention is to the carrier Al2O3Dosage do not have
Any special restriction, can satisfy the Pd/Al made2O3In loaded catalyst the load capacity of Pd 0.5wt%~
In the range of 5wt%.
In the present invention, the dipping preferably carries out under stirring conditions, and the present invention is to the no any spy of stirring
Different restriction is carried out using whipping process well known to those skilled in the art.
In the present invention, the temperature of the dipping is preferably 20~40 DEG C, and more preferably 25~35 DEG C, most preferably 28~
32℃；The time of the dipping is preferably 10~20h, more preferably 12~18h, most preferably 14~16h.
After the completion of dipping, the present invention obtains Pd/Al after preferably obtained product system is successively filtered and is dried2O3
Loaded catalyst；The present invention is to the no any special restriction of filtering, using filtering well known to those skilled in the art
?；In the present invention, the temperature of the drying is preferably 100~120 DEG C, and more preferably 105~115 DEG C；The present invention is to institute
Stating the dry time does not have any special restriction, using drying time well known to those skilled in the art and can make to filter institute
The moisture obtained in solid completely removes.
The Pd/Al2O3The mixing of loaded catalyst, L-arginine, cerous nitrate and solvent is preferably by Pd/Al2O3It is negative
Supported catalyst, water, L-arginine solution and cerous nitrate solution mixing；The solvent of the L-arginine solution is preferably deionization
Water；The concentration of the L-arginine solution is preferably 0.4~1.0mo l/L, more preferably 0.6~0.8mo l/L.In the present invention
In, the solvent of the cerous nitrate solution is preferably the mixed liquor of water and ethyl alcohol；Water and second in the mixed liquor of the water and ethyl alcohol
The volume ratio of alcohol is preferably 1:1；The concentration of the cerous nitrate solution is preferably 0.03~0.06mo l/L, more preferably 0.04~
0.05mo l/L。
In the present invention, the Pd/Al2O3The quality of loaded catalyst and the volume ratio of water are preferably (0.8~1.0)
G:(25~35) mL, more preferably (0.85~0.95) g:(28~32) mL.
In the present invention, the Pd/Al2O3Mole of the cerous nitrate in Pd and cerous nitrate solution in loaded catalyst
Than being preferably 1:(10~30), more preferably 1:(15~25), most preferably 1:(18~22).
In the present invention, the molar ratio of the cerous nitrate in the L-arginine and cerous nitrate solution in the L-arginine solution
Preferably (2.5~10): 1, more preferably (4~8): 1, most preferably (5~6): 1.
In the present invention, the Pd/Al2O3The mixing of loaded catalyst, water, L-arginine solution and cerous nitrate solution
It is preferred that carrying out at room temperature；The mixing is preferred are as follows: by Pd/Al2O3Loaded catalyst and water are mixed to get Pd/Al2O3
After the dispersion liquid of loaded catalyst；Again by the Pd/Al2O3The dispersion liquid of loaded catalyst successively with L-arginine solution
It is mixed with cerous nitrate solution.
The present invention is to the Pd/Al2O3The no any special restriction of the mixing of loaded catalyst and water, using ability
Mixed process known to field technique personnel carries out and makes the Pd/Al obtained after mixing2O3Supported catalyst agent dispersing liquid is uniformly dispersed
?.
In the present invention, the Pd/Al2O3The dispersion liquid of loaded catalyst mixes preferred stirring with L-arginine solution
Under conditions of carry out；In the present invention, the time of the stirring is preferably 30~50min, more preferably 35~45min, optimal
It is selected as 38~42min；The present invention does not have any special restriction to the rate of the stirring, using known to those skilled in the art
Stirring rate be stirred.
In the present invention, the mixing with cerous nitrate solution preferably carries out under stirring conditions；In the present invention, institute
The time for stating stirring is preferably 20~40min, more preferably 25~35min, most preferably 28~32min；The present invention is to described
The rate of stirring does not have any special restriction, is stirred using stirring rate well known to those skilled in the art.
