CN110289425A - Hollow porous rich nitrogen carbon material of a kind of double shell type and its preparation method and application - Google Patents
Hollow porous rich nitrogen carbon material of a kind of double shell type and its preparation method and application Download PDFInfo
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- CN110289425A CN110289425A CN201910687596.XA CN201910687596A CN110289425A CN 110289425 A CN110289425 A CN 110289425A CN 201910687596 A CN201910687596 A CN 201910687596A CN 110289425 A CN110289425 A CN 110289425A
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- H—ELECTRICITY
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Abstract
The present invention provide it is a kind of ZIF-67 SN complex is formed as porous rich nitrogen carbon material of precursor preparation double shell type and its preparation method and application using zeolite imidazole metalloid organic backbone (ZIF-67) and trithiocyanuric acid (SN) coordination, which is mainly characterized in that the new complex that complexation reaction preparation is shell as core, cobalt and trithiocyanuric acid (SN) with 2-methylimidazole complex using cobalt occurs for zeolite imidazole metalloid organic backbone (ZIF-67) and trithiocyanuric acid (SN)；The porous rich nitrogen carbon ORR catalysis material DSHPCs of double shell type is obtained by high temperature pyrolysis ZIF-67@SN again.The hollow porous rich nitrogen carbon material of the double shell type that the present invention prepares has many advantages, such as that manufacture craft is simple, cheap, catalytic activity is high.
Description
Technical field
The present invention relates to rich nitrogen carbon materials and preparation method thereof, specifically design a kind of hollow porous rich nitrogen carbon material of double shell type
And its preparation method and application, belong to fuel cell science and technology field.
Background technique
With the fast development of process of industrialization, the consumption of the energy is growing day by day, causes environmental pollution to be on the rise, fuel
Battery is considered as the clean energy resource conversion equipment got a good chance of.However, a wide range of use of fuel cell is by its cathode oxygen
Reduction reaction process slowly limits, and develops the economy, efficient oxygen reduction catalyst is the commercialized key of propellant battery.
Up to the present, Pt and its alloy are still most effective fuel battery negative pole hydrogen reduction (ORR) catalyst.However, because of Pt base
The problems such as high cost of catalyst, scarcity of resources, durability are poor and antitoxin poor limits its practical application.
Zeolite imidazole metalloid organic backbone (ZIFs) has become one kind by scientific research because its Nomenclature Composition and Structure of Complexes is adjusted
The carbon matrix precursor material of worker's concern.In the carbonization pyrolytic process of ZIFs material, base metal can be catalyzed the graphitization of carbon
And the base metal species (M-X) with good catalytic activity to be formed are acted on carbon, such as the Zn of R.Wu et al. synthesisxCo3- xO4(0 < x≤1) hollow polyhedron (AcsNano 2014,8,6297-6303), C.Jiao et al. utilize the manganese codoped Co/ of cobalt
Mn-ZIF preparation hollow structure Co/Mn-HD (Angew.Chem.Int.Ed., 2019,131,1008-1013) and
Carbon material NC@GC (J.Am.Chem.Soc., the 2015,137,1572- that J.Tang et al. is prepared using ZIF-8@ZIF-67
1580) excellent electrocatalysis characteristic is all shown.Wherein, the porosity of Shell Materials can make electrolyte permeability to core surface,
Stratum nucleare gap can make the container of electrolyte, effectively increase contacting with each other for material and electrolyte, make more active sites
Exposure (Chem. Commun., 2011,47,12578-12591).Moreover, core-shell structure also improves the stability of material
(Energy Environ. Sci., 2016,9,107-111) is conducive to multiple solutions reaction and controllable adjustment chemical micro-environment, into
And reinforcing material is active (J.Am. Chem.Soc., 2010,132,16271-16277).Meanwhile metal nanoparticle and carbon
Strong interaction promote electronics transfer simultaneously reduce oxygen in the adsorption energy of carbon surface, and can improve metal nanoparticle aggregation and
It flows out (Angew.Chem., Int.Ed., 2013,52,371-375).Carbon material derived from such ZIFs is at low cost, catalysis is lived
Property it is high, it might even be possible to match in excellence or beauty Pt/C, but reported based on the research of hollow core-shell structure C catalyst derived from ZIFs it is limited, and
And preparation process is complicated.
