CN108963279A - Nitrogen-doped carbon microballoon/Pd composite catalyst and its preparation method and application - Google Patents
Nitrogen-doped carbon microballoon/Pd composite catalyst and its preparation method and application Download PDFInfo
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- CN108963279A CN108963279A CN201810754183.4A CN201810754183A CN108963279A CN 108963279 A CN108963279 A CN 108963279A CN 201810754183 A CN201810754183 A CN 201810754183A CN 108963279 A CN108963279 A CN 108963279A
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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
- 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
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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
- H01M4/9041—Metals or alloys
Abstract
The present invention provides a kind of nitrogen-doped carbon microballoon/Pd composite catalyst and its preparation and application, and the preparation method comprises the following steps: (1) carbon material being added in nitric acid solution, stirring is heated and kept the temperature, and cooled and filtered is dry；(2) carbon material prepared in step (1) is heated up 300~1000 DEG C of calcinings under protective gas atmosphere, obtains black powder material；(3) black powder material, water, ammonium sulfate, ammonium persulfate and palladium nitrate that step (3) obtain are hybridly prepared into aqueous solution, stir, heats and keep the temperature, cooled and filtered is dry.Catalyst oxygen reduction catalytic activity is high in the application and stability is good, and method is simple.
Description
Technical field
The present invention relates to a kind of nitrogen-doped carbon microballoon/Pd composite catalysts and its preparation method and application.
Background technique
Zinc-air battery is environmentally protective clear energy sources.Zinc-air battery is with specific capacity is big, theoretical energy density is high, electric
The many merits such as pole material storage is abundant, performance is stable, hypotoxicity and pollution-free, technology maturation safety height, it has also become current
The exploitation hot spot in world energy sources field, shows huge market prospects.Zinc-air battery due to that can provide stabilization for a long time
Low current, navigation light, unmanned observation station, the radio relay station etc. being therefore widely used in navigation.And with zinc sky
Pneumoelectric pond is as battery of mobile phone, and cheaper by 2/3rds than commonly used nickel-metal hydride battery, lithium ion battery, the air time is longer.
However, keeping its discharge current density less than normal, thus significantly since zinc-air battery lacks suitable air diffusion electrode catalyst
Limit the application field and industrialization pace of zinc-air battery.
In zinc-air battery, plays most important functions, is also most to influence battery performance characteristic, be exactly urging for air electrode
Agent.Existing catalyst mainly has, noble metal and its alloy, active carbon, MnO2Deng.Noble metal and its alloy, such as Pt, Ag
And Pt alloy etc., the activity of this kind of catalyst is preferable, but expensive.Active carbon, MnO2Equal catalyst, although at low cost,
But catalytic activity is relatively low；Also, reaction speed of the oxygen on electrode interface is slow, using it as the battery discharge of catalyst
Current density is small, can not meet the requirement of home electronics.Metal oxide materials are due to good electro-catalysis
Activity and be concerned, the features such as however it is there are still preparation process is cumbersome, higher cost.
Therefore, need to research and develop that a kind of catalytic activity is high, chemical stability is good, the simple zinc-air battery air of preparation process
The catalyst of electrode, to meet the use demand of increasingly developed zinc-air battery.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of nitrogen-doped carbon microballoon/Pd is multiple
Catalyst and its preparation method and application is closed, for solving redox elctro-catalyst preparation cost height, technique in the prior art
Complexity, activity is low and causes zinc-air battery can not real commercialized problem.
In order to achieve the above objects and other related objects, the present invention provides a kind of nitrogen-doped carbon microballoon/Pd composite catalyst
Preparation method, the preparation method at least includes the following steps:
(1) carbon material is added in nitric acid solution, stirring is heated and kept the temperature, and cooled and filtered is dry；
(2) carbon material prepared in step (1) is heated up 300~1000 DEG C of calcinings under protective gas atmosphere, obtains black
Powder body material；
(3) the black powder material mixed preparing for obtaining water, ammonium sulfate, ammonium persulfate and palladium nitrate, step (2)
At aqueous solution, stirring is heated and is kept the temperature, and cooled and filtered is dry.
Further, the carbon material is Vulcan Carbon.It is highly preferred that carbon material is Vulcan XC-72
Carbon。
Further, the nitric acid solution in the step (1) refers to aqueous solution of nitric acid, more preferably dilute nitric acid solution.Institute
Stating dust technology concentration is 1mol/L.
