CN108832139B - Preparation method and application of core-shell structure Cu @ Pd nano electro-catalyst for fuel cell - Google Patents
Preparation method and application of core-shell structure Cu @ Pd nano electro-catalyst for fuel cell Download PDFInfo
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- CN108832139B CN108832139B CN201810603464.XA CN201810603464A CN108832139B CN 108832139 B CN108832139 B CN 108832139B CN 201810603464 A CN201810603464 A CN 201810603464A CN 108832139 B CN108832139 B CN 108832139B
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
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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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a Cu @ Pd nano electro-catalyst with a core-shell structure for a fuel cell, which takes transition metal Cu as a crystal nucleus and noble metal Pd as a shell and has a regular tetrakaidecahedron structure. Transferring the Cu seed crystal into a mixed aqueous solution of hexadecyl trimethyl ammonium chloride and potassium bromide, and dripping a glycol solution of potassium chloropalladite into the mixed solution; and dripping a sodium hydroxide glycol solution into the mixed solution, and reacting at the temperature of 120-200 ℃ for 8-12 hours to obtain the Cu @ Pd electrocatalyst for the fuel cell. According to the system, CTAC & KBr is used as a morphology control agent, and the prepared Cu @ Pd catalyst is uniform in size and regular tetrakaidecahedron in morphology. The prepared catalyst has excellent performance of electrocatalytic oxidation of ethanol, and has great application and development prospect in direct ethanol fuel cells.
Description
Technical Field
The invention belongs to the technical field of fuel cells, relates to a preparation method of a catalyst, and particularly relates to a preparation method of a core-shell structure Cu @ Pd electrocatalyst for a direct ethanol fuel cell.
Background
The Fuel Cell (FC) is a fourth generation power generation technology following thermal power, hydroelectric power and nuclear power, is a device for directly converting chemical energy in fuel into electric energy, is not limited by Carnot cycle in an energy conversion mode, is clean in emission and free of pollution, and is a high-efficiency and environment-friendly new energy technology. Direct Ethanol Fuel Cells (DEFCs) are one type of low temperature fuel cells, and because the fuel is liquid ethanol, they are superior to conventional hydrogen-oxygen fuel cells in storage, transportation, safety, and cost. The direct ethanol fuel cell system has the characteristics of simple structure, quick start, easy fuel supplement, high theoretical specific energy and the like. In the ethanol oxidation in an alkaline system, the Pd-based nano material has the electrocatalytic performance which is comparable to that of a Pt-based material, and is a Pt substitute with great potential.
Disclosure of Invention
The invention aims to prepare the Cu @ Pd electrocatalyst with excellent ethanol catalytic activity for the fuel cell by structure control and proper morphology regulation while reducing the consumption of noble metal Pd.
The technical scheme adopted by the invention for realizing the purpose is as follows:
(1) weighing Cetyl Trimethyl Ammonium Chloride (CTAC) and potassium bromide (KBr), dissolving in secondary distilled water, ultrasonic dispersing, heating in oil bath to 50-70 deg.C, stirring, introducing N2Dropwise adding anhydrous copper chloride (CuCl)2) Ethylene glycol solution (where N is passed in)2Creating an inert atmosphere to prevent Cu from being reduced by O in the system2Oxidation of (c) to produce Cu oxide); dripping a glycol solution of sodium hydroxide (NaOH) into the mixed solution, adjusting the pH value of the solution to 9.5-10, sealing, heating to 100 ℃ and 120 ℃, and removing N2 (where N is removed)2Because the system is sealed and is in an inert atmosphere, no further N is needed2) And (3) carrying out heat preservation reaction for 1-2 hours, naturally cooling to room temperature, centrifuging and washing for 2-3 times by using secondary distilled water and absolute ethyl alcohol respectively at 8000-10000 rrm/min, and drying, sealing and storing the obtained Cu seed crystal in vacuum. The mixed solution contains CTAC 10-15mg/ml, KBr 3-5 mg/ml and CuCl2The concentration of the glycol solution is 1.3-1.5 mg/ml, and the concentration of the glycol solution of NaOH is 4 mg/ml.