Based on above-mentioned analysis, in the present invention we using zeolite imidazole metalloid organic backbone ZIF-67 as template,
Synthesize the ZIF-67 SN particle of core-shell structure by the complexation reaction with trithiocyanuric acid (SN), then passes through carbonization pyrolysis system
The standby porous rich nitrogen carbon material (DSHPCs) of double shell type.Material of the invention simple, the cheap, catalytic activity with manufacture craft
The advantages that high, has certain promotion meaning to the development of fuel cell field.
Summary of the invention
The main object of the present invention is to prepare a kind of be coordinated with ZIF-67 and trithiocyanuric acid (SN) to form ZIF-67 SN use
Make the porous rich nitrogen C catalyst of precursor preparation double shell type, which is mainly characterized in that ZIF-67 matches with trithiocyanuric acid (SN)
Using cobalt and 2-methylimidazole complex as core, cobalt and trithiocyanuric acid (SN) are the new complex of shell for position reaction preparation；
The porous rich nitrogen carbon catalysis material DSHPCs of double shell type is obtained by high temperature pyrolysis ZIF-67@SN again.
The first embodiment provided according to the present invention provides a kind of hollow porous rich nitrogen carbon material of double shell type.
A kind of hollow porous rich nitrogen carbon material of double shell type, the material are prepared by the following method acquisition: passing through cobalt salt first
Complexation reaction occurs with imidazoles type organic and prepares zeolite imidazole metalloid organic backbone；Then by zeolite imidazole metalloid
Organic backbone and trithiocyanuric acid are coordinated to form zeolite imidazole metalloid organic backbone trithiocyanuric acid；Again by zeolite imidazole class
Metal organic framework@trithiocyanuric acid obtains the hollow porous rich nitrogen carbon material of double shell type by pyrolysis.
Preferably, the cobalt salt is the cobalt salt for easily dissociateing metallic cobalt ion；It is preferred that cobalt salt is cabaltous nitrate hexahydrate, four
It is hydrated one of cobalt acetate, cobalt chloride hexahydrate or a variety of.
Preferably, the imidazoles type organic is 2-methylimidazole.
Second of the embodiment provided according to the present invention provides a kind of preparation of hollow porous rich nitrogen carbon material of double shell type
Method.
A kind of preparation method of the hollow porous rich nitrogen carbon material of double shell type prepares bivalve described in the first embodiment
The method of the hollow porous rich nitrogen carbon material of type, method includes the following steps:
(1) preparation of zeolite imidazole metalloid organic backbone: cobalt salt and imidazoles type organic are dissolved in a solvent respectively,
Then it is uniformly mixed, separates, obtain zeolite imidazole metalloid organic backbone；
(2) preparation of zeolite imidazole metalloid organic backbone@trithiocyanuric acid: the zeolite miaow that step (1) is prepared
Azole metal organic framework and trithiocyanuric acid dissolve in a solvent respectively, are then uniformly mixed, and separation obtains zeolite imidazole class
Metal organic framework@trithiocyanuric acid；
(3) preparation of the hollow porous rich nitrogen carbon material of double shell type: the organic bone of zeolite imidazole metalloid that step (2) is obtained
Frame@trithiocyanuric acid obtains the hollow porous rich nitrogen carbon material of double shell type by high temperature pyrolysis.
Preferably, cobalt salt described in step (1) is the cobalt salt for easily dissociateing metallic cobalt ion；It is preferred that cobalt salt is six hydrations
One of cobalt nitrate, four hydration cobalt acetates, cobalt chloride hexahydrate are a variety of.
Preferably, the imidazoles type organic is 2-methylimidazole.
In the present invention, the molar ratio of cobalt ions and imidazoles type organic is 1:1-10 in the cobalt salt being added in step (1),
Preferably 1:1.5-8, more preferably 1:2-6.
