CN106540689A - A kind of CNT carried palladium catalyst and its preparation method and application - Google Patents
A kind of CNT carried palladium catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses the preparation method and catalyst of a kind of carbon nanotube loaded palladium catalyst and its application in catalyst combustion reaction.The catalyst is prepared for nano Pd catalyst of the uniform load inside carbon nano tube surface and tube chamber using the pressure change in system with CNT as carrier with precious metal palladium nano-particle as active component.The method according to the invention, under general process conditions, by using conventional facilities, can easily, simply and directionally control Pd nano particle distribution on the carbon nanotubes, and obtained catalyst has good catalytic combustion properties.
Description
Technical field
The present invention relates to a kind of preparation method of CNT carried palladium catalyst and the catalyst for preparing and
Its application in catalyst combustion reaction, belongs to using energy source and environmental protection technical field.
Background technology
Catalysis burning has the advantages such as initiation temperature is low, purification efficiency is high, adaptation oxygen ranges are big, is having
The common concern of people is subject in terms of machine waste gas pollution control and treatment, energy regenerating utilization and generating.At present methyl hydride catalyzed
In combustion field using wider palladium-based catalyst during the course of the reaction, palladium can assemble the transformation for concurrently giving birth to valence state
So as to cause the decline of activity.Therefore new carrier is developed, stablizing for palladium active specy is maintained, palladium base is urged
Agent further using significant.
CNT (CNTs) not only possesses traditional Carbon Materials solid as a class nanoscale novel carbon material
Some advantage (such as acid and alkali-resistance, controllable hole structure and surface texture, be easy to noble metal to reclaim etc.), it is also special
Structure, surface chemical property and Electronic Performance.Used as new catalytic material, CNT is with to reaction species
The absorption property special with product, special vestibule stereoselectivity, space confinement effect and metal
Strong interaction (SMSI) and tube wall can functional group modification the advantages of.Using CNT as carrier,
Its confinement effect can effective restricted activity component palladium particle growth, the height of CNTs than table can improve palladium point
Divergence, the electronic effect of CNTs can change the redox property of palladium.But, such as precise control active component
Load situation on the carbon nanotubes is not still solved.Additionally, CNT is all surrounded for the correlative study of carrier
Reducing atmosphere, and the research that CNT is used for oxidizing atmosphere is rarely reported.Therefore the present invention carries out
A kind of research of the preparation method of loaded palladium catalyst on the carbon nanotubes, it is desirable to which CNT is applied to oxygen-enriched
In atmosphere, particularly in terms of the catalysis burning of low-concentration methane.
The content of the invention
It is an object of the invention to provide the preparation method and catalyst of a kind of CNT carried palladium catalyst.
A further object of the present invention is that above-mentioned CNT carried palladium catalyst is used for catalyst combustion reaction.
The technical solution used in the present invention is:
The preparation method of CNT carried palladium catalyst of the present invention is, with CNT as carrier, with palladium
For active component, by regulating system pressure, controlling active component palladium load situation on the carbon nanotubes is
Tube cavity or pipe outer wall.
It is furthermore preferred that by controlling the pressure precise control active component in reactor in CNT outer wall or
It is intraluminal to be uniformly distributed.
Palladium content accounts for 0.5~10wt% of total catalyst weight, preferably 1~5wt%, and the particle diameter of palladium particle is 2~5nm.
The length of CNT is 10~50 μm, preferably 20~30 μm.Carbon nanotube diameter is 5~50nm, excellent
Select 20~30nm.Specific surface area is 60~300m2/ g, preferably 100~180m2/g。
Before load active component palladium, carbon nanotube carrier is pre-processed, carbon nanotube carrier it is pre-
Process step is:CNT is added in mixed liquor of the concentrated sulfuric acid with red fuming nitric acid (RFNA), ultrasonic disperse, heating
Backflow, washing and filtering are dried, obtain deimpurity carbon nanotube carrier.
The concentrated sulfuric acid is 1 with the volume range of red fuming nitric acid (RFNA):9~9:1, quality and the concentrated acid mixed liquor of CNT
Volume range is 1:100~1000 (g/ml), heating-up temperature are 40~160 DEG C, return time 0.5-8h,
Neutrality is washed with water to, baking temperature is 80-150 DEG C, deimpurity CNT is obtained for hydrophily.
