CN109686988A - A kind of carbon carrying transition metal atom pair elctro-catalyst and the preparation method and application thereof - Google Patents
A kind of carbon carrying transition metal atom pair elctro-catalyst and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention provides a kind of carbon carrying transition metal atom pair elctro-catalysts and the preparation method and application thereof, belong to elctro-catalyst technical field.The present invention is using nitrogenous carbon source as carbon source and nitrogen source; due to the complexing between transition metal ions and nitrogenous carbon source; through precipitation reaction; form the catalyst precursor in carbon substrate with evenly dispersed transition metal diatomic pair; the catalyst precursor is pyrolyzed and anneals so that transition metal atoms obtain elctro-catalyst to being dispersed on porous carbon materials under 500~1000 DEG C of protective atmospheres.Present invention introduces double transition metal atoms, can not only increase the number of active sites of elctro-catalyst, can also effectively improve the activity and oxygen reduction activity of elctro-catalyst, have broad application prospects in metal-air battery, fuel cell field；In addition, preparation method of the invention is simple, and the cheap of required raw material, equipment are simple, it is easy to accomplish large-scale industrial production.
Description
Technical field
The present invention relates to elctro-catalyst technical field more particularly to a kind of carbon carrying transition metal atom pair elctro-catalyst and
Preparation method and application.
Background technique
Fuel cell is a kind of device that can directly convert the chemical energy stored in fuel to electric energy, and wherein proton is handed over
Membrane cell (PEMFC) is changed using hydrogen or methanol as fuel, storage, the transport of fuel are very convenient, be suitable for electric car/
Generator, application prospect are very wide.Although PEMFC has had preliminary application, it is intended to large-scale commercial still
With many technical problems, especially to the research of catalyst.It is in sun respectively there are mainly two types of reaction in PEMFC
The fuel oxidation reaction and the oxygen reduction reaction occurred in cathode that pole occurs, need catalyst to accelerate electrochemical reaction process.
Platinum based catalyst is the cathodic oxygen reduction catalyst of practical application in current hydrogen-oxygen fuel cell, but the earth of noble metal platinum is deposited
Amount itself is limited, is the primary factor for restricting platinum based catalyst fuel cell.It was announced according to U.S. Department of Energy (DOE) in 2013
The unit power load capacity of noble metal platinum, which should be not higher than 0.14gkW, to be shown for the expected of fuel cell technology project.And
The price for announcing platinum at that time based on data is calculated, and has still accounted for proton exchange membrane combustion for the cost of platinum-based electrocatalyst
Expect battery pack is always spent 24%.Therefore, if being confined to the research of platinum based catalyst, the cost of fuel cell will be directly single
Aspect is limited by originally height monopolization and extremely unstable precious metal marketplace.
Due to the price and scarcity of platinum valuableness, non noble metal oxygen reduction catalyst is developed for hydrogen-oxygen fuel cell
Scale application is very necessary.Carbon-based non noble metal oxygen reduction catalyst, including metal-nitrogen-doped carbon (M-N-C) material and non-
Metal heteroatom adulterates carbon material, is most important at present and the widest two classes non noble metal oxygen reduction catalyst of research.It is right
The cognition of the active site of above two non noble metal oxygen reduction catalyst is one of research hotspot, and significantly improving property
It can be with the key point of magnanimity preparation.
For metal-nitrogen-doped carbon catalyst, being now subjected to the active site being widely recognized as includes: M-Nx/ C (x=1,2,
3,4)、Nx- C, cladding nano metal particles activation carbon-coating etc. (Wang Yuemin, Luo Ergui, Xiao Meiling, Ge Junjie, Liu Changpeng,
Progress [J] Chinese science of the carbon-based non noble metal oxygen reduction catalyst active site of Xing Wei: chemistry, 2017,47 (05):
554-564).Carbon material (such as nitrogen-doped carbon material) is adulterated for nonmetallic heteroatoms, the carbon atom that nitrogen-atoms adjoins generally quilt
It is considered active site.But the active site of above two non noble metal oxygen reduction catalyst is limited, to oxygen reduction catalyst
Activity and stability have certain limitation, can not be widely applied.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of carbon carrying transition metal atom pair elctro-catalyst and its preparations
Method and application, elctro-catalyst provided by the invention have excellent oxygen reduction catalytic activity and stability, can substitute existing
It is commercialized Pt/C catalyst, is had broad application prospects in metal-air battery, fuel cell field.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of carbon carrying transition metal atom pair elctro-catalyst, comprising the following steps:
(1) by nitrogenous carbon source and double transition metal sources, successively formation mixed solution soluble in water, progress precipitation reaction are obtained
Precursor system；
(2) water in precursor system that the step (1) obtains is evaporated, grinds, obtains catalyst precursor；
(3) catalyst precursor for obtaining the step (2) is successively pyrolyzed and is annealed, obtained under protective atmosphere
To the carbon carrying transition metal atom pair elctro-catalyst；
Two kinds of transition metal sources are to be dissolved in water respectively in double transition metal sources in the step (1)；
The temperature being pyrolyzed in the step (3) is 500~1000 DEG C, and the time is 4~8h.