In the present invention, the mass ratio of the zeolite imidazole metalloid organic backbone and trithiocyanuric acid that are added in step (2)
For 5-100:1, preferably 8-80:1, more preferably 10-50:1.
Preferably, step (1) specifically: cobalt salt is dissolved in solvent, is denoted as solution I；Imidazoles type organic is dissolved in
In solvent, it is denoted as solution II；Solution I is mixed with solution II, and stirring (preferably stirring 5-60min, preferably 8-40min, more
Preferably 10-30min), it stands (preferably standing 6-48h, preferably 12-36h, more preferably 18-30h at room temperature), separation
(preferable separate is using filtering, suction filtration or centrifugation), obtains zeolite imidazole metalloid organic backbone.
Preferably, gained obtains zeolite imidazole metalloid organic backbone；It is washed again using solvent, drying is (excellent
It is selected as being dried in vacuo, is dried in vacuo 12-36h at more preferably 40-80 DEG C).
Preferably, step (2) specifically: the zeolite imidazole metalloid organic backbone that step (1) prepares to be dissolved in
In solvent, it is denoted as solution III；Trithiocyanuric acid is dissolved in solvent, solution IV is denoted as；Solution III is mixed with solution IV, is surpassed
Sound (preferably ultrasonic time is 10-120min, preferably 20-60min)；Separation (preferable separate is using filtering, suction filtration or centrifugation),
Dry (being preferably dried in vacuo, be dried under vacuum to constant weight at more preferably 40-80 DEG C), obtains the organic bone of zeolite imidazole metalloid
Frame@trithiocyanuric acid.
Preferably, step (3) specifically: the three polysulfide cyanogen of zeolite imidazole metalloid organic backbone for obtaining step (2)
Acid is placed in closed reactor (preferably tube furnace), and in nitrogen or atmosphere of inert gases, heating (is preferably warming up to
600-1000 DEG C, preferably 700-900 DEG C), heat preservation (preferably heat preservation 0.2-4h, preferably 0.5-3h), cooling down obtains
The hollow porous rich nitrogen carbon material of double shell type.
Preferably, the hollow porous rich nitrogen carbon material of the double shell type of acquisition, which is placed in acid solution, (is preferably placed in 60-100
DEG C 0.2-1M sulfuric acid solution) in, stir (mixing time 12-48h), separation (preferable separate using filtering, filter or
Centrifugation), it washs (preferably adopt and be washed with deionized to neutrality), it is dry (being preferably dried in vacuo), then in nitrogen or inertia
In atmosphere, heat up (being preferably warming up to 600-1000 DEG C, preferably 700-900 DEG C), heat preservation (preferably heat preservation 0.2-
4h, preferably 0.5-3h), cooling down obtains the hollow porous rich nitrogen carbon material of double shell type of secondary carbonization.
Preferably, the solvent is organic solvent, preferably anhydrous methanol and/or dehydrated alcohol.
Preferably, the inert gas is helium and/or argon gas.
The third embodiment provided according to the present invention provides a kind of use of hollow porous rich nitrogen carbon material of double shell type
On the way.
A kind of purposes of the hollow porous rich nitrogen carbon material of double shell type, according in double shell type described in the first embodiment
Empty porous rich nitrogen carbon material or the hollow porous rich nitrogen of double shell type prepared according to any one of second of embodiment the method
Carbon material is used as oxygen reduction catalyst, and the hollow porous rich nitrogen carbon material of the double shell type is used for oxygen reduction reaction.
It is preferred that the hollow porous rich nitrogen carbon material of the double shell type to be used for the hydrogen reduction catalysis reaction of fuel cell.
