CN110148763A - A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method and application of carbon-nitrogen material - Google Patents
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method and application of carbon-nitrogen material Download PDFInfo
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- CN110148763A CN110148763A CN201910333446.9A CN201910333446A CN110148763A CN 110148763 A CN110148763 A CN 110148763A CN 201910333446 A CN201910333446 A CN 201910333446A CN 110148763 A CN110148763 A CN 110148763A
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract
The invention discloses a kind of, and the Fe with hollow nanometer frame structure adulterates Mn3O4The preparation method of carbon-nitrogen material and its application in redox reactions and zinc-air battery, 1) preparation method the following steps are included: prepare Fe (CN) respectively6 3‑/ PVP solution and Mn2+Solution；2) by the Fe (CN)6 3‑/ PVP solution and Mn2+Solution is uniformly mixed and is stood, and obtains KMnFe (CN)6The Prussian blue similar object precipitating of khaki；3) by the KMnFe (CN)6After alkali cleaning, the Fe doping Mn to get described with hollow nanometer frame structure is heat-treated with temperature programming in NaOH solution in the inert atmosphere at 250-350 DEG C for solid powder3O4Carbon-nitrogen material.Preparation method of the present invention is low in cost, simple general use, obtained material have open hollow nanometer frame structure, which can be used as redox reactions electrocatalysis material, have higher activity and excellent stability, at the same time as the application of zinc-air battery positive electrode.
Description
Technical field
The present invention relates to a kind of, and the Fe with hollow nanometer frame structure adulterates Mn3O4The preparation method of carbon-nitrogen material and its
The electro-catalysis application of resulting materials and redox reactions belongs to zinc-air battery anode catalyst technical field.
Background technique
The zinc-air battery that electrochemistry can fill has the characteristics that energy density height, aqueous electrolyte safety, economy are strong,
There is broad prospect of application in terms of electric car, portable power and large-scale energy storage, be the weight for developing green clean energy resource
Want industry direction.As very promising electrochemical energy storage device, zinc-air battery is because at low cost, resourceful, environmental-friendly
With energy density by the extensive concern of researcher the features such as high.Oxygen reduction reaction (ORR) is in metal-air battery, fuel cell
Etc. in a series of energy conversion devices in occupation of critical role.However, the reaction process is related to the transfer of multistep proton couple electronic
Process, kinetically relatively slowly, it is therefore desirable to suitable catalyst be selected to improve reaction rate and efficiency.Precious metals pt and its
Alloy is the best ORR catalyst of current performance, but its reserves is rare, expensive, is not suitable for large-scale application.Therefore,
Developing novel cheap, efficient stable new catalyst substitution precious metals pt base catalyst seems particularly critical.
In recent years, hollow micro/nano structure has a wide range of applications because of the physicochemical properties that its unique structure induces
Prospect especially receives much attention in terms of electrochemical energy storage and conversion.Wherein, Prussian blue (PB) and the like (PBA) by
In its low cost, high-performance, structure opening, the features such as adjustable is formed, has obtained a large amount of research (Advanced
Materials,2017,201706825；Advanced Materials,2018,30,201800939).Result of study shows,
Cation exchange is a kind of effective ways for preparing hollow inorganic nanoparticle, MA(MA=Fe, Mn, Ni, Cu, Zn, V, Mo, Ce,
Gd, etc.)-MB(MB=Fe, Co, etc.) PBA can be easily by metal oxide MAMBOx(MA=Fe, Mn, Ni, Cu, Zn, V,
Mo, Ce, Gd, etc.；MB=Fe, Co, etc.) prepare hollow nanometer frame structure.In terms of electro-catalysis, hollow structure is considered excellent
In solid-state structure, because hollow structure can provide higher catalysis interfacial area, to significantly improve electrocatalysis characteristic.In order to
So that PBA is obtained practical application in electrochemical energy storage, it is necessary to increase substantially ionic conductivity and electronic conductivity, and mix or
Coated with conductive carbon material (such as graphene and carbon nanotube) is the effective ways for improving electron conduction, and nano-carbon material not only may be used
Effectively to promote the electric conductivity of catalyst, and biggish specific surface area is provided, improves the stability of active specy.Meanwhile
Hetero atom (such as: N, P, S etc.) is doped into carbon matrix can be effective to be promoted by the electronic structure of the carbon atom near adjusting
Catalytic performance.Therefore, these above-mentioned collaboration superior combinations are got up, synthesizing, there is the Fe of hollow nanometer frame structure to adulterate Mn3O4
Carbon-nitrogen material is a kind of strategy of wisdom.However, often time-consuming is lasting, preparation process is numerous for the preparation process of usually this kind of material
It is trivial, yield is less.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of Fe with hollow nanometer frame structure to mix
Miscellaneous Mn3O4The preparation method and applications of carbon-nitrogen material.This method simple general use, it is low in cost, and prussian blue obtained
Mn is adulterated like object derivative Fe3O4Carbon-nitrogen material shows excellent activity and stability, together as oxygen reduction elctro-catalyst
When can be used as efficient zinc-air battery anode electrocatalyst material.