Preferably, further include in the step (1)；Sulphur source is added in mixed solution；The addition opportunity of the sulphur source is
After being added after double transition metal sources or being added one of double transition metal transition metal source；The sulphur source includes thiocarbamide or diethyl
Base nabam trihydrate.
Preferably, in the mixed solution sulphur source concentration be (0,1] mol/L.
Preferably, two kinds of transition metal in double transition metal sources include iron cobalt, zinc-magnesium, zinc-iron, cobalt magnesium, zinc cobalt or
Cobalt nickel.
Preferably, in the mixed solution in double transition metal sources the concentration of two kinds of transition metal sources independently be 0.01~
1mol/L。
Preferably, the molar ratio of two kinds of transition metal sources is 1:1~1:3 in double transition metal sources.
Preferably, the nitrogenous carbon source includes biomass, urea, melamine or glycine；Contain in the mixed solution
The concentration of nitrogen carbon source is 0.01~1mol/L.
Preferably, the temperature of the annealing is 600~1000 DEG C, and the time is 1~3h.
The carbon carrying transition metal atom pair electricity obtained the present invention also provides preparation method described in above-mentioned technical proposal is urged
Agent, the elctro-catalyst include porous carbon materials and double transition metal atoms pair；Double transition metal atoms are to uniform point
It is dispersed on porous carbon materials surface；The hole of the porous carbon materials is 1nm~50nm；The carbon carrying transition metal atom pair
The specific surface area of elctro-catalyst is 500~2500m2/g。
The present invention also provides carbon carrying transition metal atom pair elctro-catalysts described in above-mentioned technical proposal in metal-air
Application in battery, fuel cell field.
The present invention provides a kind of preparation methods of carbon carrying transition metal atom pair elctro-catalyst, comprising the following steps:
(1) by nitrogenous carbon source and double transition metal sources, successively formation mixed solution soluble in water, progress precipitation reaction obtain precursor body
System；(2) water in precursor system that the step (1) obtains is evaporated, grinds, obtains catalyst precursor；It (3) will be described
The catalyst precursor that step (2) obtains successively is pyrolyzed and is annealed under protective atmosphere, and the carbon load transitions gold is obtained
Belong to atom pair elctro-catalyst；Two kinds of transition metal sources are to be dissolved in water respectively in double transition metal sources in the step (1)；The step
Suddenly the temperature being pyrolyzed in (3) is 500~1000 DEG C, and the time is 4~8h.
The present invention is made using nitrogenous carbon source as carbon source and nitrogen source by the complexing between transition metal ions and nitrogenous carbon source
With through precipitation reaction, being formed in carbon substrate has the catalyst precursor of evenly dispersed transition metal diatomic pair, the catalysis
Agent precursor is pyrolyzed and is annealed so that transition metal atoms are porous to being dispersed under 500~1000 DEG C of protective atmospheres
On carbon material, elctro-catalyst is obtained.The present invention introduces double transition metal atoms on porous carbon materials, can not only increase electricity and urge
The number of active sites of agent can also effectively improve the stability of elctro-catalyst；Meanwhile the nitrogen in nitrogenous carbon source can
Double transition metal, which are complexed, makes double transition metal form atom pair, and has synergistic effect between double transition metal atoms pair, Ke Yizeng
The oxygen reduction activity of forceful electric power catalyst；In addition to this, preparation method of the invention is simple, and required raw material it is cheap, set
It is standby simple, it is easy to accomplish large-scale industrial production.Embodiment statistics indicate that: elctro-catalyst provided by the invention is in alkaline electro
Excellent oxygen reduction catalytic activity and stability are all had in solution liquid and acidic electrolysis bath, existing commercialization Pt/C can be substituted and urged
Agent.
Further, the addition of sulphur source can form a large amount of defects in carbon substrate, increase the active sites in carbon substrate
Point quantity, further improves the activity of elctro-catalyst.
Detailed description of the invention
Fig. 1 is the TEM figure that carbon prepared by embodiment 1 loads double transition metal atoms to elctro-catalyst；
Fig. 2 is the TEM figure that carbon prepared by embodiment 2 loads double transition metal atoms to elctro-catalyst；
Fig. 3 is the SEM figure that carbon prepared by embodiment 2 loads double transition metal atoms to elctro-catalyst；
Fig. 4 is that elctro-catalyst prepared by embodiment 1,6 and commercially available the Pt/C LSV in alkaline electrolyte scheme；
Fig. 5 is that elctro-catalyst prepared by embodiment 1,6 and commercially available the Pt/C LSV in acidic electrolysis bath scheme；
Fig. 6 is the stability curve of the elctro-catalyst and commercially available Pt/C of the preparation of embodiment 6 in alkaline electrolyte；
Fig. 7 is polarization curve of the 6 gained elctro-catalyst of embodiment in zinc-air battery；
Fig. 8 is that the XPS of 6 gained elctro-catalyst of embodiment schemes.
