CN110010907A - The method and product of Fe-N-CNT catalyst are prepared using waste plastics - Google Patents
The method and product of Fe-N-CNT catalyst are prepared using waste plastics Download PDFInfo
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- CN110010907A CN110010907A CN201910225099.8A CN201910225099A CN110010907A CN 110010907 A CN110010907 A CN 110010907A CN 201910225099 A CN201910225099 A CN 201910225099A CN 110010907 A CN110010907 A CN 110010907A
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Abstract
The invention belongs to electrochemical catalyst fields, and specifically disclose the method and product that Fe-N-CNT catalyst is prepared using waste plastics.This method includes that waste plastics powder and ferrum-based catalyst are heated to a period of time in an inert atmosphere, and the pyrolysis gas generated in waste plastics pyrolytic process is made to deposit to form carbon nanotube on ferrum-based catalyst surface；Purifying carbon nano-tube will be obtained after carbon nanotube pickling, is fully ground to obtain solid mixture after then mixing the purifying carbon nano-tube with nitrogenous compound；Solid mixture is heated under an inert atmosphere finally and carries out secondary pyrolysis, the Fe-N-CNT catalyst is made after being cooled to room temperature.The method that this patent provides on the one hand can be to avoid environmental pollution caused by waste plastics, another reverse side has also achieved the purpose that waste plastics resource utilization, significantly reduce the preparation cost of catalyst, and it because of the advantages such as easy to operate, technological parameter is easily controllable, yield is higher, is appropriate for being mass produced.
Description
Technical field
The invention belongs to electrochemical catalyst fields, prepare Fe-N-CNT catalyst more particularly, to using waste plastics
Method and product.
Background technique
Since early 20th century, plastics were found, it is durable, plastic, inexpensive because of its features such as, be widely used in many rows
Industry.However, because plastics are largely using causing the rapid growth of waste plastics total amount, and waste plastics is difficult to handle and make to environmental protection
At serious challenge.The accumulative waste plastics for generating 8,300,000,000 tons in the whole world in 2017, wherein only 30% or so waste plastics is returned
It receives, about 30% waste plastics is landfilled, is left a large amount of plastic products and is arbitrarily abandoned in the natural environment, if cannot locate in time
The problem of managing waste plastics, not only causes serious environmental pollution, while also resulting in a large amount of wasting of resources.
And fuel cell (Fuel Cells, FC) is a kind of will can continuously be stored in fuel and oxidant
Chemical energy is isothermally converted into the electrochemical generating unit of electric energy.As a kind of energy conversion device of green high-efficient, FC by compared with
It is widely believed that be current most potential substitution automobile traditional combustion engine power source and coal-burning power plant's thermal power generation mode
One of technology.Currently, the noble metals such as platinum, palladium are still used as the excellent electrocatalyst materials of fuel battery negative pole ORR reaction, but
There is preparation costs it is high, scarcity of resources is deficient and durability is poor the disadvantages of.Therefore, it is desirable to realize that fuel cell produces on a large scale
Industry is necessarily required to obtain substantive breakthroughs in new and effective base metal ORR catalyst application technology.
In recent years, metal-nitrogen-carbons (M-N-C, M indicate transition metal element) composite catalyst is thought by educational circles
It is most promising noble metal catalyst substitute and obtains extensive concern.Traditional metal-nitrogen-carbons catalyst preparation is logical
It is often by three kinds of metal, nitrogen, carbon precursor mixture high-temperature calcinations, pickling obtains catalyst later.The U.S. I not this test
Zelenay seminar design a kind of exemplary manufacturing process it is as follows: aniline mix with metal salt at 4 DEG C, polymerize generation
Polyaniline, later be added high-specific surface area Ketjen black be carbon carrier, by mixture high temperature pyrolysis, pickling obtain Fe-N-C or
Co-N-C catalyst.It can be seen that prepare transition metal-nitrogen-carbons catalyst method at present, there are processes complicated, reaction condition compared with
Carbon carrier must be used in the problems such as harsh, especially presoma, significantly increase the cost of catalyst preparation.
