CN111408366B - 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 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
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- 125000000524 functional group Chemical group 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims abstract description 18
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 239000007788 liquid 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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- 238000002156 mixing Methods 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
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- 230000006872 improvement Effects 0.000 description 3
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- 239000011943 nanocatalyst Substances 0.000 description 2
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- 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
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- 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
- 239000000463 material Substances 0.000 description 1
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- 238000011946 reduction process Methods 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
-
- 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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- Materials Engineering (AREA)
- 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, adsorbing, washing, and freeze-drying to prepare a metal-adsorbed 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, the atomic composition, the surface environment and the 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", publication No. CN109499567a, which 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 regulation and/or interface modification, however, the catalyst is synthesized by 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 method comprises the steps of firstly soaking a carbon carrier into an acid treatment solution for acid treatment, enabling the prepared carbon carrier powder rich in functional groups to be rich in adsorption group hydroxyl and carboxyl on the surface, soaking the carbon carrier powder rich in functional groups into a soluble metal salt solution, enabling the carbon carrier powder rich in functional groups to adsorb metal ions by utilizing the adsorption group on the surface, then placing a metal adsorption carbon carrier material into volatile mercaptan steam for fumigation treatment, enabling mercaptan molecules to slowly volatilize and diffuse, slowly enabling the metal adsorbed by the metal adsorption carbon carrier material to form a metal mercaptan coordination compound, preventing agglomeration of metal clusters, preparing a mercaptan-metal-carbon carrier composite material, finally conducting high-temperature calcination under a protective atmosphere, enabling the metal mercaptan coordination compound to be reduced in situ, enabling the mercaptan molecules to prevent agglomeration of the metal clusters in the high-temperature reduction process, simultaneously enabling the high-temperature calcination to carry out alkyl carbonization on the mercaptan molecules, so that a carbon-loaded metal nanocluster catalyst with sulfur fixed on the surface is obtained, enabling sulfur atoms bonded on the surface of the metal clusters to form protection on the metal agglomeration, and preventing the catalyst from being oxidized in the storage and use processes, and accordingly improving the stability of the performance of the catalyst.
Preferably, the carbon carrier 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; the soaking time is 10-48h; 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 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; the soluble metal salt solution is 0.005-5 mol/L.
Preferably, step 2) is performed with 0.1 to 3.5 parts of a soluble metal salt solution of the functional group-rich carbon support powder; the soaking is carried out at 25-99 deg.C for 5-20h.
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 thiol 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 at the temperature rising rate of 5-10 ℃/min to 300-700 ℃ and the heat preservation calcination is carried out for 1-4h.
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 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 70mL of 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 20mL of chloroplatinic acid solution 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 100mL of piranha solution for 48h, then filtering and washing with deionized water until the pH of the final filtered liquid is 6, and preparing 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 100mL of 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 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), bright spots of the carbon support loaded with the metal nanoclusters having a size of 0.1-2nm and a good dispersion degree can be seen.
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 loading of Pt was determined to be 12.5% for example 1 and compared to the ORR catalytic performance of 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 in example 1 is 5.35 mA cm -2 Commercial 20% Pt/C catalyst having an ultimate current density of 5.52 mA cm -2 (ii) a But the mass activity to convert it to Pt, the activity of the carbon-supported metal nanocluster catalyst of example 1 was 1.55 times the john Matthey type commercial 20% Pt/C catalyst, and it is clear that the increased utilization of Pt relative to the commercial catalyst can effectively reduce the amount of Pt used in the fuel cell.
Claims (7)
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, adsorbing, washing, and freeze-drying to prepare a metal-adsorbed 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; the fumigating treatment in the step 3) is fumigating for 5-100h at the temperature of 10-220 ℃ in a closed vacuum environment or an inert gas environment;
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; the soaking time is 10-48h; 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 of preparing a carbon-supported metal nanocluster catalyst as recited in claim 1, wherein said soluble metal salt solution of step 2) includes one or more mixed solution of Pt salt, au salt, ru salt, rh salt, fe salt, co salt, ni salt, pd salt, ag salt; the 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) of mixing said functional group-rich carbon support powder with a soluble metal salt solution is carried out in a ratio of 0.1 to 3.5; the soaking is carried out at 25-99 deg.C for 5-20h.
6. The method of preparing a carbon-supported metal nanocluster catalyst as claimed in claim 1, wherein said thiol of 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.
7. The method of claim 1, wherein the calcining in step 4) is performed at a temperature rise rate of 5-10 ℃/min to 300-700 ℃ for 1-4h under a heat preservation condition.
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| 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 |
| 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 |
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| JP2004268031A (en) * | 2003-02-18 | 2004-09-30 | National Institute Of Advanced Industrial & Technology | Method for synthesizing nitrogen compound directly from nitrogen molecule |
| WO2009078815A1 (en) * | 2007-12-14 | 2009-06-25 | Nanyang Technological University | A nanostructured material loaded with noble metal particles |
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| JP6760655B2 (en) * | 2016-08-24 | 2020-09-23 | 国立大学法人東京工業大学 | Method for producing Group 10 element cluster carrier with precise control of atomic number in sub-nano region, platinum cluster carrier and catalyst |
| CN110115997B (en) * | 2018-02-07 | 2020-11-27 | 中国科学院大连化学物理研究所 | Method for treating organic ligand on surface of gold cluster |
| CN108404989B (en) * | 2018-04-28 | 2021-01-26 | 东华大学 | Preparation method of gold cluster/graphene composite catalytic membrane |
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