Specific embodiment
The present invention provides a kind of preparation methods of carbon carrying transition metal atom pair elctro-catalyst, comprising the following steps:
(1) nitrogenous carbon source and double transition metal sources is successively soluble in water, precipitation reaction is carried out, precursor system is obtained；
(2) water in precursor system that the step (1) obtains is evaporated, grinds, obtains catalyst precursor；
(3) catalyst precursor for obtaining the step (2) is successively pyrolyzed and is annealed, obtained under protective atmosphere
To the carbon carrying transition metal atom pair elctro-catalyst；
Two kinds of transition metal sources are to be dissolved in water respectively in double transition metal sources in the step (1)；
The temperature being pyrolyzed in the step (3) is 500~1000 DEG C, and the time is 4~8h.
Nitrogenous carbon source and double transition metal sources successively formation mixed solution soluble in water are carried out precipitation reaction by the present invention,
Obtain precursor system.In the present invention, the nitrogenous carbon source preferably includes biomass, urea, melamine or glycine；Institute
It states biomass and preferably includes chitosan or chorion.In the present invention, the concentration of nitrogenous carbon source is preferably in the mixed solution
0.01~1mol/L, further preferably 0.01~0.5mol/L, more preferably 0.01~0.1mol/L.
In the present invention, double transition metal preferably include iron cobalt, zinc-magnesium, zinc-iron, cobalt magnesium, zinc in double transition metal sources
Cobalt or cobalt nickel.In the present invention, two kinds of transition metal sources in double transition metal sources be preferably two kinds of transition metal can
Soluble.In an embodiment of the present invention, the cobalt source preferably includes cobalt acetate, and the source of iron preferably includes iron chloride, described
Zinc source preferably includes zinc chloride, and the magnesium source preferably includes magnesium acetate, and the nickel source preferably includes nickel acetate.
In the present invention, the concentration of two kinds of transition metal sources is independently preferred in double transition metal sources in the mixed solution
For 0.01~1mol/L, further preferably 0.1~0.8mol/L, more preferably 0.4~0.6mol/L.In the present invention, institute
The molar ratio for stating two kinds of transition metal sources in double transition metal sources is preferably 1:1~1:3, further preferably 1:1.5~1:
2.5, more preferably 1:2.
In the present invention, double transition metal sources are to be dissolved in water respectively.The present invention is suitable to the addition of double transition metal sources
Sequence does not have special restriction, random order.The present invention does not have special restriction to the adding manner of double transition metal sources, with
Transition metal source solid form is directly added into or transition metal source aqueous solution is added dropwise.In the present invention, the transition gold
The rate of addition of category source aqueous solution is preferably 1~10mL/min.
The present invention, which is preferably also included in mixed solution, is added sulphur source；The sulphur source preferably includes two sulphur of thiocarbamide or diethyl
For carbamic acid sodium trihydrate.In the present invention, the concentration of the sulphur source be preferably (0,1] mol/L, further preferably
0.1~0.9mol/L, more preferably 0.4~0.5mol/L.In the present invention, the addition opportunity of the sulphur source is preferably added double
After transition metal source or after one of double transition metal sources transition metal source is added.Adding manner of the present invention to the sulphur source
There is no special restriction, is directly added into the form of dropwise addition or sulphur source solid in the form of sulphur source aqueous solution.In the present invention,
The rate of addition of the sulphur source aqueous solution is preferably 1~10mL/min.
In the present invention, the precipitation reaction preferably carries out under stirring conditions；The revolving speed of the stirring is preferably 100
~1000r/min.In the present invention, the temperature of the precipitation reaction is preferably 30~90 DEG C, and further preferably 40~80 DEG C,
More preferably 50~70 DEG C；The time of the precipitation reaction is preferably 6~10h, further preferably 7~9h, more preferably 8h.
There are complexings to transition metal ions for nitrogen in nitrogenous carbon source of the invention, can form double transition metal
Diatomic pair, and have synergistic effect between double transition metal atoms pair, the oxygen reduction activity of elctro-catalyst can be enhanced；Contain simultaneously
Complexing between nitrogen carbon source and double transition metal sources enables double transition metal sources equably to mix with nitrogenous carbon source, leads to
Precipitation reaction is crossed, forms evenly dispersed transition metal diatomic pair in carbon substrate；In addition to this, it is former that double transition metal are introduced
Son can not only increase the number of active sites of elctro-catalyst, can also effectively improve the stability of elctro-catalyst.Further
The addition on ground, sulphur source can form a large amount of defects in carbon substrate, increase the active site quantity in carbon substrate, further mention
The high activity of elctro-catalyst.
