CN113571713A - PtZn-loaded nitrogen-doped carbon catalyst, preparation method thereof and hydrogen-oxygen fuel cell - Google Patents
PtZn-loaded nitrogen-doped carbon catalyst, preparation method thereof and hydrogen-oxygen fuel cell Download PDFInfo
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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
-
- 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
- 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
- H01M4/926—Metals of platinum group 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a PtZn-loaded nitrogen-doped carbon catalyst, a preparation method thereof and a hydrogen-oxygen fuel cell. The preparation method of the PtZn-loaded nitrogen-doped carbon catalyst provided by the invention comprises the following steps of: a) mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic dianhydride for reaction to form a PtZn phthalocyanine polymer; b) carrying out pyrolysis treatment on the PtZn phthalocyanine polymer in a protective atmosphere to obtain an intermediate; c) and mixing the intermediate with acid liquor for reaction to obtain the PtZn-loaded nitrogen-doped carbon catalyst. The PtZn-loaded nitrogen-doped carbon catalyst prepared by the preparation method is efficient and stable, and has low cost and simple preparation process.
Description
Technical Field
The invention relates to the field of energy materials, in particular to a PtZn-loaded nitrogen-doped carbon catalyst, a preparation method thereof and a hydrogen-oxygen fuel cell.
Background
At present, with the development of human society, the traditional fossil energy sources face the problems of resource exhaustion, serious pollution and the like, and people are prompted to research and develop a clean and efficient storage and conversion technology of renewable energy sources. Among them, the hydrogen-oxygen fuel cell is focused by people because of its advantages of cleanness, environmental protection, no pollution, large energy density, small weight, portability and the like, and is expected to become a substitute of the traditional fossil fuel. However, the occurrence of Oxygen Reduction Reaction (ORR) at the cathode of a fuel cell is a key factor that limits its efficiency, and since oxygen reduction reaction itself has a slow kinetic process, the selection of a suitable oxygen reduction catalyst is an effective means to overcome this problem.
At present, Pt/C catalysts are widely commercially available, but it is well known that the scarcity of Pt resources causes the Pt/C catalysts to be expensive; meanwhile, the Pt/C catalyst with high activity needs to prepare nano-grade Pt nano-particles, which requires a complex and super-high preparation process; finally, an important dilemma for Pt-based noble metal catalysts is that Pt is extremely susceptible to poisoning by methanol or carbon monoxide and inevitable degradation problems occur over long periods of testing, which can lead to instability over extended operating environment testing, causing significant activity decay.
Therefore, the development of the Pt-based precious metal ORR catalyst which is low in cost, simple in preparation process, stable and efficient is a research topic with important application significance, and is considered to be a feasible path for finally realizing large-scale application.
Disclosure of Invention
In view of the above, the present invention provides a PtZn-supported nitrogen-doped carbon catalyst, a preparation method thereof, and a hydrogen-oxygen fuel cell. The Pt-based noble metal ORR catalyst provided by the invention is efficient and stable, and has low cost and simple preparation process.
The invention provides a preparation method of a PtZn-loaded nitrogen-doped carbon catalyst, which comprises the following steps:
a) mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic dianhydride for reaction to form a PtZn phthalocyanine polymer;
b) carrying out pyrolysis treatment on the PtZn phthalocyanine polymer in a protective atmosphere to obtain an intermediate;
c) and mixing the intermediate with acid liquor for reaction to obtain the PtZn-loaded nitrogen-doped carbon catalyst.
Preferably, in the step a), the reaction is carried out under the action of a catalyst;
the catalyst is ammonium chloride and ammonium molybdate.
Preferably, in the step a), the molar ratio of ammonium chloroplatinate to zinc chloride is 1: 15-25.
Preferably, in the step a), the molar ratio of ammonium chloroplatinate to urea is 1: (0.06-0.07);
the molar ratio of ammonium chloroplatinate to pyromellitic anhydride was 1: 10.
Preferably, the molar ratio of the ammonium chloroplatinate to the ammonium chloride and the ammonium molybdate is 1: 0.02: 0.7-0.8.
Preferably, in the step a), the reaction temperature is 215-225 ℃ and the reaction time is 1.5-2.5 h.
Preferably, in the step b), the temperature of the pyrolysis treatment is 920-955 ℃, and the time is 2-2.5 h.
