# Patent

## Title
Method for making carbon nanotube-metal particle composite

## Abstract

A method for making a carbon nanotube-metal particle composite is provided. Carbon nanotubes, polymer monomers, a first solution containing metal ions, and a second solution containing carboxylic acid radical ions are provided. The carbon nanotubes and the polymer monomers are mixed in a solvent to form a first mixture. The polymer monomers are adsorbed on the carbon nanotubes. A second mixture is formed by mixing the first mixture, the first solution, and the second solution. The polymer monomers, the first solution, and the second solution react with each other to form a coordination complex mixture containing the metal ions. The coordination complex mixture is adsorbed on the surface of the carbon nanotubes. A reducing agent is added into the second mixture to reduce the metal ions of the coordination complex mixture to metal particles, simultaneously, the polymer monomers are polymerize to in situ form the carbon nanotube-metal particle composite.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims all benefits accruing under 35 U.S.C. §119 from China Patent Application No. 201210231369.4, filed on Jul. 5, 2012, in the China Intellectual Property Office, the contents of which are hereby incorporated by reference. This application is related to common-assigned application entitled, “MEMBRANE ELECTRODE AND FUEL CELL USING THE SAME” filed Dec. 29, 2012 (Ser. No. 13/730,881), entitled, “CARBON NANOTUBE-METAL PARTICLE COMPOSITE AND CATALYST COMPRISING THE SAME” filed Dec. 29, 2012 (Ser. No. 13/730,883).
BACKGROUND
1. Technical Field
The present disclosure relates to a method for making carbon nanotube-metal particle composite.
2. Description of Related Art
Carbon nanotube composited with metal particles is becoming a hot research subject. Carbon nanotube is an ideal metal particle catalyst carrier for the large surface area and high electric conductivity thereof. The composite having the carbon nanotubes composited with the metal catalyst has shown great promise of use in fields of electrochemical cell, fuel cell, and biomedicine.
When using the composite as a catalyst, the uniformity and a diameter of the metal particles loaded and dispersed on the surface of the carbon nanotubes directly influence catalytic performance of the composite. Typically, the smaller the diameter of the metal particles, the more uniform the metal particles are dispersed, the better the catalytic performance of the composite. However, metal particles easily aggregate when the diameter of the metal particles is small.
The composite is commonly fabricated by physical methods or chemical methods. Metal particles are sputtered on the surface of the carbon nanotubes by physical methods. Chemical methods include colloid method, solution reduction method, immersion method, electrochemical deposition method, or supercritical fluid method. However, it is difficult to have a balance between the small diameter and the dispersing uniformity of the metal particles on the surface of the carbon nanotubes with the methods mentioned above.
What is needed, therefore, is to provide a method for making a carbon nanotube-metal particle composite having a relatively small diameter of the metal particles meanwhile having the metal particles well dispersed.



BRIEF DESCRIPTION OF THE DRAWING
Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, the emphasis instead being placed upon clearly illustrating the principles of the present embodiments.
FIG. 1 is a structural schematic view of one embodiment of a carbon nanotube-metal particle composite.
FIG. 2 is a distribution schematic view of a polymer and metal particles in the carbon nanotube-metal particle composite of FIG. 1.
FIG. 3 is a scanning transmission electron microscope image of the carbon nanotube-metal particle composite of FIG. 1.



