CN111408366A - Preparation method of carbon-supported metal nanocluster catalyst - Google Patents
Preparation method of carbon-supported metal nanocluster catalyst Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
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- 125000000524 functional group Chemical group 0.000 claims abstract description 17
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- 238000001354 calcination Methods 0.000 claims abstract description 9
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- 239000000706 filtrate Substances 0.000 claims description 4
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
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- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 2
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- 238000002156 mixing Methods 0.000 claims 1
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- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 229910001961 silver nitrate Inorganic materials 0.000 description 1
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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
- B01J23/38—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
-
- 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
- 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
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- 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
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of a carbon-loaded metal nanocluster catalyst, which relates to the field of preparation of metal nanocluster catalysts and comprises the following preparation steps: 1) soaking the carbon carrier into an acid treatment solution, and then filtering and washing to prepare carbon carrier powder rich in functional groups; 2) soaking the carbon carrier powder rich in functional groups into a soluble metal salt solution, and carrying out washing and freeze drying after adsorption to prepare a metal adsorption carbon carrier material; 3) putting the metal-adsorbed carbon carrier material into volatile mercaptan vapor for fumigation treatment to prepare a mercaptan-metal-carbon carrier composite material; 4) calcining the mercaptan-metal-carbon carrier composite material in a protective atmosphere to prepare the carbon-supported metal nanocluster catalyst; according to the invention, metal ions are adsorbed on the carbon material after acid treatment, and then the metal nanocluster catalyst with the sulfur fixed on the surface is prepared by adopting a mercaptan fumigation method, wherein the metal nanoclusters of the catalyst are small in size and good in dispersity.
Description
Technical Field
The invention relates to the field of preparation of metal cluster catalysts, in particular to a preparation method of a carbon-supported metal nanocluster catalyst.
Background
The metal cluster catalyst shows excellent catalytic performance of the nano catalytic material by virtue of unique surface effect, volume effect and quantum size effect, is widely applied to low-temperature catalysis of carbon monoxide (CO) oxidation, fuel cell reaction, low-temperature water-gas shift reaction, nitrogen oxide (NOx) catalytic decomposition and the like in the chemical field, and is called as a fourth-generation catalyst. The size and appearance, atomic composition, surface environment and carrier of the metal cluster catalyst all have important influence on the catalytic performance of the catalyst.
At present, most of metal nano-catalysts are synthesized by a solution phase, and in order to prevent agglomeration in the application process, the metal nano-catalysts are also required to be loaded on a carrier. However, a large amount of surfactant exists on the surface of the metal nanocluster catalyst synthesized in the solution phase, which seriously hinders the improvement of the catalytic performance of the metal nanocluster catalyst, and the direct removal of the surfactant on the cluster surface can cause the agglomeration of the metal nanocluster catalyst, which reduces the catalytic performance of the metal nanocluster catalyst.
For example, a chinese patent document discloses a method for preparing a metal cluster photostable catalyst and its application, and publication No. CN109499567A discloses a method for preparing a metal cluster photostable catalyst and a method for improving the photostability of a metal cluster by a combination strategy of surface property control and/or interface modification, but the catalyst is synthesized in a solution phase, and a large amount of surfactant exists on the surface, which seriously hinders the improvement of the catalytic performance.
Disclosure of Invention
The invention provides a preparation method of a carbon-supported metal nanocluster catalyst, aiming at overcoming the problems that a large amount of surfactant exists on the surface of the metal nanocluster catalyst synthesized by the existing solution phase, and the improvement of the catalytic performance of the metal nanocluster catalyst is seriously hindered, but the surfactant on the surface of the cluster is directly removed, so that the metal nanocluster catalyst is agglomerated, the catalytic performance of the metal nanocluster catalyst is reduced, and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a carbon-supported metal nanocluster catalyst comprises the following preparation steps:
1) soaking the carbon carrier into an acid treatment solution, and then filtering and washing to prepare carbon carrier powder rich in functional groups;
2) soaking the carbon carrier powder rich in functional groups into a soluble metal salt solution, and carrying out washing and freeze drying after adsorption to prepare a metal adsorption carbon carrier material;
3) putting the metal-adsorbed carbon carrier material into volatile mercaptan vapor for fumigation treatment to prepare a mercaptan-metal-carbon carrier composite material;
4) and calcining the mercaptan-metal-carbon carrier composite material under a protective atmosphere to prepare the carbon-supported metal nanocluster catalyst.