It is by carrying out taking out true to the CNT in reactor that palladium is supported on the preparation method of carbon nanotube cavity
Sky, by the precursor solution of palladium under condition of negative pressure, wicks themselves into inside tube chamber, by palladium
Grain orientation is equably supported on inside the tube chamber of CNT;
Palladium be supported on the preparation method of CNT outer wall be by pressurizeing to the CNT in reactor,
It is filled with a gas in carbon nanotubes lumen, then the precursor solution of palladium is supported on CNT outer wall.
Palladium is supported on the preparation method of carbon nanotube cavity and comprises the following steps:
(1) deimpurity carbon nanotube carrier will be gone to be put in a reactor, vacuumized with vavuum pump so that
It is in negative pressure state in reactor, vacuum is 0.001~0.01Mpa;
(2) by certain density palladium precursor solution injecting reactor, impregnate;
(3) quickly it is washed with deionized, filters;
(4) drying at room temperature, roasting;
Palladium is supported on the preparation method of CNT outer wall and comprises the following steps:
(1) deimpurity carbon nanotube carrier will be gone to be put in a reactor, reactor inflated with nitrogen will be caused
It is in barotropic state in reactor, pressure is 0.1~1MPa;
(2) by certain density palladium precursor solution injecting reactor, impregnate;
(3) 80~150 DEG C of dryings, roasting.
Palladium precursor is palladium nitrate, palladium bichloride, one or more in palladium, palladium precursor solution
For the one kind in the aqueous solution of palladium precursor, ethanol solution, acetone soln, aqueous isopropanol, before the palladium
The concentration for driving liquid solution is 3~50mg/ml, and the carbon nanotube mass with palladium precursor solution volume range is
1:1~5 (g/ml);Dip time is 1~30min;Drying time is 8~24h;Sintering temperature is 300 DEG C~500 DEG C,
Roasting time is 1~4h;The reactor is stainless steel structure, and liner is polytetrafluoroethylene (PTFE), is pressed by two
Adjusting the pressure in reactor, a connection gas bomb is used for pressurizeing power connector, another connection
Vavuum pump is used for vacuumizing, and reactor has a charge door, for adding the precursor solution of palladium.
The present invention provides a kind of carbon nanotube loaded palladium catalyst and carbon nanotube loaded palladium catalyst oxygen-enriched
Application in atmosphere, in catalyst combustion reaction.
Catalyst combustion reaction is methane catalytic combustion process or other hydrocarbons and VOC, H2、CO
The catalysis burning subtractive process of gas.
Catalyst using front in 10%H2-N2200~500 DEG C of 1~4h of pretreatment of Jing in mixed airflow, or use
2% hydrazine hydrate solution reductase 12 4h.
Described carbon nanotube loaded palladium catalyst is applied as the decentralized medium of Pd nano particle.
The catalyst that the present invention is provided is used for coalmine ventilation device in Gas catalyst combustion reaction, with preferable result,
When the concentration of methane is 0.2%, remaining is air, and gas space velocity is 20000h- 1Under conditions of can be at 400 DEG C
The conversion completely of implemented below methane.
The advantages of the present invention are:
1st, catalyst improves activity using CNT as carrier using its interaction with noble metal
The decentralization and stability of component.Carbon nanotube carrier has stronger adsorptivity, eliminates catalyst preparation
During residual chlorine ion pair activity impact.
2nd, active component is loaded using infusion process, by controlling the pressure precise control active component in reactor
CNT outer wall or it is intraluminal be uniformly distributed, preparation method is simply easily operated, active component dispersion
Uniformly.
3rd, catalyst can adapt to the problem of methane concentration dynamic change in mine ventilation gas gas, can adapt to
Contain the problem of a small amount of water vapour and sulphur in reacting gas, with preferable Activity and stabill, especially
Pd-in-CNTs catalyst has excellent hydrothermal stability.
Description of the drawings
What Fig. 1 was represented is the reactor picture for preparing CNT.
What Fig. 2 was represented is the transmission electron microscope photo of 2wt%Pd-out-CNTs catalyst.
What Fig. 3 was represented is the transmission electron microscope photo of 1wt%Pd-in-CNTs catalyst.
Specific embodiment
Unless otherwise noted, all numerals for occurring in description of the invention and claims, for example, live
The numerical value such as property component, sintering temperature and time, gas conversions are not construed as absolute exact value,
It is that the numerical value is that those of ordinary skill in the art is understood, in the error range allowed by known technology.
