CN113258083A - CoXBifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof - Google Patents

CoXBifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof Download PDF

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CN113258083A
CN113258083A CN202110313747.2A CN202110313747A CN113258083A CN 113258083 A CN113258083 A CN 113258083A CN 202110313747 A CN202110313747 A CN 202110313747A CN 113258083 A CN113258083 A CN 113258083A
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catalyst
nitrogen
doped carbon
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phosphorus doped
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CN113258083B (en
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刘乔
石青
杨为佑
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Ningbo University of Technology
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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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention belongs to the field of electrocatalysis, and relates to CoXThe P nanoparticles are embedded in a bifunctional catalyst of nitrogen and phosphorus doped carbon. The invention carries out controllable synthesis of Co by adjusting the proportion of the precursors ZIF-67 and MPSA2P、Co2The bifunctional catalyst with P/CoP and CoP nanoparticles embedded in nitrogen and phosphorus doped carbon has excellent ORR/OER catalytic activity and stability. The composite catalyst with the Co-based transition metal phosphide embedded with the heteroatom doped carbon is prepared by a simple and environment-friendly one-step carbonization method, and meanwhile, the method can also be suitable for preparing other bifunctional catalysts with the heteroatom doped carbon derived from the transition metal phosphide.

Description

CoXBifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof
Technical Field
The invention belongs to the field of electrocatalysis, and relates to CoXThe P nanoparticles are embedded in a bifunctional catalyst of nitrogen and phosphorus doped carbon.
Background
The zinc-air battery has the advantages of high theoretical energy density, low price, good safety and the like, and in recent years, the zinc-air battery has attracted wide attention on portable electronic equipment and electric automobiles. However, the lack of efficient and stable Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) dual-function catalysts has limited the development and commercial application of rechargeable zinc-air batteries. At present, Pt-based catalysts and Ir/Ru-based catalysts are ORR catalysts and OER catalysts with higher efficiency respectively. However, the noble metal catalyst has the problems of resource scarcity, high price, poor stability, poor bifunctional performance and the like. In order to further promote the development of zinc-air batteries and realize commercial application, research and development of efficient and stable ORR/OER bifunctional catalysts are urgently needed.
Transition Metal Phosphides (TMPs), including Fe, Co, Cu, Ni, etc., have excellent physicochemical properties, a diversified synthesis method, and good OER catalytic activity, etc., and in recent years, the transition metal phosphides have received much attention. ORR and OER are a pair of reversible reactions, the reaction paths are different, and the corresponding catalytic sites are different, so that the transition metal phosphide with a single active site can not effectively catalyze the ORR and OER reactions at the same time.
Chinese patent application document (application No. CN201810922115.4) discloses a phosphorus-doped porous carbon-coated cobaltosic oxide oxygen reduction catalyst, and a preparation method and application thereof, wherein a phosphorus-doped porous carbon-coated cobaltosic oxide pro-catalyst Co is prepared by taking ZIF-67 with a porous structure as a template and a precursor and taking sodium phytate as a P source3O4Catalyst Co prepared from/PPC, but with P only doped and no phosphating of the metal3O4the/PPC only shows ORR catalytic activity.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides Co with simple preparation method and excellent catalytic activity and stabilityXThe P nanoparticles are embedded in a bifunctional catalyst of nitrogen and phosphorus doped carbon.
The purpose of the invention can be realized by the following technical scheme:
coXBifunctional catalyst with P nanoparticles intercalated with nitrogen and phosphorus doped carbon, CoXP nanoparticles are Co2One or both of P and CoP.
CoP and Co2P is both an active species of ORR and/or OER. By preparing cobalt phosphide with different stoichiometric ratios, investigating the electrocatalytic performance of phosphide with different stoichiometric ratios on ORR/OER, the invention has important significance for preparing bifunctional catalyst of Co-based metal phosphide2P、Co2The P/CoP and CoP nano-particle embedded N, P carbon-doped bifunctional catalyst shows excellent ORR/OER catalytic activity.
CoXA method for preparing a bifunctional catalyst with P nanoparticles embedded in nitrogen and phosphorus doped carbon, the method comprising the steps of: mixing and grinding ZIF-67 and MPSA, and then carbonizing at high temperature in nitrogen to obtain the catalyst.
