CN113871642A - Nitrogen-doped carbon-loaded Mo/Pt alloy catalyst and application thereof - Google Patents
Nitrogen-doped carbon-loaded Mo/Pt alloy catalyst and application thereof Download PDFInfo
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- CN113871642A CN113871642A CN202110969948.8A CN202110969948A CN113871642A CN 113871642 A CN113871642 A CN 113871642A CN 202110969948 A CN202110969948 A CN 202110969948A CN 113871642 A CN113871642 A CN 113871642A
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- 239000001301 oxygen Substances 0.000 claims abstract description 20
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- 238000002156 mixing Methods 0.000 claims description 5
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- 230000001681 protective effect Effects 0.000 claims description 5
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- 239000010411 electrocatalyst Substances 0.000 claims description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- 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
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Abstract
The invention belongs to the technical field of electrochemical catalyst materials, and particularly relates to a nitrogen-doped carbon-loaded Mo/Pt alloy catalyst and application thereof. The nitrogen-doped carbon-loaded Mo/Pt alloy catalyst is prepared by directly carrying out solid-phase heat treatment on the mixed raw materials, and the process is simple. The catalyst shows high activity, stability and methanol poisoning resistance to oxygen reduction reaction.
Description
Technical Field
The invention belongs to the technical field of electrochemical catalyst materials, and particularly relates to a nitrogen-doped carbon-loaded Mo/Pt alloy catalyst and application thereof.
Background
The development of scientific technology will inevitably increase the energy demand, especially the consumption of non-renewable energy fossil fuels, and this forces people to search and produce materials favorable for the ecological environment to replace the non-renewable fuels. At present, fuel cells are widely concerned about the advantages of high energy conversion efficiency, low pollutant emission and the like, and the cathode oxygen reduction (ORR) reaction is a key step. However, there are still problems to be solved in the oxygen reduction reaction process, such as: the reaction kinetics is slow, and an ideal effect cannot be achieved; although Pt can promote the oxygen reduction reaction to be carried out with high efficiency, the long-term circulation stability and the toxicity resistance of the Pt also have a great promotion space; pt is also economically unfriendly, accounting for approximately 20% of the cost of fuel cells. Therefore, the commercial application of fuel cells is greatly limited by the problems of the Pt catalyst, such as being economically unfriendly, having poor stability, weak poisoning resistance, and reaction kinetics to be improved. In summary, it is imperative to develop a fuel cell cathode catalyst with high catalytic activity, long-term stability, strong anti-poisoning ability, and low cost. The alloy is formed by utilizing cheaper metal and noble metal, on one hand, the dosage of the noble metal can be effectively reduced by adding the other metal, and on the other hand, the catalytic performance and stability are hopefully improved by the interaction between the two metals. However, the formation of the alloy often requires higher temperature, the liquid phase reaction is only suitable for the synthesis of a small part of the alloy, and a surfactant is needed for stabilizing the product to prevent agglomeration, and finally the residual surfactant can seriously affect the activity and stability of the catalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a nitrogen-doped carbon-loaded Mo/Pt alloy catalyst and application thereof.
The technical scheme adopted by the invention is as follows: a preparation method of a nitrogen-doped carbon-loaded Mo/Pt alloy catalyst comprises the following steps:
(1) preparing nanometer spherical polypyrrole: adding propionic acid into a container, heating to 130-160 ℃, mixing pyrrole with propionic acid to obtain a pyrrole propionic acid solution, adding the pyrrole propionic acid solution into the propionic acid in the container heated to 130-160 ℃ under stirring, and reacting for at least 1.5h by using oxygen as an oxidant to obtain a black mixed solution; washing and separating the product with ethanol and water, and finally drying to obtain nano spherical polypyrrole;
(2) preparing a nitrogen-doped carbon-loaded Mo/Pt alloy catalyst: and (2) soaking molybdate and chloroplatinic acid into the pore channel of the nano spherical polypyrrole prepared in the step (1), and calcining to obtain the nitrogen-doped carbon-loaded Mo/Pt alloy catalyst.