(2) Weighing a certain amount of Cu seed crystal and CTAC & KBr, adding double distilled water, and ultrasonically dissolving; stirring at 60 ℃ for 30min, and then dropwise adding K into the mixed solution2PdCl4Finally, the ethylene glycol solution of NaOH is dropped. The concentration of CTAC in the mixed solution is 2.67 mg/ml, the concentration of KBr is 1 mg/ml, the concentration of Cu seed crystal is 0.01-0.03 mg/ml, and K is2PdCl4The concentration is 0.3-0.4 mg/ml, and the concentration of NaOH is 4 mg/ml.
(3) Transferring the uniformly mixed reaction liquid into an inner container of a polytetrafluoroethylene reaction kettle, sealing, screwing, placing in an air-blast drying box, and reacting at the temperature of 120 ℃ and 200 ℃ for 8-14 hours.
(4) Naturally cooling to room temperature, centrifugally separating at 5000-12000 rpm/min, centrifugally washing the secondary distilled water and the absolute ethyl alcohol for three to five times respectively, re-dissolving the final product in the absolute ethyl alcohol, and dispersing and storing to obtain the Cu @ Pd electrocatalyst for the fuel cell.
In the step (1), the secondary distilled water and the glycol simultaneously serve as solvents, wherein the glycol serves as a reducing agent, the CTAC & KBr serves as a morphology control agent, the KBr can be replaced by KI, and the CTAC & KBr can be replaced by Cetyl Trimethyl Ammonium Bromide (CTAB).
In the step (2), the volume of the mixed liquid in the inner container of the polytetrafluoroethylene reaction kettle is 10-30 ml.
In the step (3), in the centrifugal washing process, washing with secondary distilled water for 2-3 times, and then washing with absolute ethyl alcohol for 3-4 times to ensure that unreacted reactants are removed from the surface of the catalyst.
The Cu @ Pd electrocatalyst for the fuel cell is regular in morphology, is a typical tetrakaidecahedron, is uniform in size, and has an average particle size of 10-30 nm.
The electrochemical active area (ECSA) of the Cu @ Pd electrocatalyst for the fuel cell is 25-60 m2/gPd。
The mass percentage content of Pd in the Cu @ Pd electrocatalyst for the fuel cell is 15-65%.
The Cu @ Pd electrocatalyst for the fuel cell has the characteristics of a core-shell structure, and the Pd-rich surface greatly reduces the consumption of noble metals in a bulk phase.
The Cu @ Pd electrocatalyst for the fuel cell and the preparation method thereof have the following remarkable characteristics:
(1) the preparation method comprises two steps, wherein the first step is to synthesize a transition metal Cu core, and the second step is to synthesize a noble metal Pd shell.
(2) The glycol serves as a solvent and a reducing agent at the same time, so that the cost is low, and the method is green and pollution-free.
(3) According to the system, CTAC & KBr is used as a morphology control agent, and the prepared Cu @ Pd catalyst is uniform in size and regular tetrakaidecahedron in morphology.
(4) The prepared catalyst has excellent performance of electrocatalytic oxidation of ethanol, and has great application and development prospect in direct ethanol fuel cells.
According to the invention, by preparing the Cu @ Pd electrocatalyst with the core-shell structure, the consumption of noble metal Pd can be further reduced without losing the electrocatalytic performance, and the utilization rate of Pd atoms is effectively improved. The combination of noble metal Pd and non-noble metal is an effective means for reducing the dosage of Pd in the catalyst, and the particularity of the core-shell structure lies in the stress strain effect among different elements, and the effect can be regulated and controlled by changing the proportion of the precursor. Because the catalytic reaction is mainly carried out on the surface, the preparation of the catalyst with the core-shell structure and the special shape can greatly improve the catalytic reaction efficiency. In the invention, a Cu @ Pd catalyst which has uniform particle size, tetradecahedron characteristic and excellent ethanol oxidation performance is prepared by taking Cu as a core and applying a hydrothermal synthesis technology, wherein glycol and secondary distilled water serve as solvents, the glycol serves as a reducing agent, and CTAC & KBr serves as a morphology control agent.
Drawings
FIG. 1: transmission electron micrograph of Cu @ Pd electrocatalyst for fuel cell prepared for example 1.
FIG. 2: cyclic voltammogram of ethanol electrocatalytic oxidation using Cu @ Pd electrocatalyst for fuel cells prepared in example 1.
FIG. 3: transmission electron micrograph of Cu @ Pd electrocatalyst for fuel cell prepared for example 2.
