CN114094127A - Cobaltoside phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material and preparation method thereof - Google Patents

Cobaltoside phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material and preparation method thereof Download PDF

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CN114094127A
CN114094127A CN202111340963.2A CN202111340963A CN114094127A CN 114094127 A CN114094127 A CN 114094127A CN 202111340963 A CN202111340963 A CN 202111340963A CN 114094127 A CN114094127 A CN 114094127A
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nitrogen
doped carbon
solution
composite material
phosphorus doped
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郭兴梅
史静
张俊豪
刘山靖
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Jiangsu University of Science and 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a cobaltous phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material and a preparation method thereof. The composite material is composed of nitrogen and phosphorus doped carbon nanospheres with cobaltous phosphide nanoparticles dispersed in a matrix, wherein the size of the cobaltous phosphide nanoparticles is 5-20 nm and accounts for 0-15 wt% of the total mass of the composite material, and the diameter of the nitrogen and phosphorus doped carbon nanospheres serving as the matrix is 150-350 nm. The preparation method comprises the following steps: dissolving dopamine and F127 in a mixed solvent of water and ethanol to obtain a solution A, dissolving hexachlorocyclotriphosphazene in mesitylene to obtain a solution B, slowly adding the solution B into the solution A, and fully stirring to form a microemulsion; adding ammonia water to polymerize dopamine to form polydopamine nanospheres with a layer of hexachlorocyclotriphosphazene assembled on the surface, soaking in a cobalt chloride solution to introduce cobalt ions, freeze-drying, and calcining in an inert atmosphere to obtain the cobaltous phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material.

Description

Cobaltoside phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of electrocatalytic materials, and particularly relates to Co2P nanoparticle/nitrogen phosphorus doped carbon nanosphereComposite materials and methods for making the same.
Background
The metal-air battery has the advantages of high specific energy, good safety, stable performance and the like, but the key factor for limiting the energy conversion efficiency is the slow reaction kinetics of the anode Oxygen Reduction Reaction (ORR). Although commercial Pt/C catalysts have excellent ORR electrocatalytic activity, the problems of high cost and low stability make them impractical for large-scale applications. Therefore, the research and development of the low-cost and high-performance non-noble metal ORR electrocatalyst is a necessary way for improving the energy conversion efficiency of the metal-air battery and promoting the commercial development of the metal-air battery.
Owing to the multiple valence states and excellent electron accepting and donating ability of transition metals, transition metal compounds are the most commonly studied non-noble metal ORR electrocatalysts, such as oxides, nitrides, phosphides, sulfides, etc. However, they are semiconductor materials and often need to be compounded with a conductive carbon matrix to achieve rapid electron transport in the electrocatalytic process. Among them, the most efficient means of complexing is to support the compound in the form of fine nanoparticles in a carbon matrix, to more fully contact the electrolyte and to maintain the dispersibility of the active sites. However, it is not easy to realize this design, especially for nitride, phosphide, sulfide, etc., it is common to prepare oxide and hydroxide first, and then proceed with subsequent nitridation, phosphorization, and sulfidation, etc., the process is tedious, and the high temperature transformation process is prone to grain growth and morphology evolution, and it is difficult to obtain fine and firmly-loaded particles. Therefore, it is very important to develop a method for generating fine nanocrystals of nitrides, phosphides, and sulfides in situ and firmly supporting them in a carbon matrix.
In addition, the carbon substrate is introduced with a heteroatom such as N, P, S, which can further improve the electrocatalytic performance. If hetero atoms can be introduced into the carbon matrix in the process of in-situ generation of the compound nanocrystal, the method has important significance for obtaining the high-performance electrocatalyst.
Disclosure of Invention
The present invention has been made to overcome the above problems and disadvantages of the prior art, and an object of the present invention is to provide a Co alloy2P nanoparticles/Nitrogen phosphorus dopingA heterocarbon nanosphere composite material and a preparation method thereof.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
Co nanoparticles/nitrogen-phosphorus doped carbon nanosphere composite material formed by dispersing Co in matrix2Nitrogen and phosphorus doped carbon nanospheres of P nanoparticles, wherein Co2The diameter of the P nano-particles is 5-20 nm, the P nano-particles account for 0.1-15 wt% of the total mass of the composite material, and the diameter of the nitrogen-phosphorus doped carbon nanospheres serving as the matrix is 150-350 nm.