In some embodiments of the invention, in step (1), the pyrrole propionic acid solution is slowly added to the propionic acid in the vessel after heating at 130-160 ℃, and the step feeding time is 0-15min, preferably 5-10 min.
In some embodiments of the present invention, in step (1), the stirring speed is 450-550 rpm.
In some embodiments of the invention, in step (1), the reaction time is 180 min.
In some embodiments of the invention, in step (1), the ratio of the total volume of propionic acid to the mass of pyrrole is 15:19 to 57, wherein the most preferred ratio of the total volume of propionic acid to the mass of pyrrole is 15: 57.
In some embodiments of the present invention, in the step (2), the nano spherical polypyrrole prepared in the step (1) is dispersed in water, then glacial acetic acid is added into the polypyrrole dispersion liquid, and then molybdate and pallanate are added, stirring and impregnation are performed to impregnate the molybdate and the pallanate into the pore channels of the nano spherical polypyrrole, and calcination is performed after drying treatment.
In some embodiments of the invention, the calcination is carried out with hydrogen as the reducing atmosphere and argon as the protective atmosphere.
In some embodiments of the invention, the calcination temperature is 670-820 deg.C, with 770 deg.C being most preferred.
In some embodiments of the invention, the calcination time is from 10 to 60min, with 30min being most preferred.
In some embodiments of the invention, the total metal loading is from 1 to 6mg/25mg polypyrrole, with 4 mg/25mg polypyrrole being most preferred.
In some embodiments of the invention, the molar ratio of Mo to Pt is 2-1:1-3, with a molar ratio of 2:3 being most preferred.
Use of a nitrogen doped carbon supported Mo/Pt alloy catalyst as described above as a redox electrocatalyst.
A fuel cell wherein the catalyst employs a nitrogen-doped carbon-supported Mo/Pt alloy catalyst as described above.
The invention has the following beneficial effects: the nitrogen-doped carbon-loaded Mo/Pt alloy catalyst is prepared by directly carrying out solid-phase heat treatment on the mixed raw materials, and the process is simple. The catalyst shows high activity, stability and methanol poisoning resistance to oxygen reduction reaction.
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 introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 shows scanning electron micrographs of polyazoles prepared at different feed times: (a) 0 min; (b) 5 min; (c) 10 min; (d) 15 min;
FIG. 2 is a scanning electron micrograph of polyazoles prepared at different agitation rates (a) 300 rpm; (b) 400 rpm; (c) 500 rpm; (d) 600 rpm;
FIG. 3 is a scanning electron microscope photograph of polypyrrole prepared at different charge ratios, with a charge of 190 mg of pyrrole (a); (b) 380 mg; (c) 570 mg; (d) 760 mg;
FIG. 4 is a scanning electron micrograph of a polypyrrole prepared in comparative example 1;
FIG. 5 shows Mo0.29Pt0.71SEM picture (a), TEM picture (b), high-resolution transmission electron micrograph (C) of/N-C, and (d) is an enlarged area of the white box of the (C) picture;
FIG. 6 shows Mo0.29Pt0.71A high-angle annular dark field transmission electron microscope photograph (a) of the/N-C, a signal superposition graph (b) of Pt, Mo, C and N elements, Mo element distribution (C) and Pt element distribution (d);
FIG. 7 shows Mo0.29Pt0.71A nitrogen adsorption-desorption isotherm (a) of/N-C, a pore size distribution map (b);
FIG. 8 shows PPY and Mo0.29Pt0.71ORR polarization curve (a), Tafel slope (b) for/N-C, Pt/C (20%), Mo/N-C, Pt/N-C catalyst; mo0.29Pt0.71Active area of/N-C and Pt/C (20%) (C), kinetic current density (d), specific mass activity (e), specific area activity (f);
in FIG. 9, (a) Mo0.29Pt0.71The stability test of the N-C cycle; (b) mo0.29Pt0.71Comparison of anti-methanol poisoning ability of N-C, Pt/C (20%);
