CN108435181A - A method of coated anti-carbon catalyst is prepared based on atomic layer deposition - Google Patents
A method of coated anti-carbon catalyst is prepared based on atomic layer deposition Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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Abstract
The invention belongs to metal oxide catalysts to prepare correlative technology field, and disclose a kind of method preparing coated anti-carbon catalyst based on atomic layer deposition, including：It is distributed metal nanoparticle in the surface homoepitaxial of reaction carriers, metal-supported catalyst sample is thus made；Required catalyst prod is obtained by atomic layer deposition method deposition oxide auxiliary agent on the surface of metal-supported catalyst sample, while targeted design has been carried out to the specific process parameter of atomic layer deposition reaction.By means of the invention it is possible to so that oxides additive realizes the package of selectivity in active metal nano grain surface given activity site, while realizing discontinuous network-like growth in its multiple crystal face, while effectively improving the Activity and stabill of catalyst.
Description
Technical field
The invention belongs to metal oxide catalysts to prepare correlative technology field, and atom is based on more particularly, to one kind
The method that layer deposition prepares cladded type anti-carbon catalyst.
Background technology
With the high speed development of human society, people have far surpassed in the past the dependence of the energy, in addition the evil of ecological environment
Change, the mankind is made also to change correspondingly the Land use systems of three big basic fossil fuels (coal, petroleum and natural gas).Using various each
The catalyst of sample makes the HC compounds in coal, oil, natural gas that cracking reaction generation low-carbon product occur, and it is big to greatly improve three
The utilization rate of fossil fuel largely alleviates the energy and environmental crisis of the mankind.But it is catalyzed in these catalytic process
Agent surface is condensed carbon distribution and cracking carbon distribution frequent occurrence, and carbon distribution can be gradually formed in catalyst surface；Carbon distribution can not only cover work
Property center, and since coke accumulates, block duct, be also easy to prevent reactant from strong absorption occurs close on activated centre,
The surface utilisation of catalyst is greatly reduced, therefore, the carbon accumulation resisting ability how research improves these catalyst is just constituting this
One of the technical issues of field is paid close attention to.
For example, during the cracking of methane is converted into clean fuel, methane dry method reforms (dry
Reforming of methane, DRM) it is used as a kind of prevailing technology, attract the attention of researchers with many advantages.So
And H in the synthesis gas usually obtained by DRM processes2/ CO molar ratios are less than 1, are attributed to side reaction reverse water-gas-shift reaction
Consume product H2, therefore, to avoid the reaction from occurring, DRM reaction temperatures are usually between 600-800 DEG C.It is at present
Only, Ni bases catalyst becomes most potential and substitutes the non-expensive of noble metal because it is with higher catalytic activity in DRM catalyst
Metallic catalyst, but because side reaction methane cracking leads to carbon distribution, the carbon accumulation of generation is on active catalyst sites surface and most
Being completely covered eventually causes catalyst structure to inactivate.Therefore, how to overcome carbon distribution, the catalyst for researching and developing high stability is entirely to reform
The key of reaction.
For the above technical problem, the resolving ideas that the prior art proposes is mainly by adding auxiliary agent and regulating and controlling carrier
Acid-base property come improve Catalyst Adsorption and activation CO2Ability eliminate carbon distribution, but its carbon ability that disappears is certain, not from source
Head inhibits the generation of carbon distribution.In addition, in catalytic process, key characteristic of the catalytic activity as catalyst is to improve target production
The important method of produce rate.Although also proposed some such as screening auxiliary agents in the prior art, adjusting auxiliary agent content change activity gold
The chemical state etc. of category, or change method for preparing catalyst and improve the dispersion degree of active metal nano particle or to catalysis
Agent carrier, which is modified, carrys out anchoring activity metal etc. to provide the solution of catalytic activity, but these prior arts often can not
It makes and being effectively improved in terms of catalyst stability and active two indices simultaneously.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides one kind preparing packet based on atomic layer deposition
The method of type anti-carbon catalyst is covered, wherein by introducing atomic layer deposition method and to the critical craft etc. of its reaction route
Targetedly Curve guide impeller is re-started, the bonding mechanism especially for auxiliary agent in metal nanoparticle active site carries out
Analysis and research can not only accordingly allow metal oxide auxiliary agent to execute the heavy of selectivity in multiple crystal faces of active metal surface
Product realizes discontinuous specific position cladding, is significantly expanded the interfacial area formed between active metal-auxiliary agent, it is often more important that
It can also be passivated the easy carbon distribution site of active metal surface by selective coated, existing all kinds of technologies of preparing is effectively inhibited to be brought
Carbon distribution problem, to obtain more high stability, active catalyst prod can be effectively improved simultaneously, and be particularly suitable for methane
The application and preparation occasion of CO 2 reforming reaction catalyst etc product.
