CN105810963A - Preparation method and application of transition metal-nitrogen-carbon-based electrocatalyst - Google Patents
Preparation method and application of transition metal-nitrogen-carbon-based electrocatalyst Download PDFInfo
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- CN105810963A CN105810963A CN201610270553.8A CN201610270553A CN105810963A CN 105810963 A CN105810963 A CN 105810963A CN 201610270553 A CN201610270553 A CN 201610270553A CN 105810963 A CN105810963 A CN 105810963A
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- 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
- H01M4/96—Carbon-based electrodes
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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
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- H01M4/88—Processes of manufacture
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a preparation method and an application of a transition metal-nitrogen-carbon-based electrocatalyst. The preparation method comprises the following steps: drying biomass and grinding the biomass into biomass powder; mixing the biomass powder with deionized water and carrying out heat preservation at 180 for 10 hours; cooling the mixture to a room temperature, filtering the mixture with a filter membrane of which the aperture is 0.22 microns for twice and then centrifuging the product at 14,000 turns for 20 minutes to prepare a nitrogen-doped carbon quantum dot solution; polymerizing a transition metal ion solution and the nitrogen-doped carbon quantum dot solution by pyrrole to prepare a polymerized product; and carrying out high-temperature calcination on the polymerized product in a protective atmosphere to prepare the transition metal-nitrogen-carbon-based electrocatalyst. The preparation technology is simple; the cost is low; and the prepared electrocatalyst has excellent electrocatalytic properties.
Description
Technical field
The present invention relates to eelctro-catalyst field, particularly relate to a kind of transition metal-nitrogen-carbon back eelctro-catalyst (i.e. transition metal,
Nitrogen co-doped graphitization carbon back eelctro-catalyst) preparation method and application.
Background technology
Eelctro-catalyst is the core of the key areas such as electrochemical energy conversion, electrosynthesis, Environmental electrochemistry inspective regulation.At electricity
In Xie Shui field, the quality of eelctro-catalyst directly determines the overvoltage required for being electrolysed water and electric energy is converted to turning of Hydrogen Energy
Change efficiency.In the sustainable energy such as fuel cell, metal-air battery field, the eelctro-catalyst of oxygen evolution reaction on anode
It is the determiner of secondary cell charging process, and on negative electrode, the eelctro-catalyst of oxygen reduction reaction directly determines energy conversion effect
Rate and the height of battery cost.
At present, the most widely used oxygen reduction electro-catalyst is the alloy of noble metal platinum or platinum, but due to platinum price too
Costliness, therefore reduces or replaces the use of platinum, and development high catalytic performance, the eelctro-catalyst of low cost are always electrochemical field
Focus.It has been investigated that: a lot of nitrogen-doped carbon materials and complex thereof all have good electronic conduction ability, relatively
Big specific surface area, rational pore structure and the corrosion resistance of excellence, be very suitable for as oxygen reduction electro-catalyst；But
Being in the prior art, the preparation process of these materials needs the industrial chemical that Price-dependent is expensive, and easily produces
Environmental pollution.
Summary of the invention
For above-mentioned weak point of the prior art, the invention provides the system of a kind of transition metal-nitrogen-carbon back eelctro-catalyst
Preparation Method and application, not only preparation technology is simple, with low cost, and the electricity that prepared eelctro-catalyst has excellence is urged
Change performance.
It is an object of the invention to be achieved through the following technical solutions:
The preparation method of a kind of transition metal-nitrogen-carbon back eelctro-catalyst, comprises the following steps:
Step A, biomass are dried and grinds to form powdered biomass；Described powdered biomass is mixed with deionized water, and
It is incubated 5～20 hours at 100～220 DEG C；It is then cooled to room temperature, employing membrane filtration 1～5 times, then with 8000-14000
Leave the heart, thus prepare nitrogen-doped carbon quantum dot solution；Wherein, described powdered biomass with the mixed proportion of deionized water is:
Every 100mL deionized water uses 5g～50g powdered biomass；
Transition metal ion solution and described nitrogen-doped carbon quantum dot solution are polymerized by step B, employing pyrroles, thus
Prepare polymerizate；
Step C, described polymerizate is carried out high-temperature calcination in protective atmosphere, thus prepare transition metal-nitrogen-carbon back electricity
Catalyst.
