CN108878903A - A kind of load C o2The magnanimity preparation method of the hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle - Google Patents
A kind of load C o2The magnanimity preparation method of the hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle Download PDFInfo
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- CN108878903A CN108878903A CN201710321228.4A CN201710321228A CN108878903A CN 108878903 A CN108878903 A CN 108878903A CN 201710321228 A CN201710321228 A CN 201710321228A CN 108878903 A CN108878903 A CN 108878903A
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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
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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
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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
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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
Abstract
The invention discloses a kind of load C o2The preparation method of hollow carbon-point hydrogen reduction (ORR) elctro-catalyst of the N doping of P nano particle, belongs to new energy materials synthesis and elctro-catalyst field.The present invention uses (NH4)2HPO4As green non-poisonous phosphorus source, it is prepared on a large scale the presoma simultaneously containing carbon, nitrogen, cobalt and phosphorus using ball-milling method, does not need to remove any unreacted raw material, direct high-temperature calcination can be obtained the preferable load C o of active higher stability2The hollow carbon-point ORR elctro-catalyst of the N doping of P nano particle.The method process that the present invention synthesizes ORR catalyst is stable, safe, easily-controllable; it can be realized under mild environment using conventional ball-grinding machine; the reaction condition of the harshness such as high temperature, high pressure, vacuum anaerobic is not needed; has the characteristics that simple process, convenient for large-scale production; the combined coefficient and cost of ORR catalyst can be increased substantially, it will play the role of to the large-scale commercial application of the conversion of the clean energy resourcies such as fuel cell and storage equipment vital.
Description
Technical field
The invention belongs to new energy materials synthesis and elctro-catalyst field, specially a kind of load C o2P nano particle
The hollow carbon-point oxygen reduction electro-catalyst of N doping preparation method.
Technical background
It converts and is stored in equipment in clean energy resourcies such as fuel cells, oxygen reduction reaction (ORR) is that one of them is extremely heavy
The cathode reaction wanted.Up to the present, platinum (Pt) and its alloy are excellent because having to the slow oxygen reduction reaction of electrochemical kinetics
Different catalytic activity makes it be widely used in fuel cell technology.However, since Pt base catalyst scarcity of resources, price are high
It is expensive, in use process durability difference and easily poisoned etc. the presence of restrictive conditions by CO, seriously hinder the popularization of fuel cell with
Exploitation.Therefore, efficient, cheap, the lasting and stable non-Pt system ORR catalyst of one kind is developed for the big rule of realization fuel cell
Mould commercialization is vital.Based on this, researcher reacted elctro-catalyst to non noble metal oxygen reduction in past ten years
A large amount of research has been carried out, non-metal base and transition metal based catalysts are broadly divided into.
Among numerous base metal elctro-catalysts, nitrogen-doped carbon material/transition metal composite catalyst is because of transition gold
The concerted catalysis for belonging to excellent between its surface nitrogen species acts on, and lower cost, causes the extensive concern of researchers,
It and is considered as a kind of oxygen reduction electro-catalyst for being expected to substitution business Pt/C.So far, transition metal oxide, nitridation
The hydrogen reduction that the composite catalyst of object, carbide and sulfide and nitrogen-doped carbon material has shown great prospect is anti-
Answer electro catalytic activity.However, transition metal phosphide/nitrogen-doped carbon compound material to the research of catalytic oxygen reducing property but
It is rarely reported.
Phosphatization cobalt (CoP, Co2P etc.) because its excellent electrochemical properties and stability are in electromagnetism, heavy metal adsorption, super
Grade capacitor and sensor etc. fields, which have, to be extremely widely applied.And in recent years a large number of studies show that phosphatization cobalt and its multiple
It closes object and has also shown good electro catalytic activity when as liberation of hydrogen and oxygen evolution reaction elctro-catalyst.More importantly other cobalts
Compound (simple substance Co, Co3O4、Co9S8) and the composite catalyst of nitrogen-doped carbon be proved to there is outstanding ORR to urge
Change performance.This all provides great possibility to explore the compound ORR catalyst of phosphatization cobalt/nitrogen-doped carbon.In addition, using toxic
Problem of environmental pollution caused by phosphorus source (hydrogen phosphide, white or red phosphorus, tri octyl phosphine etc.) is existing synthesis phosphatization cobalt and its compound
Common problem in method.And most synthesis path is usually directed to complicated step and exacting terms, and it cannot
Meets the needs of in practical application.Therefore, a kind of quick, environmental-friendly, with industrial applications prospect the preparation of simplicity is developed
Efficiently phosphatization cobalt/nitrogen-doped carbon compound ORR catalyst method is still for the large-scale commercial for realizing fuel cell
One huge challenge.
