CN108172849B - Manganese dioxide-carbon nanotube composite catalyst based on palladium monoatomic atom and preparation thereof - Google Patents

Manganese dioxide-carbon nanotube composite catalyst based on palladium monoatomic atom and preparation thereof Download PDF

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CN108172849B
CN108172849B CN201810181736.1A CN201810181736A CN108172849B CN 108172849 B CN108172849 B CN 108172849B CN 201810181736 A CN201810181736 A CN 201810181736A CN 108172849 B CN108172849 B CN 108172849B
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manganese dioxide
palladium
carbon nanotube
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孙予罕
向苇凯
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杜福平
钱婧
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Shanghai Advanced Research Institute of CAS
University of Chinese Academy of Sciences
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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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • 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
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a palladium monoatomic-based manganese dioxide-carbon nanotube composite catalyst, in the catalyst, manganese dioxide and carbon nanotubes are mutually wound to form a three-dimensional nanostructure, and palladium is loaded on the surfaces of the manganese dioxide and the carbon nanotubes in a monoatomic form. The invention also discloses a preparation method of the catalyst and application of the catalyst in chargeable and dischargeable metal-air batteries. In the invention, MnO is used2The catalyst is taken as a base material, the two materials are mutually wound to form a three-dimensional nano structure by adding a proper amount of carbon nano tubes, and palladium monoatomic atoms are loaded on manganese dioxide and the carbon nano tubes, so that the conductivity, catalytic activity and stability of the catalyst are improved.

Description

Manganese dioxide-carbon nanotube composite catalyst based on palladium monoatomic atom and preparation thereof
Technical Field
The invention relates to the field of metal-air batteries, in particular to a palladium monoatomic manganese dioxide-carbon nanotube composite catalyst, a preparation method of the catalyst and application of the catalyst in a rechargeable zinc-air battery.
Background
With the rapid growth of renewable energy sources, the effective utilization and conversion of green electric energy has attracted extensive attention. The zinc-air battery has the advantages of high theoretical energy density, stable discharge voltage, long service life, simple preparation, environmental friendliness, low battery manufacturing cost and the like, and is one of ideal candidate technologies for large-scale energy storage.
The cyclic charge and discharge of the chargeable and dischargeable zinc-air battery requires the repeated catalysis of oxygen reduction reaction and oxygen evolution reaction by the electrocatalyst. Therefore, a key issue in improving the efficiency (U discharge/U charge) and cycle count of rechargeable zinc-air batteries is the development of a bifunctional catalyst with high activity and stability. The noble metals platinum, palladium, silver, and the like are well-known high-efficiency electrocatalysts, but are limited by their limited earth reserves, high price, and poor stability. Therefore, the development of a bifunctional electrocatalyst containing trace amounts of noble metals or non-noble metals has become a hot spot of current research. Researches show that the low-coordination metal atoms have high surface free energy and strong catalytic activity. Only the surface part of the nano-particles has a catalytic action, and the atom utilization rate is difficult to be maximized. The monatomic catalyst can greatly improve the specific activity of the catalyst, reduce the production cost and realize industrialized large-scale production.
At present, manganese dioxide is generally used as a catalyst of an air electrode of a zinc-air battery, but the zinc-air battery has the defects of low catalytic activity and poor stability. In order to increase the catalytic activity and stability, one of the methods is to increase the conductivity and the number of active sites of the semiconducting manganese dioxide. For example, chinese patent application No. 201510264206.X discloses a "nano-composite air electrode catalyst for zinc-air battery and a preparation method thereof", which uses manganese dioxide as a base material and adds auxiliary materials (such as carbon nanotubes, platinum, palladium, silver, etc.) to prepare a nano-composite catalyst. However, in the composite catalyst prepared by the method, silver is loaded on the surface of the carrier in a particle form, the utilization efficiency of silver atoms is low, and the mass activity of the catalyst is low.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a palladium monoatomic-based manganese dioxide-carbon nanotube composite catalyst which is low in price, strong in catalytic activity, good in stability, and high in conductivity and quality activity.
