CN105375041A - Carbon nanotube-transition metal-carbon fiber composite material and preparation method and application therefor - Google Patents

Carbon nanotube-transition metal-carbon fiber composite material and preparation method and application therefor Download PDF

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Publication number
CN105375041A
CN105375041A CN201510802158.5A CN201510802158A CN105375041A CN 105375041 A CN105375041 A CN 105375041A CN 201510802158 A CN201510802158 A CN 201510802158A CN 105375041 A CN105375041 A CN 105375041A
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tube
carbon
carbon nano
transition metal
preparation
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曾建皇
吴欣
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South China University of Technology SCUT
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South China University of Technology SCUT
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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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material 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
    • 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
    • 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

Abstract

The invention discloses a carbon nanotube-transition metal-carbon fiber composite material and a preparation method and an application therefor, and belongs to the technical field of the nanomaterial. The preparation method comprises the steps of performing sensitization and activation processing on a functionalized carbon nanotube, then putting the carbon nanotube into a chemical plating solution containing the transition metal to be subjected to a chemical plating reaction, and drying to obtain a carbon nanotube-transitional metal catalyst; then putting into a tubular furnace, raisingthe temperature to be 500-550 DEG C, pumping hydrogen and maintaining for 0.5-2 hours; then raisingthe temperature to be 600-800 DEG C, and pumping an acetylene mixed gas as the carbon source, and growing carbon fibers on the surface of the carbon nanotube-transitional metal catalyst through chemical vapor deposition to obtain the carbon nanotube-transition metal-carbon fiber composite material. The prepared carbon fibers are generated in in-situ reaction on the surface of the carbon nanotube-transitional metal catalyst; the metal/carbon interfaces are tightly combined; and the specific surface and the electrical conductivity of the prepared composite material are controllable.