The invention firstly soaks the carbon carrier into acid treatment liquid to carry out acid treatment, the prepared carbon carrier powder with rich functional groups is rich in adsorption group hydroxyl and carboxyl on the surface, the carbon carrier powder with rich functional groups adsorbs metal ions by utilizing the surface adsorption group after being soaked into soluble metal salt solution, then the metal adsorption carbon carrier material is placed into volatile mercaptan vapor to carry out fumigation treatment, at the moment, mercaptan molecules slowly volatilize and diffuse, and slowly form metal mercaptan coordination compounds with the metal adsorbed by the metal adsorption carbon carrier material to prevent the agglomeration of metal clusters to prepare the mercaptan-metal-carbon carrier composite material, finally high-temperature calcination is carried out under protective atmosphere to reduce the metal mercaptan coordination compounds in situ, at the moment, the mercaptan molecules can prevent the agglomeration of the metal clusters in the high-temperature reduction, and simultaneously, the high-temperature calcination carries out alkyl carbonization on the mercaptan molecules, therefore, the carbon-supported metal nanocluster catalyst with sulfur fixed on the surface is obtained, and at the moment, the sulfur atoms bonded on the surface of the metal nanocluster can also form protection for metal agglomeration, so that the catalyst is prevented from being oxidized in the storage and use processes, and the stability of the performance of the catalyst is improved.
Preferably, the carbon support in step 1) comprises one or more of activated carbon, conductive carbon black, carbon paper, carbon cloth and graphene.
The carbon carrier is a graphitized carbon material.
Preferably, the acid treatment solution of step 1) comprises a piranha solution; the mass ratio of the carbon carrier to the acid treatment solution is 0.5-3.5: 100; the soaking time is 10-48 h; in the filtration washing, the filtrate is washed with deionized water until the pH of the final filtrate is between 6 and 7.
At this ratio, the carbon carrier is acid-treated more effectively.
Preferably, the soluble metal salt solution in the step 2) comprises one or more mixed solutions of Pt salt, Au salt, Ru salt, Rh salt, Fe salt, Co salt, Ni salt, Pd salt and Ag salt, and the soluble metal salt solution is 0.005-5 mol/L.
Preferably, the ratio of the functional group-rich carbon support powder of step 2) to the soluble metal salt solution is 0.1-3.5: 100; the soaking is carried out at 25-99 deg.C for 5-20 h.
Under the condition of the proportion, the carbon carrier powder rich in functional groups has better adsorption effect.
Preferably, the fumigating treatment in the step 3) is fumigating for 5-100h at 10-220 ℃ in a closed vacuum environment or an inert gas environment.
Preferably, the mercaptan in step 3) comprises one or more of methyl mercaptan, ethyl mercaptan, octyl mercaptan, cyclohexyl mercaptan, cyclopentyl mercaptan, n-dodecyl mercaptan, 2-propyl mercaptan, heptyl mercaptan, phenethyl mercaptan and butyl mercaptan.
Preferably, the calcination in the step 4) is carried out by raising the temperature to 300-700 ℃ at the temperature raising rate of 5-10 ℃/min and carrying out heat preservation calcination for 1-4 h.
Therefore, the invention has the following beneficial effects: according to the invention, metal ions are adsorbed on the carbon material after acid treatment, and then the metal nanocluster catalyst with the sulfur fixed on the surface is prepared by adopting a mercaptan fumigation method, the metal nanoclusters of the catalyst are small in size and good in dispersity, the utilization rate of metal can be effectively improved, and the usage amount of metal in the fuel cell is reduced.
Drawings
Fig. 1 is a TEM image of a carbon-supported metal nanocluster catalyst of example 1 of the present invention.
Fig. 2 is a STEM graph under dark field of the carbon-supported metal nanocluster catalyst of example 1 of the present invention.
Fig. 3 is an XRD pattern of the carbon-supported metal nanocluster catalyst of example 1 of the present invention.
Figure 4 is a graph comparing the ORR catalytic performance of the carbon-supported metal nanocluster catalyst of example 1 of the present invention with a john Matthey type commercial 20% Pt/C catalyst under the same test conditions.
