CN112993281A - Fe-based multi-metal electrocatalyst, preparation and application thereof - Google Patents
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Abstract
The invention relates to a Fe-based multi-metal electrocatalyst, preparation and application thereof, in particular to a method for preparing the Fe-based multi-metal electrocatalyst, which is characterized in that Fe and trace M (M is Mn, Co, Ni and Cu) are added in the synthesis process based on a metal organic framework. The Fe loading in the catalyst can be increased nonlinearly and remarkably with the increase of the introduced amount of the second metal. By incorporating the design of the kind and content of the second metal, an oxygen-reducing electrocatalyst having high activity can be obtained. The method has the advantages of simplicity, convenience, easy implementation, low production cost and the like.
Description
Technical Field
The invention belongs to the technical field of catalysts and preparation thereof, and particularly relates to preparation and application of a cathode oxygen reduction electrocatalyst used in a secondary metal air fuel cell or a direct methanol fuel cell or a proton exchange membrane fuel cell.
Background
Due to climate change and depletion of oil supply, research and development of clean energy is crucial in the next decades. Many advanced technologies for clean energy conversion, such as fuel cells, electrolytic water, metal air batteries, and carbon dioxide fuel conversion, are receiving increasing attention. The fuel cell technology is clean and efficient, can directly convert chemical energy into electric energy, and has the advantages of high energy conversion rate, environmental friendliness, low noise and the like. However, in the fuel cell, the cathode reaction is very slow compared to the anode, resulting in a higher overpotential for the cathode compared to the anode, and thus a large amount of noble metal platinum is required to catalyze the cathode reaction. However, the limited resources and high cost of Pt also make Pt-based catalysts a major obstacle to the commercialization of fuel cells. It is therefore of significant importance to develop low platinum and non-or platinum electrocatalysts.
In recent years, Metal Organic Framework (MOF) materials have advantages of adjustable structure, rich pore channels, and the like, and thus have attracted extensive attention of researchers. In the conventional method for preparing the Fe-NC catalyst based on the ZIF-8 precursor, the number of active sites FeNx is small, and if the doping amount of Fe is increased independently in the synthesis process, inactive Fe nanoparticles are easily formed in the pyrolysis process, which seriously limits the further improvement of the electrocatalytic activity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for increasing the number of active sites of a catalyst, and an electrocatalyst applied to cathode oxygen reduction reaction of a secondary metal air fuel cell, a direct methanol fuel cell and a proton exchange membrane fuel cell, and preparation and application thereof.
In order to achieve the purpose, the invention adopts the following specific scheme to realize:
an Fe-based multimetallic electrocatalyst characterized by: taking a regular dodecahedral carbon nitrogen framework as a carrier, and respectively dispersing Zn atoms, Fe atoms and third metal atoms in the carbon nitrogen framework carrier in a monoatomic manner; the third metal atom is one or more than two of Mn, Co, Ni and Cu.
The mass percentage of the Zn atoms is 0.2-2%; the mass percentage of the Fe atom is 0.5-4%; the mass percentage of the third metal atom is 0.01-0.3%.
The third metal atom is preferably Cu and/or Ni; the mass percentage content of the Zn atoms is preferably 0.5-1%; the mass percentage content of the Fe atom is preferably 1.8% -2.5%; the content of the third metal atom by mass is preferably 0.02% to 0.04%.
The preparation method of the Fe-based polymetallic electrocatalyst comprises the following preparation steps,
1) dissolving dimethyl imidazole in a methanol solution, and stirring until the solution is clear to be A solution;
2) dissolving zinc nitrate, ferric salt and a third group of metal salt in a methanol solution, and stirring until the zinc nitrate, the ferric salt and the third group of metal salt are completely dissolved to form a solution B; the third group of metals is one or more than two of Mn, Co, Ni and Cu;
3) mixing and stirring the solution B and the solution A until a precipitate is generated, and heating to 100-150 ℃ for reaction for 4-8 hours;
4) after centrifugal separation, washing with methanol, and vacuum drying to obtain a catalyst precursor for later use;
5) taking a catalyst precursor, and carrying out pyrolysis treatment at 800-1100 ℃ to obtain the Fe-based polymetallic electrocatalyst.
