WO2020075920A1 - Catalyseur ternaire composite composé d'un support d'oxyde composite et d'un atome unique, et son procédé de préparation - Google Patents
Catalyseur ternaire composite composé d'un support d'oxyde composite et d'un atome unique, et son procédé de préparation Download PDFInfo
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- WO2020075920A1 WO2020075920A1 PCT/KR2018/016938 KR2018016938W WO2020075920A1 WO 2020075920 A1 WO2020075920 A1 WO 2020075920A1 KR 2018016938 W KR2018016938 W KR 2018016938W WO 2020075920 A1 WO2020075920 A1 WO 2020075920A1
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- catalyst
- ternary catalyst
- composite oxide
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- oxide support
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- 239000003054 catalyst Substances 0.000 title claims abstract description 142
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 149
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000004913 activation Effects 0.000 claims abstract description 13
- 230000004888 barrier function Effects 0.000 claims abstract description 13
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 19
- 230000000694 effects Effects 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 14
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000012695 Ce precursor Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 33
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000035899 viability Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000843 powder Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000000779 annular dark-field scanning transmission electron microscopy Methods 0.000 description 4
- -1 hydrocarbon Chemical compound 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- KIDPOJWGQRZHFM-UHFFFAOYSA-N platinum;hydrate Chemical compound O.[Pt] KIDPOJWGQRZHFM-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/613—10-100 m2/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
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Definitions
- the present invention relates to a ternary catalyst in which a platinum catalyst is evenly dispersed at a complex oxide support (CeO 2 -TiO 2 ) interface and a method for manufacturing the same.
- Platinum (Pt) catalysts that exhibit high catalytic reactivity for many chemical reactions are used in various catalytic reactions in the form of platinum nanoparticles.
- the demand for high-fuel vehicles is increasing due to the strengthening of regulations on carbon dioxide (CO 2 ) emissions for the entire industry, and the need for reduction of pollutants such as carbon oxides, nitrogen oxides, and hydrocarbons is increasing. It is increasing.
- Platinum catalysts are used to decompose and remove these contaminants, but despite the excellent reactivity of platinum catalysts, continuous research is being conducted to improve economic efficiency and reaction efficiency due to economic limitations due to high prices and low reserves.
- the object of the present invention is a ternary catalyst having excellent catalyst performance and structural stability, such as carbon oxide removal (CO), nitrogen oxide (NO x ) removal, or hydrocarbon compound (C x H y ) removal, and ternary advantageous for economic, commercial, and bulk It is to provide a method for producing a catalyst based.
- CO carbon oxide removal
- NO x nitrogen oxide
- C x H y hydrocarbon compound
- an object of the invention to provide a composite oxide support (CeO 2 -TiO 2) interfacial platinum danwon jacheung structure evenly dispersed and adsorbed ternary catalyst (Pt / CeO 2 -TiO 2) in the preparation method thereof, and .
- Another specific object of the present invention is to provide a ternary catalyst having a high catalytic activity and a method for manufacturing the same.
- Another specific object of the present invention is to provide a ternary catalyst having a low activation energy barrier and a method for manufacturing the same.
- Another specific object of the present invention is to provide a ternary catalyst having a high reaction area and a method for manufacturing the same.
- Another specific object of the present invention is to provide a ternary catalyst capable of operating at a lower temperature and a method for manufacturing the same, as it can elicit a reaction at a low temperature with high efficiency.
- Another specific object of the present invention is to secure a monoatomic catalytic activity control technology of a ternary catalyst having an atomic layer of a metal layer, and to derive a high reaction efficiency close to the theoretical limit of a noble metal catalyst, which is applied to various fields. And an expandable ternary catalyst and a method for manufacturing the same.
- the method for preparing a ternary catalyst according to the present invention includes the step of heat-treating a mixture comprising a cerium oxide and titanium oxide composite oxide support, a platinum precursor, and a solvent. At this time, the ternary catalyst contains platinum in an amount of 0.25% by weight or less based on the total weight of the catalyst, and platinum is dispersed and adsorbed at the interface of the composite oxide support.