Further, the step (1), which is stirred, refers at normal temperature with 90~120rpm speed stirring, 0.5~2h.
Further, it is ultrasonically treated, is reheated after stirring in the step (1), the ultrasonic treatment refers to 200
0.5~2h of~800W ultrasound.
Further, heating and keeping the temperature in the step (1) is 85-95 DEG C, time 1-3h.
Further, calcination time is 1.5~3h in the step (2), and heating rate is 3~5 DEG C/min.
Further, the step (2) is warming up to 300~1000 DEG C.
Further, the protection gas refers to reducibility gas；Further, the protection gas refers to nitrogen and lazy
Property gas.
Further, ammonium persulfate and water quality ratio are 0.6~6:100 in the step (3).
Further, ammonium sulfate and water quality ratio are 1.4~14:100 in the step (3).
Further, palladium nitrate and water quality ratio are 0.5~5:1000 in the step (3).
Further, black powder material and water quality ratio are 0.1~0.6:100 in the step (3).
Further, it is heated in the step (3) and keeps the temperature 120-150 DEG C, time 10-14h.
Further, stirring refers at normal temperature with 90~120rpm speed stirring, 0.5~2h in the step (3).
Further, it is ultrasonically treated, is reheated after stirring in the step (3), the ultrasonic treatment refers to 200
0.5~2h of~800W ultrasound.
Another aspect of the present invention provides nitrogen-doped carbon microballoon/Pd composite catalyst of above method preparation.
Further, in the catalyst in Pd particle insertion nitrogen-doped carbon microballoon, Pd exists with monatomic form, and
Load capacity is that loading is 94~96% to 0.1~0.4%, C in the catalyst.
Another aspect of the present invention provides above-mentioned catalyst in redox reaction as the purposes of catalyst.
Further, the purposes refers to application of the catalyst in zinc-air battery field.
As described above, nitrogen-doped carbon microballoon/Pd composite catalyst and its preparation method and application of the invention, has following
The utility model has the advantages that
Preparation method simple process of the present invention, at low cost, controllability is good, oxygen reduction electro-catalyst nitrogen-doped carbon obtained
Microballoon/Pd composite catalyst structure is stable, has excellent performance, favorable repeatability, can be mass-produced, palladium exists with monatomic form
In catalyst, maximize the utilization rate of precious metal palladium, to significantly reduce palladium under the premise of guaranteeing catalytic activity
Dosage.Supported palladium is monatomic on carbosphere, increases active site quantity, further improves the catalytic activity of catalyst.
Detailed description of the invention
Fig. 1 is that the transmission electron microscope photo (left side) of catalyst prepared by the embodiment of the present invention 3 and spherical aberration Electronic Speculum are shone
Piece (right side).
Fig. 2 is the nitrogen adsorption desorption isotherm figure of catalyst prepared by the embodiment of the present invention 3.
Fig. 3 is the pore size distribution figure of catalyst prepared by the embodiment of the present invention 3.
Fig. 4 is the x-ray photoelectron spectroscopy figure of catalyst prepared by the embodiment of the present invention 3.
Fig. 5 is electric current-time timing ampere curve of catalyst prepared by the embodiment of the present invention 3.
Fig. 6 be the embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4, catalyst prepared by embodiment 5 and
The rotating disk electrode (r.d.e) of business Pt/C catalyst (Johnson Marrhey) and business Pd/C catalyst at revolving speed 1600rpm
Polarization curve (test condition: rotating disk electrode (r.d.e), the 0.1M KOH solution of O2 saturation, sweeping speed is 10mV/s).
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.It should be clear that the process equipment or device that are not indicated specifically in the following example
It is all made of conventional equipment or device in the art.In addition, it should also be understood that, one or more method and step mentioned in the present invention is simultaneously
Do not repel and may be used also before and after the combination step there may also be other methods step or between these explicitly mentioned steps
To be inserted into other methods step, unless otherwise indicated；It should also be understood that one or more equipment/device mentioned in the present invention it
Between combination connection relationship do not repel before and after the unit equipment/device there may also be other equipment/device or at this
It can also be inserted into other equipment/device between the two equipment/devices specifically mentioned a bit, unless otherwise indicated.Moreover, unless another
It is described, the number of various method steps is only the convenient tool of identification various method steps, rather than is the row of limitation various method steps
Column order limits the scope of the invention, and relativeness is altered or modified, without essence change technology contents
In the case of, when being also considered as the enforceable scope of the present invention.