In one of the above-mentioned CoXIn the preparation method of the bifunctional catalyst with the P nanoparticles embedded in nitrogen and phosphorus doped carbon, the mass ratio of ZIF-67 to MPSA is 1: (0.5-1.5).
MPSA is a macromolecular polymer obtained by polymerizing phytic acid and melamine, and the content of MPSA is increased, so that the content of P is increased, and the increased content of P can lead to Co2P transitions to CoP. When the mass ratio of ZIF-67 to MPSA is 1: 0.5, the catalyst contains Co nanoparticles2The form of P exists; when the mass ratio of ZIF-67 to MPSA is 1: 1 hour, Co2Partial transition of P to CoP, so that the nanoparticles in the catalyst are Co2The form of P/CoP exists; when the mass ratio of ZIF-67 to MPSA is 1: 1.5 times, Co2P is completely converted into CoP, so that the nanoparticles in the catalyst exist in the form of CoP. The method prepares and synthesizes Co respectively by adjusting the mass ratio of ZIF-67 to MPSA2P、Co2The P/CoP and CoP nano-particle embedded N, P carbon-doped bifunctional catalyst shows excellent ORR/OER catalytic activity and excellent cycle charge and discharge stability when used as an air electrode of a zinc-air battery.
In one of the above-mentioned CoXBifunctional catalysis of P nanoparticles embedding nitrogen and phosphorus doped carbonIn the preparation method of the agent, the preparation method of the ZIF-67 comprises the following steps: firstly, respectively dissolving cobalt nitrate hexahydrate and dimethylimidazole in methanol to form a solution, then mixing the cobalt nitrate hexahydrate and the dimethylimidazole to form a turbid liquid, standing to obtain a precipitate, centrifuging and washing the precipitate, then washing with methanol, and finally drying to obtain the ZIF-67.
In one of the above-mentioned CoXIn the preparation method of the bifunctional catalyst with the P nano particles embedded with nitrogen and phosphorus doped with carbon, the preparation method of the MPSA comprises the following steps: dissolving melamine in deionized water, adding phytic acid solution after the melamine is completely dissolved, stirring, carrying out suction filtration to obtain a solid product, and finally carrying out freeze drying to obtain MPSA.
In one of the above-mentioned CoXIn the preparation method of the bifunctional catalyst with the P nano-particles embedded with nitrogen and phosphorus doped carbon, the concentration of the phytic acid solution is 65-75%.
In one of the above-mentioned CoXIn the preparation method of the bifunctional catalyst with the P nano particles embedded with nitrogen and phosphorus doped carbon, the mass ratio of melamine to phytic acid is 3 (4-5).
In one of the above-mentioned CoXIn the preparation method of the bifunctional catalyst with the P nano particles embedded with nitrogen and phosphorus doped with carbon, the temperature is raised to 850-950 ℃ at the heating rate of 3-8 ℃/min, and the temperature is kept for 2-3h and then cooled to room temperature along with the furnace. Different carbonization temperatures can affect the elemental content, morphology and structure of the catalyst, and thus the final catalytic performance.
CoXThe application of the bifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped with carbon in a rechargeable zinc-air battery comprises the steps of firstly dispersing the catalyst in a mixed solvent formed by absolute ethyl alcohol and Nafion, then carrying out ultrasonic dispersion to form ink, dripping the ink on hydrophobic carbon cloth, and drying to form a working electrode. The working electrode is used as an air electrode, the zinc sheet is used as a negative electrode, 6M KOH and 0.2M zinc acetate are used as electrolyte, and a zinc-air battery mould is adopted for assembly, so that the performance detection can be carried out.
In one of the above-mentioned CoXApplication of bifunctional catalyst with P nanoparticles embedded in nitrogen and phosphorus doped carbon in rechargeable zinc-air battery, and preparation method of bifunctional catalyst with Nafion solution and absolute ethyl alcohol in mixed solventThe volume ratio is 1: (10-12), the concentration of the Nafion solution is 5-8%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention carries out controllable synthesis of Co by adjusting the proportion of the precursors ZIF-67 and MPSA2P、Co2The bifunctional catalyst with P/CoP and CoP nanoparticles embedded in nitrogen and phosphorus doped carbon has excellent ORR/OER catalytic activity and stability.