Preferably, in step c):
the concentration of the acid liquor is 2M;
the acid liquor is selected from H2SO4Solution, HCl solution and HNO3One or more of the solutions;
the temperature of the mixing reaction is 80 ℃, and the time is 12-15 h.
The invention also provides the PtZn loaded nitrogen-doped carbon catalyst prepared by the preparation method in the technical scheme.
The invention also provides a hydrogen-oxygen fuel cell, wherein the ORR catalyst on the membrane electrode in the hydrogen-oxygen fuel cell is the PtZn-loaded nitrogen-doped carbon catalyst in the technical scheme.
Firstly, mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic dianhydride for reaction to form a PtZn phthalocyanine polymer (PtZnPPc); carrying out pyrolysis treatment on the polymer in a protective atmosphere to obtain an intermediate; and finally, mixing the intermediate with acid liquor for reaction to obtain the PtZn-loaded nitrogen-doped carbon catalyst. According to the invention, ammonium chloroplatinate which is low in price and easy to store is used as a Pt precursor, Pt atoms and the size of the PtZn alloy are anchored by utilizing the capability of coordination metal in the center of a phthalocyanine large ring, and the high-temperature evaporation of Zn is utilized to control the size of the PtZn alloy, meanwhile, the electronic structure of Pt is changed by introducing zinc atoms, so that the (111) crystal face in the PtZn is subjected to compressive strain compared with the Pt (111) crystal face, and the condition that the adsorption capability of the PtZn/NC on oxygen is weakened due to the fact that the center of a d-band moves downwards is shown, so that the PtZn/NC has ORR catalytic activity superior to that of Pt/C, and finally, the Zn has the same atomic radius as that of Pt, when the PtZn alloy is degraded to generate defects, Zn can be easily filled, which is very important for improving the stability of the catalyst, and therefore, the PtZn/NC also shows high activity and high stability superior to that of commercial Pt/C.
Experimental results show that the catalyst material prepared by the invention not only shows high-efficiency oxygen reduction catalytic activity (half-wave potential: 0.85V (vs. RHE), but also shows excellent hydrogen evolution performance which is superior to that of a commercial platinum-carbon catalyst by 0.83V (vs. RHE), and the hydrogen evolution current density of the catalyst material is 10mA/cm2Has extremely low over potential of 5mV (vs. RHE), and shows up to 1W/cm when the PtZn/NC prepared membrane-forming electrode assembly is applied to a hydrogen-oxygen fuel cell for testing2Also surpasses the hydrogen-oxygen fuel cell test results of commercial Pt/C as MEA.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a TEM image of PtZn/NC as a catalyst powder obtained in example 1; wherein FIG. 1a is a TEM image at 50nm scale and FIG. 1b is a TEM image at 10nm scale;
FIG. 2 is an XRD pattern of PtZn/NC, Pt/NC and NC of samples obtained in example 1 and comparative examples 1 to 2;
FIG. 3 is a comparative plot of oxygen reduction linear scan LSV of oxygen reduction electrodes based on catalyst samples obtained in example 1 and comparative examples 1-2 and commercial Pt/C catalysts; wherein FIG. 3a is a graph comparing LSV curves of PtZn/NC, Pt/NC, NC and commercial Pt/C under an oxygen reduction test condition, and FIG. 3b is a graph comparing LSV curves of PtZn/NC, Pt/NC, NC and commercial Pt/C under a hydrogen evolution reaction test condition;
FIG. 4 is an ADT test chart of PtZn/NC obtained as a sample in example 1;
FIG. 5 is a graph showing the stability tests of PtZn/NC and a commercial platinum-carbon catalyst of a sample obtained in example 1;
FIG. 6 is a test chart of the polarization curve of a hydrogen-oxygen fuel cell based on the catalyst PtZn/NC obtained in example 1;
FIG. 7 is a stability test chart of a hydrogen-oxygen fuel cell based on the catalyst PtZn/NC obtained in example 1;
FIG. 8 is a comparative graph of oxygen reduction LSV for the catalyst samples of example 4 based on 6 different Pt/Zn ratios.