- the platinum may be dispersed and adsorbed as a monoatomic layer at the interface of the composite oxide support.
- the composite oxide support may be prepared by heat-treating a mixture containing a cerium precursor, a titanium precursor, and a solvent.
- the heat treatment may be performed at 300 ° C or higher.
- the ternary catalyst according to the present invention includes a composite oxide support of cerium oxide and titanium oxide; And a monoatomic layer comprising platinum dispersed and adsorbed at the interface of the composite oxide support, wherein the monoatomic layer is contained in an amount of 0.25% by weight or less based on the total weight of the catalyst.
- the thickness of the single-layer magnetic layer may be less than 0.3 nm.
- the composite oxide support may include 0.5 to 2 parts by weight of the cerium oxide with respect to 100 parts by weight of the titanium oxide.
- the catalyst activity at 150 ° C may be 50 ⁇ 10 -5 mol / sec ⁇ g (Pt) or higher. .
- the catalyst activation energy barrier may be 0.70 eV or less.
- the specific surface area of the ternary catalyst according to the present invention may be 45 m 2 / g or more.
- the ternary catalyst according to the present invention can be used as a catalyst for removing carbon oxides, removing nitrogen oxides, or removing hydrocarbon compounds.
- the method for preparing a ternary catalyst according to the present invention is advantageous for economical efficiency, commerciality, and mass scale, and the ternary catalyst prepared by the above production method has excellent catalyst performance and structural stability such as carbon oxide removal, nitrogen oxide removal, or hydrocarbon compound removal. It works.
- the ternary catalyst (Pt / CeO 2 -TiO 2 ) according to the present invention is characterized in that platinum is evenly dispersed and adsorbed in a monoatomic layer structure at the interface of the composite oxide support (CeO 2 -TiO 2 ).
- the ternary catalyst according to the present invention has the effect of being able to operate at high catalyst activity, low activation energy barrier, high reaction surface area and lower temperature.
- the method of manufacturing a ternary catalyst according to the present invention can secure a single-electron catalyst activity control technology of a ternary catalyst having an atomic layer of a metal layer, and can lead to a high reaction efficiency close to the theoretical limit of the noble metal catalyst, which It has the advantage that it can be applied and extended in various fields.
- FIG. 1 is a process diagram schematically schematically showing a method of manufacturing a ternary catalyst according to the present invention.
- FIG. 2 is an image obtained by observing the composite oxide supports of Preparation Examples 1 to 3 using a high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM).
- HAADF-STEM high-angle annular dark-field scanning transmission electron microscopy
- Example 3 is an image obtained by observing the ternary catalysts of Example 1 and Comparative Examples 1 to 4 using a high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM).
- HAADF-STEM high-angle annular dark-field scanning transmission electron microscopy
- Example 1 Comparative Examples 1 to 4 the conversion rate for the carbon monoxide oxidation reaction of the ternary catalyst, the catalyst activity (Mass activity) and activation energy barrier (Activation energy barrier, E act ) and the electrochemical effective surface area ( Electrochemical active surface area (ECSA) analysis results are shown.
- ECSA Electrochemical active surface area
- the method of manufacturing a ternary catalyst (Pt / CeO 2 -TiO 2 ) comprises the steps of heat-treating a mixture comprising a cerium oxide and titanium oxide composite oxide support (CeO 2 -TiO 2 ), a platinum precursor and a solvent. Includes. At this time, the ternary catalyst contains platinum in an amount of 0.25% by weight or less based on the total weight of the catalyst, and platinum (Pt) is dispersed and adsorbed at the interface of the composite oxide support.
- ternary catalyst As the ternary catalyst is prepared such that platinum is contained in an amount of 0.25% by weight or less based on the total weight of the catalyst, a ternary catalyst adsorbed by dispersing platinum in a monoatomic layer at the interface of the composite oxide support is prepared, and also for the support interface. A ternary catalyst having a very uniform dispersion degree of platinum and stable in catalytic reaction is produced.