In order to solve the technical problems, in the manganese dioxide-carbon nanotube composite catalyst based on palladium monoatomic atoms, manganese dioxide and carbon nanotubes are mutually wound to form a three-dimensional nanostructure, and palladium is loaded on the surfaces of the manganese dioxide and the carbon nanotubes in a monoatomic form.
The mass ratio of the manganese dioxide to the carbon nanotubes is preferably 0.1-1: 1.
The second technical problem to be solved by the present invention is to provide a preparation method of the above manganese dioxide-carbon nanotube composite catalyst based on palladium monoatomic atoms, which comprises:
dispersing the carbon nano tube in water to obtain a carbon nano tube suspension;
adding manganese sulfate, ammonium persulfate and palladium nitrate into water to obtain a mixed solution;
and uniformly mixing the carbon nanotube suspension and the mixed solution, and then carrying out hydrothermal reaction to obtain the manganese dioxide-carbon nanotube composite catalyst based on the palladium monoatomic atom.
Wherein the mass ratio of the palladium nitrate to the water is preferably 0.5-5: 1000, the mass ratio of the ammonium persulfate to the water is preferably 0.6-6: 100, and the mass ratio of the carbon nano tube to the water is preferably 0.1-0.6: 100.
The temperature of the hydrothermal reaction is preferably 100-300 ℃, and the reaction time is preferably 5-24 h.
The invention also provides an application of the palladium monoatomic-based manganese dioxide-carbon nanotube composite catalyst in a chargeable and dischargeable metal-air battery.
Compared with the existing catalyst, the manganese dioxide-carbon nanotube composite catalyst based on palladium monoatomic atoms has the following advantages and beneficial effects:
1. the proper amount of carbon nano tubes are added, and the manganese dioxide and the carbon nano tubes are mutually wound to form a three-dimensional nano structure, so that the conductivity of the semiconductor manganese dioxide is greatly increased, and the catalytic activity and the stability are improved.
2. Palladium monoatomic atoms are loaded on the surfaces of manganese dioxide and carbon nano tubes, so that the number of active sites is increased, and the catalytic activity of the catalyst is improved.
3. The palladium exists in the catalyst in a single atom form, so that the utilization rate of the noble metal palladium is maximized (the mass activity of the palladium is about 27 times that of commercial Pd/C), and the using amount of the palladium is greatly reduced on the premise of ensuring the catalytic activity.
4. When the material is used for a chargeable and dischargeable metal (such as zinc) air battery, the material shows excellent electrocatalytic activity and stability, the preparation method is simple and easy to implement (the material can be prepared by one-step hydrothermal process), the cost is low, and the material is non-toxic, environment-friendly and extremely suitable for industrial large-scale production.
Drawings
FIG. 1 is an oxygen reduction polarization curve obtained by a rotating disk test for catalysts of examples 1-4 of the present invention.
FIG. 2 is an electron micrograph of catalyst No. 3 according to example of the present invention. Wherein, the figure (a) shows the surface condition of manganese dioxide nanowires; (b) and (c) shows the surface condition of the carbon nanotubes (the two images are the images of the same nanotube obtained by electron microscopy at different positions).
FIG. 3 is an X-ray absorption fine structure spectrum of catalyst No. 3 of example of the present invention.
FIG. 4 shows the oxygen reduction polarization curves and mass activities of catalysts of examples 3, 5 and 6 of the present invention obtained by the rotating disk test. Wherein the upper left inset of FIG. 4 is the mass activity of catalyst No. 3 of an example of the present invention and the commercial 20 wt% Pt/C and 20 wt% Pd/C catalysts.
FIG. 5 is a Pd3d X-ray photoelectron spectrum of catalysts Nos. 7 to 9 of examples of the present invention.
FIG. 6 is a polarization curve of the catalyst No. 3 of the present invention applied to the discharge process of a zinc-air battery.
Fig. 7 is a cyclic charge-discharge curve of catalyst No. 3 in the embodiment of the present invention applied to a zinc-air battery.
Detailed Description
In order to more specifically understand the technical content, characteristics and effects of the present invention, the technical solution of the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.