DETAILED DESCRIPTION
The disclosure is illustrated by way of example and not by way of limitation in the figures of the accompanying drawings in which like references indicate similar elements. It should be noted that references to “another,” “an,” or “one” embodiment in this disclosure are not necessarily to the same embodiment, and such references mean at least one.
One embodiment of a method for making a carbon nanotube-metal particle composite includes the following steps:
S1, providing carbon nanotubes, polymer monomers, a first solution containing metal ions, and a second solution containing carboxylic acid radical ions;
S2, mixing the carbon nanotubes and the polymer monomers in a solvent to form a first mixture, wherein the polymer monomers are adsorbed on a surface of the carbon nanotubes;
S3, forming a second mixture by mixing the first mixture, the first solution, and the second solution, wherein the polymer monomers, the first solution, and the second solution react with each other to form a coordination complex mixture containing the metal ions, the coordination complex mixture is adsorbed on the surface of the carbon nanotubes; and
S4, adding a reducing agent into the second mixture to reduce the metal ions of the coordination complex mixture to metal particles and simultaneously polymerize the polymer monomers, thereby forming the carbon nanotube-metal particle composite in situ.
In the step S1, the carbon nanotubes can be single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), multi-walled carbon nanotubes (MWCNTs), or any combination thereof. The carbon nanotubes can be fabricated by a method of arc discharge, chemical vapor deposition (CVD), or laser evaporation. In one embodiment, the MWCNTs fabricated by the CVD method are used. An inner diameter of the MWCNTs can be in a range from about 10 nanometers to about 50 nanometers. An outer diameter of the MWCNTs can be in a range from about 30 nanometers to about 80 nanometers. A length of the MWCNTs can be in a range from about 50 microns to about 100 microns.
The polymer monomers and the carbon nanotubes are adsorbed with each other. The polymer monomers can be aniline, pyrrole, thiophene, amide, propylene imine, or derivates thereof. The derivate, for example, can be acetanilide, methylpyrrole, ethylenedioxythiophene, oxamide or caprolactam. The polymer monomers can be other substances capable of having a polymerization to form a polymer coated on integral surface of single or plural of carbon nanotubes. In one embodiment, the polymer monomers are aniline.
If the carbon nanotube-metal particle composite is to be used as a catalyst, the metal ions in the first solution can be precious metal ions or some metal ions having a good catalytic performance. The precious metal ions can be at least one of gold ions (Au3+), silver ions (Ag+), platinum ions (Pt4+), rhodium ions (Rh3+), iridium ions (Ir4+). The metal ions having a good catalytic performance can be at least one of copper ions (Cu2+), ferrous ions (Fe2+), cobalt ions (Co2+), and nickel ions (Ni2+). Accordingly, the first solution can be a salt or an acid solution containing the metal ions. The first solution can be chloroauric acid (HAuCl4), gold chloride (AuCl3), silver nitrate (AgNO3), chloroplatinic acid (H2PtCl6), ruthenium chloride (RuCl3), chlororhodic acid (H3RhCl6), palladium chloride (PdCl2), hexachloroosmic acid (H2OsCl6), hexachloroiridic acid (H2IrCl6), copper sulfate (CuSO4), ferrous chloride (FeCl2), or any combination thereof. In one embodiment, the first solution is H2PtCl6 water solution. In addition, the carbon nanotube-metal particle composite can be used in other fields, thus, the metal ions are not limited to the above mentioned species.
The second solution can have a complex action with the metal ions and the polymer monomers. Thus, the metal ions and the polymer monomers can be uniformly dispersed in the second solution. The second solution can be a carboxylic acid solution or a carboxylic salt solution. In one embodiment, the carboxylic acid or the carboxylic salt in the second solution includes at least two carboxylic acid groups (—COO—). The carboxylic salt can be sodium citrate (Na3C6H5O7) or potassium citrate (K3C6H5O7). The carboxylic acid can be citric acid (C6H8O7), oxalic acid (C2H2O4), malonic acid (C3H4O4), butane diacid (C4H6O4), adipic acid (C6H10O4), terephthalic acid (C8H8O4), glutaric acid (C5H8O4), or any combination thereof. In one embodiment, the second solution is Na3C6H5O7 water solution.