Summary of the invention
The present invention is intended to provide one kind is simple and efficient and can prepare load C o with magnanimity2The N doping of P nano particle is hollow
The method of carbon-point oxygen reduction electro-catalyst, synthesis device of the present invention is simple, condition is loose, raw material is easy to get, low in cost and environment
Close friend overcomes the cumbersome step of existing synthesis oxygen reduction electro-catalyst, especially solves the fiber crops being separated by solid-liquid separation in synthesis process
It is tired, and ORR catalyst obtained shows the performance of excellent electro-catalysis oxygen reduction.
In order to achieve the above technical purposes, the present invention provides a kind of load C o2The hollow carbon-point of the N doping of P nano particle
The preparation method of oxygen reduction electro-catalyst, this method are to mix carbon, cobalt, phosphorus and nitrogen source, are dry grinded above-mentioned mixing using ball-milling method
Object obtains the presoma of carbon containing, cobalt, phosphorus and nitrogen；Gained presoma is placed in protective atmosphere, at a temperature of 550~850 DEG C at heat
Manage 2~4h after to get.
Preferably, carbon source is citric acid C6H8O7·H2O, cobalt source is cobalt acetate Co (CH3COO)2·4H2O, phosphorus and nitrogen source are
Nontoxic diammonium hydrogen phosphate (NH4)2HPO4。
Preferably, cobalt source cobalt acetate Co (CH3COO)2·4H2O and phosphorus source diammonium hydrogen phosphate (NH4)2HPO4Substance amount
The sum of be 6~9mol, cobalt source cobalt acetate Co (CH3COO)2·4H2O and phosphorus source diammonium hydrogen phosphate (NH4)2HPO4The mass ratio of the material
Example is 2:1.
Preferably, in mechanical milling process, the amount of the substance of carbon source citric acid C6H8O7H2O is 15~45mol.
Preferably, in mechanical milling process, revolving speed is 300~600rpm, and Ball-milling Time is 5~15h.
Preferably, protective atmosphere is nitrogen in heat treatment process.
Preferably, presoma heat treatment process is：It is placed under nitrogen atmosphere, is heated up with the heating rate of 2~10 DEG C/min
It is cooling after keeping the temperature 2~4h to 550~850 DEG C；Haveing suffered heat treatment process to maintain nitrogen flow rate is 50~120mL/min.
Preferably, the load C o of preparation2The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle include C, N, O,
P and Co element；Wherein each element mass percent：C is 40~65%, N is 1~5%, O is 5~10%, P is 5~10%, Co
It is 20~40%.
Preferably, the load C o of preparation2The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle mainly includes
Co2P nano particle and the hollow carbon-point component of N doping.
Preferably, Co2P partial size is between 10~100nm.
Compared with prior art, bring advantageous effects of the present invention are embodied in：
(1) material is prepared using cheap, nontoxic raw material, it is at low cost, pollution-free, and diammonium hydrogen phosphate can provide P simultaneously
And the source N, improve the utilization efficiency of raw material.
(2) load C o disclosed by the invention2The preparation side of the hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle
Method, process is stable, safe, easily-controllable, the synthesis of presoma can be realized under mild environment using conventional ball-grinding machine, no
The reaction condition for needing the harshness such as high temperature, high pressure, vacuum anaerobic has the characteristics that simple process, convenient for large-scale production, can be with
For largely preparing, commercially producing oxygen reduction electro-catalyst, it will the clean energy resourcies such as fuel cell are converted and stored with equipment
Large-scale commercial application play the role of it is vital.
(3) present invention can produce the presoma of carbon containing, cobalt, phosphorus and nitrogen in enormous quantities using ball-milling method, and not need to remove
Unreacted raw material.Gained presoma is directly thermally treated to can be obtained load C o2The hollow carbon-point oxygen of the N doping of P nano particle
Elctro-catalyst is restored, solves the synthesis oxygen reduction electro-catalyst solid-liquids such as filtering, centrifugation, sedimentation, freeze-drying in the process
Isolated trouble.
(4) load C o prepared by the present invention2Co in the hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle2P receives
Rice grain is supported in situ during heat treatment on hollow carbon-point skeleton.Therefore phosphatization cobalt nano-particle in catalytic process not
It is easy to fall off, it is ensured that the long-term stability of catalyst.