The preparation of 1 No. 1 catalyst of embodiment
1) the Vulcan Carbon after being acidified 80mg is dispersed in 20mL ultrapure water by ultrasound, and it is micro- to obtain carbon
Ball suspension；
2) 2.6g ammonium sulfate, 1.2g ammonium persulfate, 11mg palladium nitrate are added in 60mL ultrapure water, electromagnetic agitation obtains
Mixed solution；
3) 100mL after evenly mixing by carbosphere suspension and mixed solution, is transferred to polytetrafluoroethylliner liner
In water heating kettle, it is put into the baking oven that temperature is 140 DEG C and reacts 12h, be cooled to room temperature after reaction, product is washed, dry,
Obtain palladium and carbosphere composite catalyst (being denoted as No. 1 catalyst).
The preparation of 2 No. 2 catalyst of embodiment
1) by the Vulcan Carbon after acidification in 30% NH3/Ar atmosphere, 300 DEG C of guarantors are warming up to 5 DEG C/min
Hold 2h, gas flow 200mL/min.
2) the Vulcan Carbon after the heat treatment of 80mg ammonia is evenly dispersed with 20mL ultrapure water by ultrasound, it obtains
To carbosphere suspension；
3) 2.6g ammonium sulfate, 1.2g ammonium persulfate, 11mg palladium nitrate are added in 60mL ultrapure water, electromagnetic agitation obtains
Mixed solution；
4) 100mL after evenly mixing by carbosphere suspension and mixed solution, is transferred to polytetrafluoroethylliner liner
In water heating kettle, it is put into the baking oven that temperature is 140 DEG C and reacts 12h, be cooled to room temperature after reaction, product is washed, dry,
Obtain palladium and carbosphere composite catalyst (being denoted as No. 2 catalyst).
The preparation of 3 No. 3 catalyst of embodiment
1) by the Vulcan Carbon after acidification in 30% NH3/Ar atmosphere, 600 DEG C of guarantors are warming up to 5 DEG C/min
Hold 2h, gas flow 200mL/min.
2) the Vulcan Carbon after the heat treatment of 80mg ammonia is evenly dispersed with 20mL ultrapure water by ultrasound, it obtains
To carbosphere suspension；
3) 2.6g ammonium sulfate, 1.2g ammonium persulfate, 11mg palladium nitrate are added in 60mL ultrapure water, electromagnetic agitation obtains
Mixed solution；
4) 100mL after evenly mixing by carbosphere suspension and mixed solution, is transferred to polytetrafluoroethylliner liner
In water heating kettle, it is put into the baking oven that temperature is 140 DEG C and reacts 12h, be cooled to room temperature after reaction, product is washed, dry,
Obtain palladium and carbosphere composite catalyst (being denoted as No. 3 catalyst).
Fig. 1 is that the transmission electron microscope photo (left side) of catalyst prepared by the embodiment of the present invention 3 and spherical aberration Electronic Speculum are shone
Piece (right side).
Atom level structural characterization has been carried out based on the monoatomic composite catalyst of palladium to of the invention using spherical aberration Electronic Speculum.Root
According to not homoatomic contrast difference, palladium atom brightness is higher, Fig. 1, and the palladium that high degree of dispersion can be clearly apparent in carbon ball is monatomic.
Fig. 2 is the nitrogen adsorption desorption isotherm figure of catalyst prepared by the embodiment of the present invention 3.
The BET surface area of catalyst prepared by embodiment 3 is 234.7310m as the result is shown2/g。
Fig. 3 is the pore size distribution figure of catalyst prepared by the embodiment of the present invention 3.
The average pore size of catalyst prepared by embodiment 3 is 6.71803nm as the result is shown.
Fig. 4 is the x-ray photoelectron spectroscopy figure of catalyst prepared by the embodiment of the present invention 3.