After obtaining precursor system, the water in the precursor system is evaporated by the present invention, and grinding obtains body before catalyst
Body.In the present invention, the temperature being evaporated is preferably 85 DEG C；The present invention does not have special restriction to the time being evaporated, as long as
Water evaporation in precursor system is complete.In the present invention, described be evaporated preferably carries out under stirring conditions；It is described
The revolving speed of stirring is preferably 100~1000r/min.In the present invention, the partial size of the catalyst precursor be preferably 100nm~
10 μm, further preferably 200nm~5 μm.The present invention does not have special restriction to the mode and parameter of grinding, as long as can make
The partial size of catalyst precursor is 100nm~10 μm.
After obtaining catalyst precursor, the catalyst precursor under protective atmosphere, is successively pyrolyzed by the present invention
And annealing, obtain the carbon carrying transition metal atom pair elctro-catalyst.In the present invention, the protective atmosphere preferably includes nitrogen
Gas or argon gas；The purity of the protective atmosphere is preferably 99.99%.
In the present invention, the temperature of the pyrolysis be 500~1000 DEG C, preferably 600~900 DEG C, further preferably
700~800 DEG C；The time of the pyrolysis is 4~8h, preferably 5~7h, further preferably 6h.In the present invention, it is warming up to
The heating rate of pyrolysis temperature is preferably 5 DEG C/min.Nitrogenous carbon source is graphitized under the action of cobalt, and bi-metal atom is to being pyrolyzed
It mixes in carbon material in the process.
After pyrolysis, the present invention is preferably by thermal decomposition product successively through pickling, washing, filtering and drying.In the present invention,
The solution of the pickling is preferably inorganic acid solution；The concentration of the inorganic acid solution is preferably 2~5mol/L；When the pickling
It is preferred that thermal decomposition product is immersed in 6~12h in inorganic acid solution.In the present invention, the purpose of the pickling is to remove pyrolysis to produce
Metallic particles in object increases the exposure of active site in catalyst precursor.
The present invention does not have special restriction to the parameter of washing, filtering and drying, and use is well known to those skilled in the art
Washing, filtering and baking step and parameter.
In the present invention, the temperature of the annealing is preferably 600~1000 DEG C, and further preferably 700~900 DEG C, more
Preferably 800 DEG C；The time of the annealing is preferably 1~3h, further preferably 1.5~2.5h, more preferably 2.0h.At this
In invention, the heating rate for being warming up to annealing temperature is preferably 5 DEG C/min.
Catalyst precursor of the invention is pyrolyzed at 500~1000 DEG C under protective atmosphere, is annealed again, being catalyzed
Carbon conversion in agent precursor is porous carbon materials, improves the porosity and specific surface area of elctro-catalyst；Meanwhile it being pyrolyzed and annealing
Processing can uniformly divide double transition metal atoms on porous carbon materials, form the atom pair electro-catalysis of carbon carrying transition metal
Agent.
The carbon carrying transition metal atom pair electricity obtained the present invention also provides preparation method described in above-mentioned technical proposal is urged
Agent；The elctro-catalyst includes porous carbon materials and double transition metal atoms pair；Double transition metal atoms are to uniform point
It is dispersed on porous carbon materials；The hole of the porous carbon materials is 1nm~50nm；The specific surface area of the elctro-catalyst is 500
~2500m2/g。
The present invention also provides carbon carrying transition metal atom pair elctro-catalysts described in above-mentioned technical proposal in metal-air
Application in battery, fuel cell field.In the present invention, when the carbon carrying transition metal atom pair elctro-catalyst is applied to
When metal-air battery and fuel cell field, preferably the elctro-catalyst is mixed with cathode material, and is attached on cathode.
Below with reference to embodiment to carbon carrying transition metal atom pair elctro-catalyst provided by the invention and preparation method thereof
It is described in detail with application, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) 1g chitosan, 1g cobalt acetate and 100mL water are stirred evenly；Then the chlorination that 20mL concentration is 0.88mol/L is added dropwise
Zinc aqueous solution forms mixed solution, and the concentration of cobalt acetate is 0.05mol/L in mixed solution, and chlorination zinc concentration is
0.15mol/L；Mixed solution is subjected to precipitating 8h in room temperature, stirring condition, obtains precursor system；
(2) water in precursor system is evaporated at 85 DEG C, is then ground to the catalyst precursor that granularity is 10 μm；
(3) catalyst precursor is warming up to 750 DEG C with 5 DEG C/min, is pyrolyzed 4h；It then is the leaching of 1mol/L nitric acid with concentration
12h is steeped, is washed with deionized water, after filtering, drying；900 DEG C of annealing heat preservation 2h are warming up to the heating rate of 5 DEG C/min, are obtained
To carbon carrying transition metal atom pair elctro-catalyst.