(5) load C o of the present invention2The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle has excellent
Catalytic activity, the take-off potential and half wave potential value that catalytic oxidation-reduction reacts in 0.1M KOH alkaline medium can be with
The corresponding potential value of 20wt%Pt/C commodity oxygen reduction catalyst compares favourably.
(6) load C o of the present invention2The hollow carbon-point of the N doping of P nano particle is as oxygen reduction reaction elctro-catalyst
With outstanding anti methanol toxication and long-term stability, 2M methanol is added in 0.1M KOH alkaline medium, catalyst
Polarization curves of oxygen reduction does not almost generate any shadow, and remains to maintain just after the hydrogen reduction of lasting 50000s catalysis test
The 87.5% of beginning electric current overcomes the defect of 20wt%Pt/C commodity oxygen reduction catalyst methanol tolerance and stability difference.
Detailed description of the invention
Fig. 1 is the Co that embodiment 1,2,5 is prepared2P/N-HCR-1、Co2P/N-HCR-2、Co2P/N-HCR-3 catalyst
The XRD spectra of sample；
Fig. 2 is the Co that embodiment 2 is prepared2Scanning electron microscope (SEM) photo (a) of P/N-HCR-2 catalyst sample and
Transmission electron microscope (TEM) photo (b), (c)；
Fig. 3 is the Co that embodiment 2 is prepared2The XPS spectrum figure of N element in P/N-HCR-2 catalyst sample；
Fig. 4 is the Co that embodiment 1,2,5 is prepared2P/N-HCR-1、Co2P/N-HCR-2、Co2P/N-HCR-3 catalyst
The 0.1M KOH electrolytic that sample and 20wt%Pt/C commodity elctro-catalyst as performance comparison embodiment 4 are saturated in oxygen
Oxygen reduction reaction polarization curve in liquid compares figure；
Fig. 5 is the Co that embodiment 2 is prepared2P/N-HCR-2 catalyst sample and as performance comparison embodiment 4
20wt%Pt/C commodity elctro-catalyst is saturated in 0.1M KOH electrolyte and 0.1M KOH electrolyte containing 2M methanol in oxygen
Polarization curves of oxygen reduction comparison diagram；
Fig. 6 is the Co that embodiment 2 is prepared2P/N-HCR-2 catalyst sample and as performance comparison embodiment 4
Oxygen reduction reaction long-term stability of the 20wt%Pt/C commodity elctro-catalyst in oxygen saturation 0.1M KOH electrolyte can compare
Figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below that
Not constituting conflict between this can be combined with each other.
Embodiment 1
Citric acid, cobalt acetate, ammonium dihydrogen phosphate molal quantity are divided into the electro-catalysis obtained for 45,5 and 2.5mol in presoma
Agent.
(1) 45mol citric acid, 5mol cobalt acetate and 2.5mol ammonium dihydrogen phosphate are placed in vacuum at room temperature, in ball grinder
It is uniformly mixed.
(2) it is the ball milling pearl that 4g and 40 quality is 1g that 8 quality, which are added, takes out load C o after the 10h that dry grinds2P nanometers
The presoma of the hollow carbon-point oxygen reduction electro-catalyst of N doping of grain.
(3) presoma is put into quartz boat, 750 DEG C of heat treatment 3h, nitrogen is warming up to 3 DEG C/min under nitrogen protection
Room temperature is naturally cooled under atmosphere protection obtains load C o2The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle, note
For Co2P/N-HCR-1。
Fig. 1 is the Co that the present embodiment is prepared2The XRD spectra of P/N-HCR-1 catalyst sample；As seen from Figure 1,
Sample has apparent Co2P characteristic peak.Isothermal nitrogen adsorption show that the specific surface area of the sample is 187m2g-1.Each member in catalyst
Plain mass percent：Carbon is 62.88wt%, nitrogen 1.26wt%, oxygen 9.07wt%, phosphorus 5.43wt%, cobalt are
21.36wt%.
Embodiment 2
Citric acid, cobalt acetate, ammonium dihydrogen phosphate molal quantity are divided into the electro-catalysis obtained for 30,5 and 2.5mol in presoma
Agent.
(1) 30mol citric acid, 5mol cobalt acetate and 2.5mol ammonium dihydrogen phosphate are placed in vacuum at room temperature, in ball grinder
It is uniformly mixed.
