CN108155393A - It is a kind of using carbon nanotube as the method for preparing catalyst of carrier - Google Patents

It is a kind of using carbon nanotube as the method for preparing catalyst of carrier Download PDF

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CN108155393A
CN108155393A CN201711425372.9A CN201711425372A CN108155393A CN 108155393 A CN108155393 A CN 108155393A CN 201711425372 A CN201711425372 A CN 201711425372A CN 108155393 A CN108155393 A CN 108155393A
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voltage
carbon nanotube
catalyst
carrier
preparing catalyst
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CN108155393B (en
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吴丹
范书琼
米诗阳
王秀
朱威
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Zhejiang Changxin Engine Science And Technology Co Ltd
Suzhou Dynamic Power Technology Co Ltd
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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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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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  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
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Abstract

The present invention relates to a kind of using carbon nanotube as the method for preparing catalyst of carrier, step is：S1, catalyst nucleation, carbon nanotube is put into deposition solution, applies of short duration voltage to deposition solution in the environment of more than 20 DEG C, and the voltage of application is 0.25V relative to saturated calomel electrode, forms deposition core；S2, catalyst growth, pulse voltage is applied to deposition solution in the environment of less than 20 DEG C, it relative to saturated calomel electrode is 0.2V that the pulse voltage of application, which is high voltage, low-voltage is 0.25V relative to saturated calomel electrode, the pulse voltage duration is 30 minutes so that deposits karyomorphism into catalyst granules.Using catalyst made from the above method, granular size is between 4~6 nanometers and is more evenly distributed in carbon nanotube, and size is suitable, and specific surface is all higher than 40m2/ g, the activity of catalyst relative to increasing substantially in the past, and raising product quality.