Summary of the invention
For the disadvantages mentioned above and/or Improvement requirement of the prior art, Fe- is prepared using waste plastics the present invention provides a kind of
The method and product of N-CNT catalyst, wherein deposit to form carbon nanotube on ferrum-based catalyst surface by waste plastics pyrolysis gas,
And it is sufficiently mixed preparation Fe-N-CNT catalyst with nitrogenous compound, the performance of obtained catalyst can correspondingly be improved, and subtract
Few waste plastics bring environmental pollution, is therefore particularly suitable for preparing the application of oxygen reduction reaction catalyst etc.
To achieve the above object, according to one aspect of the present invention, a kind of utilization waste plastics preparation Fe-N-CNT is proposed
The method of catalyst, this method comprises the following steps:
(a) waste plastics powder and ferrum-based catalyst are respectively placed in the first heating zone and the second heating zone, in indifferent gas
A period of time is heated in atmosphere, and the pyrolysis gas generated in waste plastics pyrolytic process is made to deposit to form carbon nanometer on ferrum-based catalyst surface
Pipe；
(b) purifying carbon nano-tube will be obtained after the carbon nanotube pickling, then by the purifying carbon nano-tube and nitrogen
It is fully ground to obtain solid mixture after closing object mixing；
(c) solid mixture is heated under an inert atmosphere and carries out secondary pyrolysis, be made described after being cooled to room temperature
Fe-N-CNT catalyst.
Use liquid nitrogen pulverizer that waste plastics is mechanically pulverized as it is further preferred that the step (a) is middle, it is described
The partial size of waste plastics powder is 0.5mm~1mm.
As it is further preferred that waste plastics powder and the mass ratio of iron-based catalysis are 5:1~1:5 in the step (a).
As it is further preferred that in the step (a) heating process temperature program are as follows: by the second heating zone with 10
DEG C/min~20 DEG C/min heating rate is heated to 750 DEG C~900 DEG C, it is kept the temperature after rising to target temperature and by the first heating zone
500 DEG C~600 DEG C are heated to 5 DEG C/min~10 DEG C/min heating rate, then keeps the temperature 5min~10min.
As it is further preferred that inert atmosphere is preferably nitrogen or argon gas, inertia in the step (a) and step (c)
The flow of gas is 50mL/min~100mL/min.
As it is further preferred that in the step (b) pickling process are as follows: the carbon nanotube, which is placed in concentration, is
In 30%~50% concentrated nitric acid, 4h~6h is stirred with the revolving speed of 600rpm~1000rpm at 80 DEG C~100 DEG C, then mistake
Filter obtains solid product and washes 10 times~20 times, finally in 100 DEG C~105 DEG C of at a temperature of dry 12h~purified for 24 hours
Carbon nanotube.
As it is further preferred that nitrogenous compound is melamine or dicyandiamide in the step (b).
As it is further preferred that purifying carbon nano-tube and nitrogenous compound are in the step (b) with the matter of 1:1~1:5
For amount than mixing, milling time is 30min~60min.
As it is further preferred that secondary pyrolytic process in the step (c) are as follows: with 5 DEG C/min~10 DEG C/min liter
Warm rate is heated to 750 DEG C~900 DEG C, then keeps the temperature 0.5h~2h.