Part of zinc in the regular dodecahedral framework is replaced by Fe and/or a second group of metals in the preparation process, so that part of Fe and/or the second group of metals enter the framework and are used as coordination metals, wherein Fe and/or the second group of metals exist in the catalyst in the form of monodispersed metal monoatomic atoms.
The concentration of the dimethyl imidazole in the methanol solution in the step (1) is 30g/L-250g/L, preferably 60g/L-100 g/L.
The pyrolysis treatment time of the step (5) is 2-4 hours.
In the step (3), the volume ratio of the solution B to the solution A is 2:1-1: 2.
The ferric salt is one or more than two of ferric acetylacetonate, ferric nitrate, ferric sulfate and ferric ammonium citrate; the third metal salt is one or more than two of acetylacetone salt, nitrate and sulfate.
And 3) stirring for 1-5 hours.
And 4) the drying temperature is 60-80 ℃.
The application of the Fe-based polymetallic electrocatalyst is used as an oxygen reduction electrocatalyst for a secondary metal air fuel cell or a direct methanol fuel cell or a proton exchange membrane fuel cell.
Compared with the prior art, the novel Fe-based polymetallic electrocatalyst has the following advantages:
1. compared with a single metal doped material, the doping of the binary metal obviously improves the catalytic energy;
2. the size is adjustable;
3. the porous structure is rich, and gas mass transfer is facilitated;
the number of the FeNx active sites can be effectively regulated and controlled by introducing the amount of the third group of metals;
5. the catalyst has wide application range and can be used as an electrocatalyst for cathode oxygen reduction reaction of secondary metal air fuel cells, direct methanol fuel cells and proton exchange membrane fuel cells.
6.
Drawings
Figure 1 is an X-ray diffraction pattern (XRD) of an Fe-based multimetallic electrocatalyst prepared according to examples 1, 5, 10. As can be seen from the figure, the phase structures of the samples are consistent and are ZIF-8 type.
Fig. 2 is a Transmission Electron Micrograph (TEM) of an Fe-based multimetallic electrocatalyst prepared according to example 1. As can be seen from the figure, the resulting electrocatalyst has a dodecahedral structure.
Fig. 3 is a comparison of the performance of catalysts obtained from the pyrolysis of Fe-based multimetallic electrocatalysts prepared according to example 1 at different temperatures. The best performance is achieved when pyrolysis is carried out at 950 ℃.
Figure 4 is an oxygen reduction polarization curve of Fe-based multimetallic electrocatalysts prepared according to examples 1, 5, 10 in oxygen saturated 0.1M KOH electrolyte. It can be seen from the figure that the introduction of the second component metal greatly improves the catalytic activity and is optimized with the effect of Cu.
Figure 5 is an oxygen reduction polarization curve of Fe-based multimetallic electrocatalysts prepared according to examples 1, 5, 6, 10 in oxygen saturated 0.1M KOH electrolyte. From the figure, it can be seen that the catalytic activity is the best when the second component metal is Cu.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to examples. The invention is of course not limited to these specific embodiments.
Example 1:
weighing 1.642g of dimethyl imidazole, dissolving in 25ml of methanol solution, and stirring for 30 min; weighing 1.487g of zinc nitrate, 20mg of iron acetylacetonate and 20mg of copper acetylacetonate, dissolving in 25ml of methanol solution, stirring for 30min, adding the solution, and stirring for 2 h; then putting the mixture into a reaction kettle, heating the mixture to 120 ℃ and heating the mixture for 5 hours. Cooling to room temperature, performing centrifugal separation, washing for 3 times by using a methanol solution, washing excessive copper acetylacetonate in the washing process because the copper acetylacetonate is difficult to dope, drying in vacuum at 80 ℃ to obtain a target precursor, heating a certain amount of the precursor in a high-temperature tube furnace at 5 ℃/min to 950 ℃ in an inert atmosphere, heating for 3 hours, and cooling to room temperature to obtain the catalyst, namely (Fe, Cu) -NC-950.
XRD confirms that the crystal form of the precursor is ZIF-8 type, the particle size of the catalyst is 150nm, Fe and Cu metal exist in monodisperse metal monoatomic atoms after pyrolysis, no diffraction peak of metal particles exists, the mass percent of Fe in the catalyst is 4.0%, the mass percent of copper is 0.04%, the mass percent of Zn is 0.2%, and the mass percent of N is 5.8%.