Preparation of catalyst No. 11
1) Adding 0.9g of manganese sulfate, 2.6g of ammonium sulfate and 1.2g of ammonium persulfate into 20mL of ultrapure water, and electromagnetically stirring to obtain a mixed solution;
2) transferring the mixed solution into a 25mL hydrothermal kettle, putting the kettle into an oven with the temperature of 180 ℃ for reaction for 18h, and washing and drying the product to obtain MnO2Catalyst (catalyst No. 1).
Preparation of catalyst No. 22
In this embodiment, carbon nanotubes are added based on embodiment 1, and the specific preparation steps are as follows:
1) uniformly dispersing 0.2g of carbon nanotubes in 10mL of ultrapure water by ultrasonic to obtain a carbon nanotube suspension;
2) adding 0.9g of manganese sulfate, 2.6g of ammonium sulfate and 1.2g of ammonium persulfate into 10mL of ultrapure water, and electromagnetically stirring to obtain a mixed solution;
3) and (3) uniformly mixing the carbon nanotube suspension and the mixed solution, transferring the mixture into a 25mL hydrothermal kettle, putting the hydrothermal kettle into an oven with the temperature of 180 ℃ for reaction for 18h, and washing and drying a product to obtain the manganese dioxide-carbon nanotube composite catalyst (No. 2 catalyst).
Example 33 preparation of catalyst
In this embodiment, the noble metal palladium is added based on embodiment 2, and the specific preparation steps are as follows:
1) uniformly dispersing 0.2g of carbon nanotubes in 10mL of ultrapure water by ultrasonic to obtain a carbon nanotube suspension;
2) adding 0.9g of manganese sulfate, 2.6g of ammonium sulfate, 1.2g of ammonium persulfate and 100mg of palladium nitrate into 10mL of ultrapure water, and electromagnetically stirring to obtain a mixed solution;
3) and uniformly mixing the carbon nanotube suspension and the mixed solution, transferring the mixture into a 25mL hydrothermal kettle, putting the kettle into an oven with the temperature of 180 ℃ for reaction for 18h, and washing and drying a product to obtain the palladium monoatomic-based manganese dioxide-carbon nanotube composite catalyst (catalyst No. 3).
The catalyst No. 3 prepared in this example was characterized by its atomic structure using a spherical aberration electron microscope, as shown in fig. 2. By utilizing the contrast difference of different atomic masses, the brightness of palladium atoms is higher, and highly dispersed palladium single atoms can be clearly seen on the manganese dioxide nanowire (see fig. 2 (a)); highly dispersed palladium monoatomic atoms are also present on the surface of the carbon nanotube (see fig. 2(b), (c)).
The electronic structure and coordination state of the palladium atom are further analyzed by X-ray absorption fine structure spectrum, as shown in FIG. 3, at the bond length
Figure BDA0001589043020000031
(Pd-O) peak intensity is highest at
Figure BDA0001589043020000032
The intensity of the peak in (Pd-Pd bond) is relatively very weak, indicating that a large amount of palladium monoatomic atoms are present in catalyst No. 3.
The combination of a spherical aberration electron microscope and an X-ray absorption fine structure spectrum proves that the manganese dioxide-carbon nanotube composite catalyst based on palladium monoatomic atoms is successfully prepared by a one-step hydrothermal method.
Preparation of catalyst No. 44
In this embodiment, the content of noble metal palladium is increased based on embodiment 3, and the specific preparation steps are as follows:
1) uniformly dispersing 0.2g of carbon nanotubes in 10mL of ultrapure water by ultrasonic to obtain a carbon nanotube suspension;
2) adding 0.9g of manganese sulfate, 2.6g of ammonium sulfate, 1.2g of ammonium persulfate and 200mg of palladium nitrate into 10mL of ultrapure water, and electromagnetically stirring to obtain a mixed solution;
3) and (3) uniformly mixing the carbon nanotube suspension and the mixed solution, transferring the mixture into a 25mL hydrothermal kettle, putting the hydrothermal kettle into an oven with the temperature of 180 ℃ for reaction for 18h, and washing and drying a product to obtain the No. 4 catalyst.