In the present invention, it prepares the hollow porous rich nitrogen carbon material of double shell type: (1) passing through cabaltous nitrate hexahydrate at room temperature
(Co (NO3)2·6H2O) and 2-methylimidazole (2-Methylimidazole) is used as reaction substrate, and complexation reaction, preparation occurs
High-crystallinity zeolite imidazole metalloid organic backbone (ZIF-67)；(2) trithiocyanuric acid (SN) with ZIF-67 cobalt surface by matching
Position forms new complex ZIF-67@SN；(3) pyrolysis ZIF-67@SN obtains the hollow porous rich nitrogen of double shell type in an inert atmosphere
Carbon material (DSHPCs).The hollow porous rich nitrogen carbon material of the double shell type prepared by the method for the invention, zeolite imidazole metalloid have
Machine skeleton (ZIF-67) and trithiocyanuric acid (SN) occur complexation reaction and prepare using cobalt and 2-methylimidazole complex as core, cobalt
It is the new complex of shell with trithiocyanuric acid (SN)；The porous rich nitrogen of double shell type is obtained by high temperature pyrolysis ZIF-67@SN again
Carbon material.The material may be used as hydrogen reduction (ORR) catalysis material, for hydrogen reduction catalysis reaction.
In the present invention, cabaltous nitrate hexahydrate (Co (NO3)2·6H2O it to mix rapidly, make when) and 2-methylimidazole mixes
Its cobalt ions and methylimidazole are coordinated into rapidly small crystal nucleus.
In the present invention, complexation reaction occurs for cabaltous nitrate hexahydrate and 2-methylimidazole, as follows:
In the present invention, zeolite imidazole metalloid organic backbone ZIF-67 and trithiocyanuric acid (SN) react are as follows:
It is provided by the invention to cooperate trithiocyanuric acid (SN) to make by template of zeolite imidazole metalloid organic backbone ZIF-67
Possess following advantage for precursor preparation oxygen reduction catalyst:
For the present invention when preparing catalyst precursor, method is easy to operate, react at room temperature and the time is short, the system of presoma
It is standby have economize on resources, the time, the controllable feature of economical and effective, preparation process；The duplex shell structure catalysis material of preparation have compared with
Big specific surface area is conducive to improve contact of the material with oxygen, is conducive to the transmission of reaction process, Gao Shi with hierarchical porous structure
Blackization degree is conducive to the electric conductivity of material.In addition, the duplex shell structure catalysis material of preparation is catalyzed with good hydrogen reduction
Performance possesses excellent stability and mithridatism.
Electro-chemical test in the process is carried out in the alkaline medium (0.1M KOH) of lasting saturation oxygen, respectively
Be using Pt for electrode, Ag/AgCl as reference electrode, glass-carbon electrode be working electrode form three electrode test systems complete survey
Examination process.The ORR catalytic activity and stability of the catalyst are investigated using linear voltammetric scan method and chronoamperometry.As a result table
Bright, ORR catalyst of the invention possesses good take-off potential (E0=0.989V), half wave potential (E1/2=0.878V) and pole
Current density of rationing the power supply (JL=-4.88mAcm-2), it can compare favourably with business Pt/C catalyst.
Detailed description of the invention
Fig. 1 prepares porous richness nitrogen carbon material DSHPCs for the present invention and prepares schematic diagram；
Fig. 2 is the infrared figure that embodiment 3 prepares presoma ZIF-67@SN；
Fig. 3 is the full spectrogram of XPS that embodiment 3 prepares the porous rich nitrogen carbon material of double shell type；
Fig. 4 is the high power transmission electron microscope picture that embodiment 3 prepares the porous rich nitrogen carbon material of double shell type；
Fig. 5 is the nitrogen adsorption desorption curve figure that embodiment 3 prepares the porous rich nitrogen carbon material of double shell type；
Fig. 6 is the graph of pore diameter distribution that embodiment 3 prepares the porous rich nitrogen carbon material of double shell type；
Fig. 7 is the LSV curve that embodiment 3 prepares the porous rich nitrogen carbon material of double shell type；
Fig. 8 is the methanol tolerance the performance test results figure that embodiment 3 prepares the porous rich nitrogen carbon material of double shell type；
Fig. 9 is the stability test result figure that embodiment 3 prepares the porous rich nitrogen carbon material of double shell type.
Specific embodiment
Technical solution of the present invention is illustrated below, the claimed range of the present invention include but is not limited to
Lower embodiment.