Detailed Description
The invention is further described with reference to specific embodiments.
Example 1: a preparation method of a carbon-supported metal nanocluster catalyst comprises the following preparation steps:
1) soaking 2g of conductive carbon black powder into 70m L piranha solution for 20h, and then carrying out suction filtration and washing by using deionized water until the pH of the final filtered liquid is 7 to prepare carbon carrier powder rich in functional groups;
2) soaking 0.5g of carbon carrier powder rich in functional groups into a chloroplatinic acid solution with the concentration of 20m L and the concentration of 0.05 mol/L, preserving the temperature for 10 hours at 40 ℃, and performing freeze drying after adsorption to prepare a metal adsorption carbon carrier material;
3) putting the metal-adsorbed carbon carrier material in an argon environment, and fumigating with n-dodecyl mercaptan molecules at 50 ℃ for 10h to prepare a mercaptan-metal-carbon carrier composite material;
4) heating the thiol-metal-carbon carrier composite material to 400 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, and carrying out heat preservation and calcination for 1h to prepare the carbon-supported metal nanocluster catalyst.
Example 2: a preparation method of a carbon-supported metal nanocluster catalyst comprises the following preparation steps:
1) soaking 3.5g of activated carbon into 100m L mermaid solution for 48h, and then filtering and washing the solution by deionized water until the pH value of the final filtered liquid is 6 to prepare the carbon carrier powder rich in functional groups;
2) soaking the carbon carrier powder rich in functional groups into 5 mol/L ferric chloride solution, preserving the heat at 25 ℃ for 20 hours, and performing freeze drying after adsorption to prepare a metal adsorption carbon carrier material;
3) putting the metal-adsorbed carbon carrier material in an argon environment, and fumigating with methyl mercaptan molecules at 10 ℃ for 100h to prepare a mercaptan-metal-carbon carrier composite material;
4) heating the thiol-metal-carbon carrier composite material to 700 ℃ at a heating rate of 10 ℃/min under an argon atmosphere, and carrying out heat preservation and calcination for 2h to prepare the carbon-supported metal nanocluster catalyst.
Example 3: a preparation method of a carbon-supported metal nanocluster catalyst comprises the following preparation steps:
1) soaking 0.5g of graphene into 100m L piranha solution for 10h, and then filtering and washing with deionized water until the pH of the final filtered liquid is 6.5 to prepare the carbon carrier powder rich in functional groups;
2) soaking the carbon carrier powder rich in functional groups into 0.005 mol/L silver nitrate solution, preserving the heat for 5 hours at 99 ℃, and performing freeze drying after adsorption to prepare a metal adsorption carbon carrier material;
3) putting the metal-adsorbed carbon carrier material in a closed vacuum environment or an inert gas environment, and fumigating with a cyclohexyl mercaptan molecule at 220 ℃ for 5h to prepare a mercaptan-metal-carbon carrier composite material;
4) heating the thiol-metal-carbon carrier composite material to 300 ℃ at the heating rate of 7 ℃/min under the argon atmosphere, and carrying out heat preservation and calcination for 4h to prepare the carbon-supported metal nanocluster catalyst.
The carbon-supported metal nanocluster catalyst prepared in example 1 was characterized and the results are shown in the figure.
Example 1 TEM and dark field STEM of the carbon-supported metal nanocluster catalyst are respectively shown in fig. 1 and fig. 2, and it can be seen from the TEM spectrum of fig. 1 that the carbon support is composed of graphitized carbon spheres having a size of 20 to 80 nm; in the high-power dark field STEM (as shown in fig. 2), it can be seen that bright spots of metal nanoclusters are loaded on the carbon support, and the size of the metal nanoclusters is between 0.1 and 2nm, and the dispersion degree is good.
The XRD pattern of the carbon-supported metal nanocluster catalyst of example 1 is shown in fig. 3, in which no characteristic XRD peak of Pt metal is found, indicating that the size of Pt particles is very small.