Preferably, use pyrroles that transition metal ion solution and described nitrogen-doped carbon quantum dot solution are carried out polymerization to include:
According to every 3L pyrroles use 25mol ferric ion, 50～200L described in the ratio of nitrogen-doped carbon quantum dot solution,
Pyrroles, ferric ion solution, described nitrogen-doped carbon quantum dot solution are mixed, and stirs 4～6 hours, so
Rear centrifuge washing is also dried, thus prepares polymerizate；Or,
The peroxide that Solute mass fraction is 30% of 25mol divalent transition metal ion, 10～30L is used according to every 3L pyrroles
Change hydrogen solution, 50～200L described in the ratio of nitrogen-doped carbon quantum dot solution, by pyrroles, divalent transition metal ion solution,
Described nitrogen-doped carbon quantum dot solution mixes, and add acid pH value is adjusted to 2, be subsequently adding hydrogen peroxide molten
Liquid, stirs 4～6 hours, then centrifuge washing being dried, thus prepares polymerizate.
Preferably, described divalent transition metal ion is Fe2+、Co2+Or Ni2+In one or more.
Preferably, described in protective atmosphere, described polymerizate carried out high-temperature calcination and include: be in protective atmosphere, right
Described polymerizate heats, until temperature reaches 600～1200 DEG C, then calcines 2～3 hours with 600～1200 DEG C,
Thus prepare transition metal-nitrogen-carbon back eelctro-catalyst.
As seen from the above technical solution provided by the invention, transition metal-nitrogen that the embodiment of the present invention is provided-carbon back electricity
Cheap biomass are first converted into nitrogen-doped carbon quantum dot as carbon source by the preparation method of catalyst, are then polymerized nitrogen with pyrroles
Doping carbon quantum dot and transition metal ions, then the transition metal with excellent electrocatalysis characteristic is can be prepared by by high-temperature calcination
-nitrogen-carbon back eelctro-catalyst, therefore the preparation method cost of transition metal-nitrogen-carbon back eelctro-catalyst that the embodiment of the present invention is provided
Cheap, preparation technology is simple.Transition metal-nitrogen-carbon back eelctro-catalyst obtained by the present invention can be anti-at electrochemical oxygen reduction
, oxygen evolution reaction or Hydrogen evolving reaction should use as eelctro-catalyst, be very suitable for being applied to metal-air battery, can filling
The fields such as discharge metal-air cell, fuel cell, electrolysis water.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, in describing embodiment below, required use is attached
Figure is briefly described, it should be apparent that, the accompanying drawing in describing below is only some embodiments of the present invention, for ability
From the point of view of the those of ordinary skill in territory, on the premise of not paying creative work, it is also possible to obtain other according to these accompanying drawings attached
Figure.
Fig. 1 is that the high-resolution projection Electronic Speculum of the nitrogen-doped carbon quantum dot solution obtained by step A1 of the embodiment of the present invention 1 is shone
Sheet and size distribution plot.
Fig. 2 is the field emission scanning electron microscope picture of the black polymeric product obtained by step B1 of the embodiment of the present invention 1.
Fig. 3 is the transmission electron microscope picture one of the cobalt-nitrogen-carbon back eelctro-catalyst obtained by step C1 of the embodiment of the present invention 1.
Fig. 4 is the transmission electron microscope picture two of the cobalt-nitrogen-carbon back eelctro-catalyst obtained by step C1 of the embodiment of the present invention 1.
Fig. 5 is the isothermal nitrogen adsorption-desorption of the cobalt-nitrogen-carbon back eelctro-catalyst obtained by step C1 of the embodiment of the present invention 1
Curve synoptic diagram.
Fig. 6 is the pore-size distribution schematic diagram of the cobalt-nitrogen-carbon back eelctro-catalyst obtained by step C1 of the embodiment of the present invention 1.
Fig. 7 is step C1 of the embodiment of the present invention 1 cobalt-nitrogen-carbon back eelctro-catalyst obtained by under different calcining heats
X-ray diffracting spectrum (XRD figure spectrum).
Fig. 8 be the cobalt-nitrogen-carbon back eelctro-catalyst obtained under different calcining heats of step C1 of the embodiment of the present invention 1 with
The electrocatalysis characteristic comparison diagram of platinum carbon or ruthenium-oxide.
Fig. 9 a is the cobalt-nitrogen-carbon back eelctro-catalyst obtained by step C1 of the embodiment of the present invention 1 and platinum carbon to be catalyzed respectively
Agent is assembled in chargeable zinc-air battery and carries out charge-discharge performance test, thus the open-circuit voltage comparison diagram obtained.
Fig. 9 b is the cobalt-nitrogen-carbon back eelctro-catalyst obtained by step C1 of the embodiment of the present invention 1 and platinum carbon to be catalyzed respectively
Agent is assembled in chargeable zinc-air battery and carries out charge-discharge performance test, thus the discharge voltage current polarizing obtained is bent
Line and power density curve comparison figure.