In order to achieve the above purpose, the present invention is realized by adopting another technical scheme as follows.
A preparation method of cobaltous phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material comprises the following steps:
(1) preparation of microemulsion precursor
Dissolving dopamine and F127 together in a mixed solvent of water and ethanol to obtain a solution A, wherein the volume ratio of water to ethanol is 1: 0.5-2, and the mass concentration of the dissolved dopamine is 2-10 g L-1The mass concentration of F127 is 5-15 g L-1(ii) a Dissolving hexachlorocyclotriphosphazene in mesitylene to obtain a solution B, wherein the mass concentration of the dissolved hexachlorocyclotriphosphazene is 100-150 g L-1(ii) a And slowly adding the solution B into the solution A, controlling the volume ratio of the solution B to the solution A to be 1: 50-100, and fully stirring to form the microemulsion.
(2) Polydopamine nanosphere with surface rich in nitrogen and phosphorus obtained by polymerization-self-assembly
Adding ammonia water into the microemulsion, controlling the volume ratio of the ammonia water to the microemulsion to be 1: 10-20, fully stirring to polymerize dopamine into a spherical structure, wherein the surface of the spherical structure is surrounded by F127, the hydrophilic end of the F127 is embedded into a polydopamine nanosphere, and the lipophilic end enriched with a large amount of hexachlorocyclotriphosphazene mesitylene solution is exposed outside, and freeze-drying at-20 to-80 ℃ to obtain the polydopamine nanosphere with the surface enriched with nitrogen and phosphorus.
(3) Soaking-calcining to obtain Co2P nanoparticle/nitrogen phosphorus doped carbon nanosphere
The poly dopamine nanospheres with rich nitrogen and phosphorus on the surface are concentrated8 to 25mmol L-1Soaking in cobalt salt solution for 12-24 h to enable the internal hydrophilic structure of the polydopamine sphere to adsorb cobalt ions, washing with water and ethanol, freeze-drying at-20 to-80 ℃, and finally, in an inert atmosphere, performing freeze-drying at 0.5-10 ℃ for min-1Calcining at the heating rate of 700-900 ℃, preserving heat for 1-3 h, and naturally cooling to obtain Co2P nanoparticle/N-P doped carbon nanospheres.
Further preferably, the volume ratio of the water and ethanol mixed solvent in the step (1) is 1: 1.
Further preferably, the cobalt salt solution in the step (3) is an aqueous solution of cobalt chloride, an aqueous solution of cobalt nitrate or an aqueous solution of cobalt acetate.
Further preferably, the inert atmosphere in step (3) is nitrogen or argon.
Further preferably, the volume ratio of the water and ethanol mixed solvent in the step (3) is 1: 1.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention adopts an improved nano microemulsion assembly-calcination method to prepare and obtain the load fine Co in situ2N, P doped carbon nanospheres of P nanoparticles. The preparation method is simple and efficient, and the obtained phosphide particles are fine, dispersed and firmly loaded in the N, P doped carbon nanospheres, so that rich active sites are provided, and high ORR electrocatalytic activity and stability are obtained. The zinc-air battery assembled by using the zinc-air composite anode catalyst has high open-circuit voltage, high energy and power density and high stability.
Drawings
FIG. 1 shows Co in example 12Scanning Electron Microscopy (SEM) image of P/NP-C-800.
FIG. 2 shows Co in example 12X-ray diffraction (XRD) pattern of P/NP-C-800.
FIG. 3 shows Co in example 12Transmission Electron Microscopy (TEM) image of P/NP-C-800.
FIG. 4 shows Co in example 12P/NP-C-800 high resolution lattice diagram (a) and element distribution diagram (b-f).