Detailed Description
The invention provides a preparation method of a PtZn-loaded nitrogen-doped carbon catalyst, which comprises the following steps:
a) mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic dianhydride for reaction to form a PtZn phthalocyanine polymer;
b) carrying out pyrolysis treatment on the PtZn phthalocyanine polymer in a protective atmosphere to obtain an intermediate;
c) and mixing the intermediate with acid liquor for reaction to obtain the PtZn-loaded nitrogen-doped carbon catalyst.
Firstly, mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic dianhydride for reaction to form a PtZn phthalocyanine polymer (PtZnPPc); carrying out pyrolysis treatment on the polymer in a protective atmosphere to obtain an intermediate; and finally, mixing the intermediate with acid liquor for reaction to obtain the PtZn-loaded nitrogen-doped carbon catalyst. According to the invention, ammonium chloroplatinate which is low in price and easy to store is used as a Pt precursor, Pt atoms and the size of the PtZn alloy are anchored by utilizing the capability of coordination metal in the center of a phthalocyanine large ring, and the high-temperature evaporation of Zn is utilized to control the size of the PtZn alloy, meanwhile, the electronic structure of Pt is changed by introducing zinc atoms, so that the (111) crystal face in the PtZn is subjected to compressive strain compared with the Pt (111) crystal face, and the condition that the adsorption capability of the PtZn/NC on oxygen is weakened due to the fact that the center of a d-band moves downwards is shown, so that the PtZn/NC has ORR catalytic activity superior to that of Pt/C, and finally, the Zn has the same atomic radius as that of Pt, when the PtZn alloy is degraded to generate defects, Zn can be easily filled, which is very important for improving the stability of the catalyst, and therefore, the PtZn/NC also shows high activity and high stability superior to that of commercial Pt/C.
With respect to step a): and mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic dianhydride for reaction to form the PtZn phthalocyanine polymer.
In the invention, the four raw materials react to form the PtZn phthalocyanine polymer PtZnPPc, and the synthesis route is as follows:
in the invention, ammonium chloroplatinate is used as a Pt precursor, the price is low, the storage is easy, the preparation cost can be effectively reduced, and the PtZn phthalocyanine polymer with a certain structure can be formed by reacting with the other 3 raw materials.
In the invention, the zinc chloride is a Zn precursor. In some embodiments of the invention, the molar ratio of ammonium chloroplatinate to zinc chloride is 1: 1, 1: 5, 1: 10, 1: 20, 1: 30, or 1: 50. In the invention, the mol ratio of the ammonium chloroplatinate to the zinc chloride is preferably 1: 15-25, and more preferably 1: 20. By controlling the proportion, Pt metal can be effectively dispersed, aggregation of Pt in the subsequent pyrolysis step is avoided, if the zinc chloride proportion is too low, the distance between Pt and Pt cannot be effectively separated in the product structure, aggregation of Pt is caused, the half-wave potential of the product is lower, the oxygen reduction activity is poorer, and if the zinc chloride proportion is too high, collapse of the carbon material structure can be caused by excessive Zn in the pyrolysis evaporation step, the carbon skeleton is damaged, and the stability of the material is reduced.
In the present invention, the source of the urea is not particularly limited, and may be any commercially available product. The mol ratio of the ammonium chloroplatinate to the urea is preferably 1 to (0.06-0.07); in some embodiments of the invention, the molar ratio is 1: 0.07.
In the present invention, the source of pyromellitic anhydride is not particularly limited, and may be a commercially available product. In the invention, the mol ratio of the ammonium chloroplatinate to the pyromellitic anhydride is preferably 1: 10.
In the present invention, the above four raw materials are preferably reacted under the action of a catalyst. In the present invention, the catalyst is preferably ammonium chloride or ammonium molybdate. In the invention, the mol ratio of the ammonium chloroplatinate to the ammonium chloride and the ammonium molybdate is 1: 0.02: 0.7-0.8; in some embodiments of the invention, the molar ratio is 1: 0.02: 0.74.