Research is prepared in monatomic catalyst process, influence of the pyridine N content to catalyst activity in nitrogen.It is penetrated from X
It can be seen that nitrogen is presented in three kinds of states in photoelectron spectra figure, respectively pyridine N, pyrroles N, graphene N.Wherein,
Pyridine N has positive interaction to catalyst activity.
Fig. 5 is electric current-time timing ampere curve of catalyst prepared by the embodiment of the present invention 3.(test condition:
Rotating disk electrode (r.d.e), O2 saturation 0.1M KOH solution, sweep speed be 10mV/s, revolving speed 1600rpm, methanol be added time be about
3600s)。
The monoatomic composite catalyst of palladium of the present invention is applied into methanol tolerance test, as a result as shown in Figure 5.It can be seen that
After methanol is added, current density not anti-reflection increases, and illustrates that the methanol tolerance of catalyst is good.
The preparation of 4 No. 4 catalyst of embodiment
1) by the Vulcan Carbon after acidification in 30% NH3/Ar atmosphere, 800 DEG C of guarantors are warming up to 5 DEG C/min
Hold 2h, gas flow 200mL/min.
2) the Vulcan Carbon after the heat treatment of 80mg ammonia is evenly dispersed with 20mL ultrapure water by ultrasound, it obtains
To carbosphere suspension；
3) 2.6g ammonium sulfate, 1.2g ammonium persulfate, 11mg palladium nitrate are added in 60mL ultrapure water, electromagnetic agitation obtains
Mixed solution；
4) 100mL after evenly mixing by carbosphere suspension and mixed solution, is transferred to polytetrafluoroethylliner liner
In water heating kettle, it is put into the baking oven that temperature is 140 DEG C and reacts 12h, be cooled to room temperature after reaction, product is washed, dry,
Obtain palladium and carbosphere composite catalyst (being denoted as No. 4 catalyst).
The preparation of 5 No. 5 catalyst of embodiment
1) by the Vulcan Carbon after acidification in 30% NH3/Ar atmosphere, 1000 DEG C of guarantors are warming up to 5 DEG C/min
Hold 2h, gas flow 200mL/min.
2) the Vulcan Carbon after the heat treatment of 80mg ammonia is evenly dispersed with 20mL ultrapure water by ultrasound, it obtains
To carbosphere suspension；
3) 2.6g ammonium sulfate, 1.2g ammonium persulfate, 11mg palladium nitrate are added in 60mL ultrapure water, electromagnetic agitation obtains
Mixed solution；
4) 100mL after evenly mixing by carbosphere suspension and mixed solution, is transferred to polytetrafluoroethylliner liner
In water heating kettle, it is put into the baking oven that temperature is 140 DEG C and reacts 12h, be cooled to room temperature after reaction, product is washed, dry,
Obtain palladium and carbosphere composite catalyst (being denoted as No. 5 catalyst).
Embodiment 6
It tests application of the above-described embodiment 1~5 as catalyst in ORR: the carbon material of preparation is evenly spread to
In the mixed solution of ionized water, isopropanol and Nafion (5wt.%), above-mentioned suspension is taken to prepare coated in glassy carbon electrode surface
At working electrode.Simultaneously in order to compare, commercialization Pt/C (20%Pt, JM) and Pd/C (20%Pd) prepared by same method
Catalyst is tested under identical condition.
It is characterized using ORR activity of the LSV method to material.Test the nitrogen-doped carbon of preparation respectively using three-electrode system
The chemical property of microballoon/Pd composite catalyst and commercially available Pt/C catalyst and Pd/C catalyst, with the KOH of 0.1mol.L-1
Solution is electrolyte, and to be spotted with the rotating disk electrode (r.d.e) of catalysis material as working electrode, platinum filament is to electrode, and Ag/AgCl is
Reference electrode.Logical oxygen, makes oxygen in electrolyte reach saturation before test.For ORR performance test, LSV curve turns in difference
Speed is lower to be obtained.
The embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4, catalyst and business prepared by embodiment 5
The rotating disk electrode (r.d.e) polarization of Pt/C catalyst (Johnson Marrhey) and business Pd/C catalyst at revolving speed 1600rpm
Curve (test condition: rotating disk electrode (r.d.e), the 0.1M KOH solution of O2 saturation, sweeping speed is 10mV/s).
