CN108736031B - Self-supporting PtCo alloy nanoparticle catalyst and preparation method and application thereof - Google Patents
Self-supporting PtCo alloy nanoparticle catalyst and preparation method and application thereof Download PDFInfo
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- B82—NANOTECHNOLOGY
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- H01—ELECTRIC ELEMENTS
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- 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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- H01M4/885—Impregnation followed by reduction of the catalyst salt precursor
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- H—ELECTRICITY
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- 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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- 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]
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Abstract
The invention relates to a self-supporting PtCo alloy nanoparticle catalyst and a preparation method and application thereof, and particularly relates to a method for synthesizing a three-dimensional self-supporting cobalt-based metal organic framework (Co-MOFs) nanorod array structure on carbon cloth by a liquid phase method, obtaining a three-dimensional porous nitrogen-doped carbon-coated metal cobalt nanoparticle (Co @ N-C) nanorod structure by a high-temperature carbothermic reduction technology, taking the three-dimensional porous nitrogen-doped carbon-coated metal cobalt nanoparticle (Co @ N-C) nanorod structure as a template, and finally obtaining the nitrogen-doped carbon/PtCo (PtCo @ N-C) porous catalyst by a simple potential replacement reaction method by utilizing the difference of oxidation-reduction potentials of metal Pt and Co. Compared with the prior art, the composite catalyst disclosed by the invention does not need a binder and a conductive additive, has excellent methanol oxidation performance and CO antitoxicity, and the flexible carbon cloth substrate is used as a current collector, can be bent and folded, and has very good mechanical properties.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a self-supporting PtCo alloy nanoparticle catalyst and a preparation method and application thereof.
Background
Fuel cells, as an efficient energy conversion device, have the potential of low cost and zero emission, and are considered to be an important approach to solve the increasing energy crisis and environmental pollution problems of mankind. And the methanol has the advantages of high commercialization degree, high specific energy, good portability and the like, so that the direct methanol fuel cell has a very promising application prospect and draws wide attention of people. Platinum and platinum-based alloys remain among the most effective and stable catalysts for methanol oxidation among numerous electrocatalysts, however, platinum reserves are limited and expensive, greatly limiting its large-scale commercial use. In addition, the catalytic performance of platinum is also limited by its slow methanol oxidation kinetics and CO poisoning.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a self-supporting PtCo alloy nanoparticle catalyst with good catalytic activity, strong antitoxic ability and good mechanical property, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme: a self-supporting PtCo alloy nanoparticle catalyst comprises three-dimensional porous nitrogen-doped carbon and Pt and Co coated inside the three-dimensional porous nitrogen-doped carbon, wherein the mass ratio of the Pt to the Co is (0.5-0.6): 1 the total mass of the Pt and the Co accounts for 43-48% of the mass of the catalyst, and the three-dimensional porous nitrogen-doped carbon is in an array structure. The invention adopts Pt and Co as the effective components of the catalyst, the combination of Pt and Co reduces the electron binding energy in Pt, and promotes C-H cracking reaction under low potential, thereby improving the activity and antitoxicity of the catalyst. Meanwhile, the precursor of the cobalt-based metal organic framework material is of a three-dimensional array structure, so that the porous nitrogen-doped carbon after calcination is also of an array structure. The highly graphitized porous nitrogen-doped carbon nanorod array has large specific surface area and high conductivity, provides ideal support for the dispersion of PtCO nano particles, and is favorable for promoting the migration of ions/protons; the doped nitrogen element can enhance the interaction between alloy particles and carbon and improve the stability of the catalyst; and the intrinsic catalytic capability of the porous nitrogen-doped carbon also makes a certain contribution to the improved catalytic activity.
A method for preparing the self-supporting PtCo alloy nanoparticle catalyst as described above, comprising the steps of:
(1) putting carbon cloth into an aqueous solution of acetone for ultrasonic treatment, washing and drying, and then putting the carbon cloth into a precursor solution to form a cobalt-based metal organic framework, wherein the precursor solution is a mixed aqueous solution of cobalt nitrate and dimethylimidazole;
(2) calcining the cobalt-based metal organic framework to obtain three-dimensional porous nitrogen-doped carbon coated with Co nanoparticles;
(3) soaking the obtained Co nanoparticle-coated three-dimensional porous nitrogen-doped carbon in H2PtCl4And (3) obtaining the self-supporting PtCo alloy nano-particle catalyst in a Pt solution.