It is another aspect of this invention to provide that providing a kind of Fe-N-CNT catalyst prepared using the above method.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below
Technological merit:
1. the present invention without using carbon material as presoma, using waste plastics as raw material, by chemical vapour deposition technique,
The pyrolysis gas of waste plastics is deposited to form carbon nanotube on iron catalyst surface, the process is available to include iron nano-particle
Carbon nanotube, the cementite of formation is a kind of good active site, and carbon nanotube cladding iron can avoid reuniting, lose
It is living；
2. simultaneously on the one hand can be to avoid environmental pollution caused by waste plastics, another reverse side using the method that this patent provides
Also achieve the purpose that waste plastics resource utilization, significantly reduce the preparation cost of catalyst, and because of easy to operate, work
The advantages such as skill parameter is easily controllable, yield is higher, are appropriate for being mass produced；
3. can not only remove iron catalyst in addition, the present invention carries out pickling to carbon nanotube obtained using concentrated nitric acid
Equal impurity, and a large amount of oxygen-containing functional groups can be introduced using the strong oxidizing property of concentrated nitric acid, advantage is provided for secondary nitrating,
It chooses that the nitrogen contents such as melamine or dicyandiamide are higher simultaneously, does not introduce the substance of carbon in pyrolytic process substantially as nitrogen source progress
Secondary pyrolysis, it is final that the Fe-N-CNT catalyst with good catalytic activity is made；
4. especially, the present invention guarantees to be made catalyst with good by controlling each reaction condition of pyrolytic process twice
Catalytic performance, such as guarantee inert gas flow velocity in the range of 50mL/min~100mL/min, avoid excessively high air-flow
Cause the pyrolysis gas residence time very few, reduces the length and yield of carbon nanotube；First time pyrolytic process control the is controlled simultaneously
Two heating zones are heated to 750 DEG C~900 DEG C with 10 DEG C/min~20 DEG C/min heating rate, keep the temperature simultaneously after rising to target temperature
First heating zone is heated to 500 DEG C~600 DEG C with 5 DEG C/min~10 DEG C/min heating rate, then keep the temperature 5min~
10min causes manufactured carbon nanotube excessively very thin short and small to avoid the too low a large amount of generations for leading to agraphitic carbon of temperature,
It also to avoid generating bending since agglomeration leads to the poor rigidity of carbon nanotube when the temperature is excessively high simultaneously；Furthermore secondary pyrolysis
When be heated to 750 DEG C~900 DEG C under 5 DEG C/min~10 DEG C/min heating rate, guarantee the condition of nitrogenous compound pyrolysis
The lower consumption for reducing oxygen-containing functional group, the Fe-N-CNT catalyst ultimately generated by each reaction condition in control reaction process
Good ORR catalytic performance is shown in alkaline electrolyte, and close to commercialization Pd/C catalyst, can be used for fuel electricity
The different fields such as pond, metal-air battery.
Detailed description of the invention
Fig. 1 is the process flow chart provided by the invention that Fe-N-CNT catalyst is prepared using waste plastics；
Fig. 2 is the SEM figure of the carbon nanotube prepared in the embodiment of the present invention 3；
Fig. 3 is the SEM figure of Fe-N-CNT catalyst -3 in the embodiment of the present invention 3；
Fig. 4 is the XRD diagram of Fe-N-CNT catalyst obtained in the embodiment of the present invention 1~4；
Fig. 5 is cyclic voltammetry curve (CV) figure of Fe-N-CNT catalyst obtained in the embodiment of the present invention 1~4；
Fig. 6 is the linear scan of Fe-N-CNT catalyst and business Pd/C catalyst obtained in the embodiment of the present invention 1~4
Volt-ampere curve (LSV) figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
It is an aspect of this invention to provide that a kind of preparing Fe-N-CNT catalyst using waste plastics as shown in Figure 1, proposing
Method, this method comprises the following steps:
(a) waste plastics powder and ferrum-based catalyst are respectively placed in the first heating zone and the second heating zone, are such as set respectively
In the first heating zone (upper warm area) of two sections of vertical pyrolysis ovens of heating and the second heating zone (lower warm area), inert atmosphere is kept,
Second heating zone is heated to 750 DEG C~900 DEG C with 10 DEG C/min~20 DEG C/min heating rate, is protected after rising to target temperature
First heating zone is simultaneously heated to 500 DEG C~600 DEG C with 5 DEG C/min~10 DEG C/min heating rate by temperature, then keeps the temperature 5min
~10min makes the pyrolysis gas generated in waste plastics pyrolytic process deposit to form carbon nanotube on ferrum-based catalyst surface；
(b) by carbon nanotube be placed in concentration be 30%~50% concentrated nitric acid in be passivated, at 80 DEG C~100 DEG C with
The revolving speed of 600rpm~1000rpm stirs 4h~6h, and then filtering obtains solid product and washes 10 times~20 times, finally exists
100 DEG C~dry 12h at a temperature of 105 DEG C~obtain purifying carbon nano-tube, by the purifying carbon nano-tube and nitrogenous compound for 24 hours
It is mixed with the mass ratio of 1:1~1:5, is fully ground 30min~60min and obtains solid mixture；
(c) solid mixture obtained is heated under an inert atmosphere with 5 DEG C/min~10 DEG C/min heating rate
It 750 DEG C~900 DEG C, then keeps the temperature 0.5h~2h and carries out secondary pyrolysis, the Fe-N-CNT catalyst is made after being cooled to room temperature.