In the step S2, the polymer monomers are dissolved in the solvent and adsorbed on the surface of the carbon nanotubes. The solvent can be ethanol, diethyl ether, water, or any combination thereof. To uniformly disperse the carbon nanotubes in the solvent, the solvent can be a mixing liquid of two substances. In one embodiment, the solvent is a mixture of water and ethanol, and a volume ratio of the water to the ethanol is about 1:1. A mass ratio of the carbon nanotubes to the polymer monomers can be in a range from about 1:1 to about 1:7. In one embodiment, the mass ratio of the carbon nanotubes to the polymer monomers is 1:1.
The step S2 can further include a step of agitating the first mixture. After agitating the first mixture, the polymer monomers can be uniformly adsorbed on the surface of the carbon nanotubes, and the carbon nanotubes can be uniformly dispersed in the solvent. In one embodiment, the first mixture is ultrasonically dispersed for about 3 hours to about 8 hours.
The step S2 can further include a step of functionalizing the carbon nanotubes by using hydrophilic groups before mixing the carbon nanotubes and the polymer monomers.
The hydrophilic groups can be carboxyl groups, hydroxide groups or amide groups. In one embodiment, at least two carboxyl groups are provided by a carboxyl acid. The carboxyl acid can be C6H8O7, C2H2O4, C3H4O4, C4H6O4, C6H10O4, C8H8O4, C5H8O4, or combinations thereof. One or some of the carboxyl groups are used to surface functionalize the carbon nanotubes, thereby increasing a dispersion ability of the carbon nanotubes in water. The spare carboxyl groups that do not react with the carbon nanotubes are electrostatically attracted to the polymer monomers. Thus, an improved polymer coating of the carbon nanotubes can be obtained. The polymer monomers are adsorbed on the surface of the carbon nanotubes by the carboxyl groups.
In the step S3, a complex reaction occurs between the metal ions and the carboxylic acid radical ions, and a complex reaction occurs between the polymer monomers and the carboxylic acid radical ions, thereby forming the coordination complex mixture adsorbing on the surface of the carbon nanotubes. A molar ratio of the carboxyl acid salt or the carboxyl acid in the second solution to the metal ions of the first solution can be in a range from about 1:1 to about 5:1. In one embodiment, the molar ratio of the Na3C6H5O7 in the second solution to Pt ions of the H2PtCl6 in the first solution is about 1:1. In addition, a molar ratio of the carboxyl acid salt or the carboxyl acid in the second solution to the polymer monomers can be in a range from about 1:1 to about 1:6. In one embodiment, the molar ratio of the carboxyl acid salt or the carboxyl acid in the second solution to the polymer monomers is about 1:2.
In the step S3, the first mixture, the first solution and the second solution can be simultaneously or successively added into a reactor to form the second mixture.
In one embodiment, the step S3 further includes the sub-steps of:
S31, mixing the first solution and the second solution to form a mixing liquid; and
S32, adding the first mixture into the mixing liquid, thereby inducing a reaction between the first mixture and the mixing liquid to form the coordination complex mixture.
In the step S31, the carboxylic acid radical ions in the second solution have an excellent complexation. Thus, the metal ions existing in a form of complex ions can be stably dispersed in the mixing liquid. The carboxylic acid radical ions have a guide function to fix the reduced metal particles on the carbon nanotubes.
Furthermore, the mixing liquid can be stirred or supersonically dispersed. In one embodiment, the mixing liquid is supersonically dispersed for about 8 hours to about 12 hours.
In the step S32, to introduce the complete reaction, the first mixture can be slowly added into the mixing liquid. In addition, after adding the first mixture into the mixing liquid, a potential difference between the metal ions and the polymer monomers can be formed due to the carboxylic acid radical ions, thereby partly reducing the metal ions and partly oxidizing the polymer monomers. The carboxylic acid radical ions can have a complex reaction with the polymer monomers. Besides, the carboxylic acid radical ions can be also electrostatically attracted or chemically bonded with the polymer monomers. Thus, the carboxylic acid radical ions can be adsorbed on the surface of the carbon nanotubes. In addition, the carboxylic acid radical ions can also have a complex reaction with the metal ions to form a stable complex, whereby the metal ions in the complex can be uniformly dispersed on the surface of the carbon nanotubes.
In the step S3, a temperature of the complex reaction can be in a range from about 4° C. to about 100° C. The temperature is related to a type of the metal ions. In one embodiment, the temperature is about 15° C.