In the present invention, the temperature of the cladding is preferably 60~100 DEG C, more preferably 70~90 DEG C, most preferably 75
~85 DEG C；The time of the cladding is preferably 8~for 24 hours, more preferably 15~20h.
After being covered to complete, the present invention is preferably successively filtered, washs and dries to obtained product system；The present invention couple
The no any special restriction of filtering, is carried out using filter process well known to those skilled in the art.
In the present invention, the washing is preferably successively washed using deionized water and ethyl alcohol.
In the present invention, the temperature of the drying is preferably 100~120 DEG C, and more preferably 105~115 DEG C；The present invention couple
The time of the drying does not have any special restriction, using drying time well known to those skilled in the art.
In the present invention, the roasting carries out preferably in air atmosphere；The temperature of the roasting is preferably 500~900
DEG C, more preferably 750~850 DEG C, most preferably 780~820 DEG C；The time of the roasting is preferably 2~8h, more preferably 3~
5h。
The cerium oxide selective coated being prepared the present invention also provides the preparation method described in above-mentioned technical proposal is negative
Load type palladium catalyst, including Al2O3Be supported on the Al2O3Pd nano particle and CeO on carrier2；
The CeO2It is coated on Pd nano grain surface；The load capacity of the Pd is 0.5wt%~2.5wt%；The CeO2
It is 5.4~47.8% in the mass fraction of the cerium oxide selective coated load type palladium catalyst.
Below with reference to embodiment to cerium oxide selective coated load type palladium catalyst provided by the invention and its preparation side
Method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Under conditions of ice-water bath and stirring, according to Na2PdCl4The proportion that mass ratio with polyvinyl alcohol is 2.76:1.5,
By concentration be 2g/L poly-vinyl alcohol solution and concentration be 0.01mol/L Na2PdCl4After solution mixing 20min, it is rapidly added
Concentration is the NaBH of 2g/L4Solution is (according to Na2PdCl4With NaBH4Molar ratio be 1:5 proportion), generate Pd nanometers a large amount of
Particle obtains the product system containing Pd nanoparticle；
According to Na2PdCl4The quality and Al of Pd in solution2O3Mass ratio be 1.23:98.77 proportion, by Al2O3It is added
In product system containing Pd nanoparticle, at 30 DEG C, 12h, filtering are stirred, 120 DEG C of dryings obtain Pd/Al2O3Support type is urged
Agent；
By 0.9g Pd/Al2O3Loaded catalyst is mixed with 30mL water, and after being uniformly dispersed, 10mL concentration, which is added, is
The L-arginine solution of 0.42mol/L after stirring 40min, adds the cerous nitrate solution that 40mL concentration is 0.03mol/L, stirs
After mixing 30min, after carrying out cladding 20h under the conditions of 90 DEG C, after successively using deionized water and ethanol washing, 120 DEG C of dryings,
3h is roasted at 500 DEG C, obtains cerium oxide selective coated load type palladium catalyst, the load capacity of precious metals pd is 1% at this time.Note
For 2# catalyst sample.
Embodiment 2
Under conditions of ice-water bath and stirring, according to Na2PdCl4The proportion that mass ratio with polyvinyl alcohol is 2.76:1.5,
By concentration be 2g/L poly-vinyl alcohol solution and concentration be 0.01mol/L Na2PdCl4After solution mixing 20min, it is rapidly added
Concentration is the NaBH of 2g/L4Solution is (according to Na2PdCl4With NaBH4Molar ratio be 1:5 proportion), generate Pd nanometers a large amount of
Particle obtains the product system containing Pd nanoparticle；
According to Na2PdCl4The quality and Al of Pd in solution2O3Mass ratio be 1.46:98.54 proportion, by Al2O3It is added
In product system containing Pd nanoparticle, at 35 DEG C, 12h, filtering are stirred, 120 DEG C of dryings obtain Pd/Al2O3Support type is urged
Agent；
By 0.9g Pd/Al2O3Loaded catalyst is mixed with 30mL water, and after being uniformly dispersed, 10mL concentration, which is added, is
The L-arginine solution of 0.84mol/L after stirring 40min, adds the cerous nitrate solution that 40mL concentration is 0.06mol/L, stirs
After mixing 30min, after carrying out coating reaction 20h under the conditions of 90 DEG C, after successively using deionized water and ethanol washing, 120 DEG C of dryings,
3h is roasted at 500 DEG C, obtains cerium oxide selective coated load type palladium catalyst, the load capacity of precious metals pd is 1% at this time.