Embodiment 1
A kind of preparation method of the hollow porous rich nitrogen carbon material of double shell type, method includes the following steps:
(1) preparation of zeolite imidazole metalloid organic backbone: cobalt salt and imidazoles type organic are dissolved in a solvent respectively,
Then it is uniformly mixed, separates, obtain zeolite imidazole metalloid organic backbone；
(2) preparation of zeolite imidazole metalloid organic backbone@trithiocyanuric acid: the zeolite miaow that step (1) is prepared
Azole metal organic framework and trithiocyanuric acid dissolve in a solvent respectively, are then uniformly mixed, and separation obtains zeolite imidazole class
Metal organic framework@trithiocyanuric acid；
(3) preparation of the hollow porous rich nitrogen carbon material of double shell type: the organic bone of zeolite imidazole metalloid that step (2) is obtained
Frame@trithiocyanuric acid obtains the hollow porous rich nitrogen carbon material of double shell type by high temperature pyrolysis.
Embodiment 2
The preparation of zeolite imidazole metalloid organic backbone:
By 4.074g (0.014mol) cabaltous nitrate hexahydrate (Co (NO3)2·6H2O) it is dissolved in 400mL anhydrous methanol solvent
In, and it is named as solution I；5.248g (0.064mol) 2-methylimidazole is dissolved in 400mL anhydrous methanol solvent, and is named
For solution II.Then solution II is poured into solution I rapidly, and stirs 10min.Obtained mixed solution is stood at room temperature
24h.Purple is obtained by centrifugation to consolidate, and 60 DEG C of oven dryings are transferred to after then sufficiently being washed with methanol and obtain template within 24 hours
ZIF-67。
Embodiment 3
The preparation of the hollow porous rich nitrogen carbon material of double shell type:
(1) synthesis of ZIF-67 SN presoma: the 100mg ZIF-67 that Example 2 obtains is dispersed in 20mL without water beetle
In alcoholic solvent, and it is named as solution III；It takes 3.5mg trithiocyanuric acid (SN) to be dissolved in 10mL methanol, and is named as solution
IV；Then solution IV is poured into solution III rapidly, at room temperature ultrasound 30min.By the way that mulberry solid is collected by centrifugation, so
It is transferred to 60 DEG C of oven drying to constant weights afterwards and obtains the presoma of catalyst Z IF-67@SN；
(2) preparation of the porous rich nitrogen carbon material (DSHPCs) of double shell type: after the drying sufficiently of above-mentioned ZIF-67@SN presoma
It is placed in tube furnace center and is warming up to 800 DEG C in nitrogen atmosphere, after keeping the temperature 1h, then cooling down is to room temperature；It then, will be hot
Carbon material after solution is placed in 80 DEG C of 0.5M H2SO4Solution stirs for 24 hours, and carbon material is collected by centrifugation and is washed with deionized into
Property, same time is pyrolyzed at the same temperature again after dry.The bivalve carbon material catalyst label of the porous rich nitrogen of gained are as follows:
DSHPCs。
The bivalve carbon material DSHPCs of the porous rich nitrogen of acquisition is detected, as a result as follows:
If Fig. 3 shows that the material DSHPCs surface layer nitrogen content that the present invention prepares is abundant, be conducive to ORR performance.
If Fig. 4 shows that the material DSHPCs that the present invention prepares has double shell structurres, be conducive to electrolyte and activity
The contact in site.
It is mesoporous to be conducive to point as shown in figure 5, the material DSHPCs prepared is mesoporous material there are apparent hysteresis loop
The transmission of son and ion.
As shown in fig. 6, the material DSHPCs prepared is to be conducive to improve ORR performance there are hierarchical porous structure.
Its chemical property is investigated with linear voltammetric scan method, as a result as shown in fig. 7, the material prepared
The take-off potential (0.989Vvs RHE) of DSHPCs is apparently higher than the take-off potential (0.964V vs RHE) of Pt/C.
As shown in figure 8, methanol solvate is added at 145s, the material DSHPCs prepared is still kept its methanol tolerance
Originally 94%, Pt/C of electric current is then down to the 76% of primary current.