Embodiment 2
(1) after stirring evenly 1g glycine, 1.6g cobalt acetate and 100mL water, 1.6g diethyl-dithio amino is sequentially added
Formic acid sodium trihydrate and 2.4g iron chloride form mixed solution, and the concentration of cobalt acetate is 0.09mol/L, chlorine in mixed solution
The concentration for changing iron is 0.15mol/L, and the concentration of sodium diethyldithiocarbamate is 0.071mol/L；Mixed solution is in room
Precipitation reaction 8h is carried out under conditions of temperature, stirring, obtains precursor system；
(2) water in precursor system is evaporated at 85 DEG C, is then ground to the catalyst precursor that granularity is 10 μm；
(3) catalyst precursor is warming up to 750 DEG C with 5 DEG C/min, is pyrolyzed 4h；It then is the leaching of 1mol/L nitric acid with concentration
12h is steeped, is washed with deionized water, after filtering, drying；900 DEG C of annealing heat preservation 2h are warming up to the heating rate of 5 DEG C/min, are obtained
To carbon carrying transition metal atom pair elctro-catalyst.
Embodiment 3
(1) after 1g nickel acetate and 100mL water stir evenly, cobalt acetate that 20mL concentration is 0.678mol/L is molten by 1g chorion
Drop is added to above-mentioned solution, forms mixed solution, and the concentration of nickel acetate is 0.05mol/L, the concentration of cobalt acetate in mixed solution
For 0.15mol/L；Mixed solution carries out precipitation reaction 8h under conditions of room temperature, stirring, obtains precursor system；
(2) water in precursor system is evaporated at 85 DEG C, is then ground to the catalyst precursor that granularity is 10 μm；
(3) catalyst precursor is warming up to 800 DEG C with 5 DEG C/min, is pyrolyzed 4h；It then is the leaching of 1mol/L nitric acid with concentration
12h is steeped, is washed with deionized water, after filtering, drying；900 DEG C of annealing heat preservation 2h are warming up to the heating rate of 5 DEG C/min, are obtained
To carbon carrying transition metal atom pair elctro-catalyst.
Embodiment 4
(1) after stirring evenly 1g chitosan, 0.8g cobalt acetate and 100mL water, 3.2g magnesium chloride is added, forms mixed solution,
The concentration of cobalt acetate is 0.045mol/L, density of magnesium chloride 0.20mol/L in mixed solution；Mixed solution is in room temperature, stirring
Under conditions of carry out precipitation reaction 8h, obtain precursor system；
(2) water in precursor system is evaporated at 85 DEG C, is then ground to the catalyst precursor that granularity is 10 μm；
(3) catalyst precursor is warming up to 750 DEG C with 5 DEG C/min, is pyrolyzed 4h；It then is the leaching of 1mol/L nitric acid with concentration
12h is steeped, is washed with deionized water, after filtering, drying；900 DEG C of annealing heat preservation 2h are warming up to the heating rate of 5 DEG C/min, are obtained
To carbon carrying transition metal atom pair elctro-catalyst.
Embodiment 5
(1) after stirring evenly 1g glycine, 0.8g cobalt acetate and 100mL water, 2.4g diethyl-dithio amino is sequentially added
Formic acid sodium trihydrate and 3.2g manganese chloride form mixed solution, and the concentration of cobalt acetate is 0.045mol/L, chlorine in mixed solution
Change manganese concentration is 0.20mol/L, and the concentration of sodium diethyldithiocarbamate is 0.1mol/L；Mixed solution in room temperature, stir
Precipitation reaction 8h is carried out under conditions of mixing, and obtains precursor system；
(2) water in precursor system is evaporated at 85 DEG C, is then ground to the catalyst precursor that granularity is 10 μm；
(3) catalyst precursor is warming up to 900 DEG C with 5 DEG C/min, is pyrolyzed 4h；It then is the leaching of 1mol/L nitric acid with concentration
12h is steeped, is washed with deionized water, after filtering, drying；900 DEG C of annealing heat preservation 2h are warming up to the heating rate of 5 DEG C/min, are obtained
To carbon carrying transition metal atom pair elctro-catalyst.