FIG. 4: cyclic voltammogram of ethanol electrocatalytic oxidation using Cu @ Pd electrocatalyst for fuel cells prepared in example 2.
FIG. 5: cyclic voltammograms of the Cu @ Pd electrocatalyst for fuel cells prepared for examples 1, 2 and commercial Pd black electrocatalytic oxidation of ethanol.
FIG. 6: bar graph comparing activity of Cu @ Pd electrocatalyst for fuel cells prepared for examples 1, 2 with commercial Pd black electrocatalytic oxidation of ethanol.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific embodiments, which are set forth herein for illustrative purposes only and are not intended to limit the scope of the invention, which is defined by the claims appended hereto, as modified by those skilled in the art upon reading the present disclosure in various equivalents.
Example 1
(1) Weighing 384mg CTAC in a 50ml round bottom spherical bottle, adding 15ml secondary distilled water, and ultrasonically dissolving; adding CuCl into the mixed solution2Ethylene glycol solution (40.335mg CuCl)2Dissolving in 5ml of ethylene glycol), transferring to an oil bath kettle after ultrasonic dissolving, and introducing N2Stirring at 60 deg.C for 30 min; dropping NaOH in ethylene glycol solution (96mg NaOH dissolved in 10ml ethylene glycol), heating to 110 deg.C, and removing N2Reacting for 1-2 hours under heat preservation, naturally cooling to room temperature, respectively centrifugally washing for 2-3 times by using redistilled water and absolute ethyl alcohol at the rotating speed of 10000 rpm/min, and drying, sealing and storing the obtained Cu seed crystal in vacuum.
(2) Weighing 0.4mg of Cu seed crystal, 96mg of CTAC and 24mg of KBr in a 50ml spherical bottle, and adding 12ml of secondary distilled water for ultrasonic dissolution; stirring at 60 deg.C for 30min, and sequentially adding ethylene glycol solution of NaOH (96mg NaOH dissolved in 10ml ethylene glycol) and K2PdCl4Ethylene glycol solution (8.16mg K)2PdCl4Dissolved in 2ml of ethylene glycol) and stirred thoroughly.
(3) Transferring the mixed solution into a liner of a 30mL polytetrafluoroethylene reaction kettle, screwing the reaction kettle tightly, placing the reaction kettle in an air-blast drying oven, and reacting for 10 hours at 180 ℃.
(4) Naturally cooling to room temperature, keeping standing, centrifugally separating black precipitate obtained after reaction at 10000 r/min, washing with secondary distilled water for 3 times, then using absolute ethyl alcohol for 3 times, and finally adding the obtained product into the absolute ethyl alcohol for dispersion protection to obtain the Cu @ Pd electrocatalyst for the fuel cell.
FIG. 1 is a Transmission Electron Micrograph (TEM) of the Cu @ Pd electrocatalyst for a fuel cell prepared in this example, and it can be seen from FIG. 1a that the prepared nanoparticles maintain a planar hexagonal structure, while FIG. 1a is partially shaded, which is a phenomenon that the un-separated nanoparticles are stacked too thick to cause difficulty in electron penetration and form black spots. FIG. 1b is an enlarged view of a single hexagonal nanoparticle with 4 distinct edges on the surface, dividing the surface into 2 triangular and 2 diamond regions, in a distinct tetradecahedron structure.
The Cu @ Pd electrocatalyst prepared in the embodiment is modified on a glassy carbon electrode to prepare a working electrode, the content of Pd on the surface of the modified electrode is about 0.05mg, and the electrochemical active area (ECSA is 52 m)2/gPd) And carrying out cyclic voltammetry test on the obtained product, wherein the test conditions are as follows: the sweep range was-0.8-0.2V (vs. SCE), the sweep rate was 50 mV/s, and the solution was 1 mol/L KOH +1 mol/LC saturated with nitrogen2H5OH solution, the test results are shown in FIG. 2.
As can be seen from FIG. 2, the Cu @ Pd electrocatalyst thus prepared exhibited a maximum ethanol oxidation peak current density of about 529.66 mA/mg at a potential of-0.1VPd -1And shows the optimal activity of the electrocatalytic oxidation of ethanol.