As shown in figure 9, continuing working by 10000s, the material DSHPCs's its stability prepared remains unchanged electric current guarantor
Hold the 95% of primary current, hence it is evident that be better than the stability of Pt/C (75%).
Embodiment 4
The preparation of zeolite imidazole metalloid organic backbone:
4.982g (0.02mol) four is hydrated cobalt acetate (C4H6CoO4·4H2O) it is dissolved in 400mL anhydrous methanol solvent
In, and it is named as solution I；5.248g (0.064mol) 2-methylimidazole is dissolved in 400mL anhydrous methanol solvent, and is named
For solution II.Then solution II is poured into solution I rapidly, and stirs 20min.Obtained mixed solution is stood at room temperature
18h.Purple is obtained by centrifugation to consolidate, and 50 DEG C of oven dryings are transferred to after then sufficiently being washed with methanol and obtain template within 18 hours
ZIF-67。
Embodiment 5
The preparation of the hollow porous rich nitrogen carbon material of double shell type:
(1) synthesis of ZIF-67 SN presoma: the 100mg ZIF-67 that Example 4 obtains is dispersed in 20mL without water beetle
In alcoholic solvent, and it is named as solution III；It takes 2.5mg trithiocyanuric acid (SN) to be dissolved in 10mL methanol, and is named as solution
IV；Then solution IV is poured into solution III rapidly, at room temperature ultrasound 40min.By the way that mulberry solid is collected by centrifugation, so
It is transferred to 70 DEG C of oven drying to constant weights afterwards and obtains the presoma of catalyst Z IF-67@SN；
(2) preparation of the porous rich nitrogen carbon material (DSHPCs) of double shell type: after the drying sufficiently of above-mentioned ZIF-67@SN presoma
It is placed in tube furnace center and is warming up to 900 DEG C in nitrogen atmosphere, after keeping the temperature 2h, then cooling down is to room temperature；It then, will be hot
Carbon material after solution is placed in 70 DEG C of 0.3M H2SO4Solution stirs 36h, and carbon material is collected by centrifugation and is washed with deionized into
Property, it is dry after again in nitrogen atmosphere, be warming up to 900 DEG C, after keeping the temperature 2h, then cooling down is to room temperature；It is hollow to obtain double shell type
Porous richness nitrogen carbon material.
Embodiment 6
Embodiment 4 is repeated, 3.093g (0.13mol) cobalt chloride hexahydrate (CoCl is only used2·6H2O 4.982g) is replaced
(0.02 mol) four is hydrated cobalt acetate (C4H6CoO4·4H2O)。
Claims (10)
1. a kind of hollow porous rich nitrogen carbon material of double shell type, it is characterised in that: the material is prepared by the following method acquisition: first
Complexation reaction occurs by cobalt salt and imidazoles type organic and prepares zeolite imidazole metalloid organic backbone；Then by zeolite imidazole class
Metal organic framework and trithiocyanuric acid are coordinated to form zeolite imidazole metalloid organic backbone trithiocyanuric acid；Again by zeolite miaow
Azole metal organic framework@trithiocyanuric acid obtains the hollow porous rich nitrogen carbon material of double shell type by pyrolysis.
2. the hollow porous rich nitrogen carbon material of double shell type according to claim 1, it is characterised in that: the cobalt salt be legibility from
The cobalt salt of metal cobalt ions out；It is preferred that cobalt salt be cabaltous nitrate hexahydrate, four hydration cobalt acetates, one of cobalt chloride hexahydrate or
It is a variety of；And/or
The imidazoles type organic is 2-methylimidazole.