Correspondingly, it is proposed, according to the invention, provide a kind of side preparing cladded type anti-carbon catalyst based on atomic layer deposition
Method, which is characterized in that this method includes the following steps：
(i) aluminium oxide, titanium oxide or other analogs are chosen as reaction carriers, in its surface homoepitaxial distribution activity
Thus metal-supported catalyst sample is made in metal nanoparticle；
(ii) on the surface of obtained metal-supported catalyst sample, atomic layer deposition method deposition oxygen is continued through
Compound auxiliary agent obtains required catalyst prod, and in the process, the technological parameter of the atomic layer deposition reaction is set
It is as follows：
Using ozone and organometallic complex as presoma, nitrogen or helium as carrier gas, atomic layer deposition
Reaction temperature is 120 DEG C~220 DEG C, and the presoma burst length is 30s~60s, and carrier gas scavenging period is 60-120s, and should
Oxides additive deposits 2~10 cycles on the surface of metal-supported catalyst sample, so that metal oxide helps
Agent realizes the packet of selectivity in the active metal nano grain surface given activity site of the metal-supported catalyst sample
It wraps up in, while discontinuous network-like growth is realized in multiple crystal faces of metal nanoparticle.
By conceiving above, since atomic layer deposition method is that one kind passing through cycle alternation based on vaporous precursors in substrate
The half-reaction after substrate surface chemisorption saturation of the film preparing technology of reaction, wherein presoma stops, and before two kinds
Drive body and constitute a cycle preparation process through two half-reactions, this mode can ensure that each reaction only deposit one layer (or less than
One layer of atom), thus reach effective control that atomic scale is accurate to deposited material.By this method, by introducing atomic layer
For sedimentation to having made targeted design to its critical craft, the present invention can be on the larger carrier of specific surface area with original
Sub- form membrane growth activity metal layer by layer is conducive to the height that active metal nano particle is realized on high surface area carrier
Dispersion；In addition, auxiliary agent realizes discontinuous network-like life in atomic layer deposition process in multiple crystal faces of metal nanoparticle
It is long, accordingly while catalyst activity is greatly improved, it is often more important that activity can also be passivated by selective coated
The easy carbon distribution site in metal surface, effectively inhibits carbon distribution problem caused by existing all kinds of technologies of preparing, actual test to also indicate that choosing
Selecting property atomic layer deposition method can substantially eliminate the generation of carbon distribution problem；More specifically, the cladded type auxiliary agent oxidation of network-like production
Object nano particle even Subnano-class particle, can as possible inhibit the generation of carbon distribution, in addition from the source that product structure forms
Even if on a small quantity generate carbon whisker position equally can effectively destroying carbon nanometer tube growth continuity, finally significantly suppress product
The generation of carbon problem and the catalyst prod for obtaining high stable.
As it is further preferred that for step (ii), the metal oxide auxiliary agent is using low activity, that is, organic
The big Atomic layer deposition precursor of coordinating group (such as THD=2,2,6,6- tetramethyl -3,5- heptadione) is obtained to aoxidize, and
In this atomic layer deposition reaction process, cooling regulation and control are carried out to depositing temperature so that real reaction temperature is less than normal reaction temperature
About 50 degrees Celsius of degree or more.
Why design in this way, on the one hand, pyroreaction can improve the growth activity of Atomic layer deposition precursor, and reduction helps
Bonding bonded energy difference between agent oxide and active metal surface, lattice surface matching difference, metallic particles different parts
Surface energy difference, cannot achieve selective deposition；Therefore, on the other hand, also specially to the technique mistake of deposition aid in the present invention
Specific aim takes Low temperature regulation processing in journey, and the purpose done so is that improve presoma grows in active metal different loci
Active difference, to reach site selectivity growth.