In the invention, the reaction temperature is preferably 215-225 ℃, and more preferably 220 ℃. The reaction time is preferably 1.5-2.5 h, and more preferably 2 h. In the present invention, the above reaction is preferably carried out under an air atmosphere. The preparation method takes ammonium chloroplatinate, zinc chloride, urea and pyromellitic dianhydride as raw materials, and through the reaction, a specific phthalocyanine macrocycle is formed between the urea and the pyromellitic dianhydride, and the center of N4 of the phthalocyanine macrocycle coordinates and anchors metal Zn and Pt atoms to form PtZn phthalocyanine polymer PtZnPPc; the introduction of Zn atoms changes the electronic structure of a metal crystal face, so that a (111) crystal face in PtZn generates compressive strain compared with a Pt (111) crystal face, the adsorption capacity of the PtZn/NC on oxygen is weakened, the PtZn/NC has ORR catalytic activity exceeding Pt/C, and the Zn atoms have the same atomic radius as Pt, so that Zn can be easily filled when the PtZn alloy is degraded to generate defects, which is important for improving the stability of a catalyst, and the PtZn/NC also shows high activity and high stability exceeding commercial Pt/C. In the invention, after the light green powder is obtained through the reaction, washing treatment is carried out, and after washing, the PtZn phthalocyanine polymer PtZnPPc is obtained.
With respect to step b): and carrying out pyrolysis treatment on the PtZn phthalocyanine polymer in a protective atmosphere to obtain an intermediate.
In the present invention, the type of the protective gas of the protective atmosphere is not particularly limited, and may be any conventional inert gas known to those skilled in the art, such as nitrogen or argon.
The PtZn phthalocyanine polymer obtained in the step a) is an organic high polymer containing Pt, Zn, C, N, H and O elements, and is subjected to pyrolysis treatment in a protective atmosphere, C, N elements still remain a polymer framework after carbonization, a graphite-like structure carbon nitride material is formed, H and O elements can be separated at high pyrolysis temperature and simultaneously generate defects and metal oxides (such as zinc oxide), and Pt and Zn elements form PtZn alloy at high temperature to be loaded at the defects of the carbon nitride material, so that the PtZn-loaded nitrogen-doped carbon material is obtained. In addition, in the pyrolysis process, the evaporation of Zn can avoid the aggregation of Pt and create more pores, so that PtZn nanoparticles are effectively exposed to serve as active sites, and the oxygen reduction performance of the material is favorably improved.
In the invention, the temperature of the pyrolysis treatment is preferably 920-955 ℃, and more preferably 925 ℃. If the pyrolysis temperature is too low, the carbon nitride material has low carbonization degree and poor conductivity, and is not beneficial to mass and charge transmission; if the temperature is too high, the PtZn alloy is aggregated, particles become large, the specific surface area utilization rate of the active species (PtZn alloy) is reduced, and the product activity is reduced. In the invention, the time of the pyrolysis treatment is preferably 2-2.5 h, and more preferably 2 h; in the pyrolysis treatment link, the heating rate of the pyrolysis temperature is preferably 5 ℃/min.
With respect to step c): and mixing the intermediate with acid liquor for reaction to obtain the PtZn loaded nitrogen-doped carbon catalyst.
In the invention, the acid solution is preferably H2SO4Solution, HCl solution and HNO3One or more of the solutions. In the present invention, the concentration of the acid solution is preferably 2M.
In the invention, the use amount of the intermediate and the acid solution is not particularly limited, and the intermediate can be immersed in the acid solution.
In the present invention, after the acid washing reaction, it is preferable to further perform water washing and drying. The drying is preferably vacuum drying. And (4) after the post-treatment, obtaining the PtZn loaded nitrogen-doped carbon material.
In the invention, the temperature of the reaction of the intermediate and the acid liquor is preferably 80 ℃; the reaction time is preferably 12-15 h. The step of heat treatment in acid solution is mainly to perform double decomposition reaction between an acidic medium and a metal oxide (such as zinc oxide) so as to remove zinc oxide species without catalytic activity in the PtZn-loaded nitrogen-doped carbon material obtained in step b), thereby obtaining a highly active PtZn-loaded nitrogen-doped carbon material.