- a ternary catalyst prepared in excess of 0.25% by weight of platinum relative to the total weight of the catalyst as platinum is not formed as a monoatomic layer at the interface of the composite oxide support, catalytic activity and reaction surface area are significantly reduced, and the catalytic reaction It is forced to be carried out at this very high temperature.
- the ternary catalyst in which platinum is not formed as a monoatomic layer at the interface of the composite oxide support has excellent initial catalytic activity as the interfacial adhesion between the composite oxide support and the platinum layer significantly decreases and the structural stability of the catalyst is very poor. It is difficult to maintain.
- the used content of the composite oxide support and the platinum precursor may be any value so that the final manufactured ternary catalyst contains platinum in an amount of 0.25% by weight or less. Since the above value may vary depending on the molar mass of the platinum precursor, that is, the type, the ternary catalyst may be appropriately adjusted to a value that includes platinum in an amount of 0.25 wt% or less. As a specific example, when H 2 PtCl 8 ⁇ 6H 2 O is used as a platinum precursor, the platinum precursor may be used in an amount of 0.25% by weight or less based on 99.75 parts by weight of the composite oxide support.
- the platinum precursor may be any one that allows platinum to be formed on the composite oxide support during the ternary catalyst production process.
- H 2 PtCl x ⁇ yH 2 O x and y are independently selected from natural numbers of 1 to 8 and the like.
- this is only described as a specific example, and the type of the precursor is widely known, and the present invention is not limited to this.
- the used content of the composite oxide support is a theoretical content excluding impurities and the like, and as it can be seen that the ternary catalyst is composed of platinum and a complex oxide support, the used content of platinum described above with respect to the total weight of the ternary catalyst If it is automatically adjusted to a content that satisfies the, it is okay.
- the ternary catalyst according to the present invention can be prepared by a wet impregnation method.
- the solvent may be any material so long as it can form platinum on the composite oxide support during the preparation of the ternary catalyst, and for example, water.
- the content of the solvent may be used as long as the solvent is evaporated during the heat treatment process so that a ternary catalyst can be prepared.
- the solvent may be 100 to 100,000 for 1 part by weight of the titanium precursor. However, this is only described as a specific and preferable example, and the present invention is not necessarily limited to this.
- the heat treatment may be any temperature capable of producing a ternary catalyst, for example, 300 ° C or higher, specifically 400 ° C or higher, and 1,000 ° C or lower.
- the heat treatment temperature is 300 ° C or higher, the interface adhesion between the composite oxide support and platinum is improved.
- this is only described as a specific example, and the present invention is not limited thereto and interpreted.
- the composite oxide support means a composite of cerium oxide (CeO 2 ) and titanium oxide (TiO 2 ), and specifically, is preferably prepared by including a step of heat-treating a mixture containing a cerium precursor, a titanium precursor, and a solvent. You can.
- the content of the cerium precursor and the titanium precursor is 0.3 to 10 parts by weight, preferably 0.5 to 4 parts by weight, and more preferably 0.5 to 2 parts by weight of cerium in the final composite oxide support. Any value to be included may be used. Since the above values may vary depending on the molar mass of each precursor, that is, the type, the composite oxide support may be appropriately adjusted to a value that includes cerium as the aforementioned range.
- the cerium precursor is substantially 0.3 to 10 parts by weight, preferably 0.5 to 4 parts by weight relative to 100 parts by weight of the composite oxide support , More preferably, it may be used in 0.5 to 2 parts by weight. If this is satisfied, it is possible to secure a sufficient interface of the composite oxide support to act as an adsorption point of platinum particles as an atomic layer structure.
- the cerium precursor may be used as long as it can manufacture the composite oxide support, and may include any one or two or more selected from, for example, chlorides of cerium, oxides of cerium, nitrides of cerium, hydrates of cerium, and mixed compounds thereof, and the like. And the like. However, this is only described as a specific example, and the type of the precursor is widely known, and the present invention is not limited to this.
- the titanium precursor may be used as long as it is possible to manufacture the composite oxide support, for example, it may be titanium oxide itself, or may be in the form of a precursor forming titanium oxide.