FIG. 5 shows Co in example 12XPS full spectrum (a) and Co 2P high resolution of P/NP-C-800Spectrum (b), N1s high-resolution spectrum (c), P2P high-resolution spectrum (d).
FIG. 6 shows Co prepared in example 12LSV curves for P/NP-C-800 and commercial Pt/C in oxygen saturated KOH solutions at a scan rate of 10mV s-1The rotation speed is 1600 rpm.
FIG. 7 shows Co prepared in example 12The current-time curves for P/NP-C-800 and commercial Pt/C and the current-time for methanol addition at 500-600 s.
FIG. 8 shows a zinc-air cell testing apparatus (a), Co, assembled in example 12Discharge polarization curves and corresponding power densities (b), open circuit voltage-time curves (C), at 10mA cm for P/NP-C-800 and commercial Pt/C as positive electrode catalysts for zinc-air cells-2The following constant current discharge curve (d), specific capacity (normalized to the mass of Zn consumed) (e), discharge curve at different current densities (f).
FIG. 9 shows Co in example 22SEM image of P/NP-C-700.
FIG. 10 shows Co in example 22XRD spectrum of P/NP-C-700.
FIG. 11 shows Co prepared in example 22LSV curves for P/NP-C-700 and commercial Pt/C in oxygen saturated KOH solution at a scan rate of 10mV s-1The rotation speed is 1600 rpm.
FIG. 12 shows Co in example 32SEM image of P/NP-C-900.
FIG. 13 shows Co in example 32XRD spectrum of P/NP-C-900.
FIG. 14 shows Co prepared in example 32LSV curves for P/NP-C-900 and commercial Pt/C in oxygen saturated KOH solution at a scan rate of 10mV s-1The rotation speed is 1600 rpm.
FIG. 15 is an SEM photograph of NP-C from example 4.
FIG. 16 is an XRD spectrum of NP-C from example 4.
FIG. 17 is an LSV curve of NP-C prepared in example 4 and commercial Pt/C in oxygen saturated KOH solution at a scan rate of 10mV s-1The rotation speed is 1600 rpm.
FIG. 18 shows Co in example 52SEM picture of P/NP-C (0.4 mM).
FIG. 19 shows Co in example 52XRD pattern of P/NP-C (0.4 mM).
FIG. 20 shows Co prepared in example 52LSV curves for P/NP-C (0.4mM) and commercial Pt/C in oxygen saturated KOH solution at a scan rate of 10mV s-1The rotation speed is 1600 rpm.
FIG. 21 shows Co in example 62SEM picture of P/NP-C (0.6 mM).
FIG. 22 shows Co in example 62XRD pattern of P/NP-C (0.6 mM).
FIG. 23 shows Co prepared in example 62LSV curves for P/NP-C (0.6mM) and commercial Pt/C in oxygen saturated KOH solution at a scan rate of 10mV s-1The rotation speed is 1600 rpm.
FIG. 24 shows Co in example 72SEM picture of P/NP-C (0.8 mM).
FIG. 25 shows Co in example 72XRD pattern of P/NP-C (0.8 mM).
FIG. 26 is Co prepared in example 72LSV curves for P/NP-C (0.8mM) and commercial Pt/C in oxygen saturated KOH solution at a scan rate of 10mV s-1The rotation speed is 1600 rpm.
FIG. 27 shows Co in example 82SEM picture of P/NP-C (1.2 mM).
FIG. 28 shows Co in example 82XRD pattern of P/NP-C (1.2 mM).
FIG. 29 shows Co prepared in example 82LSV curves for P/NP-C (1.2mM) and commercial Pt/C in oxygen saturated KOH solution at a scan rate of 10mV s-1The rotation speed is 1600 rpm.
Detailed Description
In order to better understand the technical solution and the advantages of the present invention, the following is further illustrated by specific examples.
Example 1:
Co2preparation of P/NP-C-800 composite material:
(1) preparation of microemulsion precursor
Dissolving 0.25g of dopamine and 0.5g F127 in 50mL of solvent (water: ethanol ═ 1:1), and vigorously stirring at room temperature to obtain a solution a; dissolving 0.15g of hexachlorocyclotriphosphazene in 1mL of mesitylene to obtain a solution B; slowly adding the solution B into the solution A, and stirring for 30min to form the microemulsion.