It is denoted as 3# catalyst sample.
Comparative example 1
Under conditions of ice-water bath and stirring, according to Na2PdCl4The proportion that mass ratio with polyvinyl alcohol is 2.76:1.5,
By concentration be 2g/L poly-vinyl alcohol solution and concentration be 0.01mol/L Na2PdCl4After solution mixing 20min, it is rapidly added
Concentration is the NaBH of 2g/L4Solution is (according to Na2PdCl4With NaBH4Molar ratio be 1:5 proportion), generate Pd nanometers a large amount of
Particle obtains the product system containing Pd nanoparticle；
According to Na2PdCl4The quality and Al of Pd in solution2O3Mass ratio be 1:99 proportion, by Al2O3Addition contains Pd
In the product system of nanoparticle, at 30 DEG C, 12h, filtering are stirred, 120 DEG C of dryings roast 3h at 500 DEG C, obtain Pd/
Al2O3Loaded catalyst is denoted as 1# catalyst sample.
Embodiment 3
In air atmosphere, 900 DEG C of roasting 5h are cooled to room temperature the part 1# catalyst sample that comparative example 1 is obtained
To the aged samples of 1# catalyst, it is denoted as 4# catalyst sample；
In air atmosphere, 900 DEG C of roasting 5h are cooled to room temperature the part 2# catalyst sample that embodiment 1 is obtained
To the aged samples of 2# catalyst, it is denoted as 5# catalyst sample；
In air atmosphere, 900 DEG C of roasting 5h are cooled to the part 3# loaded catalyst sample that embodiment 2 is obtained
Room temperature obtains the aged samples of 3# catalyst, is denoted as 6# catalyst sample；
1#, 2#, 3#, 4#, 5#, 6# catalyst sample are subjected to three-way catalytic activity evaluation test；The composition of reaction gas
Are as follows: 1.6%CO, 0.23%H2, 500ppm HC (C3H8/C3H6=2/1), 1000ppm NOx, 1.0%O2, N2For Balance Air, gas
Body flow is V=1000mL/min；
Fig. 1 is 1#, 2#, 3# catalyst sample at different temperatures to the three way activity of CO；Fig. 2 is 1#, 2#, 3# catalyst
Sample is at different temperatures to the three way activity of HC；Fig. 3 is 1#, 2#, 3# catalyst sample at different temperatures to NOxTriple effect
Activity；By Fig. 1~3 it is found that CO, HC and NO of 1# catalyst samplexComplete conversion temperature be respectively 219 DEG C, 276 DEG C and
220℃；CO, HC and NO of 2# catalyst samplexComplete conversion temperature be respectively 177 DEG C, 234 DEG C and 179 DEG C；3# catalyst
CO, HC and NO of samplexComplete conversion temperature be respectively 180 DEG C, 256 DEG C and 198 DEG C；The catalyst that Examples 1 to 2 obtains
The three-way catalytic activity of sample is far superior to the three-way catalytic activity of comparative example 1, illustrates that preparation method of the present invention is more right
Ratio has preferable low-temperature catalytic activity；
Fig. 4 is 4#, 5#, 6# catalyst sample at different temperatures to the three way activity of CO；Fig. 5 is 4#, 5#, 6# catalyst
Sample is at different temperatures to the three way activity of HC；Fig. 6 is 4#, 5#, 6# catalyst sample at different temperatures to NOxTriple effect
Activity；By Fig. 4~6 it is found that CO, HC and NO of 4# catalyst samplexComplete conversion temperature be respectively 255 DEG C, 380 DEG C and
358℃；CO, HC and NO of 5# catalyst samplexComplete conversion temperature be respectively 218 DEG C, 276 DEG C and 219 DEG C；6# catalyst
CO, HC and NO of samplexComplete conversion temperature be respectively 198 DEG C, 253 DEG C and 199 DEG C；The catalyst that Examples 1 to 2 obtains
Three-way catalytic activity after sample aging is far superior to the three-way catalytic activity after 1 aging of comparative example, illustrates of the present invention
Preparation method has preferable high-temperature stability compared with comparative example, and before the obtained catalyst sample aging of embodiment 1 and embodiment 2
Substantially there is no biggish change, the catalyst sample for illustrating that preparation method provided by the invention obtains not only has activity afterwards
There is preferable low temperature active, also there is more excellent high high-temp stability.
