CN109768293A - Nanoscale tin nitrogen carbon material, preparation method and the application as oxygen reduction elctro-catalyst under alkaline condition - Google Patents
Nanoscale tin nitrogen carbon material, preparation method and the application as oxygen reduction elctro-catalyst under alkaline condition Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention provides a kind of nanoscale tin nitrogen carbon material, and using nitrogen carbon as skeleton, tin element is adulterated wherein.The present invention also provides one kind using ZIF-8 as template, adulterates tin element wherein, obtains the ZIF-8 of doping tin element and grinding, then calcines, the Zn-ef ficiency in ZIF-8 is removed, to obtain the preparation method of the material.The cost of material is low for this, there is good electrocatalysis to oxygen reduction under alkaline condition, there is good catalytic stability and good methanol tolerance simultaneously, therefore can be used as the elctro-catalyst of reduction oxygen and substitute currently used noble metal oxygen reduction elctro-catalyst.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of nanoscale tin nitrogen carbon material, preparation method and
Application as oxygen reduction elctro-catalyst under alkaline condition.
Background technique
With the growth of world population and gradually decreasing for fossil fuel energy, world energy supplies may be unable to satisfy day
The demand or sustainable environmental goals that benefit increases.Many countries are using development green low-carbon economy as long term object.Combustion
Material battery may be used as efficient engine technology, to replace traditional internal combustion engine, turbine or boiler, to save the energy
It is discharged with reducing.Secondly, fuel cell can be used as the new energy storing technology in renewable energy supply chain.
Fuel cell is actually a kind of electrochemical appliance, is that the oxidation process and oxygen occurred by fuel in anode exists
Chemical energy is directly changed into electric energy by the process that cathode is reduced.The performance of fuel cell is by the oxygen reduction reaction that occurs on cathode
(ORR) it determines, because of the slow several orders of magnitude of hydroxide reaction (HOR) that the speed ratio anode of ORR occurs.Therefore, we are master
Target is wanted to be placed on the research of electrocatalyst for cathode.
Currently, the cathod catalyst that business uses is mainly Pt base catalyst, because with other metal phase ratios, element Pt tool
There is high activity.However, there is also serious defects by element Pt itself, for example, it may be possible to which the competitive reaction being related to, is handed over by methanol
The poisoning of active catalyst sites caused by pitching and the dissolution of catalyst, these defects can inhibit the catalysis of Pt in practical applications
Activity.In addition, Pt is expensive, reserves are limited, seriously constrain its applicability and commercial scale.For example, current fuel
It is pem fuel electricity if battery car using Proton Exchange Membrane Fuel Cells, needs about 30g Pt, conservatively calculates
Pond itself has an increased the extra cost of several thousand dollars.
Summary of the invention
Status in view of the above technology, the present invention provides a kind of novel nanoscale tin nitrogen carbon materials, are with nitrogen carbon
Skeleton, tin element adulterate wherein, form a kind of tin nitrogen carbon nanomaterial with skeleton structure.The cost of material is low for this, in alkalinity
Under the conditions of there is good electrocatalysis to oxygen reduction, while there is good catalytic stability and good methanol to be resistant to
Property, therefore can be used as the elctro-catalyst of reduction oxygen and substitute currently used noble metal oxygen reduction elctro-catalyst.
The present invention also provides a kind of methods for preparing above-mentioned nanoscale tin nitrogen carbon material, include the following steps:
(1) tin element is adulterated for template with zinc-organic backbone (ZIF-8) wherein, obtains the ZIF-8 of doping tin element
And it grinds；
(2) ZIF-8 for the doping tin element that calcining step (1) obtains is obtained described with removing the Zn-ef ficiency in ZIF-8
Nanoscale tin nitrogen carbon material.
The ZIF-8 is one kind in zeolite imidazole metalloid organic frame (ZIFs), is by zinc ion and methylimidazole
Interact the three-dimensional net structure formed.