Example 2:
weighing 1.642g of dimethyl imidazole, dissolving in 25ml of methanol solution, and stirring for 30 min; weighing 1.487g of zinc nitrate, 20mg of iron acetylacetonate and 15mg of copper acetylacetonate, dissolving in 25ml of methanol solution, stirring for 30min, adding the solution, and stirring for 2 h; then putting the mixture into a reaction kettle, heating the mixture to 120 ℃ and heating the mixture for 5 hours. Cooling to room temperature, performing centrifugal separation, washing for 3 times by using a methanol solution, washing excessive copper acetylacetonate in the washing process because the copper acetylacetonate is difficult to dope, drying in vacuum at 80 ℃ to obtain a target precursor, heating a certain amount of the precursor to 950 ℃ at 5 ℃/min in an inert atmosphere in a high-temperature tube furnace for 3 hours, and cooling to room temperature to obtain the catalyst, namely (Fe,15Cu) -NC-950.
XRD confirms that the crystal form of the precursor is ZIF-8 type, the particle size of the catalyst is 250nm, Fe and Cu metal exist in monodisperse metal monoatomic form after pyrolysis, no diffraction peak of metal particles exists, the mass percent of Fe in the catalyst is 3.0%, the mass percent of copper is 0.03%, the mass percent of Zn is 1.5%, and the mass percent of N is 5%
Example 3:
weighing 1.642g of dimethyl imidazole, dissolving in 25ml of methanol solution, and stirring for 30 min; weighing 1.487g of zinc nitrate, 20mg of iron acetylacetonate and 10mg of copper acetylacetonate, dissolving in 25ml of methanol solution, stirring for 30min, adding the solution, and stirring for 2 h; then putting the mixture into a reaction kettle, heating the mixture to 120 ℃ and heating the mixture for 5 hours. Cooling to room temperature, performing centrifugal separation, washing for 3 times by using a methanol solution, washing excessive copper acetylacetonate in the washing process because the copper acetylacetonate is difficult to dope, drying in vacuum at 80 ℃ to obtain a target precursor, heating a certain amount of the precursor to 950 ℃ at 5 ℃/min in an inert atmosphere in a high-temperature tube furnace for 3 hours, and cooling to room temperature to obtain the catalyst, namely (Fe,10Cu) -NC-950.
XRD confirms that the crystal form of the precursor is ZIF-8 type, the particle size of the catalyst is 200nm, the monodisperse metal monoatomic ions of Fe and Cu exist after pyrolysis, no diffraction peak of the metal particles exists, the mass percent of Fe in the catalyst is 2.5%, the mass percent of copper is 0.02%, the mass percent of Zn is 0.5%, and the mass percent of N is 4%
Example 4:
weighing 1.642g of dimethyl imidazole, dissolving in 25ml of methanol solution, and stirring for 30 min; weighing 1.487g of zinc nitrate, 20mg of iron acetylacetonate and 5mg of copper acetylacetonate, dissolving in 25ml of methanol solution, stirring for 30min, adding the solution, and stirring for 2 h; then putting the mixture into a reaction kettle, heating the mixture to 120 ℃ and heating the mixture for 5 hours. Cooling to room temperature, performing centrifugal separation, washing for 3 times by using a methanol solution, washing excessive copper acetylacetonate in the washing process because the copper acetylacetonate is difficult to dope, drying in vacuum at 80 ℃ to obtain a target precursor, heating a certain amount of the precursor to 950 ℃ at 5 ℃/min in an inert atmosphere in a high-temperature tube furnace for 3 hours, and cooling to room temperature to obtain the catalyst, namely (Fe,5Cu) -NC-950.