FIG. 10 is a scanning electron micrograph of MoPt/N-C catalyst prepared at different reaction temperatures: (a) 670 ℃; (b) 720 ℃; (c) 770 ℃; (d) 820 ℃;
FIG. 11 is an ORR polarization curve of MoPt/N-C prepared at different reaction temperatures;
FIG. 12 is a scanning electron micrograph of MoPt/N-C samples prepared at different reaction times: (a) 10 min; (b) 20 min; (c) 30 min; (d) 40 min; (e) 50 min; (f) 60 min;
FIG. 13 is an ORR polarization curve of MoPt/N-C prepared for different reaction times;
FIG. 14 is a scanning electron micrograph of MoPt/N-C prepared at different loadings: (a) 1 mg; (b) 2 mg; (c) 3 mg; (d) 4 mg; (e) 5 mg; (f) 6 mg;
FIG. 15 is an ORR polarization curve for MoPt/N-C prepared at different loadings;
FIG. 16 is a scanning electron micrograph of MoPt/N-C prepared at different molar ratios (Mo/Pt): (a) 2/1, respectively; (b) 1/1, respectively; (c) 2/3, respectively; (d) 1/2, respectively; (e) 1/2.5; (f) 1/3, respectively;
FIG. 17 shows ORR polarization curves of MoPt/N-C prepared at different molar ratios (Pt/Mo 1/2, 1/1, 3/2, 2/1, 5/2, 6/2, respectively).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
105 mL of propionic acid was placed in a round bottom flask, magnetons were added, the rotation speed was set at 500rpm, and the temperature was raised to 145 ℃. Weighing 190 mg of pyrrole solution by using an electronic balance, dissolving the pyrrole solution in 45 mL of propionic acid, then dropwise adding the solution into a round-bottom flask within about 10min, reacting for 3 h, and washing with ethanol and water after the reaction is finished to obtain solid black powder, namely the nano spherical polypyrrole.
Examples 2 to 4
The charging time of the pyrrole solution in example 1 was changed to 0, 5, 15min, respectively, and the morphology of the product obtained is shown in fig. 1.
Studying the morphology of polypyrrole prepared at different feeding time, as shown in fig. 1 (a), namely, directly adding pyrrole into propionic acid under the condition of 0min, wherein the polypyrrole is in a spherical structure as a whole, but a small part of polypyrrole has an irregular shape which is not spherical; when the feeding time was slowed to 5min, as shown in FIG. 1 (b), the product consisted entirely of spheres, was relatively uniform in size, distributed around 250nm, and exhibited excellent dispersibility; when the feeding time is reduced to 10min, as shown in fig. 1 (c), the uniformity of the size distribution and the dispersibility of the product are still good, and the yield is more than 2 times of the product yield obtained under the condition of 5min feeding time; when the addition time was 15min, the product size began to become non-uniform as shown in FIG. 1 (d). In summary, the feeding time is preferably 5-10min, and the optimal feeding time is 10 min.
Examples 5 to 7:
the stirring speed in example 1 was changed to 300, 400 and 600 rpm, respectively, to obtain the product morphology as shown in FIG. 2.
The morphology of polypyrrole prepared at different stirring speeds is studied, and as shown in fig. 2 (a), the polypyrrole obtained under the condition of 300 rpm is uneven in size, has other irregular shapes, but mostly maintains a spherical structure; when the stirring speed was increased to 400 rpm, as shown in FIG. 2 (b), the spherical structure became more and more uniform and the dispersibility was improved; when the stirring speed is increased to 500rpm, as shown in fig. 2 (c), the irregular shape completely disappears, the product is all polypyrrole nanospheres, the size distribution is narrow, and the dispersibility is good; when the stirring speed was increased to 600 rpm, the product showed a broader size distribution and a certain degree of blocking occurred, as shown in fig. 2 (d). As described above, the optimum stirring speed was 500 rpm.
Examples 8 to 10:
the mass of the pyrrole in example 1 was changed to 190, 380 and 760 mg, respectively, and the morphology of the obtained product is shown in FIG. 3.