Further, waste plastics is mechanically pulverized using liquid nitrogen pulverizer in step (a), to avoid waste plastic particles
Softening polymerization occurs for overheat, and the partial size of waste plastics powder is preferably 0.5mm~1mm.
Further, waste plastics powder and the mass ratio of iron-based catalysis are preferably 5:1~1:5 in step (a).
Further, step (a) and inert atmosphere in step (c) are preferably nitrogen or argon gas, and the flow of inert gas is preferred
For 50mL/min~100mL/min.
Further, the nitrogenous compound is preferably the nitrogen contents such as melamine or dicyandiamide height, and pyrolytic process is substantially not
Introduce the substance of carbon.
It is another aspect of this invention to provide that proposing a kind of Fe-N-CNT catalyst prepared using the above method.
As shown in Fig. 2~Fig. 6, below according to the specific method and production for preparing Fe-N-CNT catalyst using waste plastics
Product, the invention will be further described.
Embodiment 1
(a) waste plastics such as waste plastics cup, plastic casing are mechanically pulverized by liquid nitrogen pulverizer, cross 18 mesh and 35 purposes
Stainless steel sieves to obtain the plastic powders that partial size is 0.5mm~1mm, then weighs the quartz that 1g plastic powders are put into the first heating zone
In hanging basket 1, weighs 0.5g ferrum-based catalyst powder and be put into the quartzy hanging basket 2 of the second heating zone, hanging basket is placed in quartz reaction
Device corresponding position, and be put into two-part vertical heater；It is passed through the argon gas 30min post-reactor that flow is 200mL/min and is in lazy
Property atmosphere, adjustment argon flow is 100mL/min and the second heating zone to be risen to 800 DEG C with the heating rate of 20 DEG C/min and is protected
Constant temperature is held, the first heating zone is then risen to 500 DEG C with the heating rate of 10 DEG C/min, naturally cools to room after keeping the temperature 10min
Temperature, the pyrolysis gas generated in waste plastics pyrolytic process deposit to form carbon nanotube on ferrum-based catalyst surface；
(b) carbon nanotube obtained in step (b) is placed in conical flask, the concentrated nitric acid that concentration is 30% is added, 80
4h is stirred with the revolving speed of 600rpm at DEG C, then filtering obtains solid product and washes 10 times, finally 105 DEG C at a temperature of it is dry
Dry 12h obtains purifying carbon nano-tube, weighs 0.2g purifying carbon nano-tube and 1g melamine is placed in mortar, be fully ground
30min make its be uniformly mixed obtain solid mixture；
(c) solid mixture is placed in quartzy hanging basket, and hanging basket is put into reactor, passing first into flow is
The argon gas of 200mL/min is in reactor in inert atmosphere, and then adjusting argon flow is 100mL/min, with 10 DEG C/min
Heating rate rise to 750 DEG C and keep the temperature 2h, cooled to room temperature after secondary pyrolysis obtains Fe-N-CNT catalyst -1.