The step S3 further includes a step of adjusting a pH value of the second mixture, by which the coordination complex mixture can be stably distributed in the solvent. In addition, the pH value of the second mixture can be adjusted at the beginning of the complex reaction, and kept up until the reaction ends. The pH value of the second mixture can be adjusted in a range from about 2 to about 5. In one embodiment, the pH value of the second mixture is adjusted to 3.
In the step S4, the polymer monomers are oxidized to form the polymer adsorbing on the surface of the carbon nanotubes under the action of the reducing agent. Meanwhile, the metal complex ions in the coordination complex mixture are reduced to form the metal particles, thereby forming the carbon nanotube-metal particle composite in situ. The reduction of the metal complex ions and the polymerization of the polymer monomers are simultaneous. Thus, the reduced metal particles are adsorbed between the carbon nanotubes and the polymer. In addition, the carboxyl groups in the second solution added in step S3 act as a bridge between the metal particles and the polymer. The carboxyl groups not only electrostatically attract or chemically bond to the polymer but also strongly absorb the metal particle. The metal particles can be stably dispersed due to the spare carboxyl groups. In addition, the carboxyl groups can improve a phase separation between the polymer and the metal particles. Thus, a plurality of pores are formed in the polymer, and the metal particles are located in the pores and adsorbed on the surface of the carbon nanotubes due to a guide function of the carboxyl groups. A dispersing uniformity of the metal particles in the carbon nanotube-metal particle composite can be improved due to the metal particles being located in the uniformly distributed pores of the polymer.
The reducing agent can reduce the metal ions to the metal particles. The reducing agent can be at least one of sodium borohydride (NaBH4), formaldehyde (CH2O), hydrogen peroxide (H2O2), C6H8O7, hydrogen (H2), and ascorbic acid. In one embodiment, the reducing agent is the NaBH4 solution. A molar ratio of the reducing agent to the metal ions can be in a range from about 10:1 to about 60:1. In one embodiment, the molar ratio of NaBH4 to HAuCl4 is about 50:1.
The carbon nanotube-metal particle composite is formed in situ due to the carboxyl groups. The metal particles in a form of nanocluster have a small diameter. The metal particles are adsorbed on the surface of the carbon nanotubes. The nanocluster is a microscopic aggregation composed of a plurality of metal atoms combined with each other by physical or chemical force. In one embodiment, the metal particles are a nanocluster composed of less than or equal to 55 metal atoms.
In the step S4, the carbon nanotube-metal particle composite is purified. Specifically, the carbon nanotube-metal particle composite can be filtered and washed for many times. Furthermore, the carbon nanotube-metal particle composite can be dried.
The above method for making the carbon nanotube-metal particle composite is simple. In the method, the metal particles are slowly reduced, thus, a shape of the metal particles can be easily controlled.
Referring to FIGS. 1 and 2, the carbon nanotube-metal particle composite 100 includes carbon nanotubes 102, a polymer layer 104 coated on the surface of the carbon nanotubes, and the metal particles 106.
The polymer layer 104 can be coated on the surface of the single carbon nanotube. A thickness of the polymer layer 104 can be in a range from about 1 nanometer to about 7 nanometers. The polymer layer 104 defines a plurality of pores 108. The plurality of pores 108 are uniformly distributed. The metal particles 106 are located in the pores 108 and spaced from each other by the polymer of the polymer layer 104. Thus, the metal particles 106 are uniformly distributed on the surface of the carbon nanotubes 102. In addition, the metal particles 106 in the pores 108 can be directly adsorbed on the surface of the carbon nanotubes 102 or partly inserted in the polymer layer 104, and exposed out from the surface of the polymer layer 104. In one embodiment, only one metal particle 106 is located in one pore 108. The metal particles 106 are adsorbed in the pores 108, thus, the metal particles 106 are uniformly dispersed in the carbon nanotube-metal particle composite 100. A diameter of the metal particles 106 is in a range from about 1 nanometer to about 5 nanometers. In one embodiment, the diameter of the metal particles 106 is in a range from about 1 nanometer to about 2 nanometers. A mass percentage of the metal particles 106 to the carbon nanotube-metal particle composite 100 can be in a range from about 20% to about 70%. A material of the polymer layer 104 is a conductive polymer, such as polyaniline (PANI), polypyrrole (PPY), polythiophene (PT), polyamide (PA), polypropyleneimine (PPI), poly(N-acetylaniline)(PNAANI), poly(N-methylpyrrole), poly(3,4-ethylendioxythiophene) (PEDT), polycaprolactam, or any combination thereof.