- the titanium precursor may be preferably titanium oxide, and in this case, it may be more preferable to be titanium dioxide on anatase. However, this is only described as a preferred example, and the present invention is not necessarily interpreted as being limited thereto.
- the composite oxide support may be prepared by a wet impregnation method.
- the solvent may be any material so long as each precursor forms an oxide to form a composite oxide support in the process of preparing a composite oxide support of cerium oxide and titanium oxide, for example, water.
- the amount of the solvent used may be as long as the solvent is evaporated in the heat treatment process so that each precursor reacts to produce a composite oxide support, for example, it may be 100 to 100,000 solvents per 1 part by weight of the titanium precursor.
- this is only described as a specific and preferable example, and the present invention is not necessarily limited to this.
- the heat treatment may be any temperature capable of producing a composite oxide support, for example, 300 ° C or higher, specifically 400 ° C or higher, and 1,000 ° C or lower. However, this is only described as a specific example, and the present invention is not limited thereto and interpreted.
- the ternary catalyst according to the present invention includes a composite oxide support of cerium oxide and titanium oxide; And a monoatomic layer comprising platinum dispersed and adsorbed on the surface of the composite oxide support, wherein the monoatomic layer is contained in an amount of 0.25% by weight or less based on the total weight of the catalyst.
- the thickness of the monoatomic layer means the thickness of the monoatomic layer of platinum, and may be less than 0.3 nm, preferably 0.25 nm or less, and more preferably 0.2 nm or less.
- the composite oxide support may preferably contain 0.3 to 10 parts by weight of cerium oxide, preferably 0.5 to 4 parts by weight, and more preferably 0.5 to 2 parts by weight based on 100 parts by weight of titanium oxide. If this is satisfied, a stable space is formed at the interface of the composite oxide support where the monoatomic layer can be dispersed and adsorbed, so that the monoatomic layer of platinum is stably formed on the support and structural stability can be further improved.
- the ternary catalyst according to the present invention has a specific surface area of 45 m 2 / g or more, specifically 45 to 90 m 2 / g, more specifically 60 to 90 m 2 / g, and more specifically 65 to 90 m 2 / g day You can.
- the ternary catalyst according to the present invention can be used in various fields as long as it can utilize a catalytic reaction caused by platinum, and as a specific example, it can be used as a catalyst for removing carbon oxides, removing nitrogen oxides, or removing hydrocarbon compounds. .
- the catalyst activity at 150 ° C is 50 ⁇ 10 -5 mol / sec ⁇ g (Pt) or higher, specifically 50 ⁇ 10 It may be -5 to 100 ⁇ 10 -5 mol / sec ⁇ g (Pt), more specifically 55 ⁇ 10 -5 to 100 ⁇ 10 -5 mol / sec ⁇ g (Pt).
- the catalyst activation energy barrier may be 0.70 eV or less, specifically 0.30 to 0.70 eV, and more specifically 0.35 to 0.65 eV. .
- Titanium oxide powder (TiO 2 , Anatase) 99 g and CeN 3 O 9 ⁇ 6H 2 O 1 g was added to 5,000 ml of distilled water and mixed at 70 ° C. for 2 hours to prepare a precursor mixture.
- the precursor mixture was dried at 110 ° C. for 12 hours, and then calcined at 500 ° C. for 8 hours to prepare a composite oxide support (CeO 2 -TiO 2 ) of cerium oxide and titanium oxide.
- a composite oxide support (CeO 2 -TiO 2 ) was prepared in the same manner as in Preparation Example 1, except that 97 g of titanium oxide powder and CeN 3 O 9 ⁇ 6H 2 O 3 g were used.
- a composite oxide support (CeO 2 -TiO 2 ) was prepared in the same manner as in Preparation Example 1, except that 94 g of titanium oxide powder and CeN 3 O 9 ⁇ 6H 2 O 6 g were used.