Description

It is a kind of using carbon nanotube as the method for preparing catalyst of carrier
Technical field
The present invention relates to the production and manufacture of fuel cell, more particularly, to a kind of using carbon nanotube as the catalyst of carrier Preparation method.
Background technology
Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, PEMFC) is a kind of incites somebody to action The chemical energy of hydrogen is converted into the power generator of electric energy by electrochemical reaction.The redox reaction of its cathode needs logical Pt metal is crossed to be catalyzed, and the quality that the generation of catalyst will influence Proton Exchange Membrane Fuel Cells.Existing technology be by Carbon nanotube substrate is put into deposition solution, applies constant current, constant potential or pulse current, metal platinum or other metallic elements are also Original is deposited on carbon nano tube surface, and electrochemical deposition method is used to be made, and electrochemical deposition process is divided into two nucleation, growth ranks Section.Nucleation stage is out-phase reaction, needs to overcome surface energy, so the voltage that electrochemical deposition applies is bigger, nucleation is more；It is raw The step of long stage is diffusion control, if requiring catalyst granules homoepitaxial, it is necessary to apply smaller voltage and slowly give birth to It is long.Carbon nano tube surface defect is less, and Pt metal needs to overcome larger Surface binding energy that could be nucleated on the carbon nanotubes, but If applying larger voltage, it may result in that Pt growths are too fast, and particle is excessive, uneven, if the voltage applied is smaller, and nothing Method forms enough deposition core, causes particle excessive.Both catalyst specific surface can be caused to reduce, reduces catalytic activity.
Invention content
In order to solve drawbacks described above, the present invention provides a kind of using carbon nanotube as the method for preparing catalyst of carrier.
The present invention solves above-mentioned technical problem and is adopted the technical scheme that：It is a kind of using carbon nanotube as the catalyst of carrier The step of preparation method, the preparation method is：
S1, catalyst nucleation, carbon nanotube are put into deposition solution, to deposition solution in the environment of more than 20 DEG C Apply of short duration voltage, the voltage of application is -0.25V relative to saturated calomel electrode, forms deposition core；
S2, catalyst growth apply pulse voltage, the pulse voltage of application in the environment of less than 20 DEG C to deposition solution Relative to saturated calomel electrode it is 0.2V for high voltage, low-voltage is -0.25V relative to saturated calomel electrode, and pulse voltage is held The continuous time is 30 minutes so that deposits karyomorphism into catalyst granules.
Further specifically, applying the alive time in the step S1 as 180s.
Further specifically, the high voltage duration of pulse voltage is 3s in the step S2, low-voltage is held The continuous time is 1s.
Further specifically, the environment temperature in the step S1 is 20 DEG C~80 DEG C.
Further specifically, the high temperature in the step S2 is 80 DEG C.
Further specifically, the low temperature in the step S2 is 4 DEG C~20 DEG C.
Further specifically, the low temperature in the step S2 is 4 DEG C.
Further specifically, the deposition solution is by H2PtCl6、H2SO4And ethylene glycol mixes.
Further specifically, the deposition solution is the H by 5mM2PtCl6, 0.5M H2SO4And the second two of 0.5M Alcohol mixes.
The beneficial effects of the invention are as follows：Using catalyst made from the above method, granular size is between 4~6 nanometers And be more evenly distributed in carbon nanotube, size is suitable, and specific surface is all higher than 40m2/ g, the active phase of catalyst For increasing substantially in the past, overall procedure is more convenient in use, and improves product quality.
Description of the drawings
Fig. 1 is the flow chart of the present invention；
Fig. 2 is the catalyst stereoscan photograph of serial number 1 in embodiment 4；
Fig. 3 is the catalyst stereoscan photograph of serial number 2 in embodiment 4；
Fig. 4 is the catalyst stereoscan photograph of serial number 3 in embodiment 4.
Specific embodiment
The present invention is explained in detail below in conjunction with the accompanying drawings.
A kind of using carbon nanotube as the method for preparing catalyst of carrier as shown in Figure 1, the step of preparation method, is：
S1, catalyst nucleation, carbon nanotube is put into deposition solution, (the preferential selection in the environment of more than 20 DEG C 20 DEG C~80 DEG C) apply of short duration voltage to deposition solution, the voltage of application is -0.25V relative to saturated calomel electrode, is applied Time for 180s, form deposition core；
S2, catalyst growth, (preferential 4 DEG C~20 DEG C of selection) is to deposition solution application pulse in the environment of less than 20 DEG C Voltage, it relative to saturated calomel electrode is that 0.2V continues 3s that the pulse voltage of application, which is high voltage, and low-voltage is sweet relative to saturation Mercury electrode continues 1s for -0.25V, and the pulse voltage duration is 30 minutes so that deposits karyomorphism into catalyst granules.
The deposition solution is by H2PtCl6、H2SO4And ethylene glycol mixes.
Embodiment 1：
Choose three kinds of H2PtCl6The different deposition solution of content, H2PtCl6Content be respectively 5mM, 10mM and 20mM, three kinds of deposition solutions are placed in 80 DEG C of environment, apply Nanowire array identical in the above method and growth pulse electricity Pressure, Pt carrying capacity and specific surface are as shown in the table.
Work as H as can be seen from the above table2PtCl6Content when being respectively 5mM, Pt carrying capacity is 0.41mg/cm2, specific surface is 41.3m2/ g, effect are best.
Embodiment 2：
Using content as the H of 5mM2PtCl6Deposition solution, respectively in the case where environment temperature is 20 DEG C, 40 DEG C, 60 DEG C and 80 DEG C Identical Nanowire array and growth voltage are imposed, Pt carrying capacity and specific surface are as shown in the table.
As can be seen from the above table, under the same conditions, the environment temperature of nucleation is controlled when 80 DEG C, and Pt carrying capacity is 0.42mg/cm2, specific surface 42.2m2/ g, effect are best.
Embodiment 3：
Using content as the H of 5mM2PtCl6Deposition solution, environment temperature for impose at 80 DEG C different Nanowire arrays (- 0.22V and -0.25V), Pt carrying capacity and specific surface are as shown in the table.
As can be seen from the above table, under the same conditions, when the voltage of nucleation stage is -0.25V, Pt carrying capacity is 0.42mg/cm2, specific surface 41m2/ g, effect are best.
Embodiment 4：
Using content as the H of 5mM2PtCl6Deposition solution, in the environment temperature of nucleation at 80 DEG C and to apply identical nucleation Voltage and growth voltage, select different growth temperatures, respectively 4 DEG C, 10 DEG C and 20 DEG C, Pt carrying capacity and specific surface It is as shown in the table.
In upper table serial number 1 stereoscan photograph as shown in Fig. 2, the stereoscan photograph of serial number 2 as shown in Fig. 3, serial number 3 stereoscan photographs are as shown in Figure 4；It can be seen from upper table and Fig. 2~4 under the same conditions, the temperature of growth phase is When 4 DEG C, Pt carrying capacity is 0.39mg/cm2, specific surface 41m2/ g, effect are best.
Embodiment 5：
Using content as the H of 5mM2PtCl6Deposition solution, in the environment temperature of nucleation be 80 DEG C and growing environment temperature is 4 At DEG C, and apply identical Nanowire array, using different growth voltage, constant voltage -0.25V and pulse electricity is respectively adopted Pressure, Pt carrying capacity and specific surface are as shown in the table.
As can be seen from the above table, temperature is identical and H2PtCl6H in deposition solution2PtCl6Content is identical and into nuclear power Press it is identical in the case of, the use of pulse voltage is best compared with the effect of constant voltage, Pt carrying capacity be 0.41 mg/cm2, specific surface For 41.3m2/g。
By above-mentioned all embodiments, the parameters of links in whole flow process are determined, in entire nucleation and life In growth process, deposition solution is the H by 5mM2PtCl6, 0.5M H2SO4And the ethylene glycol of 0.5M mixes；The temperature of nucleation Degree determines that the voltage of nucleation for -0.25V and continues 180s at 80 DEG C；The temperature of growth determines that at 4 DEG C growth is using pulse electricity Pressure, it is 3s the 0.2V duration that high voltage, which is, and it is 1s -0.25V the duration that low-voltage, which is, and pulse voltage continues 30 minutes altogether； The catalyst particle size produced is between 4~6 nanometers and is more evenly distributed in carbon nanotube, and size is closed Suitable, specific surface is all higher than 40m2/ g, the activity of catalyst relative to increasing substantially in the past.
It is emphasized that：It the above is only presently preferred embodiments of the present invention, not the present invention made in any form Limitation, any simple modification, equivalent change and modification that every technical spirit according to the present invention makees above example, In the range of still falling within technical solution of the present invention.