As it is further preferred that the Atomic layer deposition precursor of the low activity preferably selects one kind in following substance
Or combination：Ce (thd) 4, Co (acac) 2, La (acac) 3 and four (dimethylamino) zirconiums.
As it is further preferred that in step (ii), the cooling regulation process carried out for depositing temperature is preferred
It executes, and further preferably regulates and controls to 120-150 degrees Celsius of temperature model in such a way that program cools down monitoring deposition rate
It encloses.
As it is further preferred that for step (i), on reaction carriers surface, homoepitaxial distribution active metal is received
The process of rice grain preferably uses atomic layer deposition method to realize, specific process parameter further preferably setting is as follows：Using smelly
As presoma, nitrogen or helium as carrier gas, atomic layer deposition reaction temperature is 150 DEG C for oxygen and organometallic complex
~200 DEG C, the presoma burst length is 60s~120s, and carrier gas scavenging period is 60~120s, is finally deposited on the surface of the carrier
2~6 cycles.
As it is further preferred that for step (i), the active metal nano particle preferably use Ni, Fe or
Other analogs, and its average particle diameter size is preferably controlled to 2nm~6nm.
As it is further preferred that above-mentioned cladded type anti-carbon catalyst is preferably methane reforming with carbon dioxide catalysis
Agent.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below
Technological merit：
1, by introducing atomic layer deposition method and having re-started specific aim to the critical craft etc. of its reaction route
Curve guide impeller metal onidiges auxiliary agent can be allowed to be received in active metal compared with all kinds of catalyst preparation modes of the prior art
The package of selectivity is realized in rice grain surface different activities site, while realizing discontinuous network-like growth in multiple crystal faces,
It mutually should be able to be significantly expanded the interfacial area formed between active metal-auxiliary agent, therefore be conducive to effectively improve the activity of catalyst；
2, this invention particularly focuses on carbon distribution elimination problem in terms of, nanoscale even Subnano-class auxiliary agent oxide
Grain is selectively coated on the easily raw carbon potential point in given activity site i.e. metal surface of active metal, is passivated carbon distribution site, in this way
It not only can inhibit the generation of carbon distribution problem, but also the characteristic of the discontinuous network-like growth of atomic layer deposition auxiliary agent from source
Even if also capableing of the growth continuity of destroying carbon nanometer tube in the position for generating carbon whisker on a small quantity, finally significantly suppresses carbon distribution and ask
The generation of topic and the catalyst prod for obtaining high stable；
3, easy to operation according to the preparation method of this process route, controllability is strong, is therefore particularly suitable for methane titanium dioxide
The application and preparation occasion of carbon reforming reaction catalyst etc product.
Description of the drawings
Fig. 1 is to be shown as preparing coated anti-carbon based on atomic layer deposition and urge constructed by the present invention for demonstration
The process method flow chart of agent；
Fig. 2 is to be shown as the catalyst of the present invention by taking Ni base catalyst methane reforming with carbon dioxide as an example
The stability schematic diagram obtained；
Fig. 3 is to be shown as the catalyst of the present invention by taking Ni base catalyst methane reforming with carbon dioxide as an example
The thermogravimetric analysis figure of the elimination carbon distribution obtained.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
Fig. 1 is to be shown as preparing cladded type anti-carbon based on atomic layer deposition and urge constructed by the present invention for demonstration
The process method flow chart of agent.As shown in Figure 1, the present invention mainly by its reaction route and its critical craft,
Factors such as the mechanism of action etc. have re-started research and design, are accordingly desirable to substantially eliminate inevitable production in the prior art
Raw catalyst carbon deposition effect, while additionally aiding the catalysis reaction for realizing high stability, high activity.To have below to it
Body illustrates.
It is possible, firstly, to choose aluminium oxide, titanium oxide or other analogs as reaction carriers, pass through atomic layer deposition method
(can also take infusion process or other modes) is distributed active metal nano particle in its surface homoepitaxial, and metal is thus made
Loaded catalyst sample；
Then, on the surface of obtained metal-supported catalyst sample, atomic layer deposition method deposition is continued through
Auxiliary agent oxide obtains required catalyst prod, and in the process, the technological parameter of the atomic layer deposition reaction is set
It is fixed as follows：Using ozone and organometallic complex as presoma, nitrogen or helium as carrier gas, atomic layer deposition is anti-
It is 120 DEG C~220 DEG C to answer temperature, and the presoma burst length is 30s~60s, and carrier gas scavenging period is 60-120s, and the oxygen
Compound auxiliary agent deposits 2~10 cycles on the surface of metal-supported catalyst sample.
