CN109346735A - Nano carbon balls oxygen reduction catalyst and its preparation and application derived from porous polymer - Google Patents
Nano carbon balls oxygen reduction catalyst and its preparation and application derived from porous polymer Download PDFInfo
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- CN109346735A CN109346735A CN201811135980.0A CN201811135980A CN109346735A CN 109346735 A CN109346735 A CN 109346735A CN 201811135980 A CN201811135980 A CN 201811135980A CN 109346735 A CN109346735 A CN 109346735A
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- triazines
- porous polymer
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- carbon balls
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/50—Fuel cells
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Abstract
The present invention provides Nano carbon balls derived from a kind of triazines porous polymer and the preparation method and application thereof, which is made after porous Nano carbon balls presoma to be transferred under inert atmosphere to heat up be carbonized using a step solvent-thermal method and be made；The preparation method comprises the following steps: by Cyanuric Chloride, trithiocyanuric acid is dissolved in solvent, carries out solvent thermal reaction, filtering, it is centrifuged and is dried to obtain powder, acetone is added to mix, is centrifugated out slurry of solids, washs, vacuum drying obtains presoma, it is placed on heating under inert atmosphere to be carbonized, finally washes, is dried in vacuo, obtain porous Nano carbon balls material.The method of the present invention is simple, and precursor preparation is easy, and Nano carbon balls material is prepared in step carbonization, and the material catalytic performance is excellent, good cycling stability；It is relatively cheap as Nonmetal catalyst materials, above there is good prospect in the application of Proton Exchange Membrane Fuel Cells energy storage material.
Description
Technical field
The invention belongs to electrode catalyst of fuel cell Material Field, in particular to a kind of triazines porous polymer is derivative
Nano carbon balls and the preparation method and application thereof.
Background technique
With the rapid development of the global economy, the worsening of fossil fuel rapidly depleted with environmental pollution, to can hold
Continuous and renewable energy demand is continuously increased, this have stimulated researcher to high-efficiency cleaning energy conversion, develop novel storage
Equipment is furtherd investigate to meet the nervous energy demand in the following whole world.
The feature that Proton Exchange Membrane Fuel Cells is protruded due to it in various energy storage devices: such as high conversion efficiency, fuel
It is easy to get, environmental-friendly, long circulation life and outstanding stability and safety become current ubiquitous portal
The next-generation energy storage system of potential application in electronic product, power supply backup and hybrid vehicle.Recently, proton exchange membrane
Fuel cell is successfully applied to New-energy electric vehicle.
Sustainable and environment friendly material is mentioned, people expect being exactly carbon material first.The source of carbon material is very
It is abundant, be it is inexhaustible, chemical contamination is small.In general, the transfer efficiency of Proton Exchange Membrane Fuel Cells and
Catalyst material on electrode used in cyclical stability strong depend-ence.Various porous carbon materials are fired for proton exchange membrane
Expect battery electrode on the most common material of catalyst material, by electrode/electrolyte interface adsorption of oxygen carry out oxygen also
Original reaction.Active carbon (AC) based on carbon, the derivative (CDC) of carbon, the porous material such as carbon nanotube (CNT) and graphene (GR)
Expect the specific surface area height due to them, electric conductivity height and excellent chemical stability and thermal stability and is used as by further investigation
Catalyst on the electrode of Proton Exchange Membrane Fuel Cells.
Summary of the invention
Technical problem to be solved by the invention is to provide Nano carbon balls oxygen derived from a kind of triazines porous polymer also
The biggish porous polymer nanometer of specific surface area is made using solvent heat in raw catalyst and the preparation method and application thereof, the catalyst
Sulfur and nitrogen co-doped Nonmetal oxygen reduction catalyst is obtained after ball material and carbonization.
To solve the above-mentioned problems, the present invention provides Nano carbon balls hydrogen reduction derived from a kind of triazines porous polymer
Catalyst, which is characterized in that risen under an inert atmosphere after triazines porous polymer presoma is made using a step solvent-thermal method
Temperature carries out carbonization and is prepared.
Preferably, the triazines porous polymer presoma is to be made by triazines monomer by solvent-thermal method.