The Pt loading of example 1 was determined to be 12.5% and compared to the ORR catalytic performance of a john Matthey type commercial 20% Pt/C catalyst, and the results are shown. As can be seen from the graph, the limiting current density of the carbon-supported metal nanocluster catalyst of example 1 reached 5.35 mA cm-2The limiting current density of a commercial 20% Pt/C catalyst tested under the same conditions was 5.52 mA cm-2(ii) a However, the mass activity of the catalyst converted into Pt is 1.55 times that of the John Matthey type commercial 20% Pt/C catalyst in example 1, and the utilization rate of Pt is obviously improved relative to the commercial catalyst, so that the use amount of Pt in the fuel cell can be effectively reduced.
Claims (8)
1. A preparation method of a carbon-supported metal nanocluster catalyst is characterized by comprising the following preparation steps:
1) soaking the carbon carrier into an acid treatment solution, and then filtering and washing to prepare carbon carrier powder rich in functional groups;
2) soaking the carbon carrier powder rich in functional groups into a soluble metal salt solution, and carrying out washing and freeze drying after adsorption to prepare a metal adsorption carbon carrier material;
3) putting the metal-adsorbed carbon carrier material into volatile mercaptan vapor for fumigation treatment to prepare a mercaptan-metal-carbon carrier composite material;
4) and calcining the mercaptan-metal-carbon carrier composite material under a protective atmosphere to prepare the carbon-supported metal nanocluster catalyst.
2. The method of claim 1, wherein the carbon support of step 1) comprises one or more of activated carbon, conductive carbon black, carbon paper, carbon cloth, and grapheme carbon material.
3. The method for preparing a carbon-supported metal nanocluster catalyst as recited in claim 1, wherein said acid treatment liquid of step 1) includes a piranha solution; the mass ratio of the carbon carrier powder to the acid treatment solution is 0.5-3.5: 100; the soaking time is 10-48 h; in the filtration washing, the filtrate is washed with deionized water until the pH of the final filtrate is between 6 and 7.
4. The method for preparing a carbon-supported metal nanocluster catalyst as recited in claim 1, wherein said soluble metal salt solution of step 2) comprises one or more mixed solution of Pt salt, Au salt, Ru salt, Rh salt, Fe salt, Co salt, Ni salt, Pd salt, Ag salt, and said soluble metal salt solution is 0.005-5 mol/L.
5. The method for preparing a carbon-supported metal nanocluster catalyst as recited in claim 1, wherein said step 2) is performed by mixing said functional group-rich carbon support powder with a soluble metal salt solution in a ratio of 0.1-3.5: 100; the soaking is carried out at 25-99 deg.C for 5-20 h.
6. The method for preparing a carbon-supported metal nanocluster catalyst according to claim 1, wherein the fumigating treatment in step 3) is carried out in a closed vacuum environment or an inert gas environment at 10-220 ℃ for 5-100 h.
7. The method for preparing a carbon-supported metal nanocluster catalyst as recited in claim 1, wherein said thiol of said step 3) comprises one or more of methyl mercaptan, ethyl mercaptan, octyl mercaptan, cyclohexyl mercaptan, cyclopentyl mercaptan, n-dodecyl mercaptan, 2-propyl mercaptan, heptyl mercaptan, phenethyl mercaptan, and butyl mercaptan.
8. The method for preparing a carbon-supported metal nanocluster catalyst as recited in claim 1, wherein the calcination in step 4) is performed by heating to 300-700 ℃ at a heating rate of 5-10 ℃/min, and maintaining the temperature for 1-4 h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112599801A (en) * | 2020-12-16 | 2021-04-02 | 中国石油大学(华东) | Ligand protection Pt6Sub-nanocluster and preparation method thereof, catalyst and preparation method and application thereof |
| CN114602496A (en) * | 2021-12-16 | 2022-06-10 | 中国科学院金属研究所 | Nano-carbon-loaded platinum-iron bimetallic catalyst, preparation method thereof and application thereof in CO selective oxidation reaction under hydrogen-rich atmosphere |
| CN114628699A (en) * | 2022-04-01 | 2022-06-14 | 南京大学 | Preparation method of noble metal alloy/carbon material supported catalyst |
| CN114797843A (en) * | 2022-03-29 | 2022-07-29 | 杭州未名信科科技有限公司 | Carbon-supported metal nanocluster catalyst and preparation method and application thereof |
| CN116273118A (en) * | 2023-02-28 | 2023-06-23 | 西安交通大学 | Preparation and application of carbon-based bimetallic nanocluster catalyst |
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