Redox property test is carried out to Fe-N-CNT catalyst -1 obtained using rotating disk electrode (r.d.e) device, is weighed
The Fe-N-CNT catalyst -1 of 10mg simultaneously sequentially adds 100 μ L dehydrated alcohols and 40 μ L Nafion solutions, by the super of 30min
Mixed solution is obtained after sound dispersion, takes the mixed solution of 2 μ L to be equably coated on working electrode glass-carbon electrode, is furthermore to electrode
Pt electrodes, saturated calomel electrode are reference electrode；Electrification is carried out in the 0.1mol/LKOH solution of room temperature and oxygen saturation
Learn test, cyclic voltammetry curve (CV) specific test parameter are as follows: -0.8~0.2V of scanning voltage range (vs SCE, 0.2~1.2V
Vs RHE), sweep speed 10mV/s；Linear sweep voltammetry curve (LSV) specific test parameter are as follows: scanning voltage is -1~0V
(vs SCE, 0~1V vs RHE), sweep speed 5mV/s, disk electrode revolving speed are 1600rpm；
The take-off potential of Fe-N-CNT catalyst -1 is 0.887V (vs RHE), half wave potential 0.714V (vs RHE).
Embodiment 2
(a) waste plastics such as waste plastics cup, plastic casing are mechanically pulverized by liquid nitrogen pulverizer, cross 18 mesh and 35 purposes
Stainless steel sieves to obtain the plastic powders that partial size is 0.5mm~1mm, then weighs the stone that 2.5g plastic powders are put into the first heating zone
It in English hanging basket 1, weighs 0.5g ferrum-based catalyst powder and is put into the quartzy hanging basket 2 of the second heating zone, hanging basket is placed in quartzy anti-
Device corresponding position is answered, and is put into two-part vertical heater；The argon gas 30min post-reactor that flow is 200mL/min is passed through to be in
Inert atmosphere, adjustment argon flow are 50mL/min and the second heating zone are risen to 750 DEG C simultaneously with the heating rate of 10 DEG C/min
Constant temperature is kept, the first heating zone is then risen to 550 DEG C with the heating rate of 5 DEG C/min, naturally cools to room after keeping the temperature 8min
Temperature, the pyrolysis gas generated in waste plastics pyrolytic process deposit to form carbon nanotube on ferrum-based catalyst surface；
(b) carbon nanotube obtained in step (b) is placed in conical flask, the concentrated nitric acid that concentration is 40% is added, 100
6h is stirred with the revolving speed of 800rpm at DEG C, then filtering obtains solid product and washes 20 times, finally 100 DEG C at a temperature of it is dry
It is dry to obtain purifying carbon nano-tube for 24 hours, it weighs 0.5g purifying carbon nano-tube and 0.5g melamine is placed in mortar, be fully ground
40min make its be uniformly mixed obtain solid mixture；
(c) solid mixture is placed in quartzy hanging basket, and hanging basket is put into reactor, passing first into flow is
The argon gas of 200mL/min is in reactor in inert atmosphere, and then adjusting argon flow is 50mL/min, with 8 DEG C/min's
Heating rate rises to 800 DEG C and keeps the temperature 1.5h, and cooled to room temperature after secondary pyrolysis obtains Fe-N-CNT catalyst -2.