(2) The invention prepares the Co-based transition metal phosphide embedded heteroatom-doped carbon composite catalyst by a simple and environment-friendly one-step carbonization method, and meanwhile, the method can also be suitable for preparing other heteroatom-doped carbon bifunctional catalysts derived from transition metal phosphide.
(3) Co prepared by the invention2P@NPC、CoP@NPC、Co2The P/CoP @ NPC catalyst is assembled in a zinc-air cell as a catalytic layer of the zinc-air cell, such that the zinc-air cell maintains excellent cycling stability during long-term charge and discharge cycles.
Drawings
FIG. 1 is a schematic diagram of catalysts prepared in examples 1-3 and comparative example 1;
FIG. 2 shows Co obtained in example 1 of the present invention2X-ray diffraction (XRD) pattern of P @ NPC catalyst;
FIG. 3 shows Co obtained in example 12Scanning Electron Microscope (SEM) images of the P @ NPC catalyst at different magnifications; (a) SEM images at low magnification; (b) SEM images at high magnification;
FIG. 4 shows Co obtained in example 12Transmission Electron Micrograph (TEM) of P @ NPC catalyst; (a) co2TEM image at low magnification of P @ NPC; (b) co2A high resolution transmission plot of P @ C nanoparticles;
FIG. 5 shows Co obtained in example 12An energy spectrum (EDS) diagram of a transmission electron microscope image of the P @ NPC catalyst, wherein (a), (b), (c) and (d) are C, N, Co and energy spectrums of P element distribution in sequence;
FIG. 6 shows Co obtained in example 12An X-ray photoelectron spectroscopy (XPS) plot of the P @ NPC catalyst; (a) a full spectrogram; (b) c1 s fine spectrum; (c) n1 s fine spectrum; (d)P2P fine spectrum; (e) a Co 2p fine spectrum;
FIG. 7 shows Co obtained in example 12A nitrogen adsorption and desorption curve and a pore size distribution diagram of the P @ NPC catalyst; (a) a nitrogen adsorption and desorption curve; (b) pore size distribution curve;
FIG. 8 shows Co obtained in example 2 of the present invention2X-ray diffraction (XRD) pattern of P/CoP @ NPC catalyst;
FIG. 9 shows Co obtained in example 22Scanning Electron Microscope (SEM) images of P/CoP @ NPC catalyst; (a) SEM images at low magnification; (b) SEM images at high magnification;
FIG. 10 shows Co obtained in example 22Transmission Electron Micrograph (TEM) of P/CoP @ NPC catalyst; (a) low power TEM images; (b) co2P nano-particle high resolution map; (c) CoP, Co2A high resolution TEM image of the P nanoparticles; (d) co2A P nanoparticle lattice fringe pattern; (e) a CoP nanoparticle lattice fringe pattern;
FIG. 11 shows Co obtained in example 22Transmission electron micrograph (EDS) of P/CoP @ NPC catalyst; (a) c, N, P and the energy spectrum of Co element distribution are sequentially formed in the steps of (b), (c) and (d);
FIG. 12 shows Co obtained in example 22An X-ray photoelectron spectroscopy (XPS) plot of the P/CoP @ NPC catalyst; (a) a full spectrogram; (b) c1 s fine spectrum; (c) n1 s fine spectrum; (d) P2P fine spectrum; (e) a Co 2p fine spectrum;
FIG. 13 shows Co obtained in example 22A nitrogen adsorption and desorption curve and a pore size distribution diagram of the P/CoP @ NPC catalyst; (a) a nitrogen adsorption and desorption curve; (b) an aperture distribution map;
FIG. 14 is an X-ray diffraction (XRD) pattern of the CoP @ NPC catalyst prepared in example 3;
FIG. 15 is a Scanning Electron Microscope (SEM) image of the CoP @ NPC catalyst prepared in example 3; (a) low power SEM image; (b) high power SEM image;
FIG. 16 is an X-ray photoelectron spectroscopy (XPS) plot of the CoP @ NPC catalyst prepared in example 3; (a) a full spectrogram; (b) c1 s fine spectrum; (c) n1 s fine spectrum, (d) P2P fine spectrum, (e) Co 2P fine spectrum;
FIG. 17 is a graph showing the nitrogen desorption curve and the pore size distribution of the CoP @ NPC catalyst prepared in example 3; (a) a nitrogen adsorption and desorption curve; (b) an aperture distribution map;
FIG. 18 is an X-ray diffraction (XRD) pattern of the Co @ NC catalyst prepared in comparative example 1;