(2) Polydopamine nanosphere with surface rich in nitrogen and phosphorus obtained by polymerization-self-assembly
And (3) dropwise adding 3mL of ammonia water (25-28%) into the microemulsion, and continuously stirring for 3h to polymerize dopamine so as to obtain the polydopamine nanosphere with the surface enriched with hexachlorocyclotriphosphazene.
(3) Soaking-calcining to obtain Co2P nanoparticle/nitrogen phosphorus doped carbon nanosphere
0.25g of CoCl2·6H2Adding O into the polydopamine nanosphere dispersion liquid, and soaking for 12 hours; washing with water and ethanol by centrifugation for three times, freeze drying at-60 deg.C for 12 hr, and adding N2Atmosphere at 1 ℃ min-1Raising the temperature from room temperature to 800 ℃, preserving the heat for 3 hours, and naturally cooling to obtain Co2P nanoparticles/N-P doped carbon nanospheres, labeling the sample as Co2P/NP-C-800。
FIG. 1 shows Co obtained in this example2SEM image of P/NP-C-800 sample, which is in the shape of nanosphere with diameter of-300 nm. FIG. 2 shows the Co obtained in this example2The XRD pattern of the P/NP-C-800 sample proves that the obtained nanosphere contains Co2And crystallizing the compound P. FIG. 3 shows Co of this example2TEM image of P/NP-C-800 sample, more clearly reflects the nanosphere structure of the material. FIG. 4a shows Co of this example2High resolution TEM image of P/NP-C-800, further observing the detailed structure inside the nanosphere, wherein 0.236nm spaced lattice fringes correspond to Co2The (121) plane of P. Fig. 4b-f are the elemental distribution diagrams of the sample of this example, which shows that the Co, P, C and N elements are uniformly dispersed in the nanosphere matrix.
FIG. 5a shows Co of this example2The XPS full spectrum of P/NP-C-800 further shows that the material contains C, N, O, Co and P elements; FIG. 5b shows Co 2p of this example3/2High resolution spectrum, indicating that the cobalt element is mainly Co3+、Co2+And Co0Exists in the form of (1); FIG. 5c shows the high resolution spectrum of N1s for pyridine nitrogen and pyrrole nitrogen in the sample of this exampleThe nitrogen and nitrogen oxide signals of the graphite-like structure prove the existence of N doping in the carbon matrix; FIG. 5d is the P2P high resolution spectrum of the sample of this example, where P-C and P-O are mainly from P-doped atoms in the matrix, and P-O is from Co2Particles of the P compound.
Electro-catalytic oxygen reduction and zinc-air battery performance test:
the obtained catalyst is subjected to ORR electro-catalysis performance test under the alkaline (0.1mol/L KOH) condition by adopting a three-electrode system, and a working electrode is loaded with Co2The counter electrode of the P/NP-C-800 rotating disk electrode is a graphite rod, and the reference electrode is an Hg/HgO electrode. FIG. 6 shows Co of this example2Polarization curves for electrocatalytic oxygen reduction reactions of P/NP-C-800 and commercial Pt/C (20 wt%) (rotation speed of the rotating disk electrode was 1600 rpm). From the figure, Co2The initial potential of P/NP-C-800 was 0.90V vs. RHE, and the half-wave potential was 0.81V vs. RHE, both close to commercial Pt/C (0.95V vs. RHE and 0.80V vs. RHE, respectively). FIGS. 7a and b are views of Co of this example2Constant potential sweep current versus time curves for P/NP-C-800 and Pt/C in KOH electrolyte and KOH electrolyte with methanol added during the test, it can be seen that Co2The stability and methanol tolerance of the P/NP-C-800 are much better than those of commercial Pt/C, and the P/NP-C-800 is expected to be an alternative material of a Pt/C catalyst in the future.