A material of the metal particles 106 can be noble metal or catalyst metal. The noble metal can be gold (Au), silver (Ag), platinum (Pt), rhodium (Rh), iridium (Ir), or any combination thereof. The catalyst metal can be copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), or any combination thereof. The carbon nanotubes can be SWCNTs, DWCNTs, MWCNTs, or any combination thereof.
In one embodiment, the carbon nanotube-metal particle composite 100 is Pt/PANI/MWCNT composite. The Pt particle is a nanocluster having a diameter of about 1 nanometer to about 2 nanometers.
In one embodiment, a catalyst is provided. The catalyst includes the carbon nanotube-metal particle composite 100. In addition, the catalyst can further include other common catalyst material such as noble metal particles. The catalyst can be used in different devices, such as electrochemical reactors (e.g. membrane reactor using oil energy) or cells (e.g. fuel cells).
In the carbon nanotube-metal particle composite 100 of the catalyst, the carboxyl groups can strongly adsorb the metal particles, thereby increasing a loading quantity of the metal particles in the catalyst. In addition, the metal particles are uniformly dispersed in the carbon nanotube-metal particle composite 100, thereby increasing a utilization rate of the catalyst. Thus, a catalyst property of the catalyst is improved.
Example 1
Synthesis of the Pt/PANI/MWCNT Composite
MWCNTs and aniline are added into a first mixing liquid containing water and ethanol to form the first mixture. A volume ratio of the water to the ethanol is about 1:1. The first mixture is ultrasonically vibrated for about 3 hours. A Na3C6H5O7 water solution and an H2PtCl6 water solution are mixed to form a second mixing liquid. The second mixing liquid is ultrasonically vibrated for 8 hours. The first mixture is then added to the second mixing liquid to introduce a complex reaction under water bath of about 15° C., thereby forming a coordination complex mixture. The mixture of the first mixture and the second mixing liquid is ultrasonically vibrated for about 1 hour. A mass ratio among the Na3C6H5O7, the aniline, and the MWCNTs is about 1:2:2. A NaBH4 solution is then added into the mixture of the first mixture and the second mixing liquid to form a precipitate. A molar ratio of the Na3C6H5O7 to the H2PtCl6 is about 50:1. The precipitate is then filtered and washed. The washed precipitate is dried for about 3 hours under about 60° C. to form the Pt/PANI/MWCNT composite. The Pt particles in a form of the nanocluster having a diameter of about 1 nanometer to about 2 nanometers are loaded on the MWCNTs or the PANI. A mass percentage of the Pt particles to the Pt/PANI/MWCNT composite is about 30%. Referring to FIG. 3, Pt particles are uniformly dispersed on the carbon nanotubes and the PANI.
Example 2
Synthesis of the Au/PANI/MWCNT Composite
The Au/PANI/MWCNT composite is synthesized by the same method as in Example 1, except that the HAuCl4 solution replaces the H2PtCl6 solution and a temperature of water bath is about 25° C. The Au particles in the Au/PANI/MWCNT composite are in a form of a nanocluster having a diameter of about 1 nanometer to about 3 nanometers. A mass percentage of the Au particles to the Au/PANI/MWCNT composite is about 60%.
Example 3
Synthesis of the Fe/PANI/MWCNT Composite
The Fe/PANI/MWCNT composite is synthesized by the same method as in Example 1, except that the FeCl2 solution replaces the H2PtCl6 solution and a temperature of water bath is about 100° C. The Fe particles in the Au/PANI/MWCNT composite are in a form of a nanocluster having a diameter of about 2 nanometer to about 5 nanometers. A mass percentage of the Fe particles to the Fe/PANI/MWCNT composite is about 50%.
Depending on the embodiment, certain steps of methods described may be removed, others may be added, and the sequence of steps may be altered. The description and the claims drawn to a method may include some indication in reference to certain steps. However, the indication used is only to be viewed for identification purposes and not as a suggestion as to an order for the steps.
The above-described embodiments are intended to illustrate rather than limit the present disclosure. Variations may be made to the embodiments without departing from the spirit of the present disclosure as claimed. Elements associated with any of the above embodiments are envisioned to be associated with any other embodiments. The above-described embodiments illustrate the scope of the present disclosure but do not restrict the scope of the present disclosure.