The morphology of the polypyrrole prepared by different feeding ratios is researched, as shown in fig. 3 (a), under the condition that the ratio of the total volume amount of propionic acid to the mass amount of the polypyrrole is 15:19, the size distribution of the prepared polypyrrole is narrow, only slight adhesion occurs, but the yield is low; under the condition that the ratio of the total volume of the propionic acid to the mass of the pyrrole is 15:38, as shown in fig. 3 (b), the product is still in a spherical structure, but compared with (a), the size distribution is relatively wider, part of spheres are adhered to form cucurbit-shaped polypyrrole, and the yield is not high; when the ratio of the total volume of the propionic acid to the mass of the pyrrole is 15:57, as shown in fig. 3 (c), the size distribution and the dispersibility are good, and the yield is high; when the ratio of the total volume of propionic acid to the mass of pyrrole was 15:76, the nanospheres showed extremely non-uniform and severe blocking in size as shown in FIG. 3 (d). In summary, the optimal feeding ratio is that the ratio of the total volume of the propionic acid to the mass of the pyrrole is 15:57, and the ratio of the total volume of the propionic acid to the mass of the pyrrole is 15: 57.
Comparative example 1:
putting 150 mL of propionic acid and 190 mg of pyrrole solution into a round-bottom flask, adding magnetons, heating to 145 ℃, reacting for 180min, and washing with ethanol and water after the reaction is finished to obtain solid black powder.
As shown in FIG. 4, the reaction yielded spherical polypyrrole, but polypyrrole exhibited blocking and a wide size distribution, and other irregular shapes appeared.
Example 11:
(1) 25mg of polypyrrole was accurately weighed into a 20mL beaker using an electronic balance, 15 mL of water was added, and stirring was continued until the polypyrrole was well dispersed in the water. Then the dispersed polypyrrole solution is addedUltrasonic treating in ultrasonic machine, adding 0.2 mL glacial acetic acid, mixing, and adding ammonium molybdate ((NH)4)6Mo7O24·4H2O), finally adding chloroplatinic acid (the total amount of the two metals is 4mg, and the molar ratio of Mo to Pt is 2/3), continuing ultrasonic treatment, stirring and dipping for 12 h, and drying.
(2) The dried sample was placed in a quartz boat and heat-treated at a set temperature using a tube furnace with 95% Ar and 5% H2Respectively under a protective atmosphere and a reducing atmosphere, exhausting for 30min to remove air in the equipment, and after exhausting is completed, heating to 670 ℃ and preserving heat for 30 min. And after the reaction is finished, cooling to room temperature, and taking out a sample to obtain the MoPt/N-C catalyst.
The following are tested and calculated by using Inductively Coupled Plasma (ICP): the molar ratio of Mo to Pt in the sample prepared in this example was 1/2.5, and Mo was used as the MoPt/N-C catalyst prepared in this example0.29Pt0.71N-C.
Comparative example 2:
(1) 25mg of polypyrrole was accurately weighed into a 20mL beaker using an electronic balance, 15 mL of water was added, and stirring was continued until the polypyrrole was well dispersed in the water. Then putting the dispersed polypyrrole solution into an ultrasonic machine for ultrasonic treatment, adding 0.2 mL of glacial acetic acid, mixing uniformly, and then adding ammonium molybdate ((NH)4)6Mo7O24·4H2O) (the total amount of Mo is 4 mg), continuing to perform ultrasonic treatment, stirring and dipping for 12 h, and drying.
(2) The dried sample was placed in a quartz boat and heat-treated at a set temperature using a tube furnace with 95% Ar and 5% H2Respectively under a protective atmosphere and a reducing atmosphere, exhausting for 30min to remove air in the equipment, and after exhausting is completed, heating to 670 ℃ and preserving heat for 30 min. And after the reaction is finished, cooling to room temperature, and taking out a sample to obtain the Mot/N-C catalyst.
Comparative example 3:
(1) 25mg of polypyrrole was accurately weighed into a 20mL beaker using an electronic balance, 15 mL of water was added, and stirring was continued until the polypyrrole was well dispersed in the water. And then putting the dispersed polypyrrole solution into an ultrasonic machine for ultrasonic treatment, adding 0.2 mL of glacial acetic acid, uniformly mixing, adding chloroplatinic acid (the total amount of platinum is 4 mg), continuing ultrasonic treatment, stirring, dipping for 12 h, and drying.