Zinc sheet as negative electrode and Co-loaded2Carbon paper of P/NP-C catalyst (load is 1mg cm)-2) As the positive electrode, 6M KOH +0.2M Zn (OAc)2The mixed solution of (2) is an electrolyte, and a zinc-air battery is assembled for testing. While a commercial Pt/C catalyst was used as a comparative catalyst, a zinc air cell was assembled under the same conditions and tested, and the device structure is shown in FIG. 8 a. FIG. 8b is a polarization curve and power density curve of the assembled cell of this example, wherein Co2The peak power density of the P/NP-C-800 cell was 152mW cm-2Is superior to commercial Pt/C battery (131.7mW cm)-2). FIG. 8c is a graph of the open circuit voltage versus time, Co, of this embodiment2The open-circuit voltage of the P/NP-C-800 battery is gradually increased along with time, is equivalent to Pt/C after 20h, and is stabilized at 1.4V. FIG. 8d shows Co of this example2P/NP-C-800 cell at 10mA cm-2Constant current at a current density ofDischarge curve, show very good stability. In addition, as shown in FIG. 8e, at 10mA cm-2At a current density of (C), Co2The specific capacity of the P/NP-C-800 battery is 1096.7mAh gZn -1Corresponding to an energy density of 1286.0Wh kgZn -1This value is higher than Pt/C (931.2mAh gZn -1And 1146.2Wh kgZn -1). FIG. 8f shows the present example at 5, 10, 25 and 50mA cm-2Discharge curve of (Co)2Both the P/NP-C-800 and Pt/C air cathode cells exhibited a tendency for the discharge voltage to plateau and decrease with increasing current density, exhibiting excellent rate performance.
Example 2
Co2Preparation and testing of P/NP-C-700 composite:
the difference from example 1 is that in step (3), the sample is subjected to N2Raising the temperature from room temperature to 800 ℃ in the atmosphere, and changing the sample into N2The sample obtained is marked Co, increasing from room temperature to 700 ℃ in an atmosphere2P/NP-C-700. Fig. 9 is an SEM image of the sample of this example, which shows that the material obtained is also in the shape of nanospheres when the calcination temperature is 700 ℃. FIG. 10 is an XRD pattern of the sample of this example, which has two steamed bread peaks at about 24 and 44 degrees, which are derived from the locally graphitized component of the carbon matrix, and diffraction peaks appearing at other positions corresponding to Co2The P component, the diffraction peak is not significant compared with the sample calcined at 800 ℃ because of Co generated at 700 ℃ calcination2The crystallinity of P is not high. FIG. 11 shows Co of this example2Polarization curves (1600rpm) for electrocatalytic oxygen reduction reactions of P/NP-C-700 and commercial Pt/C. From the figure, Co2The limiting current density of the P/NP-C-700 was 3.70mA/cm2The initial potential was 0.85V vs. rhe, and the half-wave potential was 0.76V vs. rhe.
Example 3
Co2Preparation and testing of P/NP-C-900 composite material:
the difference from example 1 is that in step (3), the sample is subjected to N2Raising the temperature from room temperature to 800 ℃ in the atmosphere, and changing the sample into N2Increasing the temperature from room temperature to 900 ℃ in an atmosphereArticle label Co2P/NP-C-900. Fig. 12 is an SEM image of the sample of this example, and it can be seen that the spherical feature can be seen although the partial structure is disordered when the calcination temperature is 900 ℃. FIG. 13 is an XRD pattern of the sample of this example, where sharp Co was visible2P diffraction peak, indicating that the compound was well crystallized. FIG. 14 shows Co of this example2Polarization curves (1600rpm) for electrocatalytic oxygen reduction reactions of P/NP-C-900 and commercial Pt/C. From the figure, Co2The limiting current density of the P/NP-C-900 was 4.18mA/cm2The initial potential was 0.82V vs. rhe, and the half-wave potential was 0.78V vs. rhe.