## Claims

1. A method for making a carbon nanotube-metal particle composite, the method comprising:
providing carbon nanotubes, polymer monomers, a first solution containing metal ions, and a second solution containing carboxylic acid radical ions;
mixing the carbon nanotubes and the polymer monomers in a solvent to form a first mixture, wherein the polymer monomers are adsorbed on a surface of the carbon nanotubes;
forming a second mixture by mixing the first mixture, the first solution, and the second solution; wherein the polymer monomers, the first solution, and the second solution react with each other to form a coordination complex mixture containing the metal ions, and the coordination complex mixture is adsorbed on the surface of the carbon nanotubes; and
adding a reducing agent into the second mixture to reduce the metal ions of the coordination complex mixture to metal particles and simultaneously polymerize the polymer monomers to form a polymer layer on the surface of the carbon nanotubes so that at least part of the metal particles are adsorbed between the carbon nanotubes and the polymer layer.

2. The method for making the carbon nanotube-metal particle composite of claim 1, wherein a first reaction occurs between the metal ions and the carboxylic acid radical ions, and a second reaction occurs between the polymer monomers and the carboxylic acid radical ions.

3. The method for making the carbon nanotube-metal particle composite of claim 1, wherein a plurality of pores are formed during polymerizing the polymer monomers, and the metal ions are simultaneously reduced to metal particles in the plurality of pores.

4. The method for making the carbon nanotube-metal particle composite of claim 1, wherein the metal ions are selected from the group consisting of gold ions, silver ions, platinum ions, ruthenium ions, rhodium ions, palladium ions, osmium ions, iridium ions, copper ions, ferrous ions, cobalt ions, nickel ions, and any combination thereof.

5. The method for making the carbon nanotube-metal particle composite of claim 1, wherein the first solution is selected from the group consisting of chloroauric acid, gold chloride, silver nitrate, chloroplatinic acid, ruthenium chloride, chlororhodic acid, palladium chloride, hexachloroosmic acid, hexachloroiridic acid, copper sulfate, ferrous chloride, and any combination thereof.

6. The method for making the carbon nanotube-metal particle composite of claim 1, wherein the second solution comprises carboxylic acid or carboxylic salt comprising at least two carboxylic acid groups.

7. The method for making the carbon nanotube-metal particle composite of claim 6, wherein the carboxylic salt is sodium citrate or potassium citrate.

8. The method for making the carbon nanotube-metal particle composite of claim 6, wherein the carboxylic acid is selected from the group consisting of citric acid, oxalic acid, malonic acid, butane diacid, adipic acid, terephthalic acid, glutaric acid, and any combination thereof.

9. The method for making the carbon nanotube-metal particle composite of claim 1, wherein the reducing agent is selected from the group consisting of sodium borohydride, formaldehyde, hydrogen peroxide, citric acid, hydrogen, ascorbic acid, and any combination thereof.

10. The method for making the carbon nanotube-metal particle composite of claim 1, wherein the polymer monomers are selected from the group consisting of aniline, pyrrole, thiophene, amide, propylene imine, acetanilide, methylpyrrole, ethylenedioxythiophene, oxamide, caprolactam, and any combination thereof.

11. The method for making the carbon nanotube-metal particle composite of claim 1, wherein a mass ratio of the carbon nanotubes to the polymer monomers is in a range from about 1:1 to about 1:7.

12. The method for making the carbon nanotube-metal particle composite of claim 1, further comprising functionalizing the carbon nanotubes by using hydrophilic groups before mixing the carbon nanotubes and the polymer monomers.

13. The method for making the carbon nanotube-metal particle composite of claim 1, wherein the step of forming the second mixture by mixing the first mixture, the first solution, and the second solution comprises: mixing the first solution and the second solution to form a mixing liquid, and adding the first mixture into the mixing liquid.

14. The method for making the carbon nanotube-metal particle composite of claim 1, wherein a molar ratio of the carboxyl acid radical ions in the second solution to the metal ions of the first solution is in a range from about 1:1 to about 5:1.

15. The method for making the carbon nanotube-metal particle composite of claim 1, wherein a reaction temperature of forming the coordination complex mixture is in a range from about 4° C. to about 100° C.

16. The method for making the carbon nanotube-metal particle composite of claim 1, wherein a pH value of the second mixture is adjusted to be in a range from about 2 to about 5.

17. The method for making the carbon nanotube-metal particle composite of claim 1, wherein a molar ratio of the reducing agent to the metal ions is in a range from about 10:1 to about 60:1.