FIG. 19 is a Scanning Electron Microscope (SEM) image of the Co @ NC catalyst prepared in comparative example 1; (a) SEM at low magnification, (b) SEM at high magnification;
FIG. 20 is an X-ray photoelectron spectroscopy (XPS) plot of a Co @ NC catalyst prepared in comparative example 1; (a) a full spectrogram; (b) c1 s fine spectrum; (c) n1 s fine spectrum; (d) a Co 2p fine spectrum;
FIG. 21 is a graph showing the nitrogen desorption curve and the pore size distribution of the Co @ NC catalyst prepared in comparative example 1; (a) a nitrogen adsorption and desorption curve; (b) an aperture distribution map;
FIG. 22 is a linear voltammogram of the oxygen reduction catalytic activity of the catalysts obtained in examples 1-3, comparative example 1;
FIG. 23 is a linear voltammogram of the oxygen evolution catalytic activity of the catalysts obtained in examples 1-3, comparative example 1;
FIG. 24 shows Co obtained in example 12A timing current curve corresponding to the P @ NPC composite catalyst and Pt/C;
FIG. 25 shows Co obtained in example 12P @ NPC composite catalyst and RuO2A corresponding timing voltage curve;
FIG. 26 shows Co obtained in example 12P @ NPC composite catalyst and Pt/C + RuO2Respectively used as power density curves of the zinc-air battery corresponding to the air electrode catalyst;
FIG. 27 shows Co in example 42P @ NPC is taken as a cyclic charge-discharge curve of a corresponding zinc-air battery of the air electrode catalyst;
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Preparation of ZIF-67: dissolving 7mmol of cobalt nitrate hexahydrate in 50mL of methanol to form a solution A, dissolving 10mmol of dimethyl imidazole in 50mL of methanol to form a solution B, introducing the solution A into the solution B, and continuously stirring for 10min to form a suspension. Standing the suspension at room temperature for 24h, centrifuging and washing the formed precipitate, washing with methanol for three times, drying in an oven at 60 ℃ for 6h to obtain ZIF-67, and placing in a drying vessel for later use.
Preparation of MPSA: dissolving 0.75g of melamine into 300mL of deionized water, adding 1g of 70% phytic acid solution into the solution after the melamine is completely dissolved, stirring for 30min, carrying out suction filtration on the suspension, freeze-drying the solid product obtained by suction filtration, and drying to obtain MPSA which is put into a drying vessel for later use.
Example 1
Mixing 300mg of ZIF-67 and 150mg of MPSA, grinding to uniformly mix the ZIF-67 and the MPSA, and putting the mixture into a tube furnace for high-temperature carbonization under the protection of nitrogen: heating to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature along with the furnace to obtain Co2P @ NPC catalyst.
Example 2:
mixing 300mg ZIF-67 and 300mg MPSA, grinding to uniformly mix the ZIF-67 and the MPSA, putting the mixture into a tube furnace, and performing high-temperature carbonization under the protection of nitrogen: heating to 890 ℃ at the heating rate of 4 ℃/min, preserving the temperature for 2h, and cooling to room temperature along with the furnace to obtain Co2P/CoP @ NPC catalyst.
Example 3:
mixing 300mg ZIF-67 and 450mg MPSA, grinding to uniformly mix the ZIF-67 and the MPSA, putting the mixture into a tube furnace, and performing high-temperature carbonization under the protection of nitrogen: heating to 910 ℃ at the heating rate of 6 ℃/min, preserving the temperature for 3h, and cooling to room temperature along with the furnace to obtain the CoP @ NPC catalyst.
Example 4:
10mg of Co prepared in example 1 were taken2The P @ NPC catalyst is dispersed in a mixed solvent formed by 1mL of absolute ethyl alcohol and 100 mu L of 5% nafion solution, and ultrasonic dispersion is carried out for 30min to form ink. 17 μ L of the ink was dropped onto a hydrophobic carbon cloth, and naturally dried to be used as a working electrode. The prepared working electrode is used as an air electrode, a zinc sheet is used as a negative electrode, 6M KOH and 0.2M zinc acetate are used as electrolytes, and the assembly is carried out by adopting a zinc-air battery mouldAnd (6) testing.