The invention provides a method for preparing a catalyst PtZn/NC by a solid phase method, which adopts low-price and easy-to-store ammonium chloroplatinate as a Pt precursor, utilizes the capability of phthalocyanine macrocycle center coordination metal to anchor Pt atoms and controls the size of PtZn alloy by high-temperature evaporation of Zn, meanwhile, the introduction of zinc atoms changes the electronic structure of Pt, so that the (111) crystal face in PtZn generates compressive strain compared with the Pt (111) crystal face, which shows that the absorption capacity of PtZn/NC to oxygen is weakened due to the downward movement of the d-band center, thereby having ORR catalytic activity exceeding that of Pt/C, and finally, zn atoms have the same atomic radius as Pt, and when the PtZn alloy is degraded to generate defects, zn can be easily filled, which is important for improving the stability of the catalyst, thus, PtZn/NC also exhibits high activity and high stability over commercial Pt/C. The membrane-forming electrode assembly prepared by the catalyst material of the invention is applied to a hydrogen-oxygen fuel cell (particularly used as a catalyst of an air electrode in the hydrogen-oxygen fuel cell) and tests show that the membrane-forming electrode assembly is up to 1W/cm2The peak power density of the catalyst means that the catalyst has significant practical application value, and theoretical basis and experimental guidance are provided for the storage and conversion technology of hydrogen energy.
The invention also provides the PtZn loaded nitrogen-doped carbon catalyst prepared by the preparation method in the technical scheme. In the invention, the particle size of the PtZn-loaded nitrogen-doped carbon catalyst is less than or equal to 10nm, and most of the particles are less than 10 nm.
The present invention also provides an MEA assembly wherein the catalyst on the membrane electrode is a PtZn-supported nitrogen-doped carbon catalyst as described in the above-mentioned technical solution.
The invention also provides a hydrogen-oxygen fuel cell, wherein the ORR catalyst on the membrane electrode is the PtZn loaded nitrogen-doped carbon catalyst in the technical scheme.
Compared with the prior art, the PtZn-loaded nitrogen-doped carbon catalyst provided by the invention has the following beneficial effects:
1. the Pt atom is anchored by utilizing the capability of the phthalocyanine ring center for coordinating metal, and the excessive Zn atom is introduced to increase the distance between Pt and Pt, so that the aggregation of the material during pyrolysis is avoided, and therefore, the noble metal ORR catalyst with the PtZn nano size of less than 10nm is prepared, and the nano size control is the key premise that the PtZn/NC can exceed the commercial Pt/C.
2. The electronic structure of Pt is changed by introducing Zn atoms, and XRD analysis of PtZn/NC shows that (111) crystal face in PtZn generates compressive strain compared with Pt (111) crystal face, which indicates that d-band center moves downwards, which means that the adsorption capacity of PtZn/NC for oxygen is weakened, so that the PtZn/NC has ORR catalytic activity superior to that of Pt/C, and the regulation and control of the electronic structure can clearly explain the catalytic mechanism.
3. Zn atoms have the same atomic radius as Pt, and can be easily filled when the PtZn alloy is degraded to generate defects, which is important for improving the stability of the catalyst, so that the PtZn/C also shows excellent stability and durability.
4. The catalyst material prepared by the invention not only shows high-efficiency oxygen reduction catalytic activity (half-wave potential is 0.85V (vs. RHE), but also is superior to 0.83V (vs. RHE) of a commercial platinum-carbon catalyst, and simultaneously also shows excellent hydrogen evolution performance, and the hydrogen evolution performance of the catalyst material is that the current density of the hydrogen evolution is 10mA/cm2Has an extremely low overvoltage of 5mV (vs. RHE), and the PtZn/NC prepared membrane-forming electrode assembly applied to a hydrogen-oxygen fuel cell is tested to show that the potential is as high as 1W/cm2Peak power density ofThis also surpassed the commercial Pt/C as the hydrogen-oxygen fuel cell test results for MEA.
For a further understanding of the invention, reference will now be made to the following examples describing preferred embodiments of the invention, but it is to be understood that the description is intended to illustrate further features and advantages of the invention and is not intended to limit the scope of the claims.
Example 1
S1, preparation of PtZn phthalocyanine polymer (PtZnPPc):
weighing 0.5mmol ammonium chloroplatinate, 10mmol zinc chloride, 0.035mmol urea, 0.01mmol ammonium chloride, 0.37mmol ammonium molybdate and 5mmol pyromellitic dianhydride, adding into a mortar, fully grinding, transferring into a magnetic boat, placing the magnetic boat into a tube furnace, and heating at 220 ℃ for 2h in air atmosphere to obtain light green powder. Washing and filtering the PtZn phthalocyanine polymer by water, methanol and acetone in sequence to obtain the PtZnPPc.