(2) it is the ball milling pearl that 4g and 40 quality is 1g that 8 quality, which are added, takes out load C o after the 10h that dry grinds2P nanometers
The presoma of the hollow carbon-point oxygen reduction electro-catalyst of N doping of grain.
(3) presoma is put into quartz boat, 750 DEG C of heat treatment 3h, nitrogen is warming up to 3 DEG C/min under nitrogen protection
Room temperature is naturally cooled under atmosphere protection obtains load C o2The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle, note
For Co2P/N-HCR-2。
Fig. 1 is the Co that the present embodiment is prepared2The XRD spectra of P/N-HCR-2 catalyst sample；As seen from Figure 1,
Sample has apparent Co2P characteristic peak.Fig. 2 is the Co that the present embodiment is prepared2The scanning electron microscope of P/N-HCR-2 catalyst sample
(SEM) photo (a) and transmission electron microscope (TEM) photo (b), (c).As shown in Fig. 2, the Co of preparation2P/N-HCR-2 has hollow stick
Shape structure, and area load has Co2P nano particle, partial size is between 10~100nm.Isothermal nitrogen adsorption obtains the sample
The specific surface area of product is 224m2g-1.Each element mass percent in catalyst：Carbon is 50.54wt%, nitrogen 2.23wt%, oxygen
For 8.65wt%, phosphorus 8.06wt%, cobalt 30.52wt%.
Fig. 3 is the Co that the present embodiment is prepared2The XPS spectrum figure of N element in P/N-HCR-2 catalyst sample, can by figure
Know, Co2Three kinds of existence forms of nitrogen are respectively pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen in P/N-HCR-2 composite electrocatalyst.
Embodiment 3
Citric acid, cobalt acetate, ammonium dihydrogen phosphate molal quantity are divided into the elctro-catalyst obtained for 30,4 and 2mol in presoma.
(1) 30mol citric acid, 5mol cobalt acetate and 2.5mol ammonium dihydrogen phosphate are placed in vacuum at room temperature, in ball grinder
It is uniformly mixed.
(2) it is the ball milling pearl that 4g and 40 quality is 1g that 8 quality, which are added, takes out load C o after the 10h that dry grinds2P nanometers
The presoma of the hollow carbon-point oxygen reduction electro-catalyst of N doping of grain.
(3) presoma is put into quartz boat, 750 DEG C of heat treatment 3h, nitrogen is warming up to 3 DEG C/min under nitrogen protection
Room temperature is naturally cooled under atmosphere protection obtains load C o2The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle.
Embodiment 4
Citric acid, cobalt acetate, ammonium dihydrogen phosphate molal quantity are divided into the elctro-catalyst obtained for 30,6 and 3mol in presoma.
(1) 30mol citric acid, 5mol cobalt acetate and 2.5mol ammonium dihydrogen phosphate are placed in vacuum at room temperature, in ball grinder
It is uniformly mixed.
(2) it is the ball milling pearl that 4g and 40 quality is 1g that 8 quality, which are added, takes out load C o after the 10h that dry grinds2P nanometers
The presoma of the hollow carbon-point oxygen reduction electro-catalyst of N doping of grain.
(3) presoma is put into quartz boat, 750 DEG C of heat treatment 3h, nitrogen is warming up to 3 DEG C/min under nitrogen protection
Room temperature is naturally cooled under atmosphere protection obtains load C o2The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle.
Embodiment 5
Citric acid, cobalt acetate, ammonium dihydrogen phosphate molal quantity are divided into the electro-catalysis obtained for 15,5 and 2.5mol in presoma
Agent.
(1) 15mol citric acid, 5mol cobalt acetate and 2.5mol ammonium dihydrogen phosphate are placed in vacuum at room temperature, in ball grinder
It is uniformly mixed.
(2) it is the ball milling pearl that 4g and 40 quality is 1g that 8 quality, which are added, takes out load C o after the 10h that dry grinds2P nanometers
The presoma of the hollow carbon-point oxygen reduction electro-catalyst of N doping of grain.
(3) presoma is put into quartz boat, 750 DEG C of heat treatment 3h, nitrogen is warming up to 3 DEG C/min under nitrogen protection
Room temperature is naturally cooled under atmosphere protection obtains load C o2The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle, note
For Co2P/N-HCR-3。
Fig. 1 is the Co that the present embodiment is prepared2The XRD spectra of P/N-HCR-3 catalyst sample；As seen from Figure 1,
Sample has apparent Co2P characteristic peak.Isothermal nitrogen adsorption show that the specific surface area of the sample is 141m2g-1.Each member in catalyst
Plain mass percent：Carbon is 40.05wt%, nitrogen 2.96wt%, oxygen 9.03wt%, phosphorus 9.82wt%, cobalt are
38.14wt%.