- a ternary catalyst (Pt / CeO 2 -in the same manner as in Example 1, except that 99.5 g of a composite oxide support (CeO 2 -TiO 2 ) powder in Example 1 and 0.5 g of H 2 PtCl 8 ⁇ 6H 2 O were used. TiO 2 ) was prepared.
- Example 1 a ternary catalyst (Pt / CeO 2 ) was used in the same manner as in Example 1, except that 99 g of a composite oxide support (CeO 2 -TiO 2 ) powder and 1 g of H 2 PtCl 8 ⁇ 6H 2 O were used. -TiO 2 ) was prepared.
- Example 1 a ternary catalyst (Pt / CeO 2) was prepared in the same manner as in Example 1, except that 98 g of a complex oxide support (CeO 2 -TiO 2 ) powder and 2 g of H 2 PtCl 8 ⁇ 6H 2 O were used. -TiO 2 ) was prepared.
- Example 1 a ternary catalyst (Pt / CeO 2) was prepared in the same manner as in Example 1, except that 96 g of a composite oxide support (CeO 2 -TiO 2 ) powder and 4 g of H 2 PtCl 8 ⁇ 6H 2 O were used. -TiO 2 ) was prepared.
- Example 1 a catalyst was prepared in the same manner as in Example 1, except that it was calcined at 90 ° C.
- the composite oxide supports of Preparation Examples 1 to 3 were analyzed using a high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), the image of which is shown in FIG. 2.
- HAADF-STEM high-angle annular dark-field scanning transmission electron microscopy
- Example 1 The ternary catalysts of Example 1 and Comparative Examples 1 to 3 were analyzed using a high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), the image of which is shown in FIG. 3 Became.
- HAADF-STEM high-angle annular dark-field scanning transmission electron microscopy
- the ternary catalyst of Example 1 has a structure in which platinum is evenly dispersed at the interface of the composite oxide support (CeO 2 -TiO 2 ).
- Example 1 in which platinum was included in 0.25% by weight, platinum was low-dimensionally distributed on the composite oxide support (CeO 2 -TiO 2 ) and uniformly dispersed at the interface of the support, forming a monoatomic structure.
- platinum was low-dimensionally distributed on the composite oxide support (CeO 2 -TiO 2 ) and uniformly dispersed at the interface of the support, forming a monoatomic structure.
- platinum is used in an amount of 0.25% by weight or less based on the total weight of the catalyst, so that platinum is a low-dimensional monolayer on the composite oxide support. It can be confirmed that it can be dispersed and adsorbed.
- Example 1 it is possible to prepare a ternary catalyst in which platinum is dispersed and adsorbed as a monoatomic layer, platinum does not grow significantly as nano-unit particles, and a complex oxide support (CeO 2 -TiO 2 ) surface and TiO 2 It can be seen that the interface of the composite oxide support (CeO 2 -TiO 2 ) formed on the surface of the metal served as an adsorption point of platinum.
- Example 1 Comparative Examples 1 to 5 using the ternary catalyst of Comparative Example 5 as a catalyst for the oxidation reaction of carbon monoxide (CO), the catalyst activity according to temperature (Mass activity) and activation energy barrier (Activation energy barrier, E act ) Measurements, the results are shown in Figure 4 and Table 1 below.
- the ternary catalyst of Example 1 has a catalyst activity of 43% or higher per unit platinum mass compared to the ternary catalyst of Comparative Example 1. From these results, the ternary catalyst of Example 1 is obtained by dispersing and adsorbing at the interface of the composite oxide support (CeO 2 -TiO 2 ), and is due to the single-atomic structure of a single Pt atom layer. It can be seen that the ternary catalyst is based on the fact that platinum is not formed in the form of a monoatomic layer.
- a complex oxide support (CeO The surface of 2 -TiO 2 ) provides a strong adsorption point for platinum, and is formed through a process in which platinum is stably dispersed and fixed in a monoatomic form at this adsorption point.
- the ternary catalyst of Example 1 prepared through this process is used as a catalyst in a reaction such as a carbon monoxide oxidation reaction, the role of continuously supplying oxygen from the composite oxide support and the role of platinum adsorbing the reactants operate separately. . Therefore, the ternary catalyst of Example 1 has a lower activation energy barrier during the catalytic reaction, and has an effect caused by the catalytic reaction with high efficiency.