Although the accuracy for ensureing numerical value is tried hard to be in the example that the present invention is provided, due to various e measurement technologies
Standard deviation, the numerical value that any measurement is obtained all is inevitably present certain error.Below again with several
Embodiment is further described to the above.It should be noted that these embodiments are not made to the above
The restriction gone up in all senses.
The present invention is further described below in conjunction with Fig. 1:
The CNT handled well is added in reactor, if Pd-out-CNTs catalyst will be prepared, first
Use N2Punching press is carried out to system, the pressure of control system reaches desirable value, then by the precursor solution of Pd
Added by charging aperture.Equally, before Pd-in-CNTs catalyst is prepared, by vavuum pump so that system
After vacuum needed for reaching, then the precursor solution of Pd is added by charging aperture.
Embodiment 1:
It is 130m that 1g length is weighed for 10 μm, a diameter of 20nm, specific surface area2The CNT of/g, plus
Enter the ultrasonic disperse 10min in the mixed liquor of the 200ml concentrated sulfuric acids and 100ml red fuming nitric acid (RFNA)s, then under agitation in
60 DEG C of reflow treatments 8h, washing and filtering, it is neutrality to be washed to filtrate pH value, is dried 24h in 100 DEG C, obtains
To pretreated carbon nanotube carrier.Pretreated carbon nanotube carrier is put in reactor, is used
Vavuum pump is vacuumized to be made in negative pressure in reactor, and vacuum is 0.001Mpa, measures concentration for 3.37mgPd/ml
Palladium bichloride acetone soln 3ml, be injected in reactor, dipping 30min after, deionized water is quickly washed
Wash and filter, drying at room temperature 24h, then dried product is obtained in 400 DEG C of roasting 2h
1wt%Pd-in-CNTs catalyst.
Embodiment 2:
It is 260m that 1g length is weighed for 30 μm, a diameter of 10nm, specific surface area2The CNT of/g, plus
Enter the ultrasonic disperse 5min in the mixed liquor of the 100ml concentrated sulfuric acids and 800ml red fuming nitric acid (RFNA)s, then under agitation in
80 DEG C of reflow treatments 3h, washing and filtering, it is neutrality to be washed to filtrate pH value, is dried 12h in 80 DEG C, obtains
To pretreated carbon nanotube carrier.Pretreated carbon nanotube carrier is put in reactor, is used
Vavuum pump is vacuumized to be made in negative pressure in reactor, and vacuum is 0.01Mpa, measures concentration for 20.83mgPd/ml
Palladium aqueous isopropanol 2ml, be injected in reactor, dipping 2min after, deionized water is quick
Wash and filter, drying at room temperature 16h, then dried product is obtained in 350 DEG C of roasting 3h
4wt%Pd-in-CNTs catalyst.
Embodiment 3:
It is 233m that 1g length is weighed for 20 μm, a diameter of 15nm, specific surface area2The CNT of/g, plus
Enter the ultrasonic disperse 15min in the mixed liquor of the 200ml concentrated sulfuric acids and 200ml red fuming nitric acid (RFNA)s, then under agitation in
50 DEG C of reflow treatments 7h, washing and filtering, it is neutrality to be washed to filtrate pH value, is dried 2h in 150 DEG C, obtains
To pretreated carbon nanotube carrier.Pretreated carbon nanotube carrier is put in reactor, is used
Vavuum pump is vacuumized to be made in negative pressure in reactor, and vacuum is 0.003Mpa, measures concentration for 45.3mgPd/ml
Palladium nitrate ethanol solution 2.2ml, be injected in reactor, dipping 10min after, deionized water is quick
Wash and filter, drying at room temperature 8h, then dried product is obtained in 300 DEG C of roasting 4h
10wt%Pd-in-CNTs catalyst.