XRD confirms that the crystal form of the precursor is ZIF-8 type, the particle size of the catalyst is 200nm, Fe and Cu exist in monodisperse metal monoatomic form after pyrolysis, no diffraction peak of metal particles exists, the mass percent of Fe in the catalyst is 1.7%, the mass percent of copper is 0.01%, the mass percent of Zn is 1%, and the mass percent of N is 5%
Example 5:
weighing 1.642g of dimethyl imidazole, dissolving in 25ml of methanol solution, and stirring for 30 min; weighing 1.487g of zinc nitrate, 20mg of iron acetylacetonate and a mixture of the zinc nitrate and the iron acetylacetonate, dissolving the mixture in 25ml of methanol solution, stirring the mixture for 30min, adding the solution into the mixture, and stirring the mixture for 2 h; then putting the mixture into a reaction kettle, heating the mixture to 120 ℃ and heating the mixture for 5 hours. Cooling to room temperature, performing centrifugal separation, washing for 3 times by using a methanol solution, performing vacuum drying at 80 ℃ to obtain a target precursor, putting a certain amount of the precursor into a high-temperature tube furnace, heating to 950 ℃ at 5 ℃/min under an inert atmosphere for 3h, and cooling to room temperature to obtain the catalyst, namely Fe-NC-950.
XRD confirms that the crystal form of the precursor is ZIF-8 type, the particle size of the catalyst is 250nm, Fe exists in monodisperse metal monoatomic form after pyrolysis, no diffraction peak of metal particles exists, the mass percent of Fe in the catalyst is 0.5%, the mass percent of Zn is 1%, and the mass percent of N is 4%
Example 6:
weighing 1.642g of dimethyl imidazole, dissolving in 25ml of methanol solution, and stirring for 30 min; weighing 1.487g of zinc nitrate, 10mg of iron acetylacetonate and 10mg of nickel acetylacetonate, dissolving in 25ml of methanol solution, stirring for 30min, adding the solution, and stirring for 2 h; then putting the mixture into a reaction kettle, heating the mixture to 120 ℃ and heating the mixture for 5 hours. Cooling to room temperature, performing centrifugal separation, washing for 3 times by using a methanol solution, washing excessive nickel acetylacetonate in the washing process because the nickel acetylacetonate is difficult to dope, drying in vacuum at 80 ℃ to obtain a target precursor, heating a certain amount of the precursor in a high-temperature tube furnace at 5 ℃/min to 900 ℃ in an inert atmosphere, heating for 3h, and cooling to room temperature to obtain the catalyst, namely (Fe, Ni) -NC-950.
XRD confirms that the crystal form of the precursor is ZIF-8 type, the particle size of the catalyst is 200nm, Fe and Ni exist in monodisperse metal monoatomic form after pyrolysis, no diffraction peak of metal particles exists, the mass percent of Fe in the catalyst is 0.9%, the mass percent of nickel is 0.01%, the mass percent of Zn is 1.2%, and the mass percent of N is 6%
Example 7:
weighing 1.642g of dimethyl imidazole, dissolving in 25ml of methanol solution, and stirring for 30 min; weighing 1.487g of zinc nitrate, 10mg of iron acetylacetonate and 10mg of copper acetylacetonate, dissolving in 25ml of methanol solution, stirring for 30min, adding the solution, and stirring for 2 h; then putting the mixture into a reaction kettle, heating the mixture to 120 ℃ and heating the mixture for 5 hours. Cooling to room temperature, performing centrifugal separation, washing for 3 times by using a methanol solution, washing excessive copper acetylacetonate in the washing process because the copper acetylacetonate is difficult to dope, drying in vacuum at 80 ℃ to obtain a target precursor, heating a certain amount of the precursor in a high-temperature tube furnace at 5 ℃/min to 900 ℃ in an inert atmosphere, heating for 3h, and cooling to room temperature to obtain the catalyst, namely (10Fe,10Cu) -NC-950.
XRD confirms that the crystal form of the precursor is ZIF-8 type, the particle size of the catalyst is 220nm, Fe and Cu exist in monodisperse metal monoatomic form after pyrolysis, no diffraction peak of metal particles exists, the mass percent of Fe in the catalyst is 0.8%, the mass percent of copper is 0.02%, the mass percent of Zn is 1.4%, and the mass percent of N is 5%
Example 8:
weighing 1.642g of dimethyl imidazole, dissolving in 25ml of methanol solution, and stirring for 30 min; weighing 1.487g of zinc nitrate, 10mg of iron acetylacetonate and 10mg of cobalt acetylacetonate, dissolving in 25ml of methanol solution, stirring for 30min, adding the solution, and stirring for 2 h; then putting the mixture into a reaction kettle, heating the mixture to 120 ℃ and heating the mixture for 5 hours. Cooling to room temperature, performing centrifugal separation, washing for 3 times by using a methanol solution, performing vacuum drying at 80 ℃ to obtain a target precursor, putting a certain amount of the precursor into a high-temperature tube furnace, heating to 900 ℃ at the speed of 5 ℃/min under an inert atmosphere for 3h, and cooling to room temperature to obtain the catalyst, namely (Fe, Co) -NC-950.