Embodiment 6
Hydrogen reduction performance test, as a comparison with 20wt%Pt/C commodity elctro-catalyst (ETEK company).
Weigh Co made from 5mg embodiment 1,2,62P/N-HCR-1、Co2P/N-HCR-2、Co2P/N-HCR-3 and as property
0.02mL Nafion (5wt%) and 0.98mL isopropanol, ultrasound point is added in the 20wt%Pt/C commodity elctro-catalyst that can be compared
Dissipate 30min.Taking the dispersant liquid drop of 0.014ml to be added to area is 0.196cm-2Glassy carbon electrode surface, work is used as after drying at room temperature
Make electrode.Using electrochemical workstation (CHI760E), in three-electrode cell, use platinum filament for electrode, the hydrogen-oxygen of 0.1M
Change potassium solution is electrolyte, carries out Co with the speed of sweeping of 5mV/s2P/N-HCR-1、Co2P/N-HCR-2、Co2P/N-HCR-3 and
The polarization curve of 20wt%Pt/C is tested.
Fig. 4 is the Co that embodiment 1,2,5 is prepared2P/N-HCR-1、Co2P/N-HCR-2、Co2P/N-HCR-3 catalyst
The 0.1M KOH electrolytic that sample and 20wt%Pt/C commodity elctro-catalyst as performance comparison embodiment 4 are saturated in oxygen
Oxygen reduction reaction polarization curve in liquid compares figure.As seen from the figure, when citric acid content is 30mol, Co2P/N-HCR-2 is urged
Changing performance can compare favourably with 20wt%Pt/C commercial catalyst, when citric acid content is compared with increase or reduction, catalytic
It can decrease.When citric acid content is 45mol, Co2The take-off potential of P/N-HCR-1 is 0.874V, and half wave potential is
0.735V bears respectively compared to 20wt%Pt/C take-off potential and half wave potential and moves 115mV and 95mV；Citric acid content is
When 15mol, Co2The take-off potential of P/N-HCR-3 is 0.917V, half wave potential 0.775V, is originated compared to 20wt%Pt/C
Current potential and half wave potential are born respectively moves 72mV and 55mV.And when citric acid content is 30mol, Co2The starting electricity of P/N-HCR-2
Position is 0.962V, half wave potential 0.811V, born respectively compared to 20wt%Pt/C take-off potential and half wave potential move 27mV and
19mV, catalytic performance have a distinct increment compared with catalyst oxygen reduction catalytic performance obtained by other citric acid contents.
Fig. 5 is the Co that embodiment 2 is prepared2P/N-HCR-2 catalyst sample and as performance comparison embodiment 4
20wt%Pt/C commodity elctro-catalyst is saturated in 0.1M KOH electrolyte and 0.1M KOH electrolyte containing 2M methanol in oxygen
Polarization curves of oxygen reduction comparison diagram.As seen from the figure, after 2M methanol is added, the polarization curve of 20wt%Pt/C commercial catalyst goes out
The Co that embodiment 2 is prepared in the methanol for having showed an obviously methanol oxidation peak, and being added2P/N-HCR-2 catalysis
The polarization curves of oxygen reduction of agent does not almost generate any influence, illustrates Co prepared by the present invention2P/N-HCR-2 has excellent
Methanol tolerance ability.
Fig. 6 is the Co that embodiment 2 is prepared2P/N-HCR-2 catalyst sample and as performance comparison embodiment 4
Oxygen reduction reaction long-term stability of the 20wt%Pt/C commodity elctro-catalyst in oxygen saturation 0.1M KOH electrolyte can compare
Figure.As seen from the figure, after the hydrogen reduction catalysis test of lasting 50000s, 20wt%Pt/C commercial catalyst can only be maintained just
The 69.8% of beginning electric current, and the Co that embodiment 2 is prepared2P/N-HCR-2 catalyst is still gone back after the same test of experience
The 87.5% of initial current can be maintained, illustrates Co prepared by the present invention2P/N-HCR-2 equally has excellent long-acting catalysis steady
It is qualitative.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of load C o2The preparation method of the hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle, it is characterised in that：
It comprises the steps of：Carbon source, cobalt source, phosphorus source and nitrogen source are mixed to get mixture, is dry grinded the mixture, is obtained using ball-milling method
To the presoma of carbon containing, cobalt, phosphorus and nitrogen；Gained presoma is placed in protective atmosphere, at a temperature of 550~850 DEG C be heat-treated 2~
4h。
2. a kind of load C o according to claim 12The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle
Preparation method, it is characterised in that：The carbon source is citric acid C6H8O7·H2O, cobalt source is cobalt acetate Co (CH3COO)2·4H2O、
Phosphorus source and nitrogen source are diammonium hydrogen phosphate (NH4)2HPO4。
3. a kind of load C o according to claim 12The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle
Preparation method, it is characterised in that：Protective atmosphere is nitrogen in heat treatment process.