(2) The dried sample was placed in a quartz boat and heat-treated at a set temperature using a tube furnace with 95% Ar and 5% H2Respectively under a protective atmosphere and a reducing atmosphere, exhausting for 30min to remove air in the equipment, and after exhausting is completed, heating to 670 ℃ and preserving heat for 30 min. And after the reaction is finished, cooling to room temperature, and taking out a sample to obtain the Pt/N-C catalyst.
Comparative example 4:
and filling 25mg of polypyrrole into a quartz boat, and keeping the temperature of 720 ℃ for 2 h to obtain the N-C catalyst.
FIG. 5 (a) shows Mo0.29Pt0.71SEM image of/N-C sample, and (b) transmission electron micrograph. The observation of the graphs (a) and (b) shows that the N-C material still maintains the spherical structure after high-temperature annealing, and the metal nano-particles are obviously observed to be loaded in the nitrogen-carbon material, and the graph (C) of FIG. 5 shows that Mo0.29Pt0.71The high-resolution transmission electron microscope image of the/N-C shows that the size of the metal nano particles is below 10 nm, and the side surface illustrates that the carbon-nitrogen material plays an extremely important role in limiting the size of the metal particles. (d) The graph is (c) a white box enlarged part, and (d) the graph shows lattice stripe related information, 0.22 nm of intercrystalline distance corresponds to the (111) plane of the Mo-Pt alloy, and the Mo-Pt alloy phase is successfully synthesized, the 0.21 nm of lattice spacing can be attributed to that after Mo element is introduced into the catalyst, the lattice spacing of Pt is obviously compressed, and the lattice spacing is compressed from 0.221 nm to 0.21 nm of the pure Pt (111) plane, so that the adsorption energy between the catalyst and oxygen can be changed, and the reason that the performance of the catalyst is better than that of the pure Pt probably lies in the graph. As shown in FIG. 6, for Mo0.29Pt0.71The element species distribution test was performed on the/N-C sample, and (a) and (b) show that the sample contains four elements of platinum (Pt), molybdenum (Mo), nitrogen (N) and carbon (C), which are consistent with the test results of the element analysis. (c)And (d) further proves that the catalyst contains platinum (Pt) and molybdenum (Mo) elements.
And data acquisition is carried out by adopting nitrogen adsorption and desorption equipment of a physical adsorption device. FIG. 7 shows catalyst Mo0.29Pt0.71The nitrogen adsorption and desorption isothermal curve (a) of the/N-C and the research (b) of the pore size distribution thereof have obvious hysteresis loop as a mark of a mesoporous material in the isothermal curve consisting of the two curves, which indicates that the prepared Mo0.29Pt0.71the/N-C catalyst is a mesoporous material, and secondly, the total adsorption quantity of the target catalyst is 164.5 cm through the adsorption and desorption curve3g-1. To further prove the poly Mo0.29Pt0.71the/N-C is a mesoporous material, and the pore size distribution test (b) is carried out on the mesoporous material, and Mo can be seen0.29Pt0.71The pore size distribution of the/N-C catalytic material is more concentrated than that of the nitrogen-carbon material obtained after high-temperature calcination, mainly at 3.72 nm, probably because the size of the MoPt formed after calcination is more uniform, so that the cracking degree of the carbon matrix is basically consistent. In conclusion, Mo is analyzed0.29Pt0.71the/N-C material is a mesoporous material, and can provide active sites as much as possible in the catalytic process of the oxygen reduction reaction, and on the other hand, the appropriate mesopores can provide convenience for the transmission of oxygen, so that the oxygen reduction reaction can be carried out efficiently.