Preferably, the triazines monomer is Cyanuric Chloride and trithiocyanuric acid, Cyanuric Chloride and cyanuric acid or trimerization
Chlorine cyanogen and melamine, more preferably Cyanuric Chloride and trithiocyanuric acid.
The present invention also provides a kind of preparation sides of Nano carbon balls oxygen reduction catalyst derived from triazines porous polymer
Method, which comprises the following steps:
Step 1: Cyanuric Chloride and another triazines monomer being dissolved in acetonitrile, carry out hydro-thermal reaction, filtering, centrifugation is simultaneously
It is dried to obtain powder, ethyl alcohol is added, is centrifugated out slurry of solids, is washed, it is dry, obtain triazines porous polymer nanosphere
Presoma；
Step 2: triazines porous polymer presoma being heated up under an inert atmosphere and is carbonized, finally washing, vacuum
It is dry, Nano carbon balls oxygen reduction catalyst derived from triazines porous polymer can be obtained.
Preferably, the molar ratio of the Cyanuric Chloride in the step 1 and another triazine monomers is 1:1.
Preferably, another triazine monomers in the step 1 are trithiocyanuric acid, cyanuric acid or melamine.
Preferably, solvent is acetonitrile, the molar concentration 15mmol/mL of the Cyanuric Chloride made in the step 1.
Preferably, the inert atmosphere in the step 2 is argon atmosphere.
Preferably, the technological parameter of the carbonization in the step 2 are as follows: 2-5 DEG C of heating rate/min, carburizing temperature 700-
900 DEG C, soaking time 1-3h.
Preferably, 8~12h is washed with deionized to adopt in step 2 washing.
Preferably, the vacuum drying in the step 2 is 60 DEG C of dry 8~12h in vacuum drying oven.
The present invention also provides Nano carbon balls oxygen reduction catalysts derived from triazines porous polymer to prepare proton friendship
Change the application in terms of the energy storage material of membrane cell.
Compared with prior art, the beneficial effects of the present invention are:
1. the present invention obtains oxygen also after the biggish polymer nanocomposite ball material of specific surface area and carbonization is made using solvent heat
Raw catalyst.
2. the method for the present invention is simple, precursor preparation is easy, the oxygen reduction catalyst that step carbonization is prepared, catalytic
It can excellent, good cycling stability.
3. Nano carbon balls oxygen reduction catalyst derived from triazines porous polymer provided by the invention is urged as nonmetallic
Agent material, it is relatively cheap, above there is good prospect in the application of Proton Exchange Membrane Fuel Cells energy storage material.
Detailed description of the invention
Fig. 1 is a variety of multiple SEM figure of triazines polymer nanocomposite ball (PCNS-1) presoma in embodiment 1, from a to b
Respectively 10k, 20k amplification factor；
Fig. 2 is more kinds of multiple SEM figures of PCNS-1-900 in embodiment 1, is respectively 10k, 20k amplification factor from a to b；
A variety of multiple SEM figure that Fig. 3 is PCNS-2-900 in embodiment 2, is respectively 10k, 20k amplification factor from a to b；
A variety of multiple SEM figure that Fig. 4 is PCNS-3-900 in embodiment 3, is respectively 10k, 20k amplification factor from a to b；
Fig. 5 is that embodiment 1 and embodiment 2, embodiment 3 are recycled with the LSV under the sweep speed of 10mV/s and schemed；
Fig. 6 is PCNS-1-900 methanol tolerance stability test curve in embodiment 1；
The TEM figure that Fig. 7 is PCNS-1-900 in embodiment 1.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
Present embodiments provide Nano carbon balls oxygen reduction catalyst (PCNS-1- derived from a kind of triazines porous polymer
900) it, is made to heat up under an inert atmosphere after triazines porous polymer presoma using a step solvent-thermal method and carries out carbonization preparation
And it obtains.