4. a kind of load C o according to claim 22The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle
Preparation method, it is characterised in that：The cobalt source cobalt acetate Co (CH3COO)2·4H2O and phosphorus source diammonium hydrogen phosphate (NH4)2HPO4's
The sum of amount of substance is 6~9mol, cobalt source cobalt acetate Co (CH3COO)2·4H2O and phosphorus source diammonium hydrogen phosphate (NH4)2HPO4Object
The amount ratio of matter is 2:1.
5. a kind of load C o according to claim 22The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle
Preparation method, it is characterised in that：The amount of the substance of the carbon source citric acid C6H8O7H2O is 15~45mol.
6. a kind of load C o according to claim 12The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle
Preparation method, it is characterised in that：In mechanical milling process, revolving speed is 300~600rpm, and Ball-milling Time is 5~15h.
7. requiring a kind of 1~6 described in any item load C o according to claim2The hollow carbon-point oxygen of the N doping of P nano particle is also
The preparation method of former elctro-catalyst, it is characterised in that：The load C o of preparation2The hollow carbon-point hydrogen reduction of the N doping of P nano particle
Elctro-catalyst includes C, N, O, P and Co element；Wherein each element mass percent：C is 40~65%, N is 1~5%, O be 5~
10%, P is 5~10%, Co is 20~40%.
8. a kind of load C o according to claim 72The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle,
It is characterized in that：Include Co2P nano particle and the hollow carbon-point component of N doping.
9. a kind of load C o according to claim 82The hollow carbon-point oxygen reduction electro-catalyst of the N doping of P nano particle,
It is characterized in that：The Co2P partial size is between 10~100nm.
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| CN110394184A (en) * | 2019-06-26 | 2019-11-01 | 青岛科技大学 | A kind of CoP/Co with high HER and OER catalytic activity2The preparation of P composite catalyst |
| CN112028042A (en) * | 2020-09-03 | 2020-12-04 | 中国科学院地球化学研究所 | Carbon thermal reduction preparation method of CoP, product and application |
| CN113066676A (en) * | 2021-03-29 | 2021-07-02 | 深圳市吉利通电子有限公司 | Manufacturing method of super capacitor with large capacitance |
| CN113471455A (en) * | 2021-07-01 | 2021-10-01 | 湖南理工学院 | Cobalt disulfide/nitrogen and sulfur co-doped mesoporous carbon composite catalyst for zinc-air battery and preparation method thereof |
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Cited By (7)
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| CN110394184A (en) * | 2019-06-26 | 2019-11-01 | 青岛科技大学 | A kind of CoP/Co with high HER and OER catalytic activity2The preparation of P composite catalyst |
| CN110394184B (en) * | 2019-06-26 | 2022-05-27 | 青岛科技大学 | CoP/Co with high HER and OER catalytic activity2Preparation method of P composite catalyst |
| CN110327951A (en) * | 2019-07-25 | 2019-10-15 | 江南大学 | A kind of boron cobalt phosphate material and the preparation method and application thereof |
| CN112028042A (en) * | 2020-09-03 | 2020-12-04 | 中国科学院地球化学研究所 | Carbon thermal reduction preparation method of CoP, product and application |
| CN113066676A (en) * | 2021-03-29 | 2021-07-02 | 深圳市吉利通电子有限公司 | Manufacturing method of super capacitor with large capacitance |
| CN113471455A (en) * | 2021-07-01 | 2021-10-01 | 湖南理工学院 | Cobalt disulfide/nitrogen and sulfur co-doped mesoporous carbon composite catalyst for zinc-air battery and preparation method thereof |
| CN113471455B (en) * | 2021-07-01 | 2022-10-28 | 湖南理工学院 | Cobalt disulfide/nitrogen and sulfur co-doped mesoporous carbon composite catalyst for zinc-air battery and preparation method thereof |
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