FIG. 8 shows PPY, Pt/C (20%), Mo/N-C, Pt/N-C, Mo0.29Pt0.71LSV curves for catalysts such as N-C. Analysis of the LSV curve yields: first, the initial potentials PPY, Pt/C (20%), Mo/N-C, Pt/N-C, and Mo0.29Pt0.71/N-C correspond to 0.72V (vs. RHE), 0.975V (vs. RHE), 0.87V (vs. RHE), 0.985V (vs. RHE), and 1.06V (vs. RHE), with Mo being the closest to the theoretical value of 1.23V0.29Pt0.71a/N-C catalyst sufficient to illustrate Mo0.29Pt0.71Excellent in the/N-C ratio. Half-wave potential value is 0.970V (Mo)0.29Pt0.71The Mo catalysts of the target catalysts are Mo/N-C), 0.87V (Pt/N-C), 0.869V (Pt/C (20%)), 0.743V (Mo/N-C), 0.581V (PPY) relative to the reversible hydrogen electrode0.29Pt0.71The half-wave potential of the/N-C is far higher than that of Pt/C (20%) by 100 mV, which fully proves that the target catalyst has better catalytic performance. For limiting current, it can be seen that Mo0.29Pt0.71the/N-C catalyst is obviously higher than other catalysts except Pt/C (20%), thereby illustrating that the mass transfer process is better than other similar reference catalysts. (b) The Tafel slope of the plot was 59 mV dec-1（Mo0.29Pt0.71/N-C）、70 mV dec-1（Pt/C（20%））、81 mV dec-1（Pt/N-C）、88 mV dec-1（Mo/N-C）、119 mV dec-1(N-C) further indicating that the target catalyzes the fastest reaction kinetic rate. FIG. c is a graph obtained by cyclic voltammetry in an electrolyte saturated with an inert gas, Mo0.29Pt0.71The more desirable ECSA for N-C demonstrates that it can supply more active sites for the process where oxygen is reduced to ensure high quality of the reaction run. The histogram of graph (d) clearly shows that Mo0.29Pt0.71Comparison of/N-C and Pt/C (20%), Mo at each potential0.29Pt0.71The current density controlled by the N-C dynamics is the most competitive. For noble metal-containing materials, mass specific activity (MA) and area Specific Activity (SA) are also one of the important criteria for measuring the quality of catalyst materials. The histograms of the graphs (e), (f) clearly show that Mo is present at different overpotentials0.29Pt0.71Both MA and SA are better than Pt/C (20%) for the/N-C catalyst. In the case of 0.9V, Mo0.29Pt0.71The specific mass activity/N-C was 9.5 times that of Pt/C (20%) and the specific area activity was about 4.6 times that of Pt/C (20%). Fully proves Mo0.29Pt0.71the/N-C catalyst is more valuable for practical application than Pt/C (20%).
The catalyst maintains long-term operation activity and is the basis of long-term use value of the material. The stability of the samples was tested using cyclic voltammetry scanning, which was performed in a mixed region of kinetic and diffusion control. As shown in FIG. 9 (a), Mo0.29Pt0.71The catalyst/N-C was measured at 5000 cyclesThe polarization curves before and after the test can be well overlapped, which shows that the material can keep better stability. Methanol fuel cells are one type of fuel cells in which the resistance to methanol poisoning is particularly important, as shown in FIG. 9 (b), which shows a corresponding test where 1M CH is added when the reaction has proceeded for 300 s3The current of Pt/C (20%) was found to decay rapidly after the addition of the OH solution, and finally to 47.55%, in contrast to Mo0.29Pt0.71The catalyst/N-C has slight decline in one moment, but the activity is slightly recovered after the decline, and finally the activity is attenuated by only 3.9 percent, which indicates that Mo0.29Pt0.71the/N-C has excellent methanol poisoning resistance.
Examples 12 to 14:
the 720 ℃ holding temperature in step (2) in example 11 was changed to 670, 720 and 820 ℃ respectively.