Technical solution: to achieve the above object of the invention, the invention adopts the following technical scheme:
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1) Fe (CN) is prepared respectively6 3-/ PVP solution and Mn2+Solution；
2) by the Fe (CN)6 3-/ PVP solution and Mn2+Solution is uniformly mixed and is stood, and obtains KMnFe (CN)6Precipitating；
3) by the KMnFe (CN)6After precipitating carries out alkali cleaning with sodium hydroxide solution, it is warming up to 250 in an inert atmosphere
It is heat-treated at~350 DEG C, obtains the Fe doping Mn with hollow nanometer frame structure3O4Carbon-nitrogen material.
Preferably, the K3Fe(CN)6/ PVP solution the preparation method comprises the following steps:
PVP and the potassium ferricyanide are dissolved in the water, after mixing, obtain the K3Fe(CN)6/ PVP solution.
Preferably, the K3Fe(CN)6In/PVP solution, the mass fraction of PVP is 5~10%.
Preferably, described to contain Mn2+Solution the preparation method comprises the following steps:
Manganese chloride is dissolved in the water.
Preferably, the K3Fe(CN)6/ PVP solution and contain Mn2+Solution mixing after, Mn2+And Fe3+Mole
Than for 2:1~1:2.
Preferably, the concentration for the sodium hydroxide solution that the alkali cleaning uses is 0.2M, and the temperature of alkali cleaning is 40 DEG C.
Preferably, the rate of the heating is 1~10 DEG C/min, and heat treatment time is 2~4h.
Preferably, the inert atmosphere is at least one of nitrogen, argon gas, helium, carbon dioxide.
Fe derived from Prussian blue similar object obtained by above-mentioned preparation method adulterates Mn3O4Carbon-nitrogen material, can make
For zinc-air battery anode electrocatalyst, significant effect.
Reaction principle of the invention are as follows: using the potassium ferricyanide and manganese chloride as source metal, polyvinylpyrrolidone be carbon source and
Weak reductant is coordinated by cyano, previously prepared KMnFe (CN)6Prussian blue similar object, utilizes the reaction induced of NaOH solution
It acts on and in N2Fe derived from the Prussian blue similar object of hollow nanometer frame structure is prepared in high temperature cabonization effect in atmosphere
Adulterate Mn3O4Carbon-nitrogen material.The material morphology is regular, uniform.In addition, N element rich in the material, and
Since hollow nanometer frame structure and active material Fe adulterate Mn3O4Between component and structural advantage, obtained material have
Higher oxygen reduction activity and excellent stability.