Embodiment 6
(1) 1g biomass, 1.6g cobalt acetate and 100mL water are stirred evenly, sequentially adds 2.4g diethyl-dithio amino first
Sour sodium trihydrate and 3.2g zinc chloride form mixed solution, and the concentration of cobalt acetate is 0.09mol/L, chlorination in mixed solution
Zinc concentration is 0.88mol/L, and the concentration of sodium diethyldithiocarbamate is 0.1mol/L；Mixed solution is in room temperature, stirring
Under conditions of carry out precipitation reaction 8h, obtain precursor system；
(2) water in precursor system is evaporated at 85 DEG C, is then ground to the catalyst precursor that granularity is 10 μm；
(3) catalyst precursor is warming up to 800 DEG C with 5 DEG C/min, is pyrolyzed 4h；It then is the leaching of 1mol/L nitric acid with concentration
12h is steeped, is washed with deionized water, after filtering, drying；900 DEG C of annealing heat preservation 2h are warming up to the heating rate of 5 DEG C/min, are obtained
To carbon carrying transition metal atom pair elctro-catalyst.
Embodiment 7
(1) 1g chitosan, 3.2g cobalt acetate and 100mL water are stirred evenly, sequentially adds 3.2g diethyl-dithio amino first
Sour sodium trihydrate and 3.2g zinc chloride form mixed solution, and the concentration of cobalt acetate is 0.18mol/L, chlorination in mixed solution
Zinc concentration is 0.20mol/L, and the concentration of sodium diethyldithiocarbamate is 0.15mol/L；Mixed solution is in room temperature, stirring
Under conditions of carry out precipitation reaction 8h, obtain precursor system；
(2) water in precursor system is evaporated at 85 DEG C, is then ground to the catalyst precursor that granularity is 10 μm；
(3) catalyst precursor is warming up to 800 DEG C with 5 DEG C/min, is pyrolyzed 4h；It then is the leaching of 1mol/L nitric acid with concentration
12h is steeped, is washed with deionized water, after filtering, drying；900 DEG C of annealing heat preservation 2h are warming up to the heating rate of 5 DEG C/min, are obtained
To carbon carrying transition metal atom pair elctro-catalyst.
The specific surface area for measuring gained carbon carrying transition metal atom pair elctro-catalyst in Examples 1 to 7, as a result such as table 1
It is shown.As can be seen from Table 1: the carbon material specific surface area of bi-metal atom doping is all bigger, and biggish specific surface area is advantageous
In the activity for promoting catalyst.
The specific surface area of gained carbon carrying transition metal atom pair elctro-catalyst in 1 Examples 1 to 7 of table
| Serial number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Specific surface area (m2/g) | 1600 | 800 | 530 | 600 | 700 | 1164 | 1348 |
Using 1 gained carbon carrying transition metal atom pair elctro-catalyst microstructure of transmission electron microscope observing embodiment, as a result
As shown in Figure 1.The pattern of ZnCo/NC is bulk as can be seen from Figure 1.
Using 2 gained carbon carrying transition metal atom pair elctro-catalyst microstructure of transmission electron microscope observing embodiment, as a result
As shown in Figure 2.The pattern of ZnCo/NSC is dendroid as can be seen from Figure 2.
Using 2 gained carbon carrying transition metal atom pair elctro-catalyst microstructure of scanning electron microscopic observation embodiment, as a result
As shown in Figure 3.The pattern of ZnCo/NSC is dendroid as can be seen from Figure 3.
Respectively by the gained of 5mg embodiment 1 and 6 elctro-catalyst and commercially available Pt/C and 1mL isopropanol solvent and 30 μ L nafion
It is mixed and made into catalyst ink, by 10~15 μ L catalyst ink water droplets on glass-carbon electrode, is tested on a rotary disc, is turned
Speed is 1600r/min, and electrolyte is 0.1mol/l KOH or 0.1mol/LHClO4；Above-mentioned three kinds of elctro-catalysts are tested in alkalinity
LSV figure in electrolyte and acidic electrolysis bath, as a result as shown in Figure 4 and Figure 5；In Fig. 4 and Fig. 5: (Zn, Co)/NSC, which is represented, to be implemented
6 gained elctro-catalyst of example, ZnCo/NC represent 1 gained elctro-catalyst of embodiment.Fig. 4 is the LSV figure in alkaline electrolyte, and Fig. 5 is
LSV figure in acidic electrolysis bath.As can be seen from Figure 4: ZnCo/NSC has shown the half way up the mountain electricity of 0.896V in alkaline electrolysis
Position, more than ZnCo/NC and business Pt/C, illustrates that the incorporation of sulphur improves oxygen reduction activity.As can be seen from Figure 5: 6 institute of embodiment
The ZnCo/NSC catalyst of preparation has shown excellent catalytic activity in acidic electrolysis bath.It can be seen in conjunction with Fig. 4 and Fig. 5
Out: no matter elctro-catalyst provided by the present invention is all having excellent hydrogen reduction in alkaline electrolyte or acidic electrolysis bath
Activity.