Embodiment 4
Phase structure analysis is carried out to 1#, 2#, 3#, 4#, 5#, 6# catalyst sample using X-ray powder diffraction；
Fig. 7 is the XRD diagram of 1#, 2#, 3#, 4#, 5#, 6# catalyst sample；As shown in Figure 7, Al in sample2O3It is main to spread out
It penetrates peak and belongs to orthogonal and tetragonal crystal system Al2O3(JCPDS PDF#46-1215 and PDF#16-0394), CeO2Oxide belongs to
Cubic phase structure (JCPDS PDF#34-0394).The presence of PdO phase is all not detected in 1#, 3#, 5# catalyst sample；And it is old
Only have 2# sample detection to the presence of PdO phase in 2#, 4#, 6# sample after change, illustrating 1# catalyst sample, it passes through at high temperature
After reason, the sintering of noble metal is had occurred in sample；And 4#, 6# sample do not detect the presence of PdO phase, illustrate that noble metal still divides
It dissipates well, there is no the sintering of noble metal, illustrates that the method substantially increases the thermal stability of catalyst.
Embodiment 5
TEM characterization is carried out to 1#, 2#, 3#, 4#, 5#, 6# catalyst sample using transmission electron microscope；Fig. 8~13 point
Not Wei 1#, 2#, 3#, 4#, 5#, 6# catalyst sample TEM figure, as seen from the figure, the 1# catalyst sample that comparative example 1 is prepared
The partial size of middle Pd nanoparticle is 3~4nm or so, and Pd nanoparticle has apparent aggregation life in the 4# catalyst sample after aging
Long phenomenon；CeO in the 2# catalyst sample that embodiment 1 is prepared2Oxide particle is covered on the surface of Pd catalyst, aging
Redisperse phenomenon has occurred in 5# catalyst sample afterwards, still with higher point of the noble metal in catalyst after illustrating aging
Divergence, there is no the sintering phenomenons of noble metal；CeO in the 3# catalyst sample that embodiment 2 is prepared2Oxide particle covers
The surface in Pd catalyst is covered, redisperse phenomenon, the catalyst after illustrating aging have occurred in the 6# catalyst sample after aging
In noble metal dispersion degree still with higher, there is no the sintering phenomenons of noble metal.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of cerium oxide selective coated load type palladium catalyst, comprising the following steps:
By Pd/Al2O3Loaded catalyst, L-arginine, cerous nitrate and solvent mixing, are successively coated and are roasted, obtain oxygen
Change cerium selective coated load type palladium catalyst.
2. preparation method as described in claim 1, which is characterized in that the Pd/Al2O3The load of Pd in loaded catalyst
Amount is 0.5wt%~5wt%.
3. preparation method as described in claim 1, which is characterized in that the Pd/Al2O3Pd and institute in loaded catalyst
The molar ratio for stating cerous nitrate is 1:(10~30).
4. preparation method as described in claim 1, which is characterized in that the molar ratio of the L-arginine and the cerous nitrate is
(2.5~10): 1.