Embodiment 4:
It is 60m that 1g length is weighed for 40 μm, a diameter of 50nm, specific surface area2The CNT of/g, plus
Enter the ultrasonic disperse 5min in the mixed liquor of the 500ml concentrated sulfuric acids and 200ml red fuming nitric acid (RFNA)s, then under agitation in
100 DEG C of reflow treatments 1h, washing and filtering, it is neutrality to be washed to filtrate pH value, is dried 6h in 120 DEG C, obtains
To pretreated carbon nanotube carrier.Pretreated carbon nanotube carrier is put in reactor, is used
Vavuum pump is vacuumized to be made in negative pressure in reactor, and vacuum is 0.006Mpa, measures concentration for 6.6mgPd/ml
Palladium nitrate aqueous solution 4ml, be injected in reactor, dipping 20min after, deionized water quick wash
And filter, drying at room temperature 18h, then dried product is obtained in 500 DEG C of roasting 1h
2.5wt%Pd-in-CNTs catalyst.
Embodiment 5:
It is 100m that 1g length is weighed for 50 μm, a diameter of 30nm, specific surface area2The CNT of/g, plus
Enter the ultrasonic disperse 8min in the mixed liquor of the 300ml concentrated sulfuric acids and 600ml red fuming nitric acid (RFNA)s, then under agitation in
160 DEG C of reflow treatments 0.5h, washing and filtering, it is neutrality to be washed to filtrate pH value, is dried 10h in 100 DEG C,
Obtain pretreated carbon nanotube carrier.Pretreated carbon nanotube carrier is put in reactor,
Pressurising is carried out to reactor with nitrogen, reactor pressure is 0.5Mpa, concentration is measured for 4.08mgPd/ml's
The aqueous solution 5ml of palladium bichloride, is injected in reactor, and after dipping 2min, 120 DEG C are dried 15h, then will be dry
Product after dry obtains 2wt%Pd-out-CNTs catalyst in 500 DEG C of roasting 2h.
Embodiment 6:
It is 300m that 1g length is weighed for 50 μm, a diameter of 5nm, specific surface area2The CNT of/g, plus
Enter the ultrasonic disperse 5min in the mixed liquor of the 100ml concentrated sulfuric acids and 400ml red fuming nitric acid (RFNA)s, then under agitation in
40 DEG C of reflow treatments 8h, washing and filtering, it is neutrality to be washed to filtrate pH value, is dried 8h in 90 DEG C, obtains
Pretreated carbon nanotube carrier.Pretreated carbon nanotube carrier is put in reactor, nitrogen is used
Gas carries out pressurising to reactor, and reactor pressure is 0.3Mpa, measures the chlorination that concentration is 25.1mgPd/ml
The aqueous solution 2ml of palladium, is injected in reactor, and after dipping 5min, 150 DEG C are dried 10h, then after being dried
Product in 300 DEG C of roasting 4h, obtain 5wt%Pd-out-CNTs catalyst.
Embodiment 7:
It is 150m that 1g length is weighed for 30 μm, a diameter of 20nm, specific surface area2The CNT of/g, plus
Enter the ultrasonic disperse 5min in the mixed liquor of the 500ml concentrated sulfuric acids and 200ml red fuming nitric acid (RFNA)s, then under agitation in
100 DEG C of reflow treatments 1h, washing and filtering, it is neutrality to be washed to filtrate pH value, is dried 6h in 120 DEG C, obtains
To pretreated carbon nanotube carrier.Pretreated carbon nanotube carrier is put in reactor, is used
Nitrogen carries out pressurising to reactor, and reactor pressure is 0.4Mpa, measures the nitre that concentration is 1.25mgPd/ml
The ethanol solution 4ml of sour palladium, is injected in reactor, and after dipping 1min, 80 DEG C are dried 24h, then will be dry
Product after dry obtains 0.5wt%Pd-out-CNTs catalyst in 450 DEG C of roasting 2h.
Embodiment 8:
It is 80m that 1g length is weighed for 20 μm, a diameter of 50nm, specific surface area2The CNT of/g, plus
Enter the ultrasonic disperse 5min in the mixed liquor of the 500ml concentrated sulfuric acids and 200ml red fuming nitric acid (RFNA)s, then under agitation in
100 DEG C of reflow treatments 1h, washing and filtering, it is neutrality to be washed to filtrate pH value, is dried 6h in 120 DEG C, obtains
To pretreated carbon nanotube carrier.Pretreated carbon nanotube carrier is put in reactor, is used
Nitrogen carries out pressurising to reactor, and reactor pressure is 0.1Mpa, measures the vinegar that concentration is 26.7mgPd/ml
The acetone soln 3ml of sour palladium, is injected in reactor, and after dipping 5min, 80 DEG C are dried 24h, then will be dry
Product after dry obtains 8wt%Pd-out-CNTs catalyst in 350 DEG C of roasting 3h.
