CN113611885A - Preparation method of bimetallic PtCu aerogel catalyst for high-activity fuel cell - Google Patents
Preparation method of bimetallic PtCu aerogel catalyst for high-activity fuel cell Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
-
- 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
Abstract
The invention relates to a bimetallic PtCu aerogel catalyst for a high-activity fuel cell, a preparation method and application, wherein the preparation method specifically comprises the following steps: (a) adding platinum salt and copper salt into solvent, mixing, and adding excessive NaBH4Continuously mixing to form a reaction system, and reacting to obtain the bimetallic PtCu hydrogel material; (b) and (b) carrying out aftertreatment on the bimetallic PtCu hydrogel material obtained in the step (a) to obtain the PtCu aerogel catalyst. The bimetallic PtCu aerogel catalyst was used as a catalyst for fuel cells. Compared with the prior art, the catalyst prepared by the invention has high catalytic activity and good stability, can be used as an anode catalyst of a direct methanol fuel cell, and has simple preparation process.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a bimetallic PtCu aerogel catalyst for a high-activity fuel cell, a preparation method and application thereof.
Background
The global climate change and the continuously decreasing storage of fossil fuel resources make the development of new alternative energy sources an imminent important task for modern society. Direct alcohol fuel cells are not limited to the carnot cycle and have attracted considerable attention by researchers through high energy conversion efficiency, portability, and operational flexibility in the use of a variety of fuels. The most important component in fuel cells is the catalyst, which is still a noble metal, Pt, currently used in such cells, and although Pt has been widely used as an electrocatalyst for methanol oxidation, there are some disadvantages, including scarcity, high cost, and poor operational durability.
Among various carbon-supported platinum (Pt) -based nanomaterials, small-sized Pt-based alloy Nanocrystals (NCS) are considered as a promising class of Ethanol Oxidation Reaction (EOR) electrocatalysts from the viewpoint of Pt atom utilization. While the activity of the catalyst can be improved by preparing Pt nanostructure catalysts in various forms, such as core-shell, hollow, Nanotube (NT), Nanowire (NW), nano-dendrite (ND), and porous structure. However, small size Pt-based alloys generally exhibit poor stability and severe poisoning effects. Noble Metal Aerogels (NMAs) which have emerged in recent years have shown great potential in catalysis due to their unique structural characteristics. Due to their high stability, abundant active centers and efficient mass/electron transport channels, NMAs are becoming a new class of superior electrocatalysts over commercial noble metal catalysts and most metal nanoparticle (Np) materials. They have excellent performance in various electrocatalytic processes such as Methanol Oxidation Reaction (MOR), Ethanol Oxidation Reaction (EOR) and Oxygen Evolution Reaction (OER).
Disclosure of Invention
The invention aims to provide a bimetallic PtCu aerogel catalyst for a high-activity fuel cell, a preparation method and application thereof, the prepared catalyst has high catalytic activity and good stability, the electrocatalytic oxidation activity and the catalytic stability of a Pt-based catalyst to methanol are obviously improved, the CO poisoning resistance is improved, the catalyst can be used as a direct methanol fuel cell anode catalyst, and the preparation process is simple and safe.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a bimetallic PtCu aerogel catalyst for a high-activity fuel cell specifically comprises the following steps:
(a) adding lead salt and copper salt into solvent, mixing, and adding excessive NaBH4Continuously mixing to form a reaction system, reacting to obtain the bimetallic PtCu hydrogel material, wherein platinum salt and copper salt are respectively used as precursors for providing Pt and Cu elements, and NaBH4As reducing agents, stabilizers and initiators;
(b) and (b) carrying out aftertreatment on the bimetallic PtCu hydrogel material obtained in the step (a) to obtain the PtCu aerogel catalyst.
In step (a), the platinum salt is H2PtCl6·6H2O, the copper salt is CuCl2·2H2And O, wherein the solvent is ultrapure water.
In step (a), H2PtCl6·6H2O、CuCl2·2H2O、H2O and NaBH4The ratio of (0.01-0.15) mmol to (0.005-0.07) mmol to (40) ml to (2) mmol, preferably (0.015) mmol to (0.005) mmol to (40) ml to (2) mmol.