XRD confirms that the crystal form of the precursor is ZIF-8 type, the particle size of the catalyst is 200nm, Fe and Co exist in monodisperse metal monoatomic form after pyrolysis, no diffraction peak of metal particles exists, the mass percent of Fe in the catalyst is 0.8%, the mass percent of cobalt in the catalyst is 0.3%, the mass percent of Zn in the catalyst is 1.5%, and the mass percent of N in the catalyst is 3%
Example 9:
weighing 1.642g of dimethyl imidazole, dissolving in 25ml of methanol solution, and stirring for 30 min; weighing 1.487g of zinc nitrate, 10mg of iron acetylacetonate and 10mg of manganese acetylacetonate, dissolving in 25ml of methanol solution, stirring for 30min, adding the solution, and stirring for 2 h; then putting the mixture into a reaction kettle, heating the mixture to 120 ℃ and heating the mixture for 5 hours. Cooling to room temperature, performing centrifugal separation, washing for 3 times by using a methanol solution, washing excessive manganese acetylacetonate in the washing process because the manganese acetylacetonate is difficult to dope, drying in vacuum at 80 ℃ to obtain a target precursor, heating a certain amount of the precursor in a high-temperature tube furnace at 5 ℃/min to 900 ℃ in an inert atmosphere, heating for 3h, and cooling to room temperature to obtain the catalyst, namely (10Fe,10Mn) -NC-950.
XRD confirms that the crystal form of the precursor is ZIF-8 type, the particle size of the catalyst is 220nm, Fe and Mn exist in monodisperse metal monoatomic form after pyrolysis, no diffraction peak of metal particles exists, the mass percent of Fe in the catalyst is 0.6%, the mass percent of manganese is 0.02%, the mass percent of Zn is 1.8%, and the mass percent of N is 5%
Comparison 1:
weighing 1.642g of dimethyl imidazole, dissolving in 25ml of methanol solution, and stirring for 30 min; weighing 1.487g of zinc nitrate and 20mg of copper acetylacetonate, dissolving in 25ml of methanol solution, stirring for 30min, adding the solution, and stirring for 2 h; then putting the mixture into a reaction kettle, heating the mixture to 120 ℃ and heating the mixture for 5 hours. Cooling to room temperature, performing centrifugal separation, washing for 3 times by using a methanol solution, washing excessive copper acetylacetonate in the washing process because the manganese acetylacetonate is difficult to dope, drying in vacuum at 80 ℃ to obtain a target precursor, heating a certain amount of the precursor in a high-temperature tube furnace at 5 ℃/min to 900 ℃ in an inert atmosphere, heating for 3h, and cooling to room temperature to obtain the catalyst, namely Cu-NC-950.
XRD confirms that the crystal form of the precursor is ZIF-8 type, the particle size of the catalyst is 250nm, Cu exists in monodisperse metal monoatomic form after pyrolysis, no diffraction peak of metal particles exists, the mass percent of Cu in the catalyst is 0.03%, the mass percent of Zn is 1.2%, and the mass percent of N is 5%
Comparative example 2:
weighing 1.642g of dimethyl imidazole, dissolving in 25ml of methanol solution, and stirring for 30 min; weighing 1.487g of zinc nitrate, 100mg of iron acetylacetonate and a mixture of the zinc nitrate and the iron acetylacetonate, dissolving the mixture in 25ml of methanol solution, stirring the mixture for 30min, adding the solution into the mixture, and stirring the mixture for 2 h; then putting the mixture into a reaction kettle, heating the mixture to 120 ℃ and heating the mixture for 5 hours. Cooling to room temperature, performing centrifugal separation, washing for 3 times by using a methanol solution, performing vacuum drying at 80 ℃ to obtain a target precursor, putting a certain amount of the precursor into a high-temperature tube furnace, heating to 900 ℃ at the speed of 5 ℃/min under an inert atmosphere for 3h, and cooling to room temperature to obtain the catalyst, namely Fe-NC-950.