Fig. 9 c is respectively by the cobalt-nitrogen-carbon back eelctro-catalyst obtained by step C1 of the embodiment of the present invention 1 and platinum carbon-oxidation
Ruthenium catalyst is assembled in chargeable zinc-air battery and carries out charge-discharge performance test, the charging/discharging voltage electric current pole obtained
Change curve comparison figure.
Fig. 9 d is to be assembled into chargeable by the cobalt-nitrogen-carbon back eelctro-catalyst obtained by step C1 of the embodiment of the present invention 1 respectively
Zinc-air battery in and be 10mA/cm at charging and discharging currents2Time the cycle charge discharge electrical stability schematic diagram that records.
Figure 10 is ferrum-nitrogen-carbon back electro-catalysis that step C2 of the embodiment of the present invention 2 is obtained at calcining heat is 900 DEG C
The field emission scanning electron microscope picture of agent and transmission electron microscope picture.
Figure 11 is ferrum-nitrogen-carbon back electro-catalysis that step C2 of the embodiment of the present invention 2 is obtained at calcining heat is 800 DEG C
The field emission scanning electron microscope picture of agent and transmission electron microscope picture.
Figure 12 is ferrum-nitrogen-carbon back electro-catalysis that step C2 of the embodiment of the present invention 2 is obtained at calcining heat is 700 DEG C
The field emission scanning electron microscope picture of agent and transmission electron microscope picture.
Figure 13 is ferrum-nitrogen-carbon back electro-catalysis that step C2 of the embodiment of the present invention 2 is obtained at calcining heat is 600 DEG C
The field emission scanning electron microscope picture of agent and transmission electron microscope picture.
Figure 14 a is the ferrum-nitrogen-carbon back eelctro-catalyst obtained by step C2 of the embodiment of the present invention 2 and platinum carbon to be urged respectively
Agent is assembled in chargeable zinc-air battery and carries out charge-discharge performance test, thus the open-circuit voltage comparison diagram obtained.
Figure 14 b is the ferrum-nitrogen-carbon back eelctro-catalyst obtained by step C2 of the embodiment of the present invention 2 and platinum carbon to be urged respectively
Agent is assembled in chargeable zinc-air battery and carries out discharge performance test, thus the constant-current discharge test comparison obtained
Figure.
Figure 14 c is the ferrum-nitrogen-carbon back eelctro-catalyst obtained by step C2 of the embodiment of the present invention 2 and platinum carbon to be urged respectively
Agent is assembled in chargeable zinc-air battery and carries out discharge performance test, thus the discharge voltage current polarizing obtained is bent
Line comparison diagram.
Figure 14 d is respectively by the ferrum-nitrogen-carbon back eelctro-catalyst obtained by step C2 of the embodiment of the present invention 2 and platinum carbon group
Install in chargeable zinc-air battery and carry out discharge performance test, thus the long-time discharge stability obtained and this zinc-
The specific energy comparison diagram of air cell.
Figure 15 is the EDS (Energy of the ferrum-nitrogen-carbon back eelctro-catalyst obtained by step C2 of the embodiment of the present invention 2
Dispersive Spectrometer) can spectrogram.
Figure 16 is the EDS-mapping figure of the ferrum-nitrogen-carbon back eelctro-catalyst obtained by step C2 of the embodiment of the present invention 2
(element Energy distribution Surface scan analysis chart).
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely retouched
State, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on this
Bright embodiment, the every other enforcement that those of ordinary skill in the art are obtained under not paying creative work premise
Example, broadly falls into protection scope of the present invention.
Below the preparation method and application of transition metal-nitrogen-carbon back eelctro-catalyst provided by the present invention is described in detail.
The preparation method of a kind of transition metal-nitrogen-carbon back eelctro-catalyst, comprises the following steps:
Step A, biomass are dried and grinds to form powdered biomass；Described powdered biomass is mixed with deionized water, and
It is incubated 5～20 hours at 100 DEG C～220 DEG C；It is then cooled to room temperature, employing membrane filtration 1～5 times, then with
8000-14000 leaves the heart, thus prepares nitrogen-doped carbon quantum dot solution.Specifically, described powdered biomass and deionized water
Mixed proportion be: every 100mL deionized water uses 5g～50g powdered biomass；Described biomass can use shrimp
The biomass such as shell, trees, weeds, straw, owing to these biomass not containing only abundant carbon, but also
Containing a large amount of nitrogen elements, therefore doped with nitrogen in the carbon quantum dot solution obtained by this step, this is advantageous to the present invention
Synthesis transition metal-nitrogen-carbon back eelctro-catalyst eventually.