Claims (9)

  1. It is 1. a kind of using carbon nanotube as the method for preparing catalyst of carrier, which is characterized in that the step of described preparation method is：
    S1, catalyst nucleation, carbon nanotube is put into deposition solution, deposition solution is applied in the environment of more than 20 DEG C Of short duration voltage, the voltage of application are -0.25V relative to saturated calomel electrode, form deposition core；
    S2, catalyst growth apply deposition solution in the environment of less than 20 DEG C pulse voltage, and the pulse voltage of application is height Voltage is 0.2V relative to saturated calomel electrode, and low-voltage is -0.25V relative to saturated calomel electrode, when pulse voltage continues Between be 30 minutes so that deposition karyomorphism is into catalyst granules.
  2. It is 2. according to claim 1 using carbon nanotube as the method for preparing catalyst of carrier, which is characterized in that described The alive time is applied in step S1 as 180s.
  3. It is 3. according to claim 1 using carbon nanotube as the method for preparing catalyst of carrier, which is characterized in that described The high voltage duration of pulse voltage is 3s in step S2, and low-voltage duration is 1s.
  4. It is 4. according to claim 1 using carbon nanotube as the method for preparing catalyst of carrier, which is characterized in that described Environment temperature in step S1 is 20 DEG C~80 DEG C.
  5. It is 5. according to claim 2 using carbon nanotube as the method for preparing catalyst of carrier, which is characterized in that described High temperature in step S2 is 80 DEG C.
  6. It is 6. according to claim 1 using carbon nanotube as the method for preparing catalyst of carrier, which is characterized in that described Low temperature in step S2 is 4 DEG C~20 DEG C.
  7. It is 7. according to claim 4 using carbon nanotube as the method for preparing catalyst of carrier, which is characterized in that described Low temperature in step S2 is 4 DEG C.
  8. It is 8. according to claim 1 using carbon nanotube as the method for preparing catalyst of carrier, which is characterized in that described is heavy Product solution is by H2PtCl6、H2SO4And ethylene glycol mixes.
  9. It is 9. according to claim 8 using carbon nanotube as the method for preparing catalyst of carrier, which is characterized in that described is heavy Product solution is the H by 5mM2PtCl6, 0.5M H2SO4And the ethylene glycol of 0.5M mixes.
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CN104198551A (en) * 2014-09-22 2014-12-10 郑州大学 Method for manufacturing nano platinum and multiwalled carbon nanotube modified glassy carbon electrode and method for detecting estradiol by utilizing glassy carbon electrode
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