The preparation method of the ZIF-8 is unlimited, including in-situ synthesis, secondary growth method etc..As a kind of implementation,
Using zinc salt and ligand solution, the two is uniformly mixed, is then centrifuged for, dries, obtains ZIF-8.The zinc salt is unlimited, Ke Yixuan
From one or more of Zinc diacetate dihydrate, zinc chloride, zinc nitrate hexahydrate etc..In addition to methylimidazole in the ligand, also
It may include one of polyvinylpyrrolidone, hexa, cetyl trimethylammonium bromide etc. or several.
Implementation as one preferred, the step (1) are as follows:
Zeolite imidazole metalloid organic framework materials (ZIF-8) are mixed with tin-salt solution, is then centrifuged for, dries, obtain
The ZIF-8 for adulterating tin element, then grinds the ZIF-8 of the doping tin element.The pink salt is unlimited, can be selected from two chloride hydrates
One of stannous, stannous oxalate, stannous sulfate etc. are several.
In the step (1), preferably, the mass ratio of ZIF-8 and tin element is 100:1-100:10, more preferably
100:2.5-100:7.5 most preferably 100:5.
In the step (2), preferably, calcining the ZIF-8 of the doping tin element in inert gas shielding.
In the step (2), preferably, calcination temperature is 900 DEG C -1200 DEG C.
In the step (2), preferably, being gradually heated to calcination temperature in calcination process, heating rate is preferably
10℃/min-10℃/min。
In the step (2), preferably, carrying out calcining 1h-5h in calcination temperature.Compared with prior art, this hair
It is bright to have the following beneficial effects:
Using ZIF-8 as template, tin element is mixed wherein, by the Zn-ef ficiency in calcining removal ZIF-8, obtains tin dope
Nitrogen carbon material, have the following beneficial effects:
(1) using nitrogen carbon as skeleton, tin element adulterates wherein tin nitrogen carbon material provided by the invention, is formed a kind of with skeleton
The tin nitrogen carbon nanomaterial of structure；
(2) present invention provides one kind using ZIF-8 as template, mixes tin element wherein, by calcining removal ZIF-8
Zn-ef ficiency obtains the preparation method of tin nitrogen carbon material, and preparation method is simple for this, low in cost compared with noble metal；It is made
Tin nitrogen carbon material be nanoscale, no cluster and larger particles exist；
(3) tin nitrogen carbon material of the invention has good electrocatalysis to reduction oxygen under alkaline condition；Using change
Three-electrode system is learned, is in -1.2V~0V potential range to the KOH electrolytic for being saturated oxygen in opposite reversible hydrogen electrode
Matter aqueous solution carries out linear sweep voltammetry test, and test result is shown, which can reach the catalysis of business platinum base
The catalytic performance of agent, or even when the mass ratio for adjusting ZIF-8 and tin element is 100:2.5-100:7.5, carrying current can be high
In business platinum based catalyst, when the mass ratio for adjusting ZIF-8 and tin element is 100:5, take-off potential and carrying current
Higher than business platinum based catalyst.Also, the catalytic stability of the tin nitrogen carbon material is above business platinum base with methanol tolerance and urges
Agent.
Therefore, tin nitrogen carbon material of the invention can be used as the oxygen reduction catalyst agent under a kind of alkaline condition, have good
Application prospect.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of tin nitrogen carbon material made from the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope diagram of tin nitrogen carbon material made from the embodiment of the present invention 2.
The scanning electron microscope diagram of tin nitrogen carbon material made from Fig. 3 embodiment of the present invention 3.
Fig. 4 is the X-ray diffractogram of tin nitrogen carbon material made from 1-3 of the embodiment of the present invention.
Fig. 5 is the catalytic performance test knot of tin nitrogen carbon material made from 1-3 of the embodiment of the present invention Yu business platinum based catalyst
Fruit figure.
Fig. 6 is the catalytic stability test knot of tin nitrogen carbon material made from the embodiment of the present invention 1 and business platinum based catalyst
Fruit figure.