Prepared by the present invention there is Fe derived from the Prussian blue similar object of hollow nanometer frame structure to adulterate Mn3O4's
Carbon-nitrogen material has following several advantages:
1) hollow nanometer frame structure has biggish specific surface area, exposes more active sites, while can be effective
Promote contact of the electrolyte with catalyst, is conducive to the generation of reaction；
2) the relatively thin permeable shell of hollow nanometer frame structure can effectively shorten the approach of ion and electrons spread,
Orientation promotion electronics and ion quick transmission, improve rate of catalysis reaction, promote reactant reaction and product it is quick
Output；
3) hollow nanometer frame structure has biggish internal buffer, it is made to be not susceptible to reunite during the reaction,
Effectively alleviate O2Molecule and OH-Structural strain caused by ionic adsorption, diffusion process, and possible volume change is adapted to, favorably
In the integrality for maintaining structure；
4) choosing has the PVP of higher nitrogen content as carbon source and reducing agent, by controlling Fe (CN) in solution phase6 3-
With Mn2+Nucleation rate, so that its slowly uniform is generated KMnFe (CN)6Solid, while tool can be generated by high temperature cabonization reduction
There is the carbon carrier of higher degree of graphitization and better thermal stability, the doping of nitrogen can effectively change the conduction of carbon carrier
Property, to improve the hydrogen reduction performance of material.
Technical effect: compared with the existing technology, present invention has the advantage that
1) by Prussian blue similar object preparation method easy, that large-scale production can be achieved, also in conjunction with high temperature carbonization heat
Original prepares a kind of with the doping of Fe derived from the Prussian blue similar object of hollow nanometer frame structure Mn3O4Carbon nitrogen elctro-catalyst material
Material；
2) PVP and transition-metal Fe, Mn selected by, it is cheap and easy to get, zinc-air electrocatalyst materials are prepared with tradition
Method is compared, this method large-scale production simple for process, low in cost, easy to operate, achievable；
3) product morphology obtained by is regular, and unique hollow nanometer frame structure can expose more active sites,
The transmission of ion and electronics, the reaction of electrolyte and catalyst are effectively promoted, it is made compared with conventional solid-state structure material
Electrocatalyst materials derived from the Prussian blue similar object of standby hollow nanometer frame structure, have more excellent design feature and
Component advantage is a kind of potential zinc-air battery anode electrocatalyst material, it is contemplated that in following energy industry application
It has a extensive future.
Detailed description of the invention
Fig. 1 is that the Fe with hollow nanometer frame structure prepared according to the embodiment of the present invention 1 adulterates Mn3O4Carbon-nitrogen material
Low power SEM spectrum；
Fig. 2 is that the Fe with hollow nanometer frame structure prepared according to the embodiment of the present invention 1 adulterates Mn3O4Carbon-nitrogen material
TEM map；
Fig. 3 is that the Fe with hollow nanometer frame structure prepared according to the embodiment of the present invention 1 adulterates Mn3O4Carbon-nitrogen material
XRD spectrum；
Fig. 4 is that the Fe with hollow nanometer frame structure that in the present invention prepared by embodiment 1 adulterates Mn3O4Carbon-nitrogen material with
The LSV curve of other contrast materials；
Fig. 5 is that the Fe with hollow nanometer frame structure prepared according to the embodiment of the present invention 1 adulterates Mn3O4Carbon-nitrogen material
The LSV curve comparison under the test environment poisoned whether there is or not methanol；
Fig. 6 is that the Fe with hollow nanometer frame structure prepared according to the embodiment of the present invention 1 adulterates Mn3O4Carbon-nitrogen material
Tafel curve；
Fig. 7 is that the Fe with hollow nanometer frame structure prepared according to the embodiment of the present invention 1 adulterates Mn3O4Carbon-nitrogen material
Chrono-amperometric test curve；
Fig. 8 is the curve comparison that polarized according to the electric discharge of the embodiment of the present invention 1 and commercialization Pt/C material；
Fig. 9 is that the Fe with hollow nanometer frame structure prepared according to the embodiment of the present invention 1 adulterates Mn3O4Carbon-nitrogen material
TEM map after cyclical stability test.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment 1
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.0g PVP, 1.0mmol are weighed3Fe(CN)6·3H2O solid
Metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；It weighs
The MnCl of 1.5mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；By Fe