By Catalyst packing prepared in the above embodiment of the present invention in fixed-bed catalytic combustion reactor,
It is passed through simulation coalmine ventilation device in Gas, the loadings of catalyst are 0.1g, catalyst is need to be using before
10%H2-N2200~500 DEG C of Jing pretreatment, 1~4h in mixed airflow, or with 2% hydrazine hydrate solution reductase 12 4h.
In inlet gas, methane content is 0.2%, and remaining is air, and gas space velocity is 20,000h- 1.In reaction temperature
In the range of 0-400 DEG C, the initial activity (T of catalyst is investigated10, T50, T90Catalyst conversion is corresponded to respectively
Rate is 10%, 50%, reaction temperature temperature when 90%) and in the methane conversion of 400 DEG C of reaction 400h
(t=400h).The results are shown in Table 1.
1 catalyst performance table of table
Embodiment | T10/℃ | T50/℃ | T90/℃ | T=400h/% |
1 | 317 | 358 | 393 | >90 |
2 | 292 | 344 | 365 | >90 |
3 | 261 | 301 | 322 | >90 |
4 | 302 | 352 | 389 | >90 |
5 | 306 | 356 | 392 | >70 |
6 | 277 | 316 | 346 | >70 |
7 | 332 | 369 | 397 | >70 |
8 | 265 | 307 | 323 | >70 |
It is visible by above-mentioned experiment, a kind of CNT carried palladium catalyst of the present invention and preparation method thereof
And application, active component palladium load situation on the carbon nanotubes can be controlled by modulation pressure, obtained
Pd-in-CNTs and Pd-out-CNTs catalyst, is developed as application background with ventilating gas catalytic combustion technology
(methane concentration content is less than 1%), is commented to the performance of catalyst under more harsh experiment condition
Valency, as a result shows that catalyst disclosed in this patent has excellent catalysis activity and hydrothermal stability, methane
Initiation temperature and complete ignition temperature are very low, and can preferably meet low temperature ignition and high hydrothermal stability will
Ask;Wherein Pd-in-CNTs has better hydrothermal stability, this is because Pd is supported on carbon nanometer
The growth of the caliber restricted activity component Pd particle of CNT inside pipe, can be passed through during the course of the reaction,
And as the change of inhibitory activity component Pd valence state is capable of in the interaction of CNT and Pd;Meanwhile,
Catalyst prepared by the present invention is also applied for other VOC gases and H2, CO catalytic eliminating process.
And the catalyst of the present invention, its preparation process is simple, it is relatively low cost and easy to promote into product.
Claims (13)
1. a kind of preparation method of CNT carried palladium catalyst, it is characterised in that:With CNT as carrier,
With palladium as active component, by regulating system pressure, active component palladium load byte on the carbon nanotubes is controlled
It is set to tube cavity or pipe outer wall.
2. preparation method according to claim 1, it is characterised in that:Palladium content accounts for total catalyst weight
0.5~10wt%, the particle diameter of palladium particle is 2~5nm.
3. preparation method according to claim 1, it is characterised in that:The length of CNT is
10~50 μm, carbon nanotube diameter is 5~50nm, and specific surface area is 60~300m2/g。
4. preparation method according to claim 1, it is characterised in that:Before load active component palladium,
Carbon nanotube carrier is pre-processed, the pre-treatment step of carbon nanotube carrier is:CNT is added
To in mixed liquor of the concentrated sulfuric acid with red fuming nitric acid (RFNA), ultrasonic disperse is heated to reflux, washing and filtering, is dried, obtains
Go deimpurity carbon nanotube carrier.
5. preparation method according to claim 4, it is characterised in that:The volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA)
Scope is 1:9~9:1, the quality of CNT is 1 with the volume range of concentrated acid mixed liquor:100~1000
(g/ml), heating-up temperature is 40~160 DEG C, and return time 0.5-8h is washed with water to neutrality, baking temperature
For 80-150 DEG C, deimpurity CNT is obtained for hydrophily.
6. preparation method according to claim 1, it is characterised in that:
It is by carrying out taking out true to the CNT in reactor that palladium is supported on the preparation method of carbon nanotube cavity
Sky, by the precursor solution of palladium under condition of negative pressure, wicks themselves into inside tube chamber, by palladium
Grain orientation is equably supported on inside the tube chamber of CNT;
Palladium be supported on the preparation method of CNT outer wall be by pressurizeing to the CNT in reactor,
It is filled with a gas in carbon nanotubes lumen, then the precursor solution of palladium is supported on CNT outer wall.