Description

A kind of carbon nano-tube-transition metal-carbon fibre composite and preparation method thereof and application
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of carbon nano-tube-transition metal-carbon fibre composite and preparation method thereof and application.
Background technology
Carbon black is the carrier that fuel cell electro-catalyst the most often uses, and the spheroidal particle being 50 ~ 100nm by particle diameter forms.Because particle diameter is little and be spherical zero-dimension structural, therefore easily reunites under fuel cell working condition, corrode, cause catalyst striping, activity decrease.There is in carbon nano-tube and carbon fiber Dou Shi carbon family the material of one-dimentional structure and high length-diameter ratio.Unlike, carbon nano-tube has very high degree of graphitization, and therefore its conductivity is generally far longer than carbon fiber, but specific area is less than carbon fiber.As the carrier of fuel cell electro-catalyst, high conductivity and high-specific surface area are must obligato condition, and high conductivity can make the electrochemistry resistance of catalyst drop to minimum, and high-specific surface area can the most effectively disperse noble metal active component.In addition, carbon nano-tube has highly regular graphite-structure, and need functionalization ability supported catalyst active component under the conditions such as strong acid, carbon nano-fiber then can directly use as carrier.Therefore, how maximizing favourable factors and minimizing unfavourable ones, the advantage of the two effectively combined, is the important topic in fuel cell studies field.One dimension carbon nano-fiber or carbon nano-tube have very high draw ratio, are therefore particularly suitable as anti-agglomeration, corrosion resistant fuel cell electro-catalyst carrier.Moreover carbon nano-fiber or carbon nano-tube inherently can as oxygen reduction catalysts.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the present invention is the preparation method providing a kind of carbon nano-tube-transition metal-carbon fibre composite.
Another object of the present invention is to provide a kind of carbon nano-tube-transition metal-carbon fibre composite prepared by said method.
Another object of the present invention is to provide the application of above-mentioned carbon nano-tube-transition metal-carbon fibre composite in fuel cell electro-catalyst or fuel cell electro-catalyst carrier.The object of the invention is achieved through the following technical solutions:
A preparation method for carbon nano-tube-transition metal-carbon fibre composite, comprises following preparation process:
(1) preparation of carbon nano-tube-transition-metal catalyst: the carbon nano-tube of functionalization is carried out sensitization and colloid palladium activation pre-treatment, then the chemical plating fluid carbon nano-tube after pre-treatment being put into containing metal element carries out electroless plating reaction, obtains carbon nano-tube-transition-metal catalyst after oven dry;
(2) preparation of carbon nano-tube-transition metal-carbon nano-fiber composite material: the carbon nano-tube-transition-metal catalyst of step (1) is placed in tube furnace, logical nitrogen protection, by tube furnace temperature to 500 ~ 550 DEG C, passes into hydrogen and keeps 0.5 ~ 2h; Then by tube furnace temperature to 600 ~ 800 DEG C, and the gaseous mixture passing into nitrogen and acetylene is as carbon source, and at carbon nano-tube-transition-metal catalyst surface chemistry vapor deposition growth carbon nanomaterial, sedimentation time is 0.5 ~ 2h; Then the gaseous mixture of nitrogen and acetylene is converted to nitrogen, naturally cools to room temperature, obtain carbon nano-tube-transition metal-carbon fibre composite.
Further, described functionalization refers to that with containing volume ratio be the H of 3:1 2sO 4and HNO 3at 80 ~ 100 DEG C of reflow treatment 10 ~ 15h, then deionized water is washed till neutrality, dries;
Further, described sensitization refers to containing SnCl 2the solution of 20 ~ 30g/L, HCl30 ~ 50mL/L at room temperature processes 2 ~ 3min; Described colloid palladium activation refers to containing PdCl 2the solution of 0.4 ~ 0.6g/L, HCl30 ~ 50mL/L at room temperature processes 4 ~ 5min.
Further, the chemical plating fluid of described containing metal element refers to the chemical plating fluid of nickeliferous chemical plating fluid, cupric or the chemical plating fluid containing cobalt.
Further, described nickeliferous chemical plating fluid refers to containing NiSO 430g/L, NaH 2pO 210g/L, Na 3cyt(natrium citricum) 35g/L, Na 3pO 4the chemical plating fluid of 50g/L; The chemical plating fluid of described cupric refers to containing CuSO 410g/L, Na 3cyt24g/L, NiSO 43g/L, H 3bO 330g/L, NaOH10g/L and NaH 2pO 2the chemical plating fluid of 30g/L; The described chemical plating fluid containing cobalt refers to containing CoSO 428g/L, NaH 2pO 225g/L, Na 3cyt60g/L and H 3bO 3the chemical plating fluid of 30g/L.
Further, described electroless plating reaction refers to reaction 10 ~ 60min at 45 ~ 80 DEG C.
Further, in described carbon nano-tube-transition-metal catalyst, the quality of transition metal is 40% ~ 200% of carbon nanotube mass.
Further, the speed heated up described in step (2) is 10 ~ 15 DEG C/min; The speed passing into the gaseous mixture of nitrogen and acetylene is 50 ~ 100mL/min.
Further, the gaseous mixture preferred volume ratio of described nitrogen and acetylene is the nitrogen of 1:9 and the gaseous mixture of acetylene.
A kind of carbon nano-tube-transition metal-carbon fibre composite, is prepared by said method.
The application of above-mentioned carbon nano-tube-transition metal-carbon fibre composite in fuel cell electro-catalyst or fuel cell electro-catalyst carrier.