Redox property test is carried out to Fe-N-CNT catalyst -2 obtained using rotating disk electrode (r.d.e) device, is weighed
The Fe-N-CNT catalyst -2 of 10mg simultaneously sequentially adds 100 μ L dehydrated alcohols and 40 μ L Nafion solutions, by the super of 30min
Mixed solution is obtained after sound dispersion, takes the mixed solution of 2 μ L to be equably coated on working electrode glass-carbon electrode, is furthermore to electrode
Pt electrodes, saturated calomel electrode are reference electrode；Electrification is carried out in the 0.1mol/LKOH solution of room temperature and oxygen saturation
Learn test, cyclic voltammetry curve (CV) specific test parameter are as follows: -0.8~0.2V of scanning voltage range (vs SCE, 0.2~1.2V
Vs RHE), sweep speed 10mV/s；Linear sweep voltammetry curve (LSV) specific test parameter are as follows: scanning voltage is -1~0V
(vs SCE, 0~1V vs RHE), sweep speed 5mV/s, disk electrode revolving speed are 1600rpm；
The take-off potential of Fe-N-CNT catalyst -2 is 0.893V (vs RHE), half wave potential 0.707V (vs RHE).
Embodiment 3
(a) waste plastics such as waste plastics cup, plastic casing are mechanically pulverized by liquid nitrogen pulverizer, cross 18 mesh and 35 purposes
Stainless steel sieves to obtain the plastic powders that partial size is 0.5mm~1mm, then weighs the stone that 0.5g plastic powders are put into the first heating zone
It in English hanging basket 1, weighs 2.5g ferrum-based catalyst powder and is put into the quartzy hanging basket 2 of the second heating zone, hanging basket is placed in quartzy anti-
Device corresponding position is answered, and is put into two-part vertical heater；The argon gas 30min post-reactor that flow is 200mL/min is passed through to be in
Inert atmosphere, adjustment argon flow are 80mL/min and the second heating zone are risen to 900 DEG C simultaneously with the heating rate of 15 DEG C/min
Constant temperature is kept, the first heating zone is then risen to 600 DEG C with the heating rate of 8 DEG C/min, naturally cools to room after keeping the temperature 5min
Temperature, the pyrolysis gas generated in waste plastics pyrolytic process deposit to form carbon nanotube on ferrum-based catalyst surface, and Fig. 2 is carbon obtained
The SEM of nanotube schemes, and the black cake mass that ferrum-based catalyst surface deposits is carbon nanotube；
(b) carbon nanotube obtained in step (b) is placed in conical flask, the concentrated nitric acid that concentration is 50% is added, 90
5h is stirred with the revolving speed of 1000rpm at DEG C, then filtering obtains solid product and washes 15 times, finally 105 DEG C at a temperature of
Dry 18h obtains purifying carbon nano-tube, weighs 0.5g purifying carbon nano-tube and 1.5g melamine is placed in mortar, be fully ground
60min make its be uniformly mixed obtain solid mixture；
(c) solid mixture is placed in quartzy hanging basket, and hanging basket is put into reactor, passing first into flow is
The argon gas of 200mL/min is in reactor in inert atmosphere, and then adjusting argon flow is 80mL/min, with 5 DEG C/min's
Heating rate rises to 850 DEG C and keeps the temperature 0.5h, and cooled to room temperature after secondary pyrolysis obtains Fe-N-CNT catalyst -3, Fig. 3
It is the SEM figure of Fe-N-CNT catalyst -3 obtained, wherein carbon nanotube outer diameter is about 20nm~50nm, and length is up to several
Micron.
Redox property test is carried out to Fe-N-CNT catalyst -3 obtained using rotating disk electrode (r.d.e) device, is weighed
The Fe-N-CNT catalyst -3 of 10mg simultaneously sequentially adds 100 μ L dehydrated alcohols and 40 μ L Nafion solutions, by the super of 30min
Mixed solution is obtained after sound dispersion, takes the mixed solution of 2 μ L to be equably coated on working electrode glass-carbon electrode, is furthermore to electrode
Pt electrodes, saturated calomel electrode are reference electrode；Electrification is carried out in the 0.1mol/LKOH solution of room temperature and oxygen saturation
Learn test, cyclic voltammetry curve (CV) specific test parameter are as follows: -0.8~0.2V of scanning voltage range (vs SCE, 0.2~1.2V
Vs RHE), sweep speed 10mV/s；Linear sweep voltammetry curve (LSV) specific test parameter are as follows: scanning voltage is -1~0V
(vs SCE, 0~1V vs RHE), sweep speed 5mV/s, disk electrode revolving speed are 1600rpm；
The take-off potential of Fe-N-CNT catalyst -3 is 0.932V (vs RHE), half wave potential 0.773V (vs RHE).