Respectively by 5mg embodiment 6 gained elctro-catalyst ZnCo/NSC and commercially available Pt/C, with 1mL isopropanol solvent and 30 μ L
Nafion is mixed and made into catalyst ink, by 10~15 μ L catalyst ink water droplets on glass-carbon electrode, carries out on a rotary disc
Test, revolving speed 1600r/min, in electrolyte (the electrolyte O of 0.1mol KOH2Saturation) in keep 0.6V constant potential
Stability of the above two elctro-catalyst in alkaline electrolyte is tested, as a result as shown in Figure 6.ZnCo/ as can be seen from Figure 6
NSC stability conservation rate in alkaline electrolyte is 96%, is more than business platinum carbon.
It is mixed with 1mL isopropanol solvent and 30 μ L nafion respectively by 6 gained elctro-catalyst of 5mg embodiment and commercially available Pt/C
Catalyst ink is made in conjunction, is coated on carbon paper and cathode is made, and zine plate tests institute in the KOH electrolyte of 6mol/L as anode
Polarization curve of the elctro-catalyst in zinc and air cell is stated, as a result as shown in Figure 7；In Fig. 7, solid line is LSV curve, and dotted line is power
Density curve.As can be seen from Figure 7: ZnCo/NSC has the power density 150mw/g of superelevation on zinc and air cell.
6 gained carbon carrying transition metal atom pair elctro-catalyst XPS of embodiment is schemed, reacts its chemical composition, as a result such as
Shown in Fig. 8.The group of catalyst becomes Zn, Co, N, C, O and S as can be seen from Figure 8.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of carbon carrying transition metal atom pair elctro-catalyst, which comprises the following steps:
(1) by nitrogenous carbon source and double transition metal sources, successively formation mixed solution soluble in water, progress precipitation reaction obtain preceding body
Body system；
(2) water in precursor system that the step (1) obtains is evaporated, grinds, obtains catalyst precursor；
(3) catalyst precursor for obtaining the step (2) is successively pyrolyzed and is annealed, obtain institute under protective atmosphere
State carbon carrying transition metal atom pair elctro-catalyst；
Two kinds of transition metal sources are dissolved in water respectively in double transition metal sources in the step (1)；
The temperature being pyrolyzed in the step (3) is 500~1000 DEG C, and the time is 4~8h.
2. preparation method according to claim 1, which is characterized in that further include in the step (1)；In mixed solution
Sulphur source is added；The addition opportunity of the sulphur source is to be added after double transition metal sources or be added one of double transition metal transition gold
Behind category source；The sulphur source includes thiocarbamide or sodium diethyldithiocarbamate trihydrate.
3. preparation method according to claim 2, which is characterized in that in the mixed solution concentration of sulphur source be (0,1]
mol/L。
4. preparation method according to claim 1, which is characterized in that two kinds of transition metal packets in double transition metal sources
Include iron cobalt, zinc-magnesium, zinc-iron, cobalt magnesium, zinc cobalt or cobalt nickel.
5. preparation method according to claim 1 or 4, which is characterized in that in the mixed solution in double transition metal sources
The concentration of two kinds of transition metal sources independently is 0.01~1mol/L.
6. preparation method according to claim 1 or 4, which is characterized in that two kinds of transition gold in double transition metal sources
The molar ratio in category source is 1:1~1:3.
7. preparation method according to claim 1, which is characterized in that the nitrogenous carbon source includes biomass, urea, trimerization
Cyanamide or glycine；The concentration of nitrogenous carbon source is 0.01~1mol/L in the mixed solution.
8. preparation method according to claim 1, which is characterized in that the temperature of the annealing is 600~1000 DEG C, the time
For 1~3h.