XRD confirms that the crystal form of the precursor is ZIF-8 type, the particle size of the catalyst is 150nm, Fe exists in monodisperse metal monoatomic form after pyrolysis, no diffraction peak of metal particles exists, the mass percent of Fe in the catalyst is 0.5%, the mass percent of Zn is 2%, and the mass percent of N is 6%
Table 1 shows the contents of Fe and Cu in the Fe-based polymetallic electrocatalyst prepared according to examples 1, 2, 3, 4, 5, 10, it can be seen that the amount of Fe in the prepared catalyst is significantly increased with the doping of trace amount of Cu, e.g., after 0.01% by mass of Cu is added, the amount of Fe in the catalyst is increased from 0.5% to 1.7%, and when the amount of Cu is continuously increased to 0.02%, the amount of Fe is increased to 2.3%.
Table 1 mass percent Fe and Cu content in electrocatalysts prepared in examples 1, 2, 3, 4, 5, 10
Claims (10)
1. An Fe-based multimetallic electrocatalyst characterized by: taking a regular dodecahedral carbon nitrogen framework as a carrier, and respectively dispersing Zn atoms, Fe atoms and third metal atoms in the carbon nitrogen framework carrier in a monoatomic manner; the third metal atom is one or more than two of Mn, Co, Ni and Cu.
2. The Fe-based multimetallic electrocatalyst according to claim 1, wherein: in the catalyst, the mass percentage of Zn atoms is 0.2-2%; the mass percentage of the Fe atom is 0.5-4%; the mass percentage of the third metal atom is 0.01-0.3%, the mass percentage of N is 3-6%, and the particle size of the catalyst is 150-250 nm.
3. The Fe-based multimetallic electrocatalyst according to claim 1, wherein: the third metal atom is preferably Cu and/or Ni; the mass percentage content of the Zn atoms is preferably 0.5-1%; the mass percentage content of the Fe atom is preferably 1.8% -2.5%; the content of the third metal atom is preferably 0.02-0.04% by mass, the content of N is 4-5% by mass, and the particle size of the catalyst is 180-220 nm.
4. A method of preparing an Fe-based multimetallic electrocatalyst according to any one of claims 1 to 3, wherein: comprises the following preparation steps of the following steps of,
1) dissolving dimethyl imidazole in a methanol solution, and stirring until the solution is clear to be A solution;
2) dissolving zinc nitrate, organic ferric salt and salt of a third group of metals in a methanol solution, and stirring until the zinc nitrate, the organic ferric salt and the salt of the third group of metals are completely dissolved to form a solution B; the third group of metals is one or more than two of Mn, Co, Ni and Cu;
3) mixing and stirring the solution B and the solution A until a precipitate is generated, and heating to 100-150 ℃ for reaction for 4-8 hours;
4) after centrifugal separation, washing with methanol, and vacuum drying to obtain a catalyst precursor for later use;
5) taking a catalyst precursor, and carrying out pyrolysis treatment at 800-1100 ℃ to obtain the Fe-based polymetallic electrocatalyst.
5. The method of claim 4, wherein:
the concentration of the dimethyl imidazole in the methanol solution in the step (1) is 30g/L-250g/L, preferably 60g/L-100 g/L.
6. The method of claim 4, wherein:
the pyrolysis treatment time of the step (5) is 2-4 hours.
7. The production method according to claim 4 or 5, characterized in that:
in the step (3), the volume ratio of the solution B to the solution A is 2:1-1: 2.
8. The method of claim 4, wherein: the ferric salt is one or more than two of ferric acetylacetonate, ferric nitrate, ferric sulfate and ferric ammonium citrate; the third metal salt is one or more than two of acetylacetone salt, nitrate and sulfate.
9. The method of claim 4, wherein: step 3), the stirring time is 1-5 hours; and 4) the drying temperature is 60-80 ℃.
10. Use of an Fe-based multimetallic electrocatalyst according to any one of claims 1 to 3, wherein: the oxygen reduction electrocatalyst is used in a secondary metal air fuel cell or a direct methanol fuel cell or a proton exchange membrane fuel cell.
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