(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 40 DEG C, 0.2 M NaOH solution, obtained solid powdery material
It is dry, then in N2Under atmosphere, 300 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Mn is adulterated using Fe of the approach such as SEM, TEM, XRD to hollow nanometer frame structure prepared by above embodiments3O4Carbon
Nitrogen material carries out physical characterization.From SEM (Fig. 1), it can be seen that Fe derived from Prussian blue similar object adulterates Mn3O4Carbon-nitrogen material
Equally distributed hollow cube of block structure is presented, surrounding is distributed the nanometer sheet of more growth, the TEM figure (Fig. 2) being further amplified
It can be seen that obtained material is this structure, while the side length of cubic block is in 600nm or so.By Fig. 3, XRD spectrum can
To find out, the diffraction maximum of material can be with Mn3O4Standard card fit like a glove (JCPDS no.18-0804), it was demonstrated that Fe successfully mixes
Enter to Mn3O4Intracell, (002) crystal face corresponds to the diffraction maximum of graphitized carbon simultaneously.Fig. 4 is the catalyst and other samples
The LSV curve graph that hydrogen reduction performance test obtains is carried out under the test environment, it can be seen that the Fe doping Mn being prepared3O4Carbon
Nitrogen material has more excellent initial reduction current potential and half wave potential.Fig. 5 is by material whether there is or not the test wrappers that methanol poisons
The LSV curve graph that hydrogen reduction performance test obtains is carried out under border, as seen from the figure under the test environment poisoned there are methanol, twice
The LSV curve of test is still almost overlapped, and illustrates that the catalyst material has good alcohol resistance.Tafel curve (Fig. 6) measures this
The numerical value of the Tafel slope of material is only 82.3mV dec-1, this is better than most of oxygen reduction electro-catalyst material, illustrates the material
Material has faster kinetics rate.Fig. 7 is the chronoa mperometric plot of the material, and sample is surveyed by the long-time of 40000s
After examination, current density decaying is smaller, again shows that the material has excellent stable circulation performance.Fig. 8 is the material and quotient
Industry Pt/C catalyst is assembled into the charge and discharge polarization curve after zinc and air cell, it can be seen that under high current density, the material
Material has higher power density.TEM map (Fig. 9) after cyclical stability is tested shows the hollow nanometer frame of the material
Frame structure still has, and volume, without significant change, which shows that hollow structure has effective buffering effect.The above knot
Fruit illustrates that the material has a good application prospect as zinc-air battery anode catalytic agent material.
Embodiment 2
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.5g PVP, 1.0mmol are weighed3Fe(CN)6·3H2O solid
Metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；It weighs
The MnCl of 1.5mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；By Fe
(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 40 DEG C, 0.2 M NaOH solution, obtained solid powdery material
It is dry, then in N2Under atmosphere, 300 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 3
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 4.0g PVP, 1.0mmol are weighed3Fe(CN)6·3H2O solid
Metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；It weighs
The MnCl of 1.5mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；By Fe
(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 40 DEG C, 0.2 M NaOH solution, obtained solid powdery material
It is dry, then in N2Under atmosphere, 300 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 4
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.0g PVP, 0.83mmol are weighed3Fe(CN)6·3H2O is solid
Body metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；Claim
Take the MnCl of 1.67mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；It will
Fe(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 40 DEG C, 0.2 M NaOH solution, obtained solid powdery material
It is dry, then in N2Under atmosphere, 300 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 5
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.0g PVP, 1.25mmol are weighed3Fe(CN)6·3H2O is solid
Body metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；Claim
Take the MnCl of 1.25mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；It will
Fe(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 40 DEG C, 0.2 M NaOH solution, obtained solid powdery material
It is dry, then in N2Under atmosphere, 300 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 6
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.0g PVP, 1.67mmol are weighed3Fe(CN)6·3H2O is solid
Body metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；Claim