EXAMPLE 55 preparation of catalyst
1) Uniformly dispersing 0.1g of carbon nanotubes in 10mL of ultrapure water by ultrasonic to obtain a carbon nanotube suspension;
2) adding 0.9g of manganese sulfate, 2.6g of ammonium sulfate, 1.2g of ammonium persulfate and 100mg of palladium nitrate into 10mL of ultrapure water, and electromagnetically stirring to obtain a mixed solution;
3) and uniformly mixing the carbon nanotube suspension and the mixed solution, transferring the mixture into a 25mL hydrothermal kettle, putting the hydrothermal kettle into an oven with the temperature of 180 ℃ for reacting for 18h, and washing and drying a product to obtain the No. 5 catalyst.
Example 66 preparation of catalyst
1) Uniformly dispersing 0.4g of carbon nanotubes in 10mL of ultrapure water by ultrasonic to obtain a carbon nanotube suspension;
2) adding 0.9g of manganese sulfate, 2.6g of ammonium sulfate, 1.2g of ammonium persulfate and 100mg of palladium nitrate into 10mL of ultrapure water, and electromagnetically stirring to obtain a mixed solution;
3) and uniformly mixing the carbon nanotube suspension and the mixed solution, transferring the mixture into a 25mL hydrothermal kettle, putting the hydrothermal kettle into an oven with the temperature of 180 ℃ for reacting for 18h, and washing and drying a product to obtain the No. 6 catalyst.
Preparation of catalyst No. 77
1) Uniformly dispersing 0.2g of carbon nanotubes in 10mL of ultrapure water by ultrasonic to obtain a carbon nanotube suspension;
2) adding 0.9g of ammonium sulfate and 100mg of palladium nitrate into 10mL of ultrapure water, and electromagnetically stirring to obtain a mixed solution;
3) and (3) uniformly mixing the carbon nanotube suspension and the mixed solution, transferring the mixture into a 25mL hydrothermal kettle, putting the hydrothermal kettle into an oven with the temperature of 180 ℃ for reaction for 18h, and washing and drying a product to obtain the No. 7 catalyst.
EXAMPLE 88 preparation of catalyst
1) Uniformly dispersing 0.2g of carbon nanotubes in 10mL of ultrapure water by ultrasonic to obtain a carbon nanotube suspension;
2) adding 0.9g of ammonium sulfate, 1.2g of ammonium persulfate and 100mg of palladium nitrate into 10mL of ultrapure water, and electromagnetically stirring to obtain a mixed solution;
3) and uniformly mixing the carbon nanotube suspension and the mixed solution, transferring the mixture into a 25mL hydrothermal kettle, putting the hydrothermal kettle into an oven with the temperature of 180 ℃ for reacting for 18h, and washing and drying a product to obtain the No. 8 catalyst.
Preparation of catalyst No. 99
1) Uniformly dispersing 0.2g of carbon nanotubes in 10mL of ultrapure water by ultrasonic to obtain a carbon nanotube suspension;
2) adding 0.9g of ammonium sulfate, 2.4g of ammonium persulfate and 100mg of palladium nitrate into 10mL of ultrapure water, and electromagnetically stirring to obtain a mixed solution;
3) and uniformly mixing the carbon nanotube suspension and the mixed solution, transferring the mixture into a 25mL hydrothermal kettle, putting the hydrothermal kettle into an oven with the temperature of 180 ℃ for reacting for 18h, washing and drying a product to obtain the No. 9 catalyst.
The oxygen reduction polarization curves of catalysts nos. 1 to 4 prepared in examples 1 to 4 above were measured using a rotating disk, and as shown in fig. 1, it can be seen from fig. 1 that the catalytic activity of catalyst No. 2 is significantly increased due to the increase in conductivity of semiconductive manganese dioxide as compared with catalyst No. 1; compared with the No. 2 catalyst without noble metal palladium, the No. 3 catalyst has high surface free energy due to the low coordination palladium monoatomic group, and the catalytic activity is obviously increased; after increasing the content of the noble metal palladium, the half-wave potential of the catalyst No. 4 was increased as compared with the catalyst No. 3, but the catalyst No. 3 had a higher limiting current density.