Preparation principle of the present invention is: from carbon nano-tube, first obtains by electroless plating reaction the carbon nano-tube-transition-metal catalyst being carried on carbon nano-tube; Then the mode of chemical vapour deposition (CVD) is passed through at carbon nano-tube-transition-metal catalyst surface in situ Formed nanotube-transition metal-carbon fibre composite.Because first transition metal is carried on carbon nano tube surface by chemical plating mode, then at these transiting metal surface grown carbon fibers, between three, adhesion is tight, and Metal-Support interfacial effect is obvious.
Compared with prior art, preparation method of the present invention and the product tool obtained have the following advantages and beneficial effect: first (1) the present invention prepares carbon nano-tube-transition-metal catalyst, this catalyst component, structure and carrying capacity can freely regulate and control, and then can the pattern of carbon fiber of the follow-up generation of conveniently regulating and controlling; (2) the present invention is by transition-metal catalyst, achieves combining closely between carbon nano-tube and carbon fiber, contributes to strengthening the Metal-Support effect in catalyst;
(3) advantage of carbon nano-tube and carbon fiber organically combines by the present invention, conductivity and the specific area of carrier are controlled, introduce in plating process, the hetero-atom such as phosphorus and boron be entrained in transition metal, when carbon nano-tube-transition metal-carbon fibre composite of the present invention is applied in fuel cell electro-catalyst, the effect of catalyst can be played. accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1 gained nanotube-nickel-phosphorus alloy catalyst;
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 1 gained nanotube-nickel-phosphorus alloy-carbon fibre composite;
Fig. 3 is the transmission electron microscope picture of embodiment 2 gained carbon nano tube-copper-carbon fibre composite;
Fig. 4 is the linear scan figure of embodiment 3 hydrogen reduction in 0.1MKOH.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.Functionalization, weight are that the carbon nano-tube sensitization of 100mg is (with containing SnCl by embodiment 1 2: the solution of 25g/L, HCl:40mL/L at room temperature processes 3min), then carry out colloid palladium activation (with containing PdCl 2: the solution of 0.5g/L, HCl:40mL/L at room temperature processes 4min).Then chemical nickel plating is carried out (with containing NiSO 4: 30g/L, NaH 2pO 2: 10g/L, Na 3cyt:35g/L and Na 3pO 4: the chemical plating fluid of 50g/L reacts 30min at 45 DEG C), the coated nickel-phosphorus alloy of carbon nano tube surface is made to obtain carbon nano-tube-nickel-phosphorus alloy catalyst, weighing after dry and obtaining gross mass is 200mg, and wherein nickel phosphorus closes 100mg, accounts for 50% of nanotube-nickel-phosphorus alloy catalyst quality.
Above-mentioned nanotube-nickel-phosphorus alloy catalyst is placed in tube furnace, and logical nitrogen protection, is then elevated to 500 DEG C by tube furnace temperature from room temperature with the heating rate of 10 DEG C/min, passes into hydrogen and keep 1 hour; With the heating rate of 15 DEG C/min, temperature is elevated to 700 DEG C, and the acetylene gaseous mixture (nitrogen: acetylene=1:9 of 90% is passed into the speed of 100mL/min, volume ratio) as carbon source, at nickel-phosphorus alloy catalyst surface chemical vapor deposition growth carbon nano-fiber, sedimentation time is 1h; Finally acetylene gaseous mixture is converted to nitrogen, and naturally cools to room temperature in stove, obtain the carbon nano-tube-nickel-phosphorus alloy-carbon fibre composite of raised growth.As shown in Figure 1, as seen from Figure 1, carbon nanotube diameter is 20-30nm to the scanning electron microscope (SEM) photograph of gained nanotube-nickel-phosphorus alloy catalyst, and nickel-phosphorus alloy catalyst is 50 ~ 80nm.As shown in Figure 2, as seen from Figure 2, carbon nano-fiber diameter is 80-150nm to the scanning electron microscope (SEM) photograph of gained nanotube-nickel-phosphorus alloy-carbon fibre composite.The BET specific surface area of gained composite material is 296m 2/ g, conductivity is 150S/cm.
The pre-treatment step of the functionalized carbon nano-tube of embodiment 2 the present embodiment is identical with embodiment 1.After pre-treatment, carbon nano-tube is carried out electroless copper (with containing CuSO 4: 10g/L, Na 3cyt:24g/L, NiSO 4: 3g/L, H 3bO 3: 30g/L, NaOH:10g/L and NaH 2pO 2: the chemical plating fluid of 30g/L reacts 20min at 60 DEG C), make carbon nano tube surface clad nano copper obtain carbon nano tube-copper catalyst, weighing after dry and obtaining gross mass is 250mg, and wherein copper is 180mg, accounts for 72% of carbon nano tube-copper catalyst quality.
Above-mentioned carbon nano tube-copper catalyst is placed in tube furnace, and logical nitrogen protection, is then elevated to 550 DEG C by tube furnace temperature from room temperature with the heating rate of 15 DEG C/min, passes into hydrogen and keep 1 hour; With the heating rate of 15 DEG C/min, temperature is elevated to 800 DEG C, and the acetylene gaseous mixture (nitrogen: acetylene=1:9 of 90% is passed into the speed of 70mL/min, volume ratio) as carbon source, in foam copper catalyst surface chemical vapor deposition growth carbon nano-tube, sedimentation time is 40min; Finally acetylene gaseous mixture is converted to nitrogen, and naturally cools to room temperature in stove, obtain carbon nano tube-copper-carbon fibre composite.As shown in Figure 3, as seen from Figure 3, in the shape of a spiral, caliber is about 100nm to carbon fiber to the transmission electron microscope picture of gained composite material, and copper catalyst particle diameter is 10-80nm.The BET specific surface area of gained composite material is 240m 2/ g, conductivity is 190S/cm.