S2, preparation of a PtZn-loaded nitrogen-doped carbon material (PtZn/NC) catalyst:
200mg of PtZnPPc are placed in a tube furnace in N2Heating at 5 deg.C/min to 925 deg.C for 2h to obtain black powder. The resulting powder was charged into 80mL of 2M H2SO4And stirring and refluxing the solution at 80 ℃ overnight, performing suction filtration and water washing, and then putting the solution into an oven to perform vacuum drying at 60 ℃ for 24 hours to obtain catalyst powder PtZn/NC.
The transmission electron microscope test result of the obtained product is shown in FIG. 1, and FIG. 1 is a TEM image of PtZn/NC of the catalyst powder obtained in example 1; in which FIG. 1a is a TEM image on a scale of 50nm and FIG. 1b is a TEM image on a scale of 10 nm. It can be seen that the product obtained in example 1 has a particle size of < 10nm, the majority of the particles having a particle size of < 10 nm.
Comparative example 1: preparation of Pt-loaded Nitrogen-doped carbon Material (Pt/NC)
S1, the procedure of example 1 was repeated, except that zinc chloride was not added.
S2, same as example 1.
Comparative example 2: preparation of Nitrogen-doped carbon Material NC
S1, the procedure of example 1 was followed except that ammonium chloroplatinate and zinc chloride were not added.
S2, same as example 1.
Example 3
1. XRD test
X-ray diffraction (XRD) tests were carried out on the samples PtZn/NC, Pt/NC and NC obtained in example 1 and comparative examples 1 to 2, and the results are shown in FIG. 2, and FIG. 2 is an XRD pattern of the samples PtZn/NC, Pt/NC and NC obtained in example 1 and comparative examples 1 to 2.
2. Electrochemical performance test
Preparation of oxygen reduction electrode material: mixing ethanol and 5 wt% Nafion solution at a volume ratio of 20: 1 to obtain a mixed solution, adding a small amount of ultrapure water (the volume ratio of the ultrapure water to the mixed solution is 0.2: 1), mixing, weighing 5mg of catalyst, dispersing in the obtained mixed solution, and performing ultrasonic dispersion for 1h to obtain uniformly dispersed catalyst ink. Dropping 10mL of catalyst ink on a glassy carbon electrode with the diameter of 5mm, and naturally drying at room temperature (the catalyst loading is 0.5 mg/cm)2) And obtaining the oxygen reduction electrode.
Constructing a three-electrode system: the catalyst-coated glassy carbon electrode was used as a working electrode with Ag-AgCl (3M KCl solution) as a reference electrode, a carbon rod as a counter electrode, and the above. Inserting a working electrode mounted on the tester into the chamber2Saturated 0.5M H2SO4The test was carried out under solution conditions, with a scanning speed of 50 mV/s.
Results of testing oxygen reduction and hydrogen evolution performances of the obtained samples are shown in fig. 3, fig. 3 is a comparison graph of oxygen reduction linear scan LSV of oxygen reduction electrodes based on the catalyst samples obtained in example 1 and comparative examples 1-2 and commercial Pt/C catalysts, wherein fig. 3a is a comparison graph of LSV curves of PtZn/NC, Pt/NC, NC and commercial Pt/C under oxygen reduction test conditions, and fig. 3b is a comparison graph of LSV curves of PtZn/NC, Pt/NC, NC and commercial Pt/C under hydrogen evolution reaction test conditions. As can be seen from FIG. 3a, the half-wave potential of the catalyst PtZn/NC prepared in example 1 is 0.85V (vs. RHE), which is superior to that of the commercial 20 wt% Pt/C catalyst (0.83V, vs. RHE), and the catalyst PtZn/NC prepared by the invention is proved to have high oxygen reducibilityCan be used. As can be seen from FIG. 3b, the catalyst PtZn/NC obtained in example 1 was at 10mA/cm2The corresponding overpotential is 5mV (vs. RHE), which is superior to a commercial 20 wt% Pt/C catalyst (35mV, vs. RHE), and the catalyst PtZn/NC prepared by the invention has high-efficiency hydrogen evolution performance and can be used as a bifunctional electrocatalyst for oxygen gasification original reaction (ORR) and Hydrogen Evolution Reaction (HER).