Take the MnCl of 0.83mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；It will
Fe(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 40 DEG C, 0.2 M NaOH solution, obtained solid powdery material
It is dry, then in N2Under atmosphere, 300 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 7
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.0g PVP, 0.5mmol are weighed3Fe(CN)6·3H2O solid
Metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；It weighs
The MnCl of 0.75mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；By Fe
(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 40 DEG C, 0.2 M NaOH solution, obtained solid powdery material
It is dry, then in N2Under atmosphere, 300 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 8
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.0g PVP, 1.0mmol are weighed3Fe(CN)6·3H2O solid
Metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；It weighs
The MnCl of 1.5mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；By Fe
(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 40 DEG C, 2.0 M NaOH solutions, obtained solid powdery material
It is dry, then in N2Under atmosphere, 300 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 9
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.0g PVP, 1.0mmol are weighed3Fe(CN)6·3H2O solid
Metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；It weighs
The MnCl of 1.5mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；By Fe
(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 30 DEG C, 0.2 M NaOH solution, obtained solid powdery material
It is dry, then in N2Under atmosphere, 300 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 10
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.0g PVP, 1.0mmol are weighed3Fe(CN)6·3H2O solid
Metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；It weighs
The MnCl of 1.5mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；By Fe
(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 50 DEG C, 0.2 M NaOH solution, obtained solid powdery material
It is dry, then in N2Under atmosphere, 300 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 11
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.0g PVP, 1.0mmol are weighed3Fe(CN)6·3H2O solid
Metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；It weighs
The MnCl of 1.5mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；By Fe
(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 40 DEG C, 0.2 M NaOH solution, obtained solid powdery material
It is dry, then in N2Under atmosphere, 250 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 12
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.0g PVP, 1.0mmol are weighed3Fe(CN)6·3H2O solid
Metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；It weighs
The MnCl of 1.5mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；By Fe
(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 40 DEG C, 2.0 M NaOH solutions, obtained solid powdery material
It is dry, then in N2Under atmosphere, 350 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 13
A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method of carbon-nitrogen material, comprising the following steps:
1)KMnFe(CN)6The preparation of khaki precipitating: the K of 3.0g PVP, 1.0mmol are weighed3Fe(CN)6·3H2O solid
Metal salt and 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Fe (CN)6 3-/ PVP solution；It weighs
The MnCl of 1.5mmol2With 50ml H2The mixing of O solution, passes through mechanical stirring 10min at room temperature, obtains Mn2+Solution；By Fe
(CN)6 3-/ PVP solution and Mn2+Solution mixing, stands 12h, obtains KMnFe (CN)6Khaki precipitating；
2) the Fe doping Mn of hollow nanometer frame structure is prepared3O4Carbon-nitrogen material: by KMnFe made from step 1) (CN)6Soil
It is dry to first pass through centrifuge washing for yellow mercury oxide, the alkali cleaning 4h in 40 DEG C, 0.2 M NaOH solution, obtained solid powdery material
It is dry, then under an ar atmosphere, 300 DEG C are warming up to the heating rate of 5 DEG C/min and is heat-treated, and is kept at such a temperature
3h is then cooled to room temperature, and final product can be obtained.
Embodiment 14
It is same as Example 1, the difference is that:
Resulting Fe (CN)6 3-In/PVP solution, the mass fraction of PVP is 5%；Programmed rate is 1 DEG C/min, heat
Treatment temperature is 200 DEG C, time 2h.
Embodiment 15
It is same as Example 1, the difference is that:
Resulting Fe (CN)6 3-In/PVP solution, the mass fraction of PVP is 10%；Programmed rate is 10 DEG C/min,
Heat treatment temperature is 300 DEG C, time 4h.
Comparative example 1
The difference of this comparative example and embodiment 1 is only that remaining implementation condition is not without 0.2 M NaOH solution alkali cleaning
Become.
Comparative example 2
The difference of this comparative example and embodiment 1, which is only that, uses iron chloride substitution manganese chloride source metal, remaining implementation condition instead
It is constant.