Fig. 7 is the methanol tolerance test knot of tin nitrogen carbon material made from the embodiment of the present invention 1 and business platinum based catalyst
Fruit figure.
Specific embodiment
Below with reference to embodiment, present invention is further described in detail with attached drawing, it should be pointed out that reality as described below
It applies example to be intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1:
In the present embodiment, using nitrogen carbon as skeleton, tin element adulterates wherein tin nitrogen carbon material, is formed a kind of with skeleton
The tin nitrogen carbon nanomaterial of structure.
In the present embodiment, preparing for tin nitrogen carbon material is as follows:
(1) prepared by ZIF-8
120mg zinc nitrate hexahydrate is dissolved in 50mL methanol, solution A is obtained；Bis--methylimidazole of 137mg is dissolved in
In 50mL methanol, solution B is obtained；Solution B is poured into solution A, is stood at room temperature for 24 hours；It is then centrifuged for, by centrifugation product 80
12 hours are dried at DEG C, obtain ZIF-8.
(2) tin dope precursor preparation
Bis- hydrated stannous chloride of 10mg is dissolved in 100mL methanol, then 100mg ZIF-8 made from step (1) is added
In the methanol solution of stannous chloride, 6h is stirred at room temperature；It is then centrifuged for, centrifugation product is dried into 12 hours at 80 DEG C, is obtained
To tin dope presoma, it is then ground to powder.
(3) calcination processing
The tin dope presoma powder body material that step (2) obtains is put into tube furnace, with 10 under nitrogen atmosphere protection
DEG C/min heating rate rise to 900 DEG C, kept for 2 hours, Temperature fall is until room temperature later.
Morphology analysis is carried out to material obtained above, scanning electron microscope diagram is as shown in Figure 1.It can from figure
Out, partial size is in nano particle in 200nm or so.
X-ray diffraction analysis is carried out to material obtained above, X-ray diffractogram is as shown in Figure 4.It can be with from Fig. 4
Observe the characteristic peak of tin metal, it was demonstrated that obtain the nitrogen carbon material of tin dope.
Using tin nitrogen carbon material obtained above as catalyst, it is tested under alkaline condition to the electro-catalysis of oxygen reduction
Performance, while material, test method are as follows as a comparison by business platinum based catalyst:
(1) preparation of catalyst pulp: weighing 12.5 milligrams of catalyst fines, anhydrous with 652 μ L deionized waters and 326 μ L
EtOH Sonicate disperses half an hour, and 22 microlitre of 5% naphthols surfactant is added, obtains catalyst pulp.
(2) with the rotating disk electrode (r.d.e) of Shanghai Chen Hua CHI760E type electrochemical operation and PINE company, U.S. chemistry three
Electrode system carries out electrocatalysis characteristic characterization to catalyst.In glass reactor, the potassium hydroxide of oxygen is saturated with 0.1M
Aqueous solution makees electrolyte, and platinum electrode is made to electrode, makees working electrode with vitreous carbon, and working electrode area is 0.196cm2,
10 μ L catalyst pulp of working electrode surface drop coating is to carry out linearly in -1.2V~0V potential range in opposite hydrogen electrode
Voltammetry analysis is scanned, to obtain catalytic oxygen reduction activity.Electric current-is carried out in the case where opposite hydrogen electrode is -1.1V current potential
Time Method analysis, using instant electric current/initial current as ordinate, abscissa is time mapping, is sentenced according to the attenuation of electric current
Disconnected stability.Test as hereinbefore is carried out, while methanol was added at 200 seconds, is judged according to the attenuation of electric current
Methanol tolerance.
After tested, the electrocatalysis characteristic of tin nitrogen carbon material obtained above is as shown in Figure 5.From figure 5 it can be seen that-
The tin nitrogen carbon material is suitable with business platinum based catalyst as the half wave potential of catalyst in 1.2V~0V potential range, limit electricity
Stream is more than business platinum based catalyst.