3. the preparation method of the hollow porous rich nitrogen carbon material of a kind of double shell type or to prepare double shell type as claimed in claim 1 or 2 hollow
The method of porous richness nitrogen carbon material, method includes the following steps:
(1) preparation of zeolite imidazole metalloid organic backbone: in a solvent, then cobalt salt and imidazoles type organic are dissolved respectively
It is uniformly mixed, separation obtains zeolite imidazole metalloid organic backbone；
(2) preparation of zeolite imidazole metalloid organic backbone@trithiocyanuric acid: the zeolite imidazole class that step (1) is prepared
Metal organic framework and trithiocyanuric acid dissolve in a solvent respectively, are then uniformly mixed, and separation obtains zeolite imidazole metalloid
Organic backbone@trithiocyanuric acid；
(3) preparation of the hollow porous rich nitrogen carbon material of double shell type: the zeolite imidazole metalloid organic backbone@that step (2) is obtained
Trithiocyanuric acid obtains the hollow porous rich nitrogen carbon material of double shell type by high temperature pyrolysis.
4. according to the method described in claim 3, it is characterized by: cobalt salt described in step (1) be easily dissociate metallic cobalt from
The cobalt salt of son；It is preferred that cobalt salt is one of cabaltous nitrate hexahydrate, four hydration cobalt acetates, cobalt chloride hexahydrate or a variety of；And/or
The imidazoles type organic is 2-methylimidazole.
5. the method according to claim 3 or 4, it is characterised in that: cobalt ions and imidazoles in the cobalt salt being added in step (1)
The molar ratio of type organic is 1:1-10, preferably 1:1.5-8, more preferably 1:2-6；And/or
The mass ratio of the zeolite imidazole metalloid organic backbone and trithiocyanuric acid that are added in step (2) is 5-100:1, preferably
8-80:1, more preferably 10-50:1.
6. the method according to any one of claim 3-5, it is characterised in that: step (1) specifically: be dissolved in cobalt salt molten
In agent, it is denoted as solution I；Imidazoles type organic is dissolved in solvent, solution II is denoted as；Solution I is mixed with solution II, is stirred
(preferably stirring 5-60min, preferably 8-40min, more preferably 10-30min), standing (preferably stands 6- at room temperature
48h, preferably 12-36h, more preferably 18-30h), separation (preferable separate is using filtering, suction filtration or centrifugation) obtains zeolite miaow
Azole metal organic framework；
Preferably, gained obtains zeolite imidazole metalloid organic backbone；It is washed again using solvent, drying is (preferably
It is dried in vacuo, is dried in vacuo 12-36h at more preferably 40-80 DEG C).
7. the method according to any one of claim 3-6, it is characterised in that: step (2) specifically: make step (1)
The standby zeolite imidazole metalloid organic backbone obtained is dissolved in solvent, is denoted as solution III；Trithiocyanuric acid is dissolved in solvent,
It is denoted as solution IV；Solution III is mixed with solution IV, (preferably ultrasonic time is 10-120min, preferably 20- to ultrasound
60min)；Separation (preferable separate is using filtering, suction filtration or centrifugation), drying (is preferably dried in vacuo, more preferably 40-80 DEG C
Under be dried under vacuum to constant weight), obtain zeolite imidazole metalloid organic backbone@trithiocyanuric acid.
8. the method according to any one of claim 3-7, it is characterised in that: step (3) specifically: obtain step (2)
To zeolite imidazole metalloid organic backbone@trithiocyanuric acid be placed in closed reactor (preferably tube furnace), in nitrogen or
It in atmosphere of inert gases, heats up (being preferably warming up to 600-1000 DEG C, preferably 700-900 DEG C), heat preservation (is preferably kept the temperature
0.2-4h, preferably 0.5-3h), cooling down obtains the hollow porous rich nitrogen carbon material of double shell type；
Preferably, the hollow porous rich nitrogen carbon material of the double shell type of acquisition, which is placed in acid solution, (is preferably placed in 60-100 DEG C
The sulfuric acid solution of 0.2-1M) in, it stirs (mixing time 12-48h), separation (preferable separate is using filtering, suction filtration or centrifugation),
It washs (preferably adopt and be washed with deionized to neutrality), it is dry (being preferably dried in vacuo), then in nitrogen or inert gas atmosphere
In enclosing, heat up (being preferably warming up to 600-1000 DEG C, preferably 700-900 DEG C), and heat preservation (preferably heat preservation 0.2-4h, preferably
For 0.5-3h), cooling down, the hollow porous rich nitrogen carbon material of the double shell type refined.