Transition metal ion solution and described nitrogen-doped carbon quantum dot solution are polymerized by step B, employing pyrroles, thus
Prepare polymerizate.Specifically, described transition metal ion solution is Fe3+Solution, Fe2+Solution, Co2+Solution or Ni2+
Solution；This step B can use the one in following two embodiment:
(1) according to every 3L pyrroles use 25mol ferric ion, 50～200L described in nitrogen-doped carbon quantum dot solution
Ratio, mixes pyrroles, ferric ion solution, described nitrogen-doped carbon quantum dot solution, and it is little to stir 4～6
Time, it is then centrifuged for washing and is dried, thus preparing the polymerizate of black；This polymerizate is the solid microsphere being connected with each other,
And the diameter Distribution of these solid microspheres is between 100～300nm.Wherein, described ferric ion solution can be adopted
With liquor ferri trichloridi, iron nitrate solution or ferrum sulfuricum oxydatum solutum, and the concentration of this ferric ion solution is preferably
0.1mol/L。
(2) Solute mass fraction of 25mol divalent transition metal ion, 10～30L is used to be 30% according to every 3L pyrroles
Hydrogenperoxide steam generator, 50～200L described in the ratio of nitrogen-doped carbon quantum dot solution, by pyrroles, divalent transition metal ion
Solution, described nitrogen-doped carbon quantum dot solution mix, and add acid (such as: hydrochloric acid, nitric acid or sulphuric acid) general
PH value is adjusted to 1～3, is subsequently adding hydrogenperoxide steam generator, stirs 4～6 hours, then centrifuge washing being dried, thus makes
Obtain the polymerizate of black；This polymerizate is the solid microsphere being connected with each other, and the diameter Distribution of these solid microspheres exists
Between 100～300nm.Wherein, described divalent transition metal ion is Fe2+、Co2+Or Ni2+In one or more,
Thus described divalent transition metal ion solution can use ferrous chloride, ferrous sulfate, cobaltous chloride, cobalt nitrate, chlorination
One or more in nickel or nickel nitrate, and the concentration of this divalent transition metal ion solution is preferably 0.1mol/L.
Step C, described polymerizate is carried out high-temperature calcination in protective atmosphere, thus prepare transition metal-nitrogen-carbon back electricity
Catalyst (i.e. transition metal, nitrogen co-doped graphitization carbon back eelctro-catalyst).Specifically, (i.e. exist in protective atmosphere
Under the protection environment of nitrogen or argon), described polymerizate is heated, until temperature reaches 600～1200 DEG C, so
After with 600～1200 DEG C calcine 2～3 hours, thus prepare transition metal-nitrogen-carbon back eelctro-catalyst.
Further, according to the mistake prepared by the preparation method of transition metal-nitrogen-carbon back eelctro-catalyst provided by the present invention
Crossing metal-nitrogen-carbon back eelctro-catalyst, its pattern shows as transition metal or its oxide particle is carried on transition metal with nitrogen altogether
The graphitized carbon material of doping, and there is bigger specific surface area and pore structure, therefore this transition metal-nitrogen-carbon back electricity is urged
Agent can show the electrocatalysis characteristic of excellence.The preparation side of transition metal-nitrogen-carbon back eelctro-catalyst provided by the present invention
Method can prepare the carbon back eelctro-catalyst that performance is various, such as by using different transition metal: if transition metal uses
Iron ion, then obtained ferrum-nitrogen-carbon back eelctro-catalyst can be as efficient hydrogen reduction carbon back eelctro-catalyst；If crossed
Cross metal and use cobalt ion, then obtained cobalt-nitrogen-carbon back eelctro-catalyst can be as having hydrogen reduction, oxygen analysis efficiently
Go out and the carbon back eelctro-catalyst of hydrogen evolution ability；Therefore transition metal-nitrogen-carbon back the eelctro-catalyst obtained by the present invention can be
Electrochemical oxygen reduction reaction, oxygen evolution reaction or Hydrogen evolving reaction use as eelctro-catalyst, is very suitable for being applied to metal
-air cell, can the field such as discharge and recharge metal-air battery, fuel cell, electrolysis water.
As fully visible, the preparation method of transition metal-nitrogen-carbon back eelctro-catalyst provided by the present invention is made with cheap biomass
For carbon, relative inexpensiveness, preparation technology are simple, and prepared transition metal-nitrogen-carbon back eelctro-catalyst has excellent
Different electrocatalysis characteristic.
In order to more clearly from show technical scheme provided by the present invention and produced technique effect, below with concrete real
Execute example the preparation method and application of transition metal-nitrogen-carbon back eelctro-catalyst provided by the present invention is described in detail.