After tested, electrocatalysis stabilizability when tin nitrogen carbon material obtained above is as catalyst is as shown in fig. 6, can
To find out, the stable in catalytic performance of the catalyst is much higher than business platinum based catalyst；Tin nitrogen carbon material conduct obtained above
Test results are shown in figure 7 for methanol tolerance when catalyst, shows the methanol tolerance of the catalyst much higher than business platinum base
Catalyst.
Embodiment 2:
In the present embodiment, using nitrogen carbon as skeleton, tin element adulterates wherein tin nitrogen carbon material, is formed a kind of with skeleton
The tin nitrogen carbon nanomaterial of structure.
In the present embodiment, preparing for tin nitrogen carbon material is as follows:
(1) prepared by ZIF-8
It is same as Example 1.
(2) tin dope precursor preparation
It is substantially the same manner as Example 1, except that the incorporation of two hydrated stannous chlorides is 5mg.
(3) calcination processing
It is same as Example 1.
Morphology analysis is carried out to material obtained above, scanning electron microscope diagram is as shown in Figure 2.It can be with from Fig. 2
Find out, partial size is in nano particle in 200nm or so.
X-ray diffraction analysis is carried out to material obtained above, X-ray diffractogram is as shown in Figure 4.It can be with from Fig. 4
Observe the characteristic peak of tin metal, it was demonstrated that calcination processing obtains the nitrogen carbon material of tin dope at this temperature.
Using tin nitrogen carbon material obtained above as catalyst, it is tested under alkaline condition to the electro-catalysis of oxygen reduction
Performance, while material, test method are same as Example 1 as a comparison by business platinum based catalyst.Test result such as Fig. 5 institute
Show.From figure 5 it can be seen that half wave potential and pole of the tin nitrogen carbon material as catalyst in -1.2V~0V potential range
Threshold currents are suitable with business platinum based catalyst.
After tested, electrocatalysis stabilizability when tin nitrogen carbon material obtained above is as catalyst is higher than business platinum base
Catalyst, methanol tolerance are higher than business platinum based catalyst.
Embodiment 3:
In the present embodiment, using nitrogen carbon as skeleton, tin element adulterates wherein tin nitrogen carbon material, is formed a kind of with skeleton
The tin nitrogen carbon nanomaterial of structure.
In the present embodiment, preparing for tin nitrogen carbon material is as follows:
(1) prepared by ZIF-8
It is same as Example 1.
(2) tin dope precursor preparation
It is substantially the same manner as Example 1, except that the incorporation of two hydrated stannous chlorides is 15mg.
(3) calcination processing
It is same as Example 1.
Morphology analysis is carried out to material obtained above, scanning electron microscope diagram is as shown in Figure 3.It can from figure
Out, partial size is in nano particle in 200nm or so.
X-ray diffraction analysis is carried out to material obtained above, X-ray diffractogram is as shown in Figure 4.It can be with from Fig. 4
Observe the characteristic peak of tin metal, it was demonstrated that obtain the nitrogen carbon material of tin dope.
Using tin nitrogen carbon material obtained above as catalyst, it is tested under alkaline condition to the electro-catalysis of oxygen reduction
Performance, while material, test method are same as Example 1 as a comparison by business platinum based catalyst.Test result such as Fig. 5 institute
Show.From figure 5 it can be seen that half wave potential and pole of the tin nitrogen carbon material as catalyst in -1.2V~0V potential range
Threshold currents are suitable with business platinum based catalyst.
After tested, electrocatalysis stabilizability when tin nitrogen carbon material obtained above is as catalyst is higher than business platinum base
Catalyst, methanol tolerance are higher than business platinum based catalyst.
Following table be in above-described embodiment 1-3 tin nitrogen carbon material obtained as catalyst electro-catalysis oxygen when specifically test ginseng
Several test results:
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of nanoscale tin nitrogen carbon material, it is characterized in that: tin element adulterates wherein, and formation has using nitrogen carbon as skeleton
The tin nitrogen carbon nanomaterial of skeleton structure.