The pre-treatment step of the functionalized carbon nano-tube of embodiment 3 the present embodiment is identical with embodiment 1.After pre-treatment, carbon nano-tube is carried out electroless cobalt plating (with containing CoSO 4: 28g/L, NaH 2pO 2: 25g/L, Na 3cyt:60g/L and H 3bO 3: the chemical plating fluid of 30g/L reacts 10min at 80 DEG C), make carbon nano tube surface clad nano cobalt obtain carbon nanotube-nano Co catalysts.
Above-mentioned carbon nanotube-nano Co catalysts is placed in tube furnace, and logical nitrogen protection, is then elevated to 500 DEG C by tube furnace temperature from room temperature with the heating rate of 12 DEG C/min, passes into hydrogen and keep 1 hour; With the heating rate of 10 DEG C/min, temperature is elevated to 600 DEG C, and the acetylene gaseous mixture (nitrogen: acetylene=1:9 of 90% is passed into the speed of 50mL/min, volume ratio) as carbon source, at nanometer cobalt catalyst surface chemistry vapor deposition growth carbon nano-fiber, sedimentation time is 60min; Finally acetylene gaseous mixture is converted to nitrogen, and naturally cools to room temperature in stove, obtain carbon nano-tube-cobalt-carbon fibre composite.The linear scan of gained composite material hydrogen reduction in 0.1MKOH, as Fig. 4, shows that this catalyst has good oxygen reduction catalytic activity.The BET specific surface area of gained composite material is 320m 2/ g, conductivity is 140S/cm.
Above-described embodiment is the present invention's preferably execution mode; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. a preparation method for carbon nano-tube-transition metal-carbon fibre composite, is characterized in that: comprise following preparation process:
(1) preparation of carbon nano-tube-transition-metal catalyst: the carbon nano-tube of functionalization is carried out sensitization and colloid palladium activation pre-treatment, then the chemical plating fluid putting into containing metal element carries out electroless plating reaction, obtains carbon nano-tube-transition-metal catalyst after oven dry;
(2) preparation of carbon nano-tube-transition metal-carbon fibre composite: the carbon nano-tube-transition-metal catalyst of step (1) is placed in tube furnace, logical nitrogen protection, by tube furnace temperature to 500 ~ 550 DEG C, passes into hydrogen and keeps 0.5 ~ 2h; Then by tube furnace temperature to 600 ~ 800 DEG C, and the gaseous mixture passing into nitrogen and acetylene is as carbon source, and at carbon nano-tube-transition-metal catalyst surface chemistry vapor deposition growth carbon nanomaterial, sedimentation time is 0.5 ~ 2h; Then the gaseous mixture of nitrogen and acetylene is converted to nitrogen, naturally cools to room temperature, obtain carbon nano-tube-transition metal-carbon fibre composite.
2. the preparation method of a kind of carbon nano-tube-transition metal-carbon fibre composite according to claim 1, is characterized in that: the functionalization described in step (1) refers to that with containing volume ratio be the H of 3:1 2sO 4and HNO 3at 80 ~ 100 DEG C of reflow treatment 10 ~ 15h, then deionized water is washed till neutrality, dries.
3. the preparation method of a kind of carbon nano-tube-transition metal-carbon fibre composite according to claim 1, is characterized in that: the sensitization described in step (1) refers to containing SnCl 2the solution of 20 ~ 30g/L, HCl30 ~ 50mL/L at room temperature processes 2 ~ 3min; Described colloid palladium activation refers to containing PdCl 2the solution of 0.4 ~ 0.6g/L, HCl30 ~ 50mL/L at room temperature processes 4 ~ 5min.
4. the preparation method of a kind of carbon nano-tube-transition metal-carbon fibre composite according to claim 1, is characterized in that: the chemical plating fluid of step (1) described containing metal element is nickeliferous chemical plating fluid, the chemical plating fluid of cupric or the chemical plating fluid containing cobalt.
5. the preparation method of a kind of carbon nano-tube-transition metal-carbon fibre composite according to claim 4, is characterized in that: described nickeliferous chemical plating fluid refers to containing NiSO 430g/L, NaH 2pO 210g/L, Na 3cyt35g/L and Na 3pO 4the chemical plating fluid of 50g/L; The chemical plating fluid of described cupric refers to containing CuSO 410g/L, Na 3cyt24g/L, NiSO 43g/L, H 3bO 330g/L, NaOH10g/L and NaH 2pO 2the chemical plating fluid of 30g/L; The described chemical plating fluid containing cobalt refers to containing CoSO 428g/L, NaH 2pO 225g/L, Na 3cyt60g/L and H 3bO 3the chemical plating fluid of 30g/L.
6. the preparation method of a kind of carbon nano-tube-transition metal-carbon fibre composite according to claim 1, is characterized in that: the electroless plating reaction described in step (1) refers to reaction 10 ~ 60min at 45 ~ 80 DEG C; The quality of the transition-metal catalyst that electroless plating reaction generates is 40% ~ 200% of carbon nanotube mass.
7. the preparation method of a kind of carbon nano-tube-transition metal-carbon fibre composite according to claim 1, is characterized in that: the speed heated up described in step (2) is 10 ~ 15 DEG C/min; The described speed passing into the gaseous mixture of nitrogen and acetylene is 50 ~ 100mL/min.
8. the preparation method of a kind of carbon nano-tube-transition metal-carbon fibre composite according to claim 1, is characterized in that: the nitrogen described in step (2) and the gaseous mixture of acetylene refer to that volume ratio is the nitrogen of 1:9 and the gaseous mixture of acetylene.
9. a kind of carbon nano-tube-transition metal-carbon fibre composite prepared by the method described in any one of claim 1 ~ 8.
10. the application of a kind of carbon nano-tube-transition metal-carbon fibre composite according to claim 9 in fuel cell electro-catalyst or fuel cell electro-catalyst carrier.
CN201510802158.5A 2015-11-18 2015-11-18 Carbon nanotube-transition metal-carbon fiber composite material and preparation method and application therefor Pending CN105375041A (en)