Embodiment 1
A kind of transition metal-nitrogen-carbon back eelctro-catalyst, uses following steps to be prepared from:
Step A1, Crusta Penaeus seu Panulirus is dried and grinds to form Crusta Penaeus seu Panulirus powder；Take 30g Crusta Penaeus seu Panulirus powder and 300mL deionized water joins
In the polytetrafluoro reactor of 500mL, stirring is mixed is incorporated at 180 DEG C insulation 10 hours；It is then cooled to room temperature, uses
Membrane aperture is the membrane filtration 2 times of 0.22 μm, then leaves the heart 20 minutes with 14000, thus prepares nitrogen-doped carbon quantum
Point solution.
Step B1, by the pyrroles of 0.6mL, 0.1mol/L divalent cobalt ion solution (the i.e. bivalence of 0.005mol of 50mL
Cobalt ion), the nitrogen-doped carbon quantum dot solution obtained by step A1 of 20mL mixes, and adds Solute mass and divide
Number is that pH value is adjusted to 1～3 by 36% hydrochloric acid (nitric acid or sulphuric acid), and the Solute mass fraction being subsequently adding 4mL is 30%
Hydrogenperoxide steam generator, stir 4～6 hours, then centrifuge washing being dried, thus prepare black polymeric product.
Step C1, under nitrogen protection environment, the polymerizate obtained by step B1 is placed in tube furnace, and according to often
The speed of 5 DEG C of minute heating up heats, until temperature reaches 600～1000 DEG C, then with 600～1000 DEG C of calcinings 2～
3 hours, thus prepare cobalt-nitrogen-carbon back eelctro-catalyst (i.e. cobalt, nitrogen co-doped graphitization carbon back eelctro-catalyst).
Specifically, detect during using the embodiment of the present invention 1 to prepare cobalt-nitrogen-carbon back eelctro-catalyst, thus obtain
Following testing result:
(1) use high-resolution-ration transmission electric-lens (TEM, JEOL 2010) to obtained by step A1 of the embodiment of the present invention 1
Nitrogen-doped carbon quantum dot solution observe and shoot, thus obtain high-resolution as shown in Figure 1 projection electromicroscopic photograph and
Size distribution plot.As seen from Figure 1: the carbon quantum dot distribution of sizes obtained by step A1 of the embodiment of the present invention 1 exists
Between 1.5～5.5nm.
(2) field emission scanning electron microscope (FESEM, Quanta 200FEG) step B1 to the embodiment of the present invention 1 is used
Obtained black polymeric product carries out observation and shoots, thus the field emission scanning electron microscope picture as shown in Figure 2 obtained.By
Fig. 2 is it can be seen that the pattern of this black polymeric product is microspheroidal, and distribution of sizes is 100～300nm.
(3) use high-resolution-ration transmission electric-lens (TEM, JEOL 2010) that step C1 of the embodiment of the present invention 1 is finally made
Cobalt-nitrogen-carbon back the eelctro-catalyst obtained is observed and is shot, thus the scanning electricity of Flied emission as shown in Figure 3 and Figure 4 obtained
Mirror picture.By Fig. 3 and Fig. 4 it can be seen that this cobalt-nitrogen-carbon back eelctro-catalyst includes cobalt/cobalt oxide micro-nano granules and
The carbon of carbonization structure.
(4) specific surface area and the pore-size distribution test instrunment (Tristar3020M) step to the embodiment of the present invention 1 are used
The specific surface area performance of cobalt-nitrogen-carbon back eelctro-catalyst that C1 finally prepares measures, thus the nitrogen as shown in Figure 5 obtained
Gas isothermal adsorption-desorption curve schematic diagram.As seen from Figure 5: the specific surface area of this cobalt-nitrogen-carbon back eelctro-catalyst is
647.7m2/g。
(5) specific surface area and the pore-size distribution test instrunment (Tristar3020M) step to the embodiment of the present invention 1 are used
The pore-size distribution of cobalt-nitrogen-carbon back eelctro-catalyst that C1 finally prepares carries out observing to be measured, thus the hole as shown in Figure 6 obtained
Footpath scattergram.As seen from Figure 6: the pore-size distribution of this cobalt-nitrogen-carbon back eelctro-catalyst is between 1.5～2nm.
(6) use x-ray diffractometer (Philips X ' pert PRO) to step C1 of the embodiment of the present invention 1 respectively with
700 DEG C, 800 DEG C, 900 DEG C, the cobalt-nitrogen-carbon back eelctro-catalyst obtained by calcining heat of 1000 DEG C test, thus
Obtain XRD figure spectrum as shown in Figure 7；Wherein, the vertical coordinate of Fig. 7 is relative intensity, the abscissa of Fig. 7 be 2 θ (i.e.