9. the method according to any one of claim 3-8, it is characterised in that: the solvent is organic solvent, preferably
Anhydrous methanol and/or dehydrated alcohol；And/or
The inert gas is helium and/or argon gas.
10. a kind of purposes of the hollow porous rich nitrogen carbon material of double shell type, double shell type according to claim 1 or 2 are hollow more
Hole richness nitrogen carbon material or the hollow porous rich nitrogen carbon material of the double shell type prepared according to any one of claim 3-9 the method are used
Make oxygen reduction catalyst, the hollow porous rich nitrogen carbon material of the double shell type is used for oxygen reduction reaction；It is preferred that by the double shell type
Hydrogen reduction of the hollow porous rich nitrogen carbon material for fuel cell is catalyzed reaction.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112820886A (en) * | 2020-12-29 | 2021-05-18 | 北京化工大学 | Three-dimensional grading porous nonmetal carbon-based material and preparation method and application thereof |
| CN113745532A (en) * | 2021-07-01 | 2021-12-03 | 深圳大学 | Oxygen reduction electrocatalyst and preparation method and application thereof |
| CN114797900A (en) * | 2022-03-11 | 2022-07-29 | 中国绿发投资集团有限公司 | Carbon-supported cobalt sulfide electrocatalyst derived from metal organic framework and preparation method and application thereof |
| CN115845853A (en) * | 2022-12-16 | 2023-03-28 | 东华工程科技股份有限公司 | Preparation method of double-shell hollow porous carbon nanotube supported cobalt single-atom catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108067278A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation method of the porous nitrogen-doped carbon elctro-catalyst of base metal |
| CN109786764A (en) * | 2018-01-29 | 2019-05-21 | 北京化工大学 | One kind having grading-hole, the nonmetallic carbon-based oxygen reduction catalyst of nitrogen sulphur codope and preparation |
-
2019
- 2019-07-29 CN CN201910687596.XA patent/CN110289425B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108067278A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation method of the porous nitrogen-doped carbon elctro-catalyst of base metal |
| CN109786764A (en) * | 2018-01-29 | 2019-05-21 | 北京化工大学 | One kind having grading-hole, the nonmetallic carbon-based oxygen reduction catalyst of nitrogen sulphur codope and preparation |
Non-Patent Citations (2)
| Title |
|---|
| HAO TIAN ET AL.: "Metal-organic-framework-derived formation of Co–N-doped carbon materials for efficient oxygen reduction reaction", 《JOURNAL OF ENERGY CHEMISTRY》 * |
| WENJIE MA ET AL.: "Nitrogen, phosphorus, and sulfur tri-doped hollow carbon shells derived from ZIF-67@poly (cyclotriphosphazene-co-4, 4"-sulfonyldiphenol) as a robust catalyst of peroxymonosulfate activation for degradation of bisphenol A", 《CARBON》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112820886A (en) * | 2020-12-29 | 2021-05-18 | 北京化工大学 | Three-dimensional grading porous nonmetal carbon-based material and preparation method and application thereof |
| CN112820886B (en) * | 2020-12-29 | 2023-05-26 | 北京化工大学 | Three-dimensional hierarchical porous nonmetal carbon-based material, and preparation method and application thereof |
| CN113745532A (en) * | 2021-07-01 | 2021-12-03 | 深圳大学 | Oxygen reduction electrocatalyst and preparation method and application thereof |
| CN114797900A (en) * | 2022-03-11 | 2022-07-29 | 中国绿发投资集团有限公司 | Carbon-supported cobalt sulfide electrocatalyst derived from metal organic framework and preparation method and application thereof |
| CN115845853A (en) * | 2022-12-16 | 2023-03-28 | 东华工程科技股份有限公司 | Preparation method of double-shell hollow porous carbon nanotube supported cobalt single-atom catalyst |
| CN115845853B (en) * | 2022-12-16 | 2024-04-19 | 东华工程科技股份有限公司 | Preparation method of double-shell hollow porous carbon nanotube supported cobalt monoatomic catalyst |
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