So that active metal nano grain surface specific work of the oxidation agent aid in the metal-supported catalyst sample
Property site realize the package of selectivity, while realizing discontinuous network-like growth in multiple crystal faces of metal nanoparticle.Institute
State oxides additive and aoxidized using the Atomic layer deposition precursor of low activity it is obtained, and in this atomic layer deposition reaction process
In, cooling regulation and control are carried out to depositing temperature so that real reaction temperature is less than about 50 degrees Celsius of well-defined reaction temp or more, thus
Make multiple crystalline substances of the metal onidiges auxiliary agent on the active metal nano grain surface of the metal-supported catalyst sample
The deposition of selectivity is realized in face, and then realizes discontinuous network-like growth.
As the above specific explanations are conducive to because of the self-limiting characteristics of atomic layer deposition itself in high surface area carrier
The upper high dispersive for realizing active metal nano particle, while in active metal nano grain surface deposition aid clad, gold
The interfacial area formed between category-auxiliary agent is much larger than traditional preparation method, therefore is conducive to raising catalyst using this method and lives
Property.In addition more importantly so that active metal nanometer of the metal oxide auxiliary agent in the metal-supported catalyst sample
The package of selectivity is realized in particle surface given activity site, while not being connected in the realization of multiple crystal faces of active metal nano particle
Continuous network-like growth.This state can not only significantly inhibit the generation of deposited carbon effect from the source of product configurations, but also
Even for a small amount of position for generating carbon whisker equally can destroying carbon nanometer tube growth continuity.
A preferred embodiment according to the invention, the metal oxide auxiliary agent use low activity, that is, organic coordination base
The big Atomic layer deposition precursor of group's (such as THD=2,2,6,6- tetramethyl -3,5- heptadione) is obtained to aoxidize, and former herein
During sublayer deposition reaction, cooling regulation and control are carried out to depositing temperature so that real reaction temperature is less than well-defined reaction temp about 50
Degree Celsius or more.
Another preferred embodiment according to the invention, for being received in reaction carriers surface homoepitaxial distribution active metal
The process of rice grain preferably uses atomicity sedimentation to complete, and the further preferably setting of its key process parameter is as follows：Make
Use ozone and organometallic complex as presoma, nitrogen or helium as carrier gas, atomic layer deposition reaction temperature is
150 DEG C~200 DEG C, the presoma burst length is 60s~120s, and carrier gas scavenging period is 60~120s, finally in carrier surface
2~6 cycles of upper deposition.
A preferred embodiment according to the invention, the active metal nano particle preferably use Ni, Fe or other
Analog, and its average particle diameter size is preferably controlled to 2nm~6nm.
The Atomic layer deposition precursor of the low activity preferably selects one kind or combination in following substance：Ce(thd)4、
Co (acac) 2, La (acac) 3 and four (dimethylamino) zirconiums.
In addition, the cooling regulation process carried out for depositing temperature preferably uses program cooling monitoring deposition rate
Mode executes, and further preferably regulates and controls to 120-150 degrees Celsius of temperature range.
Embodiment 1
Take 2g γ-Al2O3, 850 DEG C of roasting 5h, take 0.63g nickel nitrates to be dissolved in deionized water in Muffle furnace, using etc.
Nickel nitrate solution is added in aluminium oxide by volume impregnation method, at room temperature dry 12h, 120 DEG C of dry 12h, 550 DEG C of roastings in air
6h finally restores 3h to get to Ni/Al in 650 DEG C of hydrogen atmospheres2O3Catalyst.
By the Ni/Al of preparation2O3Catalyst is put into atomic layer deposition apparatus, and the oxygen of 3/6/9 cycle is deposited on its surface
Compound auxiliary agent, is cobalt source using two (acetylacetone,2,4-pentanedione) cobalts, and another presoma is ozone.The reaction temperature of atomic layer deposition is 150
DEG C, carrier gas is nitrogen, and the presoma burst length is 60s, and nitrogen scavenging period is 60s.Finally in active metal Ni nano particles
Surface has obtained the cobalt oxide nanometer layer of selective growth.