In the step (a), ultrasonic stirring is carried out while all raw materials are added, and NaBH is added4Then stirred vigorously for 1 min.
In the step (a), the reaction temperature is normal temperature, preferably 25 ℃, and the reaction time is 4-8 h, preferably 8 h.
In the step (b), the post-treatment process specifically comprises: and (3) washing, solvent exchange, liquid nitrogen quick freezing and freeze drying the bimetal PtCu hydrogel material in sequence.
And washing the bimetallic PtCu hydrogel material for 1-2 days by adopting ultrapure water.
And exchanging the washed bimetallic PtCu hydrogel material for 1-2 d by using acetone.
And (3) freeze-drying the quick-frozen PtCu hydrogel in vacuum at the drying temperature of-50 to-46 ℃, preferably at the drying temperature of-48 ℃ for 24 to 48 hours.
The bimetal PtCu aerogel catalyst in the catalyst is a 3D self-supporting structure with self-assembled nanowires, and carrier corrosion under an acidic condition is effectively avoided.
The application of the bimetallic PtCu aerogel catalyst for the high-activity fuel cell in the fuel cell, particularly the direct alcohol fuel cell.
In the invention, Pt and other metals are alloyed to adjust the electronic structure of Pt, thereby weakening the adsorption of CO and promoting the oxidation performance of methanol to be greatly improved, in the catalysis process, the surface of the PtCu aerogel catalyst not only has active sites (Pt atoms) for dehydrogenation reaction of methanol but also has active sites (Cu) capable of providing oxygen-containing species on the surface, the addition of Cu can obviously reduce the oxidation potential of CO on the surface of Pt and promote the oxidation of CO on the Pt sites, and the two are mutually cooperated to ensure that the methanol is completely oxidized into carbon dioxide.
In addition, the 3D self-supporting macroscopic skeleton can eliminate the stent corrosion problem. Secondly, a large specific surface area can expose more active sites, and finally, a special porous structure is beneficial to mass transfer and exposure of active centers. NaBH4The PtCu aerogel catalyst is used as a reducing agent, a stabilizing agent and an initiator to induce the formation of PtCu hydrogel, and finally the PtCu aerogel catalyst with excellent performance on the electrocatalytic oxidation of methanol is obtained.
Compared with the prior art, the PtCu aerogel catalyst with a self-supporting structure is synthesized in one step by a sol-gel method, the reaction steps are simplified, the PtCu aerogel material self-assembled by the PtCu nanowires is obtained, the catalyst has high catalytic activity and good stability, compared with the traditional Pt/C catalyst, the catalyst reduces the using amount of noble metals, improves the utilization rate of the catalyst, obviously improves the electrocatalytic oxidation activity and catalytic stability of a Pt-based material on methanol by utilizing the intermetallic synergistic action, simultaneously improves the CO poisoning resistance, can be used as an anode catalyst of a direct methanol fuel cell, is simple and safe in preparation process, and is lower in cost because the price of Cu is lower than that of Pt.
Drawings
FIG. 1 is a scanning electron microscope SEM image of the bimetallic PtCu aerogel prepared in example 1;
FIG. 2 is a TEM image of a bimetallic PtCu aerogel prepared in example 1;
FIG. 3 is a Selected Area Electron Diffraction (SAED) plot of the bimetallic PtCu aerogel prepared in example 1;
FIG. 4 is an XRD pattern of the bimetallic PtCu aerogel prepared in example 1;
fig. 5 is a nitrogen adsorption and desorption isotherm and a BJH pore size distribution curve of the bimetallic PtCu aerogel prepared in example 1;
FIG. 6 shows the catalyst of example 1 and comparative example 1 at 0.5M H2SO4+1M CH3Comparison graph of cyclic voltammetry test in mixed solution of OH;
FIG. 7 shows the catalyst of example 1 and comparative example 1 at 0.5M H2SO4+1M CH3Comparative plot of chronoamperometry in OH mixed solution.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A preparation method of a bimetallic PtCu aerogel catalyst for a high-activity fuel cell specifically comprises the following steps:
(a) h is to be2PtCl6·6H2O and CuCl2·2H2Adding O into ultrapure water, ultrasonically stirring, and adding excessive NaBH4Forming a reaction system, violently stirring for 1min, and reacting at normal temperature for 4-8H to obtain the bimetallic PtCu hydrogel material, wherein in the step (a), H2PtCl6·6H2O、CuCl2·2H2O、H2O and NaBH4The addition amount ratio of (0.01-0.15) mmol, (0.005-0.07) mmol, 40ml, 2 mmol;
(b) washing the bimetal PtCu hydrogel obtained in the step (a) with ultrapure water for 1-2 days in sequence, exchanging acetone solvent for 1-2 days, quickly freezing with liquid nitrogen, and carrying out freeze drying at-50-46 ℃ for 24-48 hours (in vacuum) to obtain the PtCu aerogel material. In the present example, a commercially available product may be used as the raw material unless otherwise specified.