ADT and stability tests were carried out on the above three-electrode system, and the results are shown in FIGS. 4 and 5, FIG. 4 is an ADT test chart of the sample PtZn/NC obtained in example 1, and FIG. 5 is a stability test chart of the sample PtZn/NC obtained in example 1 and a commercial platinum-carbon catalyst. As can be seen from FIGS. 4-5, the half-wave potential of PtZn/NC obtained in example 1 decays only 35mV after 10000 cycles of cycle, and 92% of the original current density can be maintained after 20000s of operation, thus proving that the catalyst PtZn/NC prepared by the invention has excellent stability.
3. Preparation and testing of MEA Membrane electrodes
The catalyst PtZn/NC obtained in example 1 was spray coated to prepare an MEA Assembly: anode: 0.1mgPt/cm2(ii) a Cathode: 0.1mgPt/cm2，5cm2(ii) a Proton membrane: nafion 211; hot pressing conditions are as follows: 0.2MPa, 90 s. The machine model is as follows: multi-range fuel cell test system (850e, Scribner Associates Inc.). Testing the test strip: 80 ℃, 1.5bar (150kPa), 100% RH (relative humidity).
Test results referring to FIGS. 6 and 7, FIG. 6 is a test chart of the polarization curve of a hydrogen-oxygen fuel cell based on the catalyst PtZn/NC obtained in example 1, and FIG. 7 is a test chart of the stability of a hydrogen-oxygen fuel cell based on the catalyst PtZn/NC obtained in example 1. As can be seen from FIG. 6, the application of the PtZn/NC prepared membrane-forming electrode assembly to hydrogen-oxygen fuel cells for testing showed as high as 1W/cm2The peak power density of (1) surpasses the test results of hydrogen-oxygen fuel cells (0.7W/cm) with commercial Pt/C as MEA2) And the membrane electrode prepared by PtZn/NC is proved to have excellent hydrogen-oxygen fuel cell properties. As can be seen from FIG. 7, in the hydrogen-oxygen fuel cell test, the peak power density of PtZn/NC can still be maintained above 92% after 30000 cycles of circulation, which proves that the membrane electrode prepared from PtZn/NCHas excellent cycle stability.
Example 4
S1, preparation of PtZn phthalocyanine polymer (PtZnPPc):
0.035mmol (2.1g) of urea, 0.01mmol (0.5g) of ammonium chloride, 0.37mmol (0.13g) of ammonium molybdate and 5mmol (1.1g) of pyromellitic dianhydride are weighed and added into a mortar, then ammonium chloroplatinate and zinc chloride (wherein, the molar weight of the ammonium chloroplatinate is fixed to be 0.5mmol) are respectively added according to the Pt: Zn molar ratio of 1: 1, 1: 5, 1: 10, 1: 20 (corresponding to the example 1), 1: 30 and 1: 50, the mixture is fully ground and transferred into a magnetic boat, the magnetic boat is placed into a tubular furnace, and the mixture is heated and treated for 2 hours at 220 ℃ in the air atmosphere, so that light green powder is obtained. Washing and filtering the PtZn phthalocyanine polymer powder by water, methanol and acetone in sequence to obtain PtZn phthalocyanine polymer powder which is respectively named as: pt1Zn1PPc、Pt1Zn5PPc、Pt1Zn10PPc、Pt1Zn20PPc、Pt1Zn30PPc、 Pt1Zn50PPc。
S2, preparing a PtZn-loaded nitrogen-doped carbon material catalyst:
the procedure of example 1 was followed and the catalyst powders obtained were respectively designated: pt1Zn1/NC、 Pt1Zn5/NC、Pt1Zn10/NC、Pt1Zn20/NC (i.e., product of example 1), Pt1Zn30/NC、Pt1Zn50/NC。
The 6 catalyst samples were prepared into oxygen reduction electrode materials according to example 3, and oxygen reduction linear scan LSV curves were tested according to example 3, and the results are shown in fig. 8, where fig. 8 is a comparison graph of oxygen reduction LSV of the catalyst samples based on 6 different Pt/Zn ratios in example 4. The main comparative index of the oxygen reduction property of the catalyst is a half-wave potential, that is, a potential corresponding to a half value of a limiting current density (current density J corresponding to 0.2V on the abscissa in the figure), and a larger (positive) value indicates a more rapid reduction of oxygen and a more excellent oxygen reduction property.