Catalytic methane CO 2 reforming reaction is can be applied to by the sample obtained by above example 1, it is used
Reaction condition is：T=650 DEG C, GHSV=36000h-1, CH4/CO2=1:1.
It is the stability test figure of four catalyst methane reforming with carbon dioxide as shown in Figure 2, can sees
Going out the stability of Ni base catalyst after oxides additive selective coated is improved；As shown in Figure 3, it is catalyst first
The thermogravimetric analysis figure of carbon distribution after alkane CO 2 reforming reaction, it can be seen that the carbon deposition quantity for the catalyst that cobalt oxide coats in figure
It is apparent less, arrive 9cycCoOxWhen coating Ni base catalyst, the catalyst after reaction shows atomic layer deposition almost without carbon distribution
Selective growth oxides additive successfully inhibits the formation of carbon distribution in Ni base catalyst activities metal surface.
Embodiment 2
Take 0.2g γ-Al2O3, 850 DEG C of roasting 5h, are put into atomic layer deposition apparatus in Muffle furnace, are deposited on its surface
The nickel oxide of 5 cycles is nickel source using dicyclopentadienyl nickel, and another presoma is ozone, and the reaction temperature of atomic layer deposition is 150
DEG C, carrier gas is nitrogen, and the presoma burst length is 60s, and nitrogen scavenging period is 60s, obtains NiO/Al2O3, finally at 650 DEG C
3h is restored in hydrogen atmosphere to get to Ni/Al2O3Catalyst.
By the Ni/Al of preparation2O3Catalyst is put into atomic layer deposition apparatus, and 3/6/9 cycle is deposited on its surface,
Oxides additive, is cobalt source using two (acetylacetone,2,4-pentanedione) cobalts, and another presoma is ozone.The reaction temperature of atomic layer deposition is
150 DEG C, carrier gas is nitrogen, and the presoma burst length is 60s, and nitrogen scavenging period is 60s.Finally in active metal Ni nanometers
Grain surface has obtained the cobalt oxide nanometer layer of selective growth.
Embodiment 3
Take 2g TiO2, 650 DEG C of roasting 5h, ferric nitrate are dissolved in deionized water, using incipient impregnation in Muffle furnace
Iron nitrate solution is added in titanium oxide by method, at room temperature dry 12h, 120 DEG C of dry 12h, 650 DEG C of roasting 6h in air, finally
Reductase 12 h is to get to Fe/TiO in 550 DEG C of hydrogen atmospheres2Catalyst.
By the Fe/TiO of preparation2Catalyst is put into atomic layer deposition apparatus, and the oxygen of 2/5/8 cycle is deposited on its surface
Compound auxiliary agent, is lanthanum source using tri acetylacetonato lanthanum, and another presoma is ozone.The reaction temperature of atomic layer deposition is 160
DEG C, carrier gas is nitrogen, and the presoma burst length is 60s, and nitrogen scavenging period is 60s.Finally in active metal Fe nano particles
Surface has obtained the lanthana nanometer layer of selective growth.
Embodiment 4
Take 2g γ-Al2O3, 850 DEG C of roasting 5h, take 0.63g nickel nitrates to be dissolved in deionized water in Muffle furnace, using etc.
Nickel nitrate solution is added in aluminium oxide by volume impregnation method, at room temperature dry 12h, 120 DEG C of dry 12h, 550 DEG C of roastings in air
6h finally restores 3h to get to Ni/Al in 650 DEG C of hydrogen atmospheres2O3Catalyst.
By the Ni/Al of preparation2O3Catalyst is put into atomic layer deposition apparatus, and the oxygen of 3/6/9 cycle is deposited on its surface
Compound auxiliary agent is cerium source using four (2,2,6,6,-tetramethyl -3,5- heptadione acid) ceriums, and another presoma is ozone.Atomic layer
The reaction temperature of deposition is 160 DEG C, and carrier gas is nitrogen, and the presoma burst length is 60s, and nitrogen scavenging period is 60s.Finally exist
Active metal Ni nano grain surfaces have obtained the cerium oxide nano layer of selective growth.