Examples 5 and 6 based on example 3, the optimum carbon nanotube content was found by adjusting the amount of carbon nanotube charged. Theoretical calculations indicate that the palladium monoatomic atoms on manganese dioxide have higher catalytic activity than the palladium monoatomic atoms on carbon nanotubes. The content of the carbon nano tube is too low, which is not beneficial to improving the conductivity; too high a content leads to a decrease in the number of active sites, and therefore an optimum content of carbon nanotubes must be present. The optimum content of carbon nanotubes was found to be 0.2g by the rotating disk oxygen reduction polarization curve test (see fig. 4).
Examples 7-9 were conducted to investigate the effect of the content of the oxidant ammonium persulfate on the palladium loading in the catalyst during the preparation of palladium monoatomic manganese dioxide-carbon nanotube based composite catalysts. As shown in fig. 5, the X-ray photoelectron spectroscopy results showed that the amount of palladium supported increased with the increase in the content of ammonium persulfate, and that the amount of palladium supported was almost zero without adding ammonium persulfate. Through Pd3d peak finding (shown in figure 5), in the hydrothermal reaction, ammonium persulfate reacts Pd with Pd2+Oxidation of ions to higher valence Pd4+. Therefore, the content of ammonium persulfate is one of the key influencing factors for preparing the manganese dioxide-carbon nano tube composite catalyst based on palladium monoatomic atom。
The manganese dioxide-carbon nanotube composite catalyst (catalyst No. 3) based on palladium monoatomic atoms prepared in the embodiment of the invention is applied to a zinc-air battery, a linear scanning curve is adopted to test the polarization curve of the discharge process of the zinc-air battery, and the test electrode adopts a two-electrode system and comprises a working electrode and a counter electrode, wherein the working electrode is a carbon paper electrode coated with a catalyst layer, the counter electrode is a zinc sheet, and an electrolyte solution is 6mol/L potassium hydroxide solution. The results of the polarization test in the discharge process are shown in FIG. 6, and the catalyst No. 3 has a very high current density of 190.7mA/cm at 1.0V2(159 mA/cm higher than commercial PtRu/C catalyst2) (ii) a And the maximum energy density is as high as 296.1mW/cm2(higher than 201.7/cm for commercial PtRu/C catalyst2). Then, a zinc-air battery cyclic charge and discharge test is carried out, and the result is shown in fig. 7, after the commercial PtRu/C catalyst is circulated for 80 circles, the discharge voltage of the commercial PtRu/C catalyst is sharply reduced, and the catalyst is deactivated; and the No. 3 catalyst realizes 300-turn cyclic charge and discharge.

Claims (5)

1. A preparation method of a palladium monoatomic-based manganese dioxide-carbon nanotube composite catalyst is characterized by comprising the following steps of:
dispersing the carbon nano tube in water to obtain a carbon nano tube suspension;
adding manganese sulfate, ammonium persulfate and palladium nitrate into water to obtain a mixed solution;
uniformly mixing the carbon nanotube suspension and the mixed solution, performing hydrothermal reaction, and mixing Pd with ammonium persulfate2+Oxidation of ions to higher valence Pd4+Obtaining a palladium monoatomic-based manganese dioxide-carbon nanotube composite catalyst;
wherein the mass ratio of palladium nitrate, ammonium persulfate, carbon nano tubes and water in the hydrothermal reaction system is 5:60:10: 1000; the temperature of the hydrothermal reaction is 100-300 ℃, and the reaction time is 5-24 h.
2. A palladium monoatomic-based manganese dioxide-carbon nanotube composite catalyst prepared according to the method of claim 1.
3. The catalyst of claim 2, wherein the manganese dioxide and the carbon nanotubes are intertwined to form a three-dimensional nanostructure, and the palladium is supported on the surfaces of the manganese dioxide and the carbon nanotubes in a monoatomic form.
4. The catalyst according to claim 3, wherein the mass ratio of the manganese dioxide to the carbon nanotubes is 0.1 to 1: 1.
5. Use of the catalyst of any one of claims 2 to 4 in a rechargeable metal-air battery.
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