5. preparation method as described in claim 1, which is characterized in that the temperature of the cladding is 60~100 DEG C, the cladding
Time be 8~for 24 hours.
6. preparation method as described in claim 1, which is characterized in that the temperature of the roasting is 500~900 DEG C, the roasting
The time of burning is 2~8h.
7. preparation method as described in claim 1, which is characterized in that the Pd/Al2O3The preparation method of loaded catalyst,
The following steps are included:
By poly-vinyl alcohol solution, Na2PdCl4Solution and NaBH4Solution mixing, occurs reduction reaction, obtains containing Pd nanoparticle
Product system；
By the product system containing Pd nanoparticle and carrier Al2O3Mixing, is impregnated, obtains Pd/Al2O3Support type is urged
Agent.
8. preparation method as claimed in claim 7, which is characterized in that the Na2PdCl4Na in solution2PdCl4With polyethylene
The mass ratio of polyvinyl alcohol is (2~3): (4~6) in alcoholic solution；
The Na2PdCl4Na in solution2PdCl4With NaBH4NaBH in solution4Molar ratio be 1:(4~6).
9. preparation method as claimed in claim 7, which is characterized in that the temperature of the dipping is 20~40 DEG C, the dipping
Time be 10~20h.
10. the cerium oxide selective coated load type palladium catalysis that preparation method according to any one of claims 1 to 9 is prepared
Agent, including Al2O3Be supported on the Al2O3Pd nano particle and CeO on carrier2；
The CeO2Selective coated is in Pd nano grain surface.
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| CN111841631A (en) * | 2020-08-05 | 2020-10-30 | 济南大学 | Polypyrrole-cerium dioxide-gold composite nano material |
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| CN113058598A (en) * | 2021-03-18 | 2021-07-02 | 北京工业大学 | Improved ALD method for depositing CeO2Method (2) |
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| CN114029053A (en) * | 2021-11-22 | 2022-02-11 | 中国科学院大连化学物理研究所 | Preparation method of supported catalyst and application of supported catalyst in preparation of methyl glycolate from ethylene glycol |
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| CN111111676A (en) * | 2020-03-13 | 2020-05-08 | 福州大学 | Coated nickel-based catalyst and preparation method thereof |
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| CN111841631A (en) * | 2020-08-05 | 2020-10-30 | 济南大学 | Polypyrrole-cerium dioxide-gold composite nano material |
| CN111841631B (en) * | 2020-08-05 | 2021-11-02 | 济南大学 | Polypyrrole-cerium dioxide-gold composite nano material |
| CN112916000A (en) * | 2021-01-15 | 2021-06-08 | 兰州大学 | Photocatalytic material for reducing nitrogen to produce ammonia and preparation method and application thereof |
| CN113058598A (en) * | 2021-03-18 | 2021-07-02 | 北京工业大学 | Improved ALD method for depositing CeO2Method (2) |
| CN113404573A (en) * | 2021-06-08 | 2021-09-17 | 大连理工大学 | Application of supported palladium-cerium-based catalyst for storing nitrogen oxides at low temperature in automobile cold start reaction |
| WO2022267202A1 (en) * | 2021-06-23 | 2022-12-29 | 广东西敦千江粉漆科学研究有限公司 | Method for preparing low-temperature cured powder coating by means of post-mixing, and related composite nano low-temperature cured catalyst and preparation method therefor |
| CN113578326A (en) * | 2021-08-18 | 2021-11-02 | 哈尔滨工业大学（深圳） | SiO2Ni-loaded double-layer core-shell catalyst and preparation method and application thereof |
| CN114011405A (en) * | 2021-11-22 | 2022-02-08 | 中国科学院大连化学物理研究所 | Preparation method of composite oxide supported catalyst and application of composite oxide supported catalyst in preparation of methyl glycolate from ethylene glycol |
| CN114029053A (en) * | 2021-11-22 | 2022-02-11 | 中国科学院大连化学物理研究所 | Preparation method of supported catalyst and application of supported catalyst in preparation of methyl glycolate from ethylene glycol |
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