The carbon cloth woven by the carbon fibers is a good three-dimensional conductive substrate material, so that the specific surface area of the prepared material can be increased, and the active sites can be increased; on the other hand, the active material grown on the carbon cloth can be directly used as a catalytic electrode, and the step of preparing the electrode like other powder catalysts is omitted. In the whole preparation process, Co is gradually replaced by Pt from outside to inside to form alloy particles.
The time for carrying out ultrasonic treatment on the carbon cloth in the aqueous solution of acetone is 20-30 min, and the carbon cloth is cleaned by ultrasonic.
Deionized water is adopted for washing, and the drying temperature is 60-80 ℃.
In the precursor solution, the molar ratio of cobalt nitrate to dimethyl imidazole is 1 (15-20).
The calcination is carried out on Ar and H2Wherein Ar is Ar and H290 to 95 percent of the total volume. H2The addition of the carbon nano-tube can promote the catalytic action of Co in the calcining process, and a plurality of carbon nano-tubes grow on the surface of the array structure, so that the specific surface area of the structure is increased.
Heating to 700-900 ℃ at a speed of less than 5 ℃/min, preserving heat for 2-4 h, and naturally cooling to room temperature. The cobalt-based metal organic framework array can be highly graphitized at 700-900 ℃, and the conductivity is increased.
Said H2PtCl4The concentration of the Pt solution is 0.5-2 mmol/L, and the Co nano-particle coated three-dimensional porous nitrogen-doped carbon is in H2PtCl4The soaking time in the Pt solution is 2-4 min.
Use of a self-supporting PtCo alloy nanoparticle catalyst as described above for use in the anode of a methanol fuel cell. The anode of the methanol fuel cell generates methanol oxidation reaction, and the cathode generates oxygen reduction reaction. The material prepared by the invention is a methanol oxidation catalyst, so the material is used for an anode of a methanol fuel cell.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
(1) when the catalyst is used for the anode of a methanol fuel cell, the initial potential of methanol oxidation is high, and the current density of the anode is high;
(2) when the catalyst is used for an anode of a methanol fuel cell, the CO toxicity resistance and the durability are excellent.
Drawings
FIG. 1 is a three-dimensional porous Co @ N-C scanning electron microscope picture;
FIG. 2 is a planar scanning electron microscope image of a three-dimensional PtCo @ N-C catalyst;
FIG. 3 shows PtCo @ N-C and Pt/C at 0.5M H2SO4Is measured at a sweep rate of 50 mV/s.
FIG. 4 shows PtCo @ N-C and Pt/C at 0.5M CH3OH+0.5M H2SO4Is measured at a sweep rate of 50 mV/s.
FIG. 5 shows PtCo @ N-C and Pt/C at 0.5M CH3OH+0.5M H2SO4The peak current density of the electrolyte solution of (2) was compared with that of the electrolyte solution with the increase of the cycle number.
FIG. 6 shows PtCo @ N-C and Pt/C at 0.5M H2SO4The CV curve for CO antitoxicity tested in the electrolyte of (a).
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
A preparation method of a self-supporting PtCo alloy nanoparticle catalyst comprises the following steps:
preparation of Co-MOFs nanorod array on carbon cloth
Firstly, selecting carbon cloth as a substrate, wherein the model is as follows: WOS 1002. And respectively putting the carbon cloth into acetone and deionized water for ultrasonic treatment for 20 minutes, finally washing with the deionized water, and putting into a forced air drying oven for drying.
Preparing a Co-MOFs precursor solution: 40ml of 25mM cobalt nitrate (Co (NO)3)2·6H2O) was added rapidly to 40ml of 0.4M dimethylimidazole (C)4H6N2) In an aqueous solution, and then stirred.
And soaking the treated carbon cloth in the Co-MOFs precursor solution at 30 ℃ for reaction for 4 hours. Then washing the product by deionized water.
And repeating the steps, and secondarily growing the Co-MOFs under the same temperature and reaction time.
Preparation of Co @ N-C nanorod array on carbon cloth
The Co-MOFs nanorod array prepared on the carbon cloth is subjected to Ar/H reaction at 800 DEG C2(5％H295% Ar) for 2 hours, wherein the heating rate is 5 ℃/min. Naturally cooling to obtain the Co @ N-C nanorod array structure (figure 1).
Preparation of PtCo @ N-C nanorod array on carbon cloth
The prepared PtCo @ N-C nanorod array on the carbon cloth was placed in a stirred 1mM chloroplatinic acid (H)2PtCl6·6H2O) for 3 minutes, labeled PtCo @ N-C. The reaction equation is:
Co+PtCl4 2-→Co2++Pt+4Cl-
the PtCo @ N-C nanorod array prepared on the carbon cloth is subjected to Ar/H reaction at 400 DEG C2(5％H295% Ar) for 1 hour, wherein the heating rate is 3.5 ℃/min. And naturally cooling to obtain the PtCo @ N-C nanorod array structure (shown in figure 2).