Example 5:
10mg of Co prepared in example 2 were taken2The P/CoP @ NPC catalyst is dispersed in a mixed solvent formed by 1mL of absolute ethyl alcohol and 100 mu L of 5% nafion, and ultrasonic dispersion is carried out for 30min to form ink. 17 μ L of the ink was dropped onto a hydrophobic carbon cloth, and naturally dried to be used as a working electrode. The prepared working electrode is used as an air electrode, a zinc sheet is used as a negative electrode, 6M KOH and 0.2M zinc acetate are used as electrolytes, and a zinc-air battery mould assembly is adopted for testing.
Example 6:
10mg of the CoP @ NPC catalyst prepared in example 3 was dispersed in a mixed solvent of 1mL of absolute ethanol and 100. mu.L of 5% nafion, and ultrasonically dispersed for 30min to form an ink. 17 μ L of the ink was dropped onto a hydrophobic carbon cloth, and naturally dried to be used as a working electrode. The prepared working electrode is used as an air electrode, a zinc sheet is used as a negative electrode, 6M KOH and 0.2M zinc acetate are used as electrolytes, and a zinc-air battery mould assembly is adopted for testing.
Comparative example 1:
300mg of ZIF-67 is put into a porcelain boat, the porcelain boat is put into a tube furnace, the temperature is increased to 900 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen, the temperature is kept at 900 ℃ for 2h, and then the porcelain boat is cooled along with the furnace, so that black powder, namely Co @ NC, is obtained.
Comparative example 2:
5mg of the CoP @ NPC catalyst prepared in comparative example 1 was dispersed in a mixed solvent of 1mL of absolute ethanol and 100. mu.L of 5% nafion, and ultrasonically dispersed for 30min to form an ink. 17mL of the ink was dropped onto a hydrophobic carbon cloth, and the ink was allowed to dry naturally and used as a working electrode. The prepared working electrode is used as an air electrode, a zinc sheet is used as a negative electrode, 6M KOH and 0.2M zinc acetate are used as electrolytes, and a zinc-air battery mould assembly is adopted for testing.
FIG. 1 is a schematic diagram of the preparation of composite catalysts of examples 1 to 3 and comparative example 1, when the mass ratio of ZIF-67 to MPSA is 1: 0.5, the catalyst contains Co nanoparticles2The form of P exists; when the mass ratio of ZIF-67 to MPSA is 1: 1 hour, Co2Partial transition of P to CoP, so that the nanoparticles in the catalyst are Co2Of P/CoPThe form exists; when the mass ratio of ZIF-67 to MPSA is 1: 1.5 times, Co2P is completely transited to CoP, so that the nanoparticles in the catalyst exist in the form of CoP; the nanoparticles in the catalyst prepared directly by ZIF-67 were present in the form of Co.
Co prepared in example 12The XRD diffractogram of P @ NPC is shown in FIG. 2, where typical Co is present2Diffraction peak of P phase, which proves that the prepared catalyst contains Co2And P. FIG. 3 is Co2SEM images of P @ NPC at different magnifications, from which Co can be seen2P @ NPC is an irregular polyhedral structure, and metal particles are uniformly distributed on the irregular polyhedral structure. In FIG. 4, (a) and (b) are Co2TEM and HRTEM of P @ NPC, evidence of Co2The P nano-particles are coated in 3-4 graphitic carbon layers. FIG. 5 shows Co2EDS diagram of P @ NPC, it can be seen that C, N, Co and P elements are uniformly distributed. FIG. 6 shows Co2XPS plot of P @ NPC, further demonstrating Co2The presence of C, N, Co and P four elements and N and P elements in P @ NPC is doped into the carbon skeleton. FIG. 7 shows Co2The nitrogen adsorption and desorption curve and the pore size distribution diagram corresponding to the P @ NPC show that the P @ NPC is a typical mesoporous material, and a hierarchical pore structure of micropores and macropores also exists.