Test results are shown in figure 4 by the LSV for the oxygen reduction reaction accordingly tested, the material not obtained by NaOH alkali cleaning
Most negative initial reduction current potential and the smallest current density are shown, worst hydrogen reduction performance is shown；Replacement source metal obtains
The Fe arrived3O4Carbon nitrogen electrocatalysis material, which is shown, adulterates Mn compared with Fe3O4The poor hydrogen reduction performance of carbon-nitrogen material.Overall performance
Contrast table reveals Fe-Mn3O4>Fe3O4>Fe-Mn3O4The sequence of (not passing through NaOH alkali cleaning).The hollow nanometer frame being prepared
The Fe of frame structure adulterates Mn3O4Carbon-nitrogen material electro-catalysis shows the hydrogen reduction performance that can be compared favourably with commercialization Pt/C, and answers
There is higher specific capacity and superior stable circulation performance in zinc-air battery.
Claims (10)
1. a kind of Fe with hollow nanometer frame structure adulterates Mn3O4The preparation method of carbon-nitrogen material, which is characterized in that including
Following steps:
1) K is prepared respectively3Fe(CN)6/ PVP solution and contain Mn2+Solution；
2) by the K3Fe(CN)6/ PVP solution and contain Mn2+Solution mix, obtain KMnFe (CN)6Precipitating；
3) by the KMnFe (CN)6After precipitating carries out alkali cleaning with sodium hydroxide solution, it is warming up to 250~350 in an inert atmosphere
It is heat-treated at DEG C, obtains the Fe doping Mn with hollow nanometer frame structure3O4Carbon-nitrogen material.
2. the Fe with hollow nanometer frame structure adulterates Mn as described in claim 13O4The preparation method of carbon-nitrogen material,
It is characterized in that, the K3Fe(CN)6/ PVP solution the preparation method comprises the following steps:
PVP and the potassium ferricyanide are dissolved in the water, after mixing, obtain the K3Fe(CN)6/ PVP solution.
3. the Fe with hollow nanometer frame structure adulterates Mn as claimed in claim 23O4The preparation method of carbon-nitrogen material,
It is characterized in that, the K3Fe(CN)6In/PVP solution, the mass fraction of PVP is 5~10%.
4. the Fe with hollow nanometer frame structure adulterates Mn as described in claim 13O4The preparation method of carbon-nitrogen material,
It is characterized in that, it is described to contain Mn2+Solution the preparation method comprises the following steps:
Manganese chloride is dissolved in the water.
5. the Fe with hollow nanometer frame structure adulterates Mn as described in claim 13O4The preparation method of carbon-nitrogen material,
It is characterized in that, the K3Fe(CN)6/ PVP solution and contain Mn2+Solution mixing after, Mn2+And Fe3+Molar ratio be 2:1~1:2.
6. the Fe with hollow nanometer frame structure adulterates Mn as described in claim 13O4The preparation method of carbon-nitrogen material,
It is characterized in that, the concentration for the sodium hydroxide solution that the alkali cleaning uses is 0.2M, and the temperature of alkali cleaning is 40 DEG C.
7. the Fe with hollow nanometer frame structure adulterates Mn as described in claim 13O4The preparation method of carbon-nitrogen material,
It is characterized in that, the rate of the heating is 1~10 DEG C/min, and heat treatment time is 2~4h.
8. the Fe with hollow nanometer frame structure adulterates Mn as described in claim 13O4The preparation method of carbon-nitrogen material,
It is characterized in that, the inert atmosphere is at least one of nitrogen, argon gas, helium, carbon dioxide.
9. the Fe doping Mn with hollow nanometer frame structure that a kind of preparation method as described in claim 1 obtains3O4Carbon nitrogen material
Material.
10. the Fe as claimed in claim 9 with hollow nanometer frame structure adulterates Mn3O4Carbon-nitrogen material is as zinc-air battery
The purposes of positive electrode.
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