Specific step is as follows for the preparation method of Nano carbon balls oxygen reduction catalyst derived from the triazines porous polymer:
(1) 9mmol Cyanuric Chloride and 9mmol trithiocyanuric acid are dissolved in acetonitrile, mole of the Cyanuric Chloride made
Concentration is 15mmol/mL, is transferred in reaction kettle after stirring and carries out hydro-thermal reaction, and the reaction time is for 24 hours, to take out sediment mistake
Filter, is centrifuged and is transferred to 100 DEG C of dryings in vacuum oven, and dry 8-12h obtains uniformly mixed powder, is then added
The ethyl alcohol of 100ml stirs evenly, and then uses supercentrifuge, and centrifugal speed is that 8000rpm isolates slurry of solids and uses deionized water
Washing, in triplicate.60 DEG C of dry 12h, obtain triazines porous polymer nanosphere (PCNS-1) forerunner in vacuum drying oven
Body, as shown in Figure 1.
(2) powder of 200mg PCNS-1 presoma is poured into porcelain crucible, puts tube furnace into, lead to argon gas, in argon gas gas
Heating is carbonized under atmosphere, and heating rate is 2-5 DEG C/min, and the temperature of carbonization is 700-900 DEG C, soaking time 2h, uses
Deionized water washs 10h, and 60 DEG C of dry 12h are spare in vacuum drying oven, and carbon derived from triazines porous polymer can be obtained
Nanosphere oxygen reduction catalyst, is named as PCNS-1-900.
(3) with PCNS-1-900: dehydrated alcohol: Nafion (water content 5wt%)=5mg:350 μ L:95 μ L ratio is matched
Slurrying material, ultrasound 30min, is then coated on glass-carbon electrode (d=2mm) in ultrasonic machine, controls active material 0.6mg/cm2。
(4) using silver chloride electrode as reference electrode, graphite rod is to electrode, and electrolyte selects the potassium hydroxide of 0.1mol/L molten
Liquid tests its chemical property with Shanghai Chen Hua electrochemical workstation, as a result as shown in Figure 5 and Figure 6.
Fig. 6 shows: when being 200s between when tested, 1M methanol, PCNS-1-900 being added dropwise into test solution (0.1KOH)
Curve is stablized straight, illustrates that PCNS-1-900 in embodiment 1 has good methanol tolerance stability.
Fig. 5 shows after methanol is added, and catalyst PCNS-1-900 curve is without significant change, and under platinum carbon catalyst is obvious
Drop, illustrate that PCNS-1-900 stability is more stable than platinum carbon, and have excellent hydrogen reduction catalytic performance, half wave potential with
Pt/C is suitable, shows that the catalytic performance of this oxygen reduction catalyst material is excellent.
Fig. 1 and Fig. 2 show: still keeping stable after finding out that PCNS-1 presoma is successfully prepared and is carbonized from SEM figure
Pattern is that nanometer is spherical.
Embodiment 2
It is prepared according to the preparation method of embodiment 1, unlike, the reaction monomers are Cyanuric Chloride and melamine
Acid, the presoma of preparation gone out are PCNS-2, Nano carbon balls derived from the triazines porous polymer obtained after corresponding carbonization
Oxygen reduction catalyst is named as PCNS-2-900.
Fig. 3 shows: the PCNS-2-900 in embodiment 2, finds out that the catalyst PCNS-2-900 being prepared is from SEM figure
Nanometer is spherical.
Embodiment 3
It is prepared according to the preparation method of embodiment 1, unlike, the reaction monomers are Cyanuric Chloride and melamine
Amine, the precursor product being prepared are named as PCNS-3, derived from the triazines porous polymer obtained after corresponding carbonization
Nano carbon balls oxygen reduction catalyst is named as PCNS-3-900.
Fig. 4 shows: the PCNS-3-900 in embodiment 3, finds out that the catalyst PCNS-3-900 being prepared is from SEM figure
Nanometer is spherical.
Claims (10)
1. Nano carbon balls oxygen reduction catalyst derived from a kind of triazines porous polymer, it is characterised in that: use a step solvent
Carbonization is carried out in inert atmosphere heating after the obtained triazines porous polymer presoma of heat to be prepared.
2. Nano carbon balls oxygen reduction catalyst derived from triazines porous polymer as described in claim 1, which is characterized in that
The triazines porous polymer presoma is to be made by triazines monomer by solvent-thermal method.
3. Nano carbon balls oxygen reduction catalyst derived from triazines porous polymer as claimed in claim 2, which is characterized in that
The triazines monomer is Cyanuric Chloride and trithiocyanuric acid, Cyanuric Chloride and cyanuric acid or Cyanuric Chloride and melamine.