Example 2 Co preparation2The XRD diffractogram of P/CoP @ NPC is shown in FIG. 8, demonstrating Co2Co in P/CoP2Two phases, P and CoP. FIG. 9 shows Co2P/CoP @ NPC Scanning Electron Microscope (SEM) picture, it can be seen from the figure that the irregular polyhedral structure begins to collapse, and metal particles with uneven sizes are distributed on the spherical-like nanoparticles. FIG. 10 shows Co2TEM and HRTEM images of P/CoP @ NPC demonstrated at Co2P/CoP @ NPC Co-Presence2P nanoparticles and Co2P/CoP composite nanoparticles. FIG. 11 shows Co2EDS diagram of P/CoP @ NPC, which demonstrates C, N, P, Co that four elements are evenly distributed. FIG. 12 shows Co2The XPS plot of P/CoP @ NPC also confirms the presence of the 4 elements described above and the doping of the N and P elements into the carbon skeleton. FIG. 13 shows Co2The P/CoP @ NPC nitrogen adsorption and desorption curve and the corresponding pore size distribution diagram prove that the mesoporous material is a typical mesoporous material.
The X-ray diffraction (XRD) pattern of the CoP @ NPC prepared in example 3 is shown in FIG. 14, and a typical CoP phase diffraction peak exists in the XRD pattern, so that the CoP is contained in the prepared catalyst. FIG. 15 is an SEM image of CoP @ NPC at different magnifications, from which it can be seen that CoP @ NPC is an irregular polyhedral structure on which metal particles are uniformly distributed. FIG. 16 is an XPS plot of CoP @ NPC, further demonstrating that C, N, Co and four elements P and N and P are present in CoP @ NPC doped into the carbon backbone. Fig. 17 is a nitrogen adsorption/desorption curve and a pore size distribution diagram corresponding thereto, and it is confirmed that it is also a typical mesoporous material, and a hierarchical pore structure of both micropores and macropores is present.
The X-ray diffraction (XRD) pattern of the Co @ NC catalyst prepared in comparative example 1 is shown in fig. 18, demonstrating that direct carbonization of ZIF-67 forms metallic Co simple substance. The corresponding SEM images at different magnifications are shown in fig. 19, and it can be seen that Co @ NC is an irregular polyhedral structure on which metal particles are distributed. Fig. 20 is an X-ray photoelectron spectroscopy (XPS) picture corresponding to Co @ NC, where C: 1s, O: 1s, N: 1s and Co: 2p, demonstrating the presence of the element in 4 above in Co @ NC. FIG. 21 is a graph of the nitrogen desorption curve and pore size distribution of Co @ NC, which shows that Co @ NC is a typical mesoporous material.
From FIG. 22, Co can be seen2P @ NPC has a slightly poorer initial potential than Pt/C, but has an ORR catalytic activity superior to that of other comparative samples, in which Co2The ORR catalytic activity of P/CoP @ NPC and CoP @ NPC is significantly reduced.
From FIG. 23, Co can be seen2OER catalytic activity of P/CoP @ NPC is optimal, Co2P @ NPC, where Co2The OER catalytic activity of P @ NPC is superior to that of Co2P @ NPC, description of Co2The OER intrinsic catalytic activity of P is superior to that of CoP.
From FIG. 24, Co can be seen2After the P @ NPC is subjected to a stability test for 20h, the current density is still maintained at 90%, and the Pt/C is reduced to 70%, indicating that Co2The ORR catalytic stability of P @ NPC is superior to that of Pt/C.
From FIG. 25, it can be seen that at 10mA cm-2At a current density of (2), sample Co2P @ NPC was tested for 24h stability at a voltage of 1.56V to 1.60V and at a 40mV increase, versus a RuO sample2After 12h of test, the voltage of the material is increased by 50mV, which shows that Co2The OER catalytic stability of P @ NPC is superior to that of RuO2。
From FIG. 26, Co can be seen2The power density of a zinc-air battery with P @ NPC as an air electrode catalyst is 157mW cm-2Greater than Pt/C + RuO2Power Density (100mW cm) of Zinc air cell assembled as air electrode catalyst-2)。
From FIG. 27, it can be seen that Co2Zinc air battery with P @ NPC as air electrode catalyst at 10mA cm-2The current density of the battery can keep good charge-discharge cycle stability, and the charge-discharge voltage does not change obviously after 140 hours of charge-discharge cycle.