- the catalyst activity was very low as platinum was used in a low content during the catalyst preparation process and the calcination temperature was very low.
- the catalyst of Comparative Example 5 has a calcination temperature of 100 ° C. or less, which is very low compared to that of the Example, so that impurities on the surface of the catalyst cannot be sufficiently removed, and the interface of the composite oxide support cannot be sufficiently secured. Since the stabilization becomes difficult to form a ruler-shaped platinum, the catalytic activity is very low.
- Example 1 The ternary catalysts of Example 1 and Comparative Examples 1 to 4 were analyzed for electrochemical active surface area (ECSA), and the results are shown in FIG. 4.
- ECSA electrochemical active surface area
- Example 1 has a very high surface area compared to Comparative Examples.
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Abstract
Un procédé de préparation d'un catalyseur ternaire, selon la présente invention, est avantageux en termes de faisabilité économique, viabilité commerciale et production de masse, et un catalyseur ternaire préparé par le procédé de préparation présente une excellente stabilité structurale et d'excellentes performances catalytiques telles que celle de l'élimination d'oxyde de carbone, de l'élimination d'oxyde d'azote ou de l'élimination de composés hydrocarbonés. En particulier, le catalyseur ternaire (Pt/CeO 2-TiO 2), selon la présente invention, est caractérisé en ce que le platine est uniformément dispersé dans une seule structure de couche atomique et est adsorbé sur l'interface d'un support d'oxyde composite (CeO 2-TiO 2), et a une activité catalytique élevée, une barrière à faible énergie d'activation et une zone de surface de réaction élevée. De plus, le procédé de préparation d'un catalyseur ternaire, selon la présente invention, peut assurer une technique de contrôle de l'activité catalytique à atome unique d'un catalyseur ternaire comprenant une couche métallique atomique, dériver une efficacité de réaction élevée qui est proche de la limite théorique d'un catalyseur noble, et peut l'appliquer et l'étendre celle-ci divers domaines.
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CN111530458A (zh) * | 2020-05-15 | 2020-08-14 | 江南大学 | 一种单原子催化剂及其在二氧化碳加氢反应中的应用 |
CN112452346A (zh) * | 2020-10-14 | 2021-03-09 | 浙江大学 | 一种制备金属单原子碳基催化剂的普适性方法及应用 |
CN113713805A (zh) * | 2021-08-09 | 2021-11-30 | 清华大学 | 一种Pt系催化剂的制备方法及其应用 |
CN114471539A (zh) * | 2022-02-21 | 2022-05-13 | 南京大学 | 一种高性能铂钛单原子催化剂及其制备方法和应用 |
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KR20240063404A (ko) | 2022-11-03 | 2024-05-10 | 울산과학기술원 | 고활성 및 재사용성을 갖는 하이드로포밀화 반응용 촉매, 이의 제조방법 및 이의 용도 |
CN116272967A (zh) * | 2023-03-28 | 2023-06-23 | 华中师范大学 | 一种二氧化钛单原子Pt催化剂及其制备方法和应用 |
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CN111530458A (zh) * | 2020-05-15 | 2020-08-14 | 江南大学 | 一种单原子催化剂及其在二氧化碳加氢反应中的应用 |
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CN112452346A (zh) * | 2020-10-14 | 2021-03-09 | 浙江大学 | 一种制备金属单原子碳基催化剂的普适性方法及应用 |
CN113713805A (zh) * | 2021-08-09 | 2021-11-30 | 清华大学 | 一种Pt系催化剂的制备方法及其应用 |
CN114471539A (zh) * | 2022-02-21 | 2022-05-13 | 南京大学 | 一种高性能铂钛单原子催化剂及其制备方法和应用 |
CN114471539B (zh) * | 2022-02-21 | 2024-04-09 | 南京大学 | 一种高性能铂钛单原子催化剂及其制备方法和应用 |
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