The bimetal PtCu aerogel catalyst in the catalyst is a 3D self-supporting structure with self-assembled nanowires, and carrier corrosion under an acidic condition is effectively avoided.
The application of the bimetallic PtCu aerogel catalyst for the high-activity fuel cell in the fuel cell.
Example 1
A bimetal PtCu aerogel catalyst for a high-activity fuel cell is prepared by the following preparation method:
0.015mmol of H2PtCl6·6H2O (available from Shanghai Aladdin Biotechnology Ltd., the same applies hereinafter) and 0.005mmol of CuCl2·2H2Adding O (purchased from Shanghai chemical reagent Co., Ltd., the same below) into 40ml of ultrapure water, ultrasonically stirring to uniformly disperse the reagent (the power of ultrasound adopts the parameter values commonly adopted in laboratories to achieve the effect of uniform dispersion, the same below), and then adding 2mmol of NaBH4(purchased from Shanghai chemical reagents Co., Ltd., China pharmaceutical Co., Ltd., the same below) is vigorously stirred for 1min to form a reaction system, the reaction system is kept at 25 ℃ for 8h to react, the bimetallic PtCu hydrogel material is obtained through the reaction, then ultrapure water is used for washing for 1.5d, and then the washed hydrogel is subjected to acetone solvent exchange for 1.5 d. And then quickly freezing the hydrogel through liquid nitrogen. And then drying the mixture in a chamber of a freeze dryer at the temperature of-48 ℃ for 48 hours, and grinding the dried sample for later use to obtain the bimetallic PtCu aerogel catalyst.
Fig. 1 is a SEM image of a bimetallic PtCu aerogel (scale bar of a is 1 μm and scale bar of b is 100nm in fig. 1), and it can be seen from fig. 1 that the PtCu aerogel has a typical three-dimensional porous structure in which extended ultrathin nanowires are connected to each other.
Fig. 2 is a TEM image of a bimetallic PtCu aerogel (scale bar of a in fig. 2 is 100nm, scale bar of b is 50nm, scale bar of c is 20nm, and scale bar of d is 10nm), and from fig. 2, it can be seen that the PtCu aerogel has many branched thin nanowire building blocks, indicating obvious morphological characteristics of the metallic aerogel. Also evident is the 0.22nm lattice fringe, corresponding to the 111 plane of Pt, clearly seen in fig. 2 d.
Fig. 3 is a selected area electron diffraction SAED diagram of a bimetallic PtCu aerogel, from which distinct polycrystalline diffraction rings can be seen, illustrating that the bimetallic PtCu aerogel is polycrystalline in nature, and that the diffraction rings of different radii correspond to different crystal planes, which have been labeled as (111), (200), (310), and (311) for (111), (200), (310), and (311), respectively.
Fig. 4 is an XRD pattern of the bimetallic PtCu aerogel, and it is seen that the PtCu aerogel exhibits a relatively distinct diffraction peak for Pt, indicating that the PtCu aerogel forms a bimetallic nanostructure composed of crystallized Pt and amorphous Cu, rather than a well-defined PdCu alloy.