Example 2
(1) Weighing 384mg CTAC in a 50ml round bottom spherical bottle, adding 15ml secondary distilled water, and ultrasonically dissolving; adding CuCl into the mixed solution2Ethylene glycol solution (40.335mg CuCl)2Dissolving in 5ml of ethylene glycol), transferring to an oil bath kettle after ultrasonic dissolving, and introducing N2Stirring at 60 deg.C for 30 min; dropping NaOH in ethylene glycol solution (96mg NaOH dissolved in 10ml ethylene glycol), heating to 110 deg.C, and removing N2Reacting for 1-2 hours under heat preservation, naturally cooling to room temperature, respectively centrifugally washing for 2-3 times by using redistilled water and absolute ethyl alcohol at the rotating speed of 10000 rpm/min, and drying, sealing and storing the obtained Cu seed crystal in vacuum.
(2) Weighing 0.4mg of Cu seed crystal, putting 96mg of CTAC in a 50ml spherical bottle, and adding 12ml of secondary distilled water for ultrasonic dissolution; stirring at 60 deg.C for 30min, and sequentially adding ethylene glycol solution of NaOH (96mg NaOH dissolved in 10ml ethylene glycol) and K2PdCl4Ethylene glycol solution (8.16mg K)2PdCl4Dissolved in 2ml of ethylene glycol) and stirred thoroughly.
(3) Naturally cooling to room temperature, keeping standing, centrifugally separating black precipitate obtained after reaction at 10000 r/min, washing with secondary distilled water for 3 times, then using absolute ethyl alcohol for 3 times, and finally adding the obtained product into the absolute ethyl alcohol for dispersion protection to obtain the Cu @ Pd electrocatalyst for the fuel cell.
Fig. 2 is a transmission electron image (TEM) of the Cu @ Pd electrocatalyst for a fuel cell prepared in this example, and it can be seen that the prepared nanoparticles have a distinct grain boundary profile and substantially exhibit a random spherical shape in the absence of KBr.
The Cu @ Pd electrocatalyst prepared in the embodiment is modified on a glassy carbon electrode to prepare a working electrode, the content of Pd on the surface of the modified electrode is about 0.05mg, and the electrochemical active area (ECSA is 52 m)2/gPd) And carrying out cyclic voltammetry test on the obtained product, wherein the test conditions are as follows: the sweep range was-0.8-0.2V (vs. SCE), the sweep rate was 50 mV/s, and the solution was 1 mol/L KOH +1 mol/LC saturated with nitrogen2H5OH solution, the test results are shown in FIG. 2.
As can be seen from FIG. 2, the prepared Cu @ Pd electrocatalyst has a maximum ethanol oxidation peak current density of about 393.44 mA/mg at a potential of-0.13VPd -1And shows better activity of electrocatalytic oxidation of ethanol.
FIG. 5 is a plot of cyclic voltammograms of the Cu @ Pd electrocatalyst for fuel cells prepared in examples 1 and 2 and the ethanol electrocatalytic oxidation of commercial Pd black catalyst,
FIG. 6 is a bar graph comparing the activity of Cu @ Pd electrocatalyst for fuel cells prepared in examples 1 and 2 with that of commercial Pd black catalyst for electrocatalytic oxidation of ethanol, which is listed as the current density value at the respective peak potentials, and it can be more intuitively seen from the figure that the electrocatalytic oxidation of ethanol in examples 1 and 2 is superior to that of commercial Pd black, wherein the ethanol in example 1 has the highest catalytic mass activity, about 1.34 times that of example 2, and 1.67 times that of commercial Pd black; the ethanol catalytic activity of example 2 was the highest, about 1.37 times that of example 1, which is 1.84 times that of commercial Pd black.