As a result such as Fig. 6, show No. 3 catalyst (based on the monoatomic composite catalyst of palladium) activity preferably, and can be with quotient
The Pt/C of industry, Pd/C catalyst are compared, but its starting voltage, than commercialization Pt/C, Pd/C catalyst is poor.
Above embodiment is can not to be interpreted as in order to illustrate embodiment disclosed by the invention to limit of the invention
System.In addition, in various modifications and invention listed herein method, composition variation, do not departing from the scope of the present invention
Be obvious for those skilled in the art under the premise of spirit.Although having combined of the invention a variety of specific
Preferred embodiment has carried out specific description to the present invention, it is to be understood that, the present invention should not be limited only to these specific embodiments.
In fact, various obviously modify as described above for those skilled in the art to obtain invention all should include
Within the scope of the invention.
Claims (10)
1. a kind of preparation method of nitrogen-doped carbon microballoon/Pd composite catalyst, the preparation method at least include the following steps:
(1) carbon material is added in nitric acid solution, stirring is heated and kept the temperature, and cooled and filtered is dry；
(2) carbon material prepared in step (1) is heated up 300~1000 DEG C of calcinings under protective gas atmosphere, obtains black powder
Material；
(3) the black powder material that water, ammonium sulfate, ammonium persulfate and palladium nitrate step (2) obtain is hybridly prepared into water-soluble
Liquid, stirring, heats and keeps the temperature, cooled and filtered, dry.
2. the preparation method of nitrogen-doped carbon microballoon/Pd composite catalyst according to claim 1, it is characterised in that: described
Carbon material is Vulcan Carbon.
3. the preparation method of nitrogen-doped carbon microballoon/Pd composite catalyst according to claim 1, it is characterised in that: described
It is ultrasonically treated, is reheated after stirring in step (1), the ultrasonic treatment refers to 200~800W ultrasound, 0.5~2h.
4. the preparation method of nitrogen-doped carbon microballoon/Pd composite catalyst according to claim 1, it is characterised in that: described
Heating and keeping the temperature in step (1) is 85-95 DEG C, time 1-3h.
5. the preparation method of nitrogen-doped carbon microballoon/Pd composite catalyst according to claim 1, it is characterised in that: described
Step (2) further includes at least one of following technical characteristic:
A. the calcination time is 1.5~3h, and heating rate is 3~5 DEG C/min；
B. described to be warming up to 300~1000 DEG C.
6. the preparation method of nitrogen-doped carbon microballoon/Pd composite catalyst according to claim 1, it is characterised in that: described
Preparation method further includes any one or a few in following technical characteristic:
A. ammonium persulfate and water quality ratio are 0.6~6:100 in the step (3)；
B. ammonium sulfate and water quality ratio are 1.4~14:100 in the step (3)；
C. palladium nitrate and water quality ratio are 0.5~5:1000 in the step (3)；
D. black powder material and water quality ratio are 0.1~0.6:100 in the step (3)；
E. it is heated in the step (3) and keeps the temperature 120-150 DEG C, time 10-14h；
F. stirring refers at normal temperature with 90~120rpm speed stirring, 0.5~2h in the step (3)；
G. it is ultrasonically treated, is reheated after stirring in the step (3), the ultrasonic treatment refers to 200~800W ultrasound
0.5~2h.
7. a kind of nitrogen obtained by any one of the claim 1~6 nitrogen-doped carbon microballoon/Pd method for preparing composite catalyst is mixed
Miscellaneous carbosphere/Pd composite catalyst.
8. nitrogen-doped carbon microballoon/Pd composite catalyst according to claim 7, it is characterised in that: the composite catalyst is
It is embedded in nitrogen-doped carbon microballoon by Pd particle, Pd exists with monatomic form, and load capacity is that 0.1~0.4%, C is being catalyzed
Loading is 94~96% in agent.
9. nitrogen-doped carbon microballoon/Pd composite catalyst as described in claim 7~8 any one claim is as catalyst
Purposes.
10. purposes according to claim 9, it is characterised in that: the purposes refers to the catalyst in zinc-air battery
Application in field.
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| CN112133929B (en) * | 2020-09-18 | 2021-08-10 | 济南大学 | Preparation method of ZIF-8-derived Au-N-C oxygen reduction electrocatalyst |
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| CN108963279B (en) | 2021-06-08 |
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