Fig. 5 a is a diagram of the nitrogen adsorption and desorption isotherms of the bimetallic PtCu aerogel, and fig. 5 b is a graph of the BJH pore size distribution of the bimetallic PtCu aerogel. The adsorption isotherms of the PtCu aerogel catalysts combine the characteristics of type II and type IV adsorption isotherms, indicating that extensive mesopores and macropores are present in the aerogel. And the specific surface area of the PtCu aerogel is 38.771m according to the calculation result of a Brunauer-Emmett-Teller equation2g-1。
The bimetallic PtCu aerogel catalyst was placed at 0.5M H2SO4+1M CH3Cyclic voltammetry was performed in a mixed solution of OH (same test conditions) as a half cell reaction using methanol as an anode active material (same below), and the test results are shown in fig. 6.
The bimetallic PtCu aerogel catalyst was subjected to a-0.2 v (vs sce)3600s chronoamperometric test, the test results of which are shown in fig. 7.
Example 2
A bimetal PtCu aerogel catalyst for a high-activity fuel cell is prepared by the following preparation method:
0.01mmol of H2PtCl6·6H2O and 0.01mmol of CuCl2·2H2Adding O into 40ml of ultrapure water, ultrasonically stirring to uniformly disperse the reagent (the ultrasonic power adopts the parameter values commonly adopted in laboratories to achieve the effect of uniform dispersion, the same applies below), adding 2mmol of NaBH at the reaction system temperature of 25 DEG C4And keeping for 8h, reacting to obtain the bimetallic PtCu hydrogel, washing for 1-2 d by using ultrapure water, and exchanging the washed hydrogel for 1-2 d by using an acetone solvent. And then quickly freezing the hydrogel through liquid nitrogen. And then drying the obtained product in a chamber of a freeze dryer at the temperature of-48 ℃ for 48 hours, and grinding the dried sample for later use to obtain the bimetallic PtCu aerogel catalyst with a typical three-dimensional porous structure.
Example 3
A bimetal PtCu aerogel catalyst for a high-activity fuel cell is prepared by the following preparation method:
0.013mmol of H2PtCl6·6H2O and 0.07mmol of CuCl2·2H2Adding O into 40ml of ultrapure water, ultrasonically stirring to uniformly disperse the reagent (the ultrasonic power adopts the parameter values commonly adopted in laboratories to achieve the effect of uniform dispersion, the same applies below), adding 2mmol of NaBH at the reaction system temperature of 25 DEG C4And keeping for 8h, reacting to obtain the bimetallic PtCu hydrogel, washing for 1-2 d by using ultrapure water, and exchanging the washed hydrogel for 1-2 d by using an acetone solvent. And then quickly freezing the hydrogel through liquid nitrogen. And then drying the obtained product in a chamber of a freeze dryer at the temperature of-48 ℃ for 48 hours, and grinding the dried sample for later use to obtain the bimetallic PtCu aerogel catalyst with a typical three-dimensional porous structure.
Comparative example 1
A commercial catalyst JM 20% Pt/C, obtained from Johnson-Matthery, was subjected to a linear cyclic voltammetry test, the results of which are shown in detail in FIG. 6, and a chronoamperometry test, the results of which are shown in detail in FIG. 7.
As can be seen from fig. 6, the initial potential of the bimetallic PtCu aerogel catalyst shifts significantly to the left (the initial oxidation potential is the potential at which oxidation begins to occur, the lower left dotted line in fig. 6 corresponds to the initial oxidation potential of the PtCu aerogel,the lower right dotted line corresponds to the starting oxidation potential of JM 20% Pt/C), indicating an improvement in its resistance to CO poisoning and a significant enhancement in oxidation peak current density of 3775mA mg-1 PtAbout the commercial catalyst JM 20% Pt/C (at 575mA mg)-1 Pt) 6.6 times of that of the PtCu aerogel, which shows that the introduction of the Cu element and the unique structure of the PtCu aerogel can enable the catalyst to have obvious catalytic activity for methanol electrooxidation.
From FIG. 7, it can be seen that the commercial catalyst JM 20% Pt/C is affected by CO or some intermediates (both generated during the reaction) and the current density is from 626.5mA mg after 3600s-1 PtTending to 105mA mg-1 PtThe attenuation process of the bimetallic PtCu aerogel catalyst is obviously mild, and the current density is increased from 3015mA mg after 3600s-1 PtStill as high as 930mA mg-1 Pt. The bimetallic PtCu aerogel catalyst provided by the invention has the advantage that the catalytic stability is obviously improved in the methanol electrooxidation process.