Claims (5)
1. The Cu @ Pd nano electro-catalyst for the fuel cell is a binary core-shell structure Cu @ Pd nano electro-catalyst with a regular tetrakaidecahedron structure and taking transition metal Cu as a crystal nucleus and noble metal Pd as a shell, the average particle size of the core-shell structure Cu @ Pd nano electro-catalyst is 10-50 nm, the electrochemical active area is 25-60 m2The Pd alloy material is characterized by comprising the following specific steps of:
(1) weighing hexadecyl trimethyl ammonium chloride and potassium bromide, dissolving in secondary distilled water, ultrasonic dispersing, heating to 50-70 deg.C in oil bath, stirring, and introducing N2Dropwise adding an ethylene glycol solution of anhydrous copper chloride; dripping a glycol solution of sodium hydroxide into the mixed solution, adjusting the pH value of the solution to 9.5-10, sealing, heating to 100 ℃ and 120 ℃, and removing N2Reacting for 1-2 hours under heat preservation, naturally cooling to room temperature, centrifuging and washing for 2-3 times by using secondary distilled water and absolute ethyl alcohol respectively at 8000-10000 rpm, and drying and sealing the obtained Cu seed crystal in vacuum for storage;
(2) taking Cu seed crystals, transferring the Cu seed crystals to a mixed aqueous solution of hexadecyl trimethyl ammonium chloride and potassium bromide, and dripping a glycol solution of potassium chloropalladite into the mixed solution; dripping a glycol solution of sodium hydroxide into the mixed solution, adjusting the pH value of the solution to 9.5-10, quickly transferring the mixed solution into an inner container of a polytetrafluoroethylene reaction kettle, sealing, placing the mixed solution into a blast drying oven, and reacting for 8-12 hours at the temperature of 200 ℃;
(3) naturally cooling to room temperature, centrifuging and washing for 2-3 times by using secondary distilled water and absolute ethyl alcohol respectively at 8000-10000 rpm to obtain the Cu @ Pd electrocatalyst for the fuel cell.
2. The method of claim 1, wherein in step (1), the cetyltrimethylammonium chloride is at a concentration of 10-15mg/ml, the potassium bromide is at a concentration of 3-5 mg/ml, and the CuCl is added2The concentration of the ethylene glycol solution is 1.3-1.5 mg/ml, and the concentration of the ethylene glycol solution of NaOH is 3-5 mg/ml.
3. The method for preparing a Cu @ Pd electrocatalyst for a fuel cell according to claim 1, wherein in the step (2), the concentration of cetyltrimethylammonium chloride is 2.67 mg/ml, the concentration of KBr is 1 mg/ml, the concentration of Cu seed crystal is 0.01-0.03 mg/ml, the concentration of potassium chloropalladite in ethylene glycol solution is 0.3-0.4 mg/ml, and the concentration of NaOH in ethylene glycol solution is 3-5 mg/ml.
4. The method of claim 1, wherein cetyltrimethylammonium chloride and potassium bromide are replaced with cetyltrimethylammonium bromide in steps (1) and (2).
5. The method for preparing a Cu @ Pd electrocatalyst for a fuel cell according to claim 1, wherein in the step (2), the volume of the mixed solution is 3/5-4/5 in the polytetrafluoroethylene reaction kettle inner container.
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| CN114373952A (en) * | 2021-12-20 | 2022-04-19 | 三峡大学 | Preparation method and application of surface-reconstructed PdFe/Cu nano electro-catalyst for fuel cell |
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| CN102088091A (en) * | 2010-12-17 | 2011-06-08 | 北京化工大学 | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof |
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| CN106252670A (en) * | 2015-06-10 | 2016-12-21 | 通用汽车环球科技运作有限责任公司 | Use the electrode added with crystal seed by the nucleocapsid catalyst volume to volume manufacture to high performance fuel cell electrode |
| CN106910907A (en) * | 2017-04-14 | 2017-06-30 | 中国科学院深圳先进技术研究院 | A kind of catalyst with core-casing structure, Preparation Method And The Use |
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| KR101304219B1 (en) * | 2011-09-05 | 2013-09-06 | 한국과학기술연구원 | Core-shell structured electrocatalysts for fuel cells and the preparation method thereof |
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| CN101656313A (en) * | 2009-09-11 | 2010-02-24 | 太原理工大学 | Preparation method of catalyst for cathode of direct methanol fuel cell |
| CN102665968A (en) * | 2009-09-17 | 2012-09-12 | 耶路撒冷希伯来大学伊森姆研究发展公司 | Cage nanostructures and preparation thereof |
| CN102088091A (en) * | 2010-12-17 | 2011-06-08 | 北京化工大学 | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof |
| CN106252670A (en) * | 2015-06-10 | 2016-12-21 | 通用汽车环球科技运作有限责任公司 | Use the electrode added with crystal seed by the nucleocapsid catalyst volume to volume manufacture to high performance fuel cell electrode |
| CN106910907A (en) * | 2017-04-14 | 2017-06-30 | 中国科学院深圳先进技术研究院 | A kind of catalyst with core-casing structure, Preparation Method And The Use |
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