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CN108520954A (en) * 2018-04-23 2018-09-11 吉林大学 A kind of multi-walled carbon nanotube/ordered mesoporous carbon composite material, preparation method and applications
CN109081324A (en) * 2018-07-27 2018-12-25 青岛科技大学 A kind of preparation method of racemosus shape carbon fiber/amorphous carbon composite material
CN112323091A (en) * 2020-11-01 2021-02-05 南开大学 Preparation method of carbon-coated transition metal catalyst with bamboo-like carbon nanotube through yolk-eggshell structure
CN113398972A (en) * 2021-06-17 2021-09-17 佛山市诺蓝环保科技有限公司 Carbon nano tube loaded transition metal oxide catalyst and preparation method thereof
CN115888710A (en) * 2022-10-17 2023-04-04 大连理工大学 Preparation and functionalization method of integral catalytic reactor

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CN112323091B (en) * 2020-11-01 2022-02-22 南开大学 Preparation method of carbon-coated transition metal catalyst with bamboo-like carbon nanotube through yolk-eggshell structure
CN113398972A (en) * 2021-06-17 2021-09-17 佛山市诺蓝环保科技有限公司 Carbon nano tube loaded transition metal oxide catalyst and preparation method thereof
CN115888710A (en) * 2022-10-17 2023-04-04 大连理工大学 Preparation and functionalization method of integral catalytic reactor

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Application publication date: 20160302