2. the preparation method of nanoscale tin nitrogen carbon material as described in claim 1, it is characterized in that: including the following steps:
(1) using ZIF-8 as template, tin element is adulterated wherein, obtains the ZIF-8 of doping tin element and grinding；
(2) ZIF-8 for the doping tin element that calcining step (1) obtains obtains described receive to remove the Zn-ef ficiency in ZIF-8
Meter level tin nitrogen carbon material.
3. the preparation method of nanoscale tin nitrogen carbon material as claimed in claim 2, it is characterized in that: the step (1) is as follows:
ZIF-8 is mixed with tin-salt solution, is then centrifuged for, dries, the ZIF-8 of doping tin element is obtained, then grinds the doping
The ZIF-8 of tin element.
4. the preparation method of nanoscale tin nitrogen carbon material as claimed in claim 3, it is characterized in that: the pink salt is selected from two hydrations
One of stannous chloride, stannous oxalate, stannous sulfate are several.
5. the preparation method of nanoscale tin nitrogen carbon material as claimed in claim 2, it is characterized in that: in the step (1),
The mass ratio of ZIF-8 and tin element is 100:1-100:10, preferably 100:2.5-100:7.5, more preferably 100:5.
6. the preparation method of nanoscale tin nitrogen carbon material as claimed in claim 2, it is characterized in that: in the step (2),
The ZIF-8 of the doping tin element is calcined in inert gas shielding；
Preferably, calcination temperature is 900 DEG C -1200 DEG C in the step (2)；
Preferably, calcining 1h-5h in calcination temperature in the step (2).
7. the preparation method of nanoscale tin nitrogen carbon material as claimed in claim 2, it is characterized in that: being forged in the step (2)
Calcination temperature is gradually heated to during burning；
Preferably, heating rate is 10 DEG C/min-10 DEG C/min.
8. the preparation method of nanoscale tin nitrogen carbon material as claimed in claim 2, it is characterized in that: molten using zinc salt and ligand
The two is uniformly mixed, is then centrifuged for, dries by liquid, obtains ZIF-8.
9. the preparation method of nanoscale tin nitrogen carbon material as claimed in claim 8, it is characterized in that: the zinc salt is selected from two hydrations
One or more of zinc acetate, zinc chloride, zinc nitrate hexahydrate；
Preferably, further including polyvinylpyrrolidone, hexa, hexadecane in addition to methylimidazole in the ligand
One of base trimethylammonium bromide is several.
10. application of the nanoscale tin nitrogen carbon material as described in claim 1 as the oxygen reduction catalyst agent under alkaline condition.
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Cited By (3)
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| CN110041531A (en) * | 2019-05-20 | 2019-07-23 | 河南师范大学 | The method of one step solvent structure Zn-MOF or Zn-Sn-MOF metal organic framework |
| CN110416548A (en) * | 2019-08-15 | 2019-11-05 | 合肥工业大学 | A kind of preparation method and applications of the two-dimensional structure of N doping porous carbon |
| CN112138697A (en) * | 2020-09-14 | 2020-12-29 | 广州大学 | Preparation method and application of manganese-nitrogen co-doped carbon nanosheet electrocatalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110041531A (en) * | 2019-05-20 | 2019-07-23 | 河南师范大学 | The method of one step solvent structure Zn-MOF or Zn-Sn-MOF metal organic framework |
| CN110416548A (en) * | 2019-08-15 | 2019-11-05 | 合肥工业大学 | A kind of preparation method and applications of the two-dimensional structure of N doping porous carbon |
| CN110416548B (en) * | 2019-08-15 | 2020-11-03 | 合肥工业大学 | Preparation method and application of two-dimensional structure of nitrogen-doped porous carbon |
| CN112138697A (en) * | 2020-09-14 | 2020-12-29 | 广州大学 | Preparation method and application of manganese-nitrogen co-doped carbon nanosheet electrocatalyst |
| CN112138697B (en) * | 2020-09-14 | 2022-12-20 | 广州大学 | Preparation method and application of manganese-nitrogen co-doped carbon nanosheet electrocatalyst |
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Application publication date: 20190517 |