Example 4
Preparation and testing of NP-C:
the difference from example 1 is that in step (3), "0.25 g of CoCl2·6H2Adding O into the polydopamine nanosphere dispersion liquid, omitting the operation of soaking for 12h ″, directly centrifugally cleaning the polydopamine nanospheres with rich nitrogen and phosphorus on the surfaces obtained in the step (2), freeze-drying, and performing freeze-drying on the polydopamine nanospheres in the presence of N2Raising the temperature from room temperature to 800 ℃ in the atmosphere, and preserving the temperature for 3h to obtain NP-C. FIG. 15 is an SEM image of a sample of this example, in which CoCl is not observed2·6H2The carbon spheres calcined by soaking in the O solution have uniform shapes and are in a nano spherical structure with the diameter of 300 nm. FIG. 16 is an XRD pattern of a sample of this example, showing that NP-C contains no compound crystals. FIG. 17 is a polarization curve (1600rpm) for the electrocatalytic oxygen reduction reaction of NP-C and commercial Pt/C of this example. It can be seen that the limiting current density of NP-C is 1.59mA/cm2The initial potential was 0.82V vs. RHE, the half-wave potential was 0.77V vs. RHE, and the electrocatalytic activity was poor because NP-C was not loaded with Co2The reason for P.
Example 5
Co2A preparation method and application of a P/NP-C (0.4mM) composite material are as follows:
the difference from example 1 is that 0.25g of CoCl was added in step (3)2·6H2Changing O to 0.1g CoCl2·6H2O (0.4mM), the sample obtained being marked Co2P/NP-C (0.4 mM). FIG. 18 is an SEM image of a sample of this example, showing that the morphology of the material is regular,is in a nano-sphere shape. FIG. 19 is an XRD pattern of a sample of this example demonstrating the conversion of cobalt ions to Co2And P. FIG. 20 shows Co of this example2Polarization curves (1600rpm) for electrocatalytic oxygen reduction reactions of P/NP-C (0.4mM) and commercial Pt/C. From the figure, Co2The limiting current density of P/NP-C (0.4mM) was 4.33mA/cm2The initial potential was 0.88V vs. RHE, and the half-wave potential was 0.77V vs. RHE.
Example 6
Co2Preparation method and application of P/NP-C (0.6mM) composite material:
the difference from example 1 is that 0.25g of CoCl was added in step (3)2·6H2Changing O to 0.15g CoCl2·6H2O (0.6mM), the sample obtained being marked Co2P/NP-C (0.6 mM). The SEM image of the obtained sample is shown in fig. 21, and the nano-spherical structure can be seen. FIG. 22 is an XRD pattern of a sample of this example illustrating the conversion of cobalt ions to Co2And P. FIG. 23 shows Co of this example2Polarization curves (1600rpm) for electrocatalytic oxygen reduction reactions of P/NP-C (0.6mM) and commercial Pt/C. Co2The limiting current density of P/NP-C (0.6mM) was 4.34mA/cm2The initial potential was 0.89V vs. rhe, and the half-wave potential was 0.80V vs. rhe.
Example 7
Co2Preparation method and application of P/NP-C (0.8mM) composite material:
the difference from example 1 is that 0.25g of CoCl was added in step (3)2·6H2Changing O to 0.2g CoCl2·6H2O (0.8mM), the sample obtained being marked Co2P/NP-C (0.8 mM). The SEM image of the obtained sample is shown in fig. 24, and the nano-spherical structure can be seen. FIG. 25 is an XRD pattern of a sample of this example, illustrating the conversion of cobalt ions to Co2And P. FIG. 26 shows Co of this example2Polarization curves (1600rpm) for electrocatalytic oxygen reduction reactions of P/NP-C (0.8mM) and commercial Pt/C. Co2The limiting current density of P/NP-C (0.8mM) was 4.48mA/cm2The initial potential was 0.90V vs. rhe, and the half-wave potential was 0.80V vs. rhe.