Embodiment 4
(a) waste plastics such as waste plastics cup, plastic casing are mechanically pulverized by liquid nitrogen pulverizer, cross 18 mesh and 35 purposes
Stainless steel sieves to obtain the plastic powders that partial size is 0.5mm~1mm, then weighs the quartz that 1g plastic powders are put into the first heating zone
In hanging basket 1, weighs 1g ferrum-based catalyst powder and be put into the quartzy hanging basket 2 of the second heating zone, hanging basket is placed in quartz reactor
Corresponding position, and be put into two-part vertical heater；It is passed through the argon gas 30min post-reactor that flow is 200mL/min and is in inertia
Atmosphere, adjustment argon flow are 100mL/min and the second heating zone are risen to 850 DEG C with the heating rate of 18 DEG C/min and is kept
Then first heating zone is risen to 530 DEG C with the heating rate of 6 DEG C/min, keeps the temperature cooled to room temperature after 10min by constant temperature,
The pyrolysis gas generated in waste plastics pyrolytic process deposits to form carbon nanotube on ferrum-based catalyst surface；
(b) carbon nanotube obtained in step (b) is placed in conical flask, the concentrated nitric acid that concentration is 30% is added, 100
4h is stirred with the revolving speed of 1000rpm at DEG C, then filtering obtains solid product and washes 20 times, finally 100 DEG C at a temperature of
Drying obtains purifying carbon nano-tube for 24 hours, weighs 0.5g purifying carbon nano-tube and 1g dicyandiamide is placed in mortar, be fully ground
30min make its be uniformly mixed obtain solid mixture；
(c) solid mixture is placed in quartzy hanging basket, and hanging basket is put into reactor, passing first into flow is
The argon gas of 200mL/min is in reactor in inert atmosphere, and then adjusting argon flow is 50mL/min, with 7 DEG C/min's
Heating rate rises to 900 DEG C and keeps the temperature 1h, and cooled to room temperature after secondary pyrolysis obtains Fe-N-CNT catalyst -4.
Redox property test is carried out to Fe-N-CNT catalyst -4 obtained using rotating disk electrode (r.d.e) device, is weighed
The Fe-N-CNT catalyst -4 of 10mg simultaneously sequentially adds 100 μ L dehydrated alcohols and 40 μ L Nafion solutions, by the super of 30min
Mixed solution is obtained after sound dispersion, takes the mixed solution of 2 μ L to be equably coated on working electrode glass-carbon electrode, is furthermore to electrode
Pt electrodes, saturated calomel electrode are reference electrode；Electrification is carried out in the 0.1mol/LKOH solution of room temperature and oxygen saturation
Learn test, cyclic voltammetry curve (CV) specific test parameter are as follows: -0.8~0.2V of scanning voltage range (vs SCE, 0.2~1.2V
Vs RHE), sweep speed 10mV/s；Linear sweep voltammetry curve (LSV) specific test parameter are as follows: scanning voltage is -1~0V
(vs SCE, 0~1V vs RHE), sweep speed 5mV/s, disk electrode revolving speed are 1600rpm；
The take-off potential of Fe-N-CNT catalyst -4 is 0.910V (vs RHE), half wave potential 0.773V (vs RHE).