The angle of diffraction, its unit is degree).As seen from Figure 7: cobalt ion is first converted into cobalt/cobalt oxide, then converts to zeroth order cobalt.
(7) to step C1 of the embodiment of the present invention 1 respectively with 700 DEG C, 800 DEG C, 900 DEG C, the calcining temperature of 1000 DEG C
Cobalt-nitrogen-carbon back eelctro-catalyst obtained by degree and platinum carbon or ruthenium-oxide carry out electrocatalysis characteristic test, thus obtain such as Fig. 8
Shown electrocatalysis characteristic comparison diagram.Wherein, Fig. 8 a is to divide with 10mV/S sweep speed in the KOH solution of 0.1mol/L
Other be 700 DEG C to platinum carbon and calcining heat, 800 DEG C, 900 DEG C, the cobalt-nitrogen-carbon back eelctro-catalyst of 1000 DEG C carry out hydrogen reduction
Performance linear scanning thus the hydrogen reduction performance comparison figure that obtains, its abscissa represents voltage (unit is V), its vertical coordinate table
Show that (unit is mA/cm to electric current density2)；Fig. 8 b is with 5mV/S sweep speed difference in the KOH solution of 0.1mol/L
Be 700 DEG C to ruthenium-oxide and calcining heat, 800 DEG C, 900 DEG C, the cobalt-nitrogen-carbon back eelctro-catalyst of 1000 DEG C carry out oxygen precipitation
Performance linear scanning thus the oxygen that obtains separates out performance comparison figure, its abscissa represents voltage (unit is V), its vertical coordinate table
Show that (unit is mA/cm to electric current density2)；Fig. 8 c is with 5mV/S sweep speed difference in the KOH solution of 0.1mol/L
Be 700 DEG C to platinum carbon and calcining heat, 800 DEG C, 900 DEG C, the cobalt-nitrogen-carbon back eelctro-catalyst of 1000 DEG C carry out hydrogen evolution
Can linear scanning thus the hydrogen evolution performance comparison figure that obtains, its abscissa represents voltage (unit is V), and its vertical coordinate represents
(unit is mA/cm to electric current density2).As seen from Figure 8: compared with platinum carbon of the prior art and ruthenium-oxide, this
Cobalt-nitrogen-carbon back eelctro-catalyst obtained by bright embodiment 1 all table in oxygen reduction reaction, oxygen evolution reaction and Hydrogen evolving reaction
Reveal the electrocatalysis characteristic of excellence.
(8) respectively cobalt-nitrogen-carbon back the eelctro-catalyst obtained by step C1 of the embodiment of the present invention 1 and platinum carbon are assembled into
In chargeable zinc-air battery and carry out charge-discharge performance test, thus obtain charge-discharge performance contrast as shown in Figure 9
Figure.Wherein, Fig. 9 a is the open-circuit voltage comparison diagram of both zinc-air batteries, and (unit is for dividing for its abscissa express time
Clock), its vertical coordinate represents open-circuit voltage (unit is V)；Fig. 9 b is the discharge voltage current polarizing of both zinc-air batteries
Curve and power density curve comparison figure, its abscissa represents that (unit is mA/cm to electric current density2), vertical coordinate table on the left of it
Showing voltage (unit is V), on the right side of it, vertical coordinate represents that (unit is mW/cm to power density2)；Fig. 9 c is both zinc-sky
The charging voltage and current polarization curve comparison diagram in pneumoelectric pond, its abscissa represents that (unit is mA/cm to electric current density2), it is indulged
Coordinate representation voltage (unit is V)；Fig. 9 d is the zinc using the cobalt-nitrogen-carbon back eelctro-catalyst obtained by the embodiment of the present invention 1
-air cell is 10mA/cm at charging and discharging currents2Time cycle charge discharge electrical stability schematic diagram, its abscissa express time
(unit be hour), its vertical coordinate represents voltage (unit is V).As seen from Figure 9: use the embodiment of the present invention 1
The zinc-air battery of obtained cobalt-nitrogen-carbon back eelctro-catalyst, its open-circuit voltage is 1.4V, its discharge energy density is the highest can
Reach 157mW/cm2, its initiation of charge voltage be 1.92V, its firing potential be 1.25V；Fill 100 circulations
After discharge test, the initiation of charge voltage of this zinc-air battery is 2.05V, its firing potential is 1.19V；Obviously,
The zinc-air battery using cobalt-nitrogen-carbon back eelctro-catalyst obtained by the embodiment of the present invention 1 shows excellent cell performance
Energy.