Example 8
Co2P/NP-C (1.2mM) compositeThe preparation method and the application thereof are as follows:
the difference from example 1 is that 0.25g of CoCl was added in step (3)2·6H2Changing O to 0.29g CoCl2·6H2O (1.2mM), the sample obtained being marked Co2P/NP-C (1.2 mM). The SEM image of the obtained sample is shown in fig. 27, and a nano-spherical structure can be seen. FIG. 28 is an XRD pattern of a sample from this example, illustrating the conversion of cobalt ions to Co2And P. FIG. 29 shows Co of this example2Polarization curves (1600rpm) for electrocatalytic oxygen reduction reactions of P/NP-C (1.2mM) and commercial Pt/C. Co2The limiting current density of P/NP-C (1.2mM) was 4.55mA/cm2The initial potential was 0.90V vs. rhe, and the half-wave potential was 0.78V vs. rhe.
The foregoing examples illustrate the principles and features of the present invention in detail, but the invention is not limited to the embodiments. Based on the embodiments of the present invention, those skilled in the art can make modifications and variations to the present invention, but these modifications and variations are limited in the scope of the present invention.

Claims (6)

1. The cobaltous phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material is characterized in that Co is dispersed in a matrix2Nitrogen and phosphorus doped carbon nanospheres of P nanoparticles, wherein Co2The diameter of the P nano-particles is 5-20 nm, the P nano-particles account for 0.1-15 wt% of the total mass of the composite material, and the diameter of the nitrogen-phosphorus doped carbon nanospheres serving as the matrix is 150-350 nm.
2. The preparation method of the cobaltous phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material as set forth in claim 1, wherein the preparation method comprises the following steps:
(1) preparation of microemulsion precursor
Dissolving dopamine and F127 together in a mixed solvent of water and ethanol to obtain a solution A, wherein the volume ratio of water to ethanol is 1: 0.5-2, and the mass concentration of the dissolved dopamine is 2-10 g L-1The mass concentration of F127 is 5-15 g L-1(ii) a Dissolving hexachlorocyclotriphosphazene in mesitylene to obtain solution BThe mass concentration of the hexachlorocyclotriphosphazene after dissolution is 100-150 g L-1(ii) a Slowly adding the solution B into the solution A, controlling the volume ratio of the solution B to the solution A to be 1: 50-100, and fully stirring to form a microemulsion;
(2) polydopamine nanosphere with surface rich in nitrogen and phosphorus obtained by polymerization-self-assembly
Adding ammonia water into the microemulsion, controlling the volume ratio of the ammonia water to the microemulsion to be 1: 10-20, fully stirring to polymerize dopamine into a spherical structure, wherein the surface of the spherical structure is surrounded by F127, the hydrophilic end of the F127 is embedded into a polydopamine nanosphere, and the lipophilic end enriched with a large amount of hexachlorocyclotriphosphazene mesitylene solution is exposed outside, and freeze-drying at-20 to-80 ℃ to obtain the polydopamine nanosphere with the surface enriched with nitrogen and phosphorus;
(3) soaking-calcining to obtain Co2P nanoparticle/nitrogen phosphorus doped carbon nanosphere
The concentration of the polydopamine nanospheres with rich nitrogen and phosphorus on the surface is 8-25 mmol L-1Soaking in cobalt salt solution for 12-24 h to enable the internal hydrophilic structure of the polydopamine sphere to adsorb cobalt ions, washing with water and ethanol, freeze-drying at-20 to-80 ℃, and finally, in an inert atmosphere, performing freeze-drying at 0.5-10 ℃ for min-1Calcining at the heating rate of 700-900 ℃, preserving heat for 1-3 h, and naturally cooling to obtain Co2P nanoparticle/N-P doped carbon nanospheres.
3. The preparation method of the cobaltous phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material as claimed in claim 2, wherein the volume ratio of the water and ethanol mixed solvent in the step (1) is 1: 1.
4. The method for preparing the cobaltous phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material as claimed in claim 2, wherein the cobalt salt solution in the step (3) is an aqueous solution of cobalt chloride, cobalt nitrate or cobalt acetate.
5. The preparation method of the cobaltous phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material as claimed in claim 2, wherein the inert atmosphere in the step (3) is nitrogen or argon.
6. The preparation method of the cobaltous phosphide nanoparticle/nitrogen-phosphorus doped carbon nanosphere composite material as claimed in claim 2, wherein the volume ratio of the water and ethanol mixed solvent in the step (3) is 1: 1.
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