Fig. 4 is the XRD spectra of the Fe-N-CNT catalyst prepared in Examples 1 to 4, in Fe-N-CNT catalyst obtained
Contain Fe, Fe3C etc. has the ingredient of facilitation to hydrogen reduction catalytic process；
Fig. 5 is the cyclic voltammetry curve figure of the Fe-N-CNT catalyst prepared in Examples 1 to 4, Fe-N-CNT obtained
There is apparent oxygen reduction peak in 0.7V or so in catalyst, illustrates that the catalyst oxygen reduction reaction process is more apparent；
Fig. 6 is that the linear sweep voltammetry of the Fe-N-CNT catalyst and commercialization Pd/C catalyst prepared in Examples 1 to 4 is bent
Line chart, Fe-N-CNT catalyst -3 have the take-off potential and half wave potential of corrigendum, and the close commercialization Pd/C catalyst of performance.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of method for preparing Fe-N-CNT catalyst using waste plastics, which is characterized in that this method comprises the following steps:
(a) waste plastics powder and ferrum-based catalyst are respectively placed in the first heating zone and the second heating zone, in an inert atmosphere
Heating a period of time, the pyrolysis gas generated in waste plastics pyrolytic process is made to deposit to form carbon nanotube on ferrum-based catalyst surface；
(b) purifying carbon nano-tube will be obtained after the carbon nanotube pickling, then by the purifying carbon nano-tube and nitrogenous compound
It is fully ground to obtain solid mixture after mixing；
(c) solid mixture is heated under an inert atmosphere and carries out secondary pyrolysis, the Fe-N- is made after being cooled to room temperature
CNT catalyst.
2. the method for preparing Fe-N-CNT catalyst using waste plastics as described in claim 1, which is characterized in that the step
(a) waste plastics is mechanically pulverized using liquid nitrogen pulverizer in, the partial size of the waste plastics powder is 0.5mm~1mm.
3. the method for preparing Fe-N-CNT catalyst using waste plastics as claimed in claim 1 or 2, which is characterized in that described
Waste plastics powder and the mass ratio of iron-based catalysis are 5:1~1:5 in step (a).
4. the method as claimed in any one of claims 1 to 3 for preparing Fe-N-CNT catalyst using waste plastics, feature exist
In the temperature program of heating process in the step (a) are as follows: by the second heating zone with 10 DEG C/min~20 DEG C/min heating speed
Rate is heated to 750 DEG C~900 DEG C, keeps the temperature and by the first heating zone after rising to target temperature with 5 DEG C/min~10 DEG C/min liter
Warm rate is heated to 500 DEG C~600 DEG C, then keeps the temperature 5min~10min.
5. the method for preparing Fe-N-CNT catalyst using waste plastics as described in claim 1, which is characterized in that the step
(a) and in step (c) inert atmosphere is nitrogen or argon gas, and the flow of inert gas is 50mL/min~100mL/min.
6. the method for preparing Fe-N-CNT catalyst using waste plastics as described in claim 1, which is characterized in that the step
(b) process of pickling in are as follows: be placed in the carbon nanotube in the concentrated nitric acid that concentration is 30%~50%, at 80 DEG C~100 DEG C
Under 4h~6h stirred with the revolving speed of 600rpm~1000rpm, then filtering obtains solid product and washes 10 times~20 times, finally
At 100 DEG C ,~105 DEG C at a temperature of dry 12h~obtain purifying carbon nano-tube for 24 hours.
7. the method for preparing Fe-N-CNT catalyst using waste plastics as described in claim 1, which is characterized in that the step
(b) nitrogenous compound is preferably melamine or dicyandiamide in.
8. the method for preparing Fe-N-CNT catalyst using waste plastics as described in claim 1, which is characterized in that the step
(b) purifying carbon nano-tube is mixed with nitrogenous compound with the mass ratio of 1:1~1:5 in, and milling time is 30min~60min.
9. the method for preparing Fe-N-CNT catalyst using waste plastics as described in claim 1, which is characterized in that the step
(c) secondary pyrolytic process in are as follows: be heated to 750 DEG C~900 DEG C with 5 DEG C/min~10 DEG C/min heating rate, then keep the temperature
0.5h~2h.
10. a kind of Fe-N-CNT catalyst using such as the method preparation of any one of claim 1~9.
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