Embodiment 2
A kind of transition metal-nitrogen-carbon back eelctro-catalyst, uses following steps to be prepared from:
Step A2, Crusta Penaeus seu Panulirus is dried and grinds to form Crusta Penaeus seu Panulirus powder；Take 30g Crusta Penaeus seu Panulirus powder and 300mL deionized water joins
In the polytetrafluoro reactor of 500mL, stirring is mixed is incorporated at 180 DEG C insulation 10 hours；It is then cooled to room temperature, uses
Membrane aperture is the membrane filtration 2 times of 0.22 μm, then leaves the heart 20 minutes with 14000, thus prepares nitrogen-doped carbon quantum
Point solution.
Step B2, by the pyrroles of 0.6mL, 0.1mol/L ferric ion solution (the i.e. trivalent of 0.005mol of 50mL
Iron ion), the nitrogen-doped carbon quantum dot solution obtained by step A2 of 20mL mix, stir 4～6 hours, then
Centrifuge washing is also dried, thus prepares black polymeric product.
Step C2, under nitrogen protection environment, the polymerizate obtained by step B2 is placed in tube furnace, and according to often
The speed of 5 DEG C of minute heating up heats, until temperature reaches 600～900 DEG C, then with 600～900 DEG C of calcinings 2～3
Hour, thus prepare ferrum-nitrogen-carbon back eelctro-catalyst (i.e. the graphitization carbon back eelctro-catalyst of Fe-Mn cycle and transference).
Specifically, detect during using the embodiment of the present invention 2 to prepare ferrum-nitrogen-carbon back eelctro-catalyst, thus obtain
Following testing result:
(1) use field emission scanning electron microscope (FESEM, Quanta 200FEG) and high-resolution-ration transmission electric-lens (TEM,
JEOL 2010) respectively to step C2 of the embodiment of the present invention 2 calcining heat be 900 DEG C, 800 DEG C, 700 DEG C, 600
Ferrum-nitrogen-carbon back eelctro-catalyst obtained at DEG C is observed and is shot, thus obtain such as Figure 10, Figure 11, Figure 12, figure
Field emission scanning electron microscope picture shown in 13 and transmission electron microscope picture.By Figure 10, Figure 11, Figure 12 and Figure 13 it can be seen that
Ferrum-nitrogen-carbon back eelctro-catalyst that the embodiment of the present invention 2 prepares under different calcining heats all includes ferroso-ferric oxide micro-nano
Rice grain and the carbon of carbonization structure.
(2) ferrum-nitrogen-carbon back eelctro-catalyst obtained by step C2 of the embodiment of the present invention 2 and platinum carbon being assembled into respectively can
In the zinc-air battery of charging and carry out charge-discharge performance test, thus obtain charge-discharge performance comparison diagram as shown in figure 14.
Wherein, Figure 14 a is the open-circuit voltage comparison diagram of both zinc-air batteries, its abscissa express time (unit be minute),
Its vertical coordinate represents open-circuit voltage (unit is V)；Figure 14 b is the constant-current discharge test comparison figure of both zinc-air batteries,
Its abscissa express time (unit be minute), its vertical coordinate represents voltage (unit is V)；Figure 14 c be both zinc-
The discharge voltage current polarizing curve comparison figure of air cell, its abscissa represents that (unit is mA/cm to electric current density2),
On the left of it, vertical coordinate represents voltage (unit is V), and on the right side of it, vertical coordinate represents that (unit is mW/cm to power density2)；Figure
14d is the long-time discharge stability of the zinc-air battery using the ferrum-nitrogen-carbon back eelctro-catalyst obtained by the embodiment of the present invention 2
Property with the specific energy comparison diagram of this zinc-air battery, its abscissa represents specific capacity (unit is mA h/g), its vertical coordinate
Represent voltage (unit is V).As seen from Figure 14: use the ferrum-nitrogen-carbon back electro-catalysis obtained by the embodiment of the present invention 2
The zinc-air battery of agent, its open-circuit voltage is 1.45V, its discharge energy density reaches as high as 112mW/cm2, its specific energy
Reach 596mAh/g；Obviously, the zinc-air battery table of employing ferrum-nitrogen-carbon back eelctro-catalyst obtained by the embodiment of the present invention 2
Reveal excellent battery performance.
(3) high-resolution-ration transmission electric-lens (TEM, JEOL 2010) and energy disperse spectroscopy (EDS Oxford, Link ISIS) are used
Ferrum-nitrogen-carbon back eelctro-catalyst obtained by step C2 of the embodiment of the present invention 2 is measured, thus obtain such as Figure 15
Shown EDS energy spectrum analysis figure.As seen from Figure 15: this ferrum-nitrogen-carbon back eelctro-catalyst comprises ferrum element and nitrogen unit
Element, in this explanation Fe-Mn cycle and transference to graphitized carbon structure.