To sum up, atomic layer deposition method can be used through overtesting in designed reaction route and technological parameter through the invention
Be conducive to realize the high dispersive of active metal nano particle on high surface area carrier, while in active metal nano grain surface
When deposition aid clad, metal-auxiliary agent interfacial characteristics are controllable；In addition, on the carbon distribution site of active metal nano particle
Coated catalyst of the selective deposition oxides additive to inhibit carbon distribution to be formed, can be adjusted by controlling growth technique
The cladding site of clad and cladding thickness.Demonstrate effectiveness of the invention, feasibility and controllability.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (5)
1. a kind of method preparing coated anti-carbon catalyst based on atomic layer deposition, which is characterized in that under this method includes
Row step：
(i) aluminium oxide, titanium oxide or other analogs are chosen as reaction carriers, are distributed active metal in its surface homoepitaxial
Thus metal-supported catalyst sample is made in nano particle；
(ii) on the surface of obtained metal-supported catalyst sample, atomic layer deposition reaction method deposition oxygen is continued through
Compound auxiliary agent obtains required catalyst prod, and in the process, the technological parameter of the atomic layer deposition reaction is set
It is as follows：
Using ozone or oxygen and organometallic complex as presoma, nitrogen or helium as carrier gas, atomic layer deposition
Product reaction temperature is 120 DEG C~220 DEG C, and the presoma burst length is 30s~60s, and carrier gas scavenging period is 60-120s, and
The oxides additive deposits 2~10 cycles on the surface of metal-supported catalyst sample, so that oxidation agent aid
The package of selectivity is realized in the active metal nano grain surface given activity site of the metal-supported catalyst sample,
Simultaneously discontinuous network-like growth is realized in multiple crystal faces of noble metal nano particles.
2. the method as described in claim 1, which is characterized in that for step (ii), the oxides additive is using low
Active namely big organic coordination group Atomic layer deposition precursor oxidation is made, and in this atomic layer deposition reaction process
In, cooling regulation and control are carried out to depositing temperature so that real reaction temperature is less than about 50 degrees Celsius of well-defined reaction temp or more.
3. method as claimed in claim 1 or 2, which is characterized in that the Atomic layer deposition precursor of the low activity is preferably selected
Select one kind in following substance or combination：Ce (thd) 4, Co (acac) 2, La (acac) 3 and four (dimethylamino) zirconiums.
4. the method as described in claim 1-3 any one, which is characterized in that in step (ii), for depositing temperature into
The capable cooling regulation process executes preferably in such a way that program cools down monitoring deposition rate, and further preferably regulates and controls
To 120-150 degrees Celsius of temperature range.
5. the method as described in claim 1-4 any one, which is characterized in that the active metal nano particle preferably uses
Ni, Fe or other analogs, and its average particle diameter size is preferably controlled to 2nm~6nm.
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Cited By (4)
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| CN110026196A (en) * | 2019-05-06 | 2019-07-19 | 中国科学院山西煤炭化学研究所 | A kind of supported, heterogeneous catalyst and its preparation method and application |
| CN112246245A (en) * | 2020-09-16 | 2021-01-22 | 华南理工大学 | Supported nickel-based catalyst and preparation method and application thereof |
| CN114042452A (en) * | 2021-12-03 | 2022-02-15 | 中汽研（天津）汽车工程研究院有限公司 | Ammonia oxidation catalyst for diesel vehicle tail gas, preparation method and application thereof |
| CN115443190A (en) * | 2020-04-08 | 2022-12-06 | 韩华思路信株式会社 | Method for preparing metal catalyst deposited with inorganic film based on ALD process and metal catalyst with improved activity based on the same |
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| CN112246245A (en) * | 2020-09-16 | 2021-01-22 | 华南理工大学 | Supported nickel-based catalyst and preparation method and application thereof |
| CN114042452A (en) * | 2021-12-03 | 2022-02-15 | 中汽研（天津）汽车工程研究院有限公司 | Ammonia oxidation catalyst for diesel vehicle tail gas, preparation method and application thereof |
| CN114042452B (en) * | 2021-12-03 | 2024-03-15 | 中汽研汽车检验中心（天津）有限公司 | Ammonia oxidation catalyst for diesel vehicle tail gas, preparation method and application thereof |
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