As can be seen from FIG. 8, Pt1Zn5Half wave power of/NCBit 0.71V, Pt1Zn10The half-wave potential of/NC is 0.80V, Pt1Zn20Half-wave potential 0.85V, Pt of/NC1Zn30Half-wave potential 0.80V, Pt of/NC1Zn50Half-wave potential of 0.65V/NC, wherein Pt1Zn20the/NC showed the most excellent oxygen reduction activity, i.e. half-wave potential of 0.85V, significantly higher than the other molar ratio catalysts, and higher than the commercial platinum-carbon catalyst (0.83V, vs. When the Pt/Zn ratio is 1: 1, 1: 5 and 1: 10, the Zn ratio is too small, and the distance between Pt and Pt is not effectively separated, so that Pt is aggregated; when the Pt/Zn ratio is 1: 30 or 1: 50, excessive Zn evaporation at the pyrolysis temperature causes collapse of the carbon material structure, and the carbon skeleton is destroyed, so that the material stability is lowered.
It can be seen from the above embodiments that the present invention provides a method for preparing a catalyst PtZn/NC by a solid phase method, wherein ammonium chloroplatinate which is low in price and easy to store is used as a Pt precursor, the ability of coordination metal of a phthalocyanine macrocycle center is utilized to anchor Pt atoms and the size of a PtZn alloy is controlled by high temperature evaporation of Zn, and meanwhile, the introduction of zinc atoms changes the electronic structure of Pt, so that the (111) crystal face in PtZn is subjected to compressive strain compared with the Pt (111) crystal face, which indicates that the d-band center is shifted down to weaken the adsorption ability of PtZn/NC for oxygen, thereby having an ORR catalytic activity superior to that of Pt/C, and finally, the Zn atoms have the same atomic radius as Pt, and when the PtZn alloy is degraded to generate defects, Zn can be easily filled, which is crucial for improving the stability of the catalyst, PtZn/NC also showed high activity and high stability over commercial Pt/C. The membrane-forming electrode assembly prepared by the catalyst material of the invention is tested in a hydrogen-oxygen fuel cell and shows up to 1W/cm2The peak power density means that the catalyst has significant practical application value, and theoretical basis and experimental guidance are provided for storage and conversion technology of hydrogen energy sources.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall into the protection scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A preparation method of a PtZn-loaded nitrogen-doped carbon catalyst is characterized by comprising the following steps:
a) mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic dianhydride for reaction to form a PtZn phthalocyanine polymer;
b) carrying out pyrolysis treatment on the PtZn phthalocyanine polymer in a protective atmosphere to obtain an intermediate;
c) and mixing the intermediate with acid liquor for reaction to obtain the PtZn-loaded nitrogen-doped carbon catalyst.
2. The preparation method according to claim 1, wherein in the step a), the reaction is carried out under the action of a catalyst;
the catalyst is ammonium chloride and ammonium molybdate.
3. The preparation method according to claim 1, wherein in the step a), the molar ratio of ammonium chloroplatinate to zinc chloride is 1: 15-25.
4. The preparation method according to claim 1, wherein in the step a), the molar ratio of ammonium chloroplatinate to urea is 1: (0.06-0.07);
the molar ratio of ammonium chloroplatinate to pyromellitic anhydride was 1: 10.
5. The method according to claim 5, wherein the molar ratio of ammonium chloroplatinate to ammonium chloride and ammonium molybdate is 1: 0.02: 0.7-0.8.
6. The preparation method of claim 1, wherein in the step a), the reaction temperature is 215-225 ℃ and the reaction time is 1.5-2.5 h.
7. The preparation method of claim 1, wherein in the step b), the temperature of the pyrolysis treatment is 920-955 ℃, and the time is 2-2.5 h.
8. The method of claim 1, wherein in step c):
the concentration of the acid liquor is 2M;
the acid liquor is selected from H2SO4Solution, HCl solution and HNO3One or more of the solutions;
the temperature of the mixing reaction is 80 ℃, and the time is 12-15 h.
9. A PtZn-supported nitrogen-doped carbon catalyst prepared by the preparation method of any one of claims 1 to 8.
10. A hydrogen-oxygen fuel cell, characterized in that the ORR catalyst on a membrane electrode in the hydrogen-oxygen fuel cell is the PtZn-supported nitrogen-doped carbon catalyst of claim 9.
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