(4) high-resolution-ration transmission electric-lens (TEM, JEOL 2010) and energy disperse spectroscopy (EDS Oxford, Link ISIS) are used
Ferrum-nitrogen-carbon back eelctro-catalyst obtained by step C2 of the embodiment of the present invention 2 is measured, thus obtain such as Figure 16
Shown element Energy distribution Surface scan analysis chart.In conjunction with Figure 15 and Figure 16 it can be seen that in the carbon-coating of carbonization structure
Include ferrum and nitrogen element, in this explanation Fe-Mn cycle and transference to graphitized carbon structure.
As fully visible, the embodiment of the present invention not only preparation technology is simple, with low cost, and prepared eelctro-catalyst tool
There is the electrocatalysis characteristic of excellence.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, and appoints
How those familiar with the art is in the technical scope that the invention discloses, the change that can readily occur in or replacement, all
Should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection domain of claims
It is as the criterion.
Claims (9)
1. the preparation method of transition metal-nitrogen-carbon back eelctro-catalyst, it is characterised in that comprise the following steps:
Step A, biomass are dried and grinds to form powdered biomass；Described powdered biomass is mixed with deionized water, and
It is incubated 5～20 hours at 100～220 DEG C；It is then cooled to room temperature, employing membrane filtration 1～5 times, then with 8000-14000
Leave the heart, thus prepare nitrogen-doped carbon quantum dot solution；Wherein, described powdered biomass with the mixed proportion of deionized water is:
Every 100mL deionized water uses 5g～50g powdered biomass；
Transition metal ion solution and described nitrogen-doped carbon quantum dot solution are polymerized by step B, employing pyrroles, thus
Prepare polymerizate；
Step C, described polymerizate is carried out high-temperature calcination in protective atmosphere, thus prepare transition metal-nitrogen-carbon back electricity
Catalyst.
Preparation method the most according to claim 1, it is characterised in that described employing pyrroles is molten to transition metal ions
Liquid and described nitrogen-doped carbon quantum dot solution carry out polymerization and include:
According to every 3L pyrroles use 25mol ferric ion, 50～200L described in the ratio of nitrogen-doped carbon quantum dot solution,
Pyrroles, ferric ion solution, described nitrogen-doped carbon quantum dot solution are mixed, and stirs 4～6 hours, so
Rear centrifuge washing is also dried, thus prepares polymerizate；
Or,
The peroxide that Solute mass fraction is 30% of 25mol divalent transition metal ion, 10～30L is used according to every 3L pyrroles
Change hydrogen solution, 50～200L described in the ratio of nitrogen-doped carbon quantum dot solution, by pyrroles, divalent transition metal ion solution,
Described nitrogen-doped carbon quantum dot solution mixes, and add acid pH value is adjusted to 2, be subsequently adding hydrogen peroxide molten
Liquid, stirs 4～6 hours, then centrifuge washing being dried, thus prepares polymerizate.
Preparation method the most according to claim 2, it is characterised in that described divalent transition metal ion is Fe2+、
Co2+Or Ni2+In one or more.
Preparation method the most according to any one of claim 1 to 3, it is characterised in that described in protective atmosphere
Described polymerizate is carried out high-temperature calcination include: in protective atmosphere, described polymerizate is heated, until temperature
Reach 600～1200 DEG C, then calcine 2～3 hours with 600～1200 DEG C, thus prepare transition metal-nitrogen-carbon back electricity and urge
Agent.
5. transition metal-nitrogen-carbon back eelctro-catalyst, it is characterised in that use according to any one of Claims 1-4
The preparation method of transition metal-nitrogen-carbon back eelctro-catalyst is prepared from.
6. transition metal-nitrogen-carbon back the eelctro-catalyst described in claim 5 is at electrochemical oxygen reduction reaction, oxygen evolution reaction
Or the application in Hydrogen evolving reaction.
7. transition metal-nitrogen-carbon back the eelctro-catalyst described in claim 5 is in the application in electrolysis water field.
8. transition metal-nitrogen-carbon back the eelctro-catalyst described in claim 5 is in the application of fuel cell field.
9. transition metal-the nitrogen described in claim 5-carbon back eelctro-catalyst application in metal-air battery field.
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| CN110975913A (en) * | 2019-10-22 | 2020-04-10 | 上海电力大学 | Electrocatalyst for electrocatalytic hydrogen production and preparation method thereof |
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