7. preparation method according to claim 6, it is characterised in that:Palladium is supported on carbon nanotube cavity
Preparation method is comprised the following steps:
(1) deimpurity carbon nanotube carrier will be gone to be put in a reactor, vacuumized with vavuum pump so that
It is in negative pressure state in reactor, vacuum is 0.001~0.01Mpa;
(2) by certain density palladium precursor solution injecting reactor, impregnate;
(3) quickly it is washed with deionized, filters;
(4) drying at room temperature, roasting;
Palladium is supported on the preparation method of CNT outer wall and comprises the following steps:
(1) deimpurity carbon nanotube carrier will be gone to be put in a reactor, reactor inflated with nitrogen will be caused
It is in barotropic state in reactor, pressure is 0.1~1MPa;
(2) by certain density palladium precursor solution injecting reactor, impregnate;
(3) 80~150 DEG C of dryings, roasting.
8. preparation method according to claim 7, it is characterised in that:Palladium precursor be palladium nitrate, palladium bichloride,
One or more in palladium, palladium precursor solution is the aqueous solution of palladium precursor, ethanol solution,
One kind in acetone soln, aqueous isopropanol, the concentration of the palladium precursor solution is 3~50mg/ml, described
Carbon nanotube mass is 1 with palladium precursor solution volume range:1~5 (g/ml);Dip time is 1~30min;
Drying time is 8~24h;Sintering temperature is 300 DEG C~500 DEG C, and roasting time is 1~4h;The reactor is
Stainless steel structure, liner are polytetrafluoroethylene (PTFE), adjust the pressure in reactor by two press-in connection mouths,
One connection gas bomb is used for pressurizeing, and another connection vavuum pump is used for vacuumizing, and reactor has one
Charge door, for adding the precursor solution of palladium.
9. the carbon nanotube loaded palladium catalyst that a kind of arbitrary preparation method of claim 1-8 is prepared.
10. carbon nanotube loaded palladium catalyst according to claim 9 in oxygen-enriched atmosphere, burn by catalysis
Application in reaction.
11. applications according to claim 10, it is characterised in that:Catalyst combustion reaction is methyl hydride catalyzed combustion
Burning process or other hydrocarbons and VOC, H2, CO gases catalysis burning subtractive process.
12. applications according to claim 10 or 11, it is characterised in that:Catalyst using it is front
10%H2-N2200~500 DEG C of Jing pretreatment, 1~4h in mixed airflow, or with 2% hydrazine hydrate solution reductase 12 4h.
13. carbon nanotube loaded palladium catalysts according to claim 9 are situated between as the dispersion of Pd nano particle
Matter is applied.
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CN107185542A (en) * | 2017-05-05 | 2017-09-22 | 北京石油化工学院 | A kind of support type Fe Zn/CNTs catalyst and preparation method thereof |
CN107185542B (en) * | 2017-05-05 | 2020-05-22 | 北京石油化工学院 | Supported Fe-Zn/CNTs catalyst and preparation method thereof |
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CN107469832B (en) * | 2017-07-24 | 2019-02-05 | 广东本立环保技术有限公司 | One kind is for chlorinated organics waste gas catalytic combustion catalyst and preparation method thereof |
CN109201040A (en) * | 2018-09-28 | 2019-01-15 | 东北大学秦皇岛分校 | A kind of carbon nanotube-manganese oxide composite material of efficient catalytic methane and preparation method thereof |
CN109967078A (en) * | 2019-03-26 | 2019-07-05 | 南京工业大学 | Preparation method of morphology-controllable carbon nanotube-based gas catalytic membrane |
CN109967078B (en) * | 2019-03-26 | 2022-02-22 | 南京工业大学 | Preparation method of morphology-controllable carbon nanotube-based gas catalytic membrane |
CN114433095A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method and application thereof |
CN114433095B (en) * | 2020-10-20 | 2024-05-03 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method and application thereof |
CN115966719A (en) * | 2023-03-16 | 2023-04-14 | 国家电投集团氢能科技发展有限公司 | Anode catalyst, preparation method thereof and proton exchange membrane fuel cell |
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