The obtained product has the appearance as shown in fig. 10, and as a whole, after high-temperature annealing, the spherical structure does not collapse, the structure of the precursor is still well maintained, and as can be seen at a high rate of 1 μm, when the temperature is 670 ℃, as shown in a graph (a), the obtained sample is almost consistent with the appearance of the N-C material, and no metal nanoparticles are found on the outer surface of the N-C material. When the temperature is 720 ℃, as shown in the graph (b), the sample can be found to be basically consistent with the morphology of the N-C material, but the careful observation can find that many small metal nanoparticles exist on the surface of the nanosphere, probably because of the insufficient high temperature, and the small nanoparticles can not break through the carbon layer. When the temperature is increased to 770 ℃, as shown in the graph (c), it can be clearly seen that the surface of the nanosphere becomes very rough, a large amount of fine metal particles are loaded on the nanosphere, the sesame-like spherical structure can reveal more active sites, and the relatively open structure also provides convenience for the continuous transmission of oxygen molecules.
As shown in FIG. 11, polarization curves of the MoPt/N-C catalyst obtained at different temperatures. Important electrochemical parameters for distinguishing the advantages and the disadvantages of the redox reaction performance are the limit current density and the half-wave potential, and compared with the test performance of samples prepared at other temperatures, an LSV curve obtained by testing the sample at 770 ℃ has the maximum limit current density and the highest half-wave potential.
From the above analysis, 770 ℃ was confirmed as the optimum reaction temperature.
Examples 15 to 19:
the 30min holding time of step (2) in example 11 was changed to 10min, 20min, 40min, 50min, and 60min, respectively, and the morphology of the obtained product is shown in fig. 12.
FIGS. 12 (a) - (e) are SEM images of MoPt/N-C prepared at different reaction times (10 min, 20min, 30min, 40min, 50min, 60 min). And (3) sampling. The surface appearance of the samples in the graphs (a) and (b) is still different from that of the samples annealed for a long time (more than 30 min) due to the short annealing time, and the degree of etching of the N-C material by the metal is not enough, because the surfaces of the nitrogen-carbon materials in the graphs (a) and (b) are not rough enough, the relatively closed state is not beneficial to the transmission of protons and reactants in the oxygen reduction reaction process. However, in the samples prepared under the annealing conditions of (e) 50min and (f) 60min, a part of N — C is etched away by the metal, leaving the agglomerated metal nanoparticles exposed, and in the ORR reaction (fig. 13), the metal nanoparticles are easily coated with the reactant and the hydroxide existing in the solution, so that the reactivity is also affected. When the annealing temperature is 30min, the surface of the N-C nanosphere forms a rough structure, and metal particles are uniformly dispersed on the rough structure, so that better catalytic activity can be achieved. The performance of MoPt/N-C samples prepared under different reaction time conditions is characterized by Linear Sweep Voltammetry (LSV). The half-wave potential of the prepared sample is the most positive at 30min, and the absolute value of the limiting current density is the largest, which proves that the oxygen reduction is the best at 30 min.
Examples 20 to 24:
the total amounts of Mo and Pt in step (1) of example 11 were changed to 1mg, 2mg, 3mg, 5mg and 6mg, respectively, and the morphology of the obtained product is shown in FIG. 14.
FIGS. 14 (a) - (f) are electron micrographs of prepared samples at total metal loadings of 1mg, 2mg, 3mg, 4mg, 5mg, 6 mg. At low loading, as shown in the graphs (a), (b) and (C), the surface morphology of the sample photographed by SEM is almost consistent with that of polypyrrole, which may be attributed to that the amount of metal in the polypyrrole channels is too small, and after high temperature annealing, polypyrrole has sufficient confinement capacity to coat the metal particles in the channels, and in addition, a small amount of metal nanoparticles are found outside the N — C material, because a small amount of metal salt does not remain outside the polypyrrole during impregnation, and when high temperature annealing, the metal nanoparticles are agglomerated together to form nanoparticles with larger size. When the metal loading is slightly high, the metal particles gathered on the outer layer of the polypyrrole can nucleate at high temperature, and the polypyrrole can be broken through coating to a certain extent, so that the surface of the polypyrrole is rough, more active sites are formed, the contact between oxygen and the active sites is improved, and the activity of the redox reaction is improved.