The mass of Pt and Co in the prepared PtCo @ N-C is 0.278mg cm-2And 0.533mg cm-2The corresponding atomic ratio is 14: 86.
The invention synthesizes a three-dimensional Co-MOFs nanorod structure with large specific surface area by a liquid phase method, obtains a Co @ N-C structure through annealing treatment, takes the Co @ N-C structure as a carrier, prepares a series of Pt loaded PtCo @ N-C catalysts by adopting a simple Pt precursor soaking method, and carries out system test and analysis on the electrocatalytic performance of the catalysts.
The electrocatalytic performance of the prepared PtCo @ N-C catalyst is tested by an electrochemical workstation under a three-electrode system. The PtCo @ N-C catalyst is used as a working electrode, Ag/AgCl (+0.197V vs RHE) soaked in a saturated KCl solution is used as a reference electrode, and a graphite rod is used as a counter electrode.
Before measurement, high-purity Ar is introduced into the electrolyte for 20 minutes,to remove CO and O in the solution2。
The electrochemical active area of the prepared PtCo @ N-C catalyst is 0.5M H2SO4In a solution of (a), wherein the test voltage is in the range of 0 to 1.0V vs RHE and the sweep rate is 50mV s-1。
The electrochemical active areas of the prepared PtCo @ N-C and Pt/C catalysts are respectively 20m2G and 14.2m2The/g, PtCo @ N-C catalyst exhibited a larger electrochemically active area (FIG. 3).
The methanol oxidation performance of the prepared PtCo @ N-C catalyst was improved by including 0.5M H2SO4And 0.5M CH3Obtained by testing a voltammetry Curve (CV) in an OH mixed solution, wherein the test voltage range is 0-1.2V vs. RHE, and the sweep rate is 50mV s-1。
The prepared PtCo @ N-C catalyst has more negative initial voltage (0.563V) than the Pt/C catalyst<0.642V) and greater positive peak current density (433.5mA mg-1>140mA mg-1). Thus, the PtCo @ N-C catalyst exhibited superior methanol oxidation activity (FIG. 4).
The methanol oxidation stability of the prepared PtCo @ N-C catalyst is 0.5M H2SO4And 0.5M CH3Obtained by testing a CV curve of 100 continuous cycles in an OH mixed solution, wherein the test voltage interval is 0-1.2V vs. RHE, and the sweep rate is 50mV s-1。
The anode peak current density retention of the prepared PtCo @ N-C and Pt/C catalysts after 100 cycles was 94.4% and 68.7% of the peak, respectively, indicating that the durability of the PtCo @ N-C catalysts was due to commercial Pt/C (FIG. 5).
The CO antitoxic performance of the prepared PtCo @ N-C catalyst is 0.5M H of CO saturation2SO4The test voltage interval is-0.1-1.4V vs RHE, and the sweep rate is 50mV s-1. High purity CO gas and A r gas were passed into the electrolyte for 15 minutes each before the measurement to ensure that the catalyst active sites were covered with sufficient CO and that the solution was free of CO.
The prepared PtCo @ N-C and Pt/C catalysts have CO desorption peaks at 0.92V and 1.03V respectively, and the more negative CO desorption peaks of PtCo @ N-C prove that the prepared PtCo @ N-C has more excellent CO CO-solubility (figure 6).
Thus, the PtCo @ N-C catalyst prepared in this example has excellent methanol oxidation current density, CO poisoning resistance, and durability.
Example 2
A similar preparation method to that of example 1 was employed, except that:
(1) the ultrasonic treatment time of the carbon cloth in the aqueous solution of acetone is 20min, and the drying temperature of the carbon cloth is 60 ℃;
(2) the molar ratio of cobalt nitrate to dimethyl imidazole in the precursor solution is 1: 15.
(3) calcining at Ar and H2Wherein Ar accounts for 90% of the total gas volume; the calcining temperature is 700 ℃, and the calcining time is 4 hours;
(4) h for soaking2PtCl4The concentration of the Pt solution is 0.5m mol/L, and the soaking time is 4 min.
The catalyst prepared in the embodiment is used for an anode of a methanol fuel cell, and tests show that the catalyst has higher current density and good CO anti-toxicity performance.