4. the preparation method of Nano carbon balls oxygen reduction catalyst, feature derived from triazine quasi polymer described in claim 1 exist
In, comprising the following steps:
Step 1: Cyanuric Chloride and another triazines monomer being dissolved in acetonitrile, carry out hydro-thermal reaction, filtering is centrifuged and dry
Powder is obtained, ethyl alcohol is added, is centrifugated out slurry of solids, is washed, it is dry, obtain triazines porous polymer nanosphere forerunner
Body；
Step 2: triazines porous polymer presoma is heated up under an inert atmosphere and is carbonized, finally washes, be dried in vacuo,
Nano carbon balls oxygen reduction catalyst derived from triazines porous polymer can be obtained.
5. the preparation method of Nano carbon balls oxygen reduction catalyst derived from triazines porous polymer as claimed in claim 4,
It is characterized in that, the molar ratio of Cyanuric Chloride and another triazines monomer in the step 1 is 1:1.
6. the preparation method of Nano carbon balls oxygen reduction catalyst derived from triazines porous polymer as claimed in claim 4,
It is characterized in that, another triazines monomer in the step 1 is trithiocyanuric acid, cyanuric acid or melamine.
7. the preparation method of Nano carbon balls oxygen reduction catalyst derived from triazines porous polymer as claimed in claim 4,
It is characterized in that, solvent is acetonitrile, the molar concentration 15mmol/mL of the Cyanuric Chloride made in the step 1.
8. the preparation method of Nano carbon balls oxygen reduction catalyst derived from triazines porous polymer as claimed in claim 4,
It is characterized in that, the inert atmosphere in the step 2 is argon atmosphere.
9. the preparation method of Nano carbon balls oxygen reduction catalyst derived from triazines porous polymer as described in claim 1,
It is characterized by: the technological parameter of the carbonization in the step 2 are as follows: 2-5 DEG C of heating rate/min, 700-900 DEG C of carburizing temperature,
Soaking time 1-3h；8~12h is washed with deionized to adopt in washing in the step 2；Vacuum drying in the step 2 is
60 DEG C of dry 8~12h in vacuum drying oven.
10. Nano carbon balls oxygen reduction catalyst derived from a kind of triazines porous polymer is preparing Proton Exchange Membrane Fuel Cells
Energy storage material in terms of application.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112795010A (en) * | 2021-01-21 | 2021-05-14 | 宝鸡文理学院 | Covalent organic framework nano material, preparation method thereof and application of covalent organic framework nano material as oil-based lubricating additive |
| CN114920231A (en) * | 2022-05-01 | 2022-08-19 | 三峡大学 | Carbon microsphere material with ultrahigh pyridine nitrogen content, and preparation method and application thereof |
| CN115194144A (en) * | 2022-07-15 | 2022-10-18 | 三峡大学 | Preparation method of iron-coordinated covalent triazine polymer derived nanocluster material |
| CN115312775A (en) * | 2022-07-27 | 2022-11-08 | 江西盛源新材料有限公司 | Carbon nanotube composite conductive slurry and preparation method thereof |
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Cited By (6)
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| CN112795010A (en) * | 2021-01-21 | 2021-05-14 | 宝鸡文理学院 | Covalent organic framework nano material, preparation method thereof and application of covalent organic framework nano material as oil-based lubricating additive |
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| CN114920231A (en) * | 2022-05-01 | 2022-08-19 | 三峡大学 | Carbon microsphere material with ultrahigh pyridine nitrogen content, and preparation method and application thereof |
| CN115194144A (en) * | 2022-07-15 | 2022-10-18 | 三峡大学 | Preparation method of iron-coordinated covalent triazine polymer derived nanocluster material |
| CN115194144B (en) * | 2022-07-15 | 2023-09-19 | 三峡大学 | Preparation method of iron coordinated covalent triazine polymer derived nanocluster material |
| CN115312775A (en) * | 2022-07-27 | 2022-11-08 | 江西盛源新材料有限公司 | Carbon nanotube composite conductive slurry and preparation method thereof |
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Application publication date: 20190215 |