In conclusion, the invention carries out controllable synthesis of Co by adjusting the proportion of the precursors ZIF-67 and MPSA2P、Co2The bifunctional composite catalyst with the P/CoP and CoP nanoparticles embedded in nitrogen and phosphorus doped carbon has excellent ORR/OER catalytic activity and stability. When the zinc-air battery electrolyte is applied to a zinc-air battery, good cycle stability can be kept in a long-time charge-discharge cycle process, and the potential application prospect of the zinc-air battery electrolyte in a rechargeable zinc-air battery is shown.
The technical scope of the invention claimed by the embodiments of the present application is not exhaustive, and new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the invention claimed by the present application; in all the embodiments of the present invention, which are listed or not listed, each parameter in the same embodiment only represents an example (i.e., a feasible embodiment) of the technical solution, and there is no strict matching and limiting relationship between the parameters, wherein the parameters may be replaced with each other without departing from the axiom and the requirements of the present invention, unless otherwise specified.

Claims (10)

1. CoXP nanoparticles intercalating nitrogenAnd phosphorus-doped carbon, characterized in that said Co isXP nanoparticles are Co2One or both of P and CoP.
2. Co as claimed in claim 1XThe preparation method of the bifunctional catalyst with the P nano particles embedded with nitrogen and phosphorus doped carbon is characterized by comprising the following steps of: mixing and grinding ZIF-67 and MPSA, and then carbonizing at high temperature in nitrogen to obtain the composite catalyst.
3. Co according to claim 2XThe preparation method of the bifunctional catalyst with the P nanoparticles embedded with nitrogen and phosphorus doped carbon is characterized in that the mass ratio of ZIF-67 to MPSA is 1: (0.5-1.5).
4. A Co according to claim 2 or 3XThe preparation method of the bifunctional catalyst with the P nano particles embedded with nitrogen and phosphorus doped carbon is characterized in that the preparation method of the ZIF-67 comprises the following steps: firstly, respectively dissolving cobalt nitrate hexahydrate and dimethylimidazole in methanol to form a solution, then mixing the cobalt nitrate hexahydrate and the dimethylimidazole to form a turbid liquid, standing to obtain a precipitate, centrifuging and washing the precipitate, then washing with methanol, and finally drying to obtain the ZIF-67.
5. A Co according to claim 2 or 3XThe preparation method of the bifunctional catalyst with the P nano particles embedded with nitrogen and phosphorus doped carbon is characterized in that the preparation method of the MPSA comprises the following steps: dissolving melamine in deionized water, adding phytic acid solution after the melamine is completely dissolved, stirring, carrying out suction filtration to obtain a solid product, and finally carrying out freeze drying to obtain MPSA.
6. Co according to claim 5XThe preparation method of the bifunctional catalyst with the P nano particles embedded with nitrogen and phosphorus doped carbon is characterized in that the concentration of the phytic acid solution is 65-75%.
7. The method of claim 5CoXThe preparation method of the bifunctional catalyst with the P nano particles embedded with nitrogen and phosphorus doped carbon is characterized in that the mass ratio of melamine to phytic acid is 3: (4-5).
8. Co according to claim 2XThe preparation method of the bifunctional catalyst with the P nano particles embedded with nitrogen and phosphorus doped with carbon is characterized in that the temperature rise rate of the high-temperature carbonization is increased to 850-950 ℃ at the speed of 3-8 ℃/min, and the temperature is kept for 2-3h and then cooled to room temperature along with the furnace.
9. Co as claimed in claim 1XThe application of the bifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon in a rechargeable zinc-air battery is characterized in that the catalyst is dispersed in a mixed solvent formed by absolute ethyl alcohol and Nafion solution, then the catalyst is subjected to ultrasonic dispersion to form ink, the ink is dripped onto hydrophobic carbon cloth, and the working electrode is formed after the ink is dried.
10. Co according to claim 9XThe application of the bifunctional catalyst with P nanoparticles embedded into nitrogen and phosphorus doped carbon in a rechargeable zinc-air battery is characterized in that the volume ratio of Nafion solution to absolute ethyl alcohol in a mixed solvent is 1: (10-12), the concentration of the Nafion solution is 5-8%.
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