Example 3
A similar preparation method to that of example 1 was employed, except that:
(1) the ultrasonic treatment time of the carbon cloth in the aqueous solution of acetone is 30min, and the drying temperature of the carbon cloth is 80 ℃;
(2) the molar ratio of cobalt nitrate to dimethyl imidazole in the precursor solution is 1: 20.
(3) Calcining at Ar and H2Wherein Ar accounts for 90 to 95 percent of the total gas volume; the calcining temperature is 900 ℃, and the calcining time is 2 hours;
(4) h for soaking2PtCl4The concentration of the Pt solution is 2m mol/L, and the soaking time is 2 min.
The catalyst prepared in the embodiment is used for an anode of a methanol fuel cell, and tests show that the catalyst has higher current density and good CO anti-toxicity performance.
Claims (9)
1. A self-supporting PtCo alloy nanoparticle catalyst is characterized in that the catalyst is used for an anode of a methanol fuel cell and comprises three-dimensional porous nitrogen-doped carbon and Pt and Co coated inside the three-dimensional porous nitrogen-doped carbon, wherein the mass ratio of the Pt to the Co is (0.5-0.6): 1, the total mass of Pt and Co accounts for 43-48% of the mass of the catalyst, and the three-dimensional porous nitrogen-doped carbon is in an array structure;
the preparation method of the catalyst comprises the following steps:
(1) putting carbon cloth into an aqueous solution of acetone for ultrasonic treatment, washing and drying, and then putting the carbon cloth into a precursor solution to form a cobalt-based metal organic framework, wherein the precursor solution is a mixed aqueous solution of cobalt nitrate and dimethylimidazole;
(2) calcining the cobalt-based metal organic framework to obtain three-dimensional porous nitrogen-doped carbon coated with Co nanoparticles;
(3) soaking the obtained Co nanoparticle-coated three-dimensional porous nitrogen-doped carbon in H2PtCl4Obtaining the self-supporting PtCo alloy nano-particle catalyst in a Pt solution;
in the step (1), soaking the treated carbon cloth in a precursor solution at 30 ℃ for reaction for 4 hours, and then washing the carbon cloth clean by deionized water; and repeating the steps, secondarily growing Co-MOFs under the same temperature and reaction time, and synthesizing the three-dimensional Co-MOFs nanorod structure with large specific surface area by a liquid phase method.
2. A method of making the self-supporting PtCo alloy nanoparticle catalyst of claim 1, comprising the steps of:
(1) putting carbon cloth into an aqueous solution of acetone for ultrasonic treatment, washing and drying, and then putting the carbon cloth into a precursor solution to form a cobalt-based metal organic framework, wherein the precursor solution is a mixed aqueous solution of cobalt nitrate and dimethylimidazole;
(2) calcining the cobalt-based metal organic framework to obtain three-dimensional porous nitrogen-doped carbon coated with Co nanoparticles;
(3) soaking the obtained Co nanoparticle-coated three-dimensional porous nitrogen-doped carbon in H2PtCl4And (3) obtaining the self-supporting PtCo alloy nano-particle catalyst in a Pt solution.
3. The method for preparing the self-supporting PtCo alloy nanoparticle catalyst as recited in claim 2, wherein the time for the carbon cloth to be subjected to ultrasonic treatment in the acetone aqueous solution is 20-30 min.
4. The method for preparing the self-supporting PtCo alloy nanoparticle catalyst as recited in claim 2, wherein the washing is performed with deionized water and the drying temperature is 60-80 ℃.
5. The preparation method of the self-supporting PtCo alloy nanoparticle catalyst as recited in claim 2, wherein the molar ratio of the cobalt nitrate to the dimethylimidazole in the precursor solution is 1 (15-20).
6. The method of claim 2, wherein the calcining is performed on Ar and H2In a mixed atmosphere of (A), wherein Ar is Ar and H290% -95% of the total volume.
7. The method of claim 6, wherein the calcining step comprises: heating to 700-900 ℃ at a speed of less than 5 ℃/min, preserving heat for 2-4 h, and naturally cooling to room temperature.
8. The method of claim 2, wherein the H comprises a catalyst selected from the group consisting of Pt, and Pt, wherein the H comprises a metal oxide, a metal alkoxide, an organic acid or a metal alkoxide, or a combination thereof2PtCl4The concentration of the Pt solution is 0.5-2 mmol/L, and the Pt solution is coatedThree-dimensional porous nitrogen-doped carbon of Co nano-particles in H2PtCl4The soaking time in the Pt solution is 2-4 min.
9. Use of the self-supporting PtCo alloy nanoparticle catalyst of claim 1 for the anode of a methanol fuel cell.
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