In summary, the present invention provides a simple-to-operate method for synthesizing bimetallic PtCu aerogel catalysts having a typical three-dimensional porous structure in which extended ultrathin nanowires are interconnected. The catalyst can be used in the oxidation process of methanol and shows remarkably enhanced electrochemical performance.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a bimetallic PtCu aerogel catalyst for a high-activity fuel cell is characterized by comprising the following steps:
(a) adding platinum salt and copper salt into solvent, mixing, and adding excessive NaBH4Continuously mixing to form a reaction system, and reacting to obtain the bimetallic PtCu hydrogel material;
(b) and (b) carrying out aftertreatment on the bimetallic PtCu hydrogel material obtained in the step (a) to obtain the PtCu aerogel catalyst.
2. The method for preparing the bimetallic PtCu aerogel catalyst for the high-activity fuel cell as claimed in claim 1, wherein in the step (a), the platinum salt is H2PtCl6·6H2O, the copper salt is CuCl2·2H2And O, wherein the solvent is ultrapure water.
3. The method for preparing a bimetallic PtCu aerogel catalyst for a high activity fuel cell as claimed in claim 2, wherein in the step (a), H is added2PtCl6·6H2O、CuCl2·2H2O、H2O and NaBH4The ratio of the amount of (1) to (2) is (0.01-0.15) mmol, (0.005-0.07) mmol, (40 ml).
4. The method for preparing the bimetallic PtCu aerogel catalyst for the high-activity fuel cell as claimed in claim 1, wherein in the step (a), the reaction temperature is normal temperature, and the reaction time is 4-8 h.
5. The method for preparing the bimetallic PtCu aerogel catalyst for the high-activity fuel cell as claimed in claim 1, wherein in the step (b), the post-treatment process is specifically as follows: and (3) washing, solvent exchange, liquid nitrogen quick freezing and freeze drying the bimetal PtCu hydrogel material in sequence.
6. The method for preparing the bimetallic PtCu aerogel catalyst for the high-activity fuel cell as claimed in claim 5, wherein the bimetallic PtCu hydrogel material is washed with ultrapure water for 1-2 days.
7. The method for preparing the bimetallic PtCu aerogel catalyst for the high-activity fuel cell as claimed in claim 5, wherein the washed bimetallic PtCu hydrogel material is exchanged with acetone for 1-2 days.
8. The preparation method of the bimetallic PtCu aerogel catalyst for the high-activity fuel cell as claimed in claim 5, wherein the quick-frozen PtCu hydrogel is freeze-dried under vacuum at a temperature of-50 to-46 ℃ for 24 to 48 hours.
9. A bimetallic PtCu aerogel catalyst for a high-activity fuel cell prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the bimetallic PtCu aerogel catalyst for high activity fuel cells according to claim 9 in fuel cells.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103227336A (en) * | 2013-04-03 | 2013-07-31 | 上海交通大学 | Band-shaped carbon-carrier metal catalyst, preparation method and application thereof |
| CN108654641A (en) * | 2018-04-28 | 2018-10-16 | 中南大学 | A kind of carbon dioxide methane reforming catalyst and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103227336A (en) * | 2013-04-03 | 2013-07-31 | 上海交通大学 | Band-shaped carbon-carrier metal catalyst, preparation method and application thereof |
| CN108654641A (en) * | 2018-04-28 | 2018-10-16 | 中南大学 | A kind of carbon dioxide methane reforming catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHENGZHOU ZHU 等: "《Efficient Synthesis of MCu (M = Pd, Pt, and Au) Aerogels with Accelerated Gelation Kinetics and their High Electrocatalytic Activity》", 《ADV. MATER.》 * |
| RAN DU 等: "《Unveiling reductant chemistry in fabricating noble metal aerogels for superior oxygen evolution and ethanol oxidation》", 《NATURE COMMUNICATIONS》 * |
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Application publication date: 20211105 |