In order to verify the relation between the appearance structure of the sample and the catalytic performance of the oxygen reduction reaction, the performance of the samples with different loading amounts is tested (figure 15), and by combining a corresponding scanning electron microscope picture, it can be seen that the limiting current density of the oxygen reduction reaction of the samples of 1mg and 2mg is at a lower level due to the fact that the polypyrrole is coated relatively tightly, and when the loading amount is relatively high, the surface of the polypyrrole becomes rough and more metal active sites are exposed, and the limiting current is increased accordingly. The half-wave potential is most positive when the total metal loading is 4 mg. Therefore, the analysis of experimental results shows that the performance is optimal when the loading amount is 4 mg.
Examples 25 to 29:
the molar ratios of Mo and Pt in step (1) of example 11 were changed to 2/1, 1/1, 1/2, 1/2.5 and 1/3, respectively, and the morphology of the product was as shown in FIG. 16.
FIGS. 16 (a) - (e) are SEM images of MoPt/N-C catalysts prepared when the molar ratios of the two metals Mo and Pt were 2/1, 1/1, 2/3, 1/2, 1/2.5, 1/3. Since the total metal loading is the same, the differences between samples prepared under different conditions when observed on an electron microscope image are not large, the spherical structure of polypyrrole is maintained, and the difference is that the surface of polypyrrole becomes rough when the loading of Pt is increased. FIG. 17 is a polarization curve of oxygen reduction reaction for preparing MoPt/N-C under different metal molar ratio conditions, and it can be seen from the curve that when the molar ratio of Mo and Pt is greater than 1, the difference of the electrocatalytic oxygen reduction reaction performance is not very large, and when the molar ratio is 3/2, the half-wave potential is dominant, i.e. the optimal metal molar ratio is Mo/Pt 2/3.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (9)
1. The nitrogen-doped carbon-loaded Mo/Pt alloy catalyst is characterized in that the preparation method comprises the following steps:
(1) preparing nanometer spherical polypyrrole: adding propionic acid into a container, heating to 130-160 ℃, mixing pyrrole with propionic acid to obtain a pyrrole propionic acid solution, adding the pyrrole propionic acid solution into the propionic acid in the container heated to 130-160 ℃ under stirring, and reacting for at least 1.5h by using oxygen as an oxidant to obtain a black mixed solution; washing and separating the product with ethanol and water, and finally drying to obtain nano spherical polypyrrole;
(2) preparing a nitrogen-doped carbon-loaded Mo/Pt alloy catalyst: and (2) soaking molybdate and chloroplatinic acid into the pore channel of the nano spherical polypyrrole prepared in the step (1), and calcining to obtain the nitrogen-doped carbon-loaded Mo/Pt alloy catalyst.
2. The nitrogen-doped carbon-supported Mo/Pt alloy catalyst of claim 1, wherein: in the step (2), the nano spherical polypyrrole prepared in the step (1) is dispersed in water, glacial acetic acid is added into polypyrrole dispersion liquid, molybdate and pallanate are added, stirring and impregnation are carried out, the molybdate and the pallanate are impregnated into pore channels of the nano spherical polypyrrole, and calcination is carried out after drying treatment.
3. The nitrogen-doped carbon-supported Mo/Pt alloy catalyst of claim 1, wherein: during calcination, hydrogen was used as a reducing atmosphere and argon was used as a protective atmosphere.
4. The nitrogen-doped carbon-supported Mo/Pt alloy catalyst of claim 1, wherein: the calcination temperature is 670-820 ℃.
5. The nitrogen-doped carbon-supported Mo/Pt alloy catalyst of claim 4, wherein: the calcination time is 10-60 min.
6. The nitrogen-doped carbon-supported Mo/Pt alloy catalyst of claim 1, wherein: the total metal loading is 1-6mg/25mg polypyrrole.
7. The nitrogen-doped carbon-supported Mo/Pt alloy catalyst of claim 6, wherein: the molar ratio of Mo to Pt is 2-1: 1-3.
8. Use of the nitrogen doped carbon supported Mo/Pt alloy catalyst of any one of claims 1-7 as a redox electrocatalyst.
9. A fuel cell, characterized by: wherein the catalyst adopts the nitrogen-doped carbon-supported Mo/Pt alloy catalyst as described in any one of claims 1-7.
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