9. the carbon carrying transition metal atom pair elctro-catalyst that any one of claim 1~8 preparation method obtains, feature
It is, the elctro-catalyst includes porous carbon materials and double transition metal atoms pair；Double transition metal atoms are to uniform point
It is dispersed on porous carbon materials surface；The hole of the porous carbon materials is 1nm~50nm；The carbon carrying transition metal atom pair
The specific surface area of elctro-catalyst is 500~2500m2/g。
10. carbon carrying transition metal atom pair elctro-catalyst as claimed in claim 9 is in metal-air battery, fuel cell field
In application.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111864222A (en) * | 2020-06-22 | 2020-10-30 | 江苏大学 | Preparation method of zinc-based bimetallic-nitrogen carbon-doped material and application of zinc-based bimetallic-nitrogen carbon-doped material to electrode catalyst |
| CN112421060A (en) * | 2019-08-20 | 2021-02-26 | 中国科学院大连化学物理研究所 | Nitrogen-doped ferrous sulfide iron oxide reduction catalyst material and preparation application thereof |
| CN112853390A (en) * | 2020-12-31 | 2021-05-28 | 武汉度美迪新能源科技有限公司 | Oxygen reduction catalyst and preparation method thereof |
| CN112864402A (en) * | 2021-01-11 | 2021-05-28 | 杭州楚佩科技有限公司 | Preparation and application of Fe-N co-doped mesoporous carbon oxygen reduction catalyst |
| CN114976070A (en) * | 2022-06-29 | 2022-08-30 | 华南理工大学 | Method for preparing non-noble metal-nitrogen co-doped porous carbon material and application thereof |
| CN115064705A (en) * | 2022-07-05 | 2022-09-16 | 清华大学 | Catalyst of dissimilar metal atom pair, preparation method and application thereof |
| WO2023246000A1 (en) * | 2022-06-23 | 2023-12-28 | 复旦大学 | Transition metal-nitrogen/sulfur/selenium doped porous carbon catalyst and neutral zinc-air battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106876728A (en) * | 2017-02-14 | 2017-06-20 | 中国科学技术大学 | Monatomic graphene-based catalyst of load of high density transition metal and preparation method thereof |
| CN107180972A (en) * | 2017-05-12 | 2017-09-19 | 南京师范大学 | A kind of method for adjusting the nitrogen content in the monatomic iron catalyst of carbon nitrogen base |
| CN107803207A (en) * | 2017-10-18 | 2018-03-16 | 中南大学 | A kind of carbon-based double metallic composite material, preparation and its application |
| CN108400343A (en) * | 2018-02-13 | 2018-08-14 | 山东大学 | A kind of nitrogen load carbon nanosheet lithium oxygen battery anode catalytic agent material and preparation method thereof that high-performance cobalt granule is modified |
| CN108686693A (en) * | 2018-04-19 | 2018-10-23 | 重庆大学 | A kind of preparation method of monatomic cobalt-based nitrogen sulphur codope carbon material catalyst |
-
2018
- 2018-12-27 CN CN201811609302.3A patent/CN109686988A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106876728A (en) * | 2017-02-14 | 2017-06-20 | 中国科学技术大学 | Monatomic graphene-based catalyst of load of high density transition metal and preparation method thereof |
| CN107180972A (en) * | 2017-05-12 | 2017-09-19 | 南京师范大学 | A kind of method for adjusting the nitrogen content in the monatomic iron catalyst of carbon nitrogen base |
| CN107803207A (en) * | 2017-10-18 | 2018-03-16 | 中南大学 | A kind of carbon-based double metallic composite material, preparation and its application |
| CN108400343A (en) * | 2018-02-13 | 2018-08-14 | 山东大学 | A kind of nitrogen load carbon nanosheet lithium oxygen battery anode catalytic agent material and preparation method thereof that high-performance cobalt granule is modified |
| CN108686693A (en) * | 2018-04-19 | 2018-10-23 | 重庆大学 | A kind of preparation method of monatomic cobalt-based nitrogen sulphur codope carbon material catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 高庆文: "过渡金属、氮共掺杂碳材料的制备及其ORR催化活性的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112421060A (en) * | 2019-08-20 | 2021-02-26 | 中国科学院大连化学物理研究所 | Nitrogen-doped ferrous sulfide iron oxide reduction catalyst material and preparation application thereof |
| CN111864222A (en) * | 2020-06-22 | 2020-10-30 | 江苏大学 | Preparation method of zinc-based bimetallic-nitrogen carbon-doped material and application of zinc-based bimetallic-nitrogen carbon-doped material to electrode catalyst |
| CN112853390A (en) * | 2020-12-31 | 2021-05-28 | 武汉度美迪新能源科技有限公司 | Oxygen reduction catalyst and preparation method thereof |
| CN112864402A (en) * | 2021-01-11 | 2021-05-28 | 杭州楚佩科技有限公司 | Preparation and application of Fe-N co-doped mesoporous carbon oxygen reduction catalyst |
| WO2023246000A1 (en) * | 2022-06-23 | 2023-12-28 | 复旦大学 | Transition metal-nitrogen/sulfur/selenium doped porous carbon catalyst and neutral zinc-air battery |
| CN114976070A (en) * | 2022-06-29 | 2022-08-30 | 华南理工大学 | Method for preparing non-noble metal-nitrogen co-doped porous carbon material and application thereof |
| CN114976070B (en) * | 2022-06-29 | 2024-01-30 | 华南理工大学 | Method for preparing non-noble metal-nitrogen co-doped porous carbon material and application thereof |
| CN115064705A (en) * | 2022-07-05 | 2022-09-16 | 清华大学 | Catalyst of dissimilar metal atom pair, preparation method and application thereof |
| CN115064705B (en) * | 2022-07-05 | 2024-05-24 | 清华大学 | Heterometallic atom pair catalyst and preparation method and application thereof |
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