CN112151820A - Carbon-supported platinum-copper alloy porous nanowire catalyst for fuel cell and preparation method thereof - Google Patents
Carbon-supported platinum-copper alloy porous nanowire catalyst for fuel cell and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carbon-supported platinum-copper alloy porous nanowire catalyst for a fuel cell and a preparation method thereof, belonging to the technical field of electrochemistry; the catalyst comprises the following components in percentage by mass: 70-80%, copper: 3-10%, platinum: 10 to 27 percent. The method adopts the copper nanowire as a sacrificial template, forms the platinum-copper alloy porous nanowire by utilizing the displacement reaction, has simple preparation method and is suitable for large-scale production. The combination of the alloy structure, the porous structure and the nanowire structure can effectively improve the activity and stability of the low platinum catalyst at the same time, and is beneficial to promoting the development of the low platinum catalyst of the fuel cell.
Description
Technical Field
The invention relates to a carbon-supported platinum-copper alloy porous nanowire catalyst (PtCu PNWs/C) for a fuel cell and a preparation method thereof, belonging to the technical field of electrochemistry.
Technical Field
A fuel cell is an energy conversion device for directly converting chemical energy into electrical energy, and is considered as the most promising energy conversion device due to its advantages of high energy conversion rate, cleanness, no pollution, and the like, and the development of the fuel cell is increasingly regarded by people. However, the fuel cell also has the problem of low cost and long life, wherein the cost of the cathode oxygen reduction catalyst is about 30% of the total equipment because a large amount of platinum (Pt) is required, which is one of the most important reasons for the high cost of the fuel cell.
In the proton exchange membrane fuel cell, hydrogen at the anode is oxidized to generate electrons and hydrogen ions, the hydrogen ions are conducted to the cathode through the proton exchange membrane, oxygen at the cathode is subjected to reduction reaction and is combined with the hydrogen ions to generate water, and the electrons are conducted through an external circuit to supply power. In order to improve the reaction rate of Hydrogen Oxidation Reaction (HOR) and Oxygen Reduction Reaction (ORR), both electrodes are catalyzed by catalysts, the reaction rate of HOR on platinum (Pt) is very high, and the required platinum (Pt) loading amount can be as low as 0.05mg/cm2. However, the ORR reaction kinetics of the cathode is very slow, and a large amount of platinum (Pt) is needed for catalysis, so that the energy loss caused by electrode polarization can be relieved, and the excellent fuel cell performance can be realized. However, platinum (Pt) is in short supply and expensive, which seriously hinders the progress of commercialization of fuel cells, and therefore, the development of new materials that can replace the platinum (Pt) -based catalyst is being actively pursued.
In order to reduce the amount of platinum (Pt), a great deal of research is being conducted. The research shows that: the electronic structure of the platinum (Pt) can be adjusted by doping the transition metal, so that the activity of the platinum (Pt) per unit mass is effectively improved, and the consumption of the platinum (Pt) is reduced. In addition, the utilization rate of platinum (Pt) can be improved by regulating the structure, wherein the porous structure can effectively improve the specific surface area of the catalyst, thereby exposing more active sites, and being a method for effectively improving the utilization rate of platinum (Pt). The one-dimensional nano structure can effectively improve the stability of the catalyst due to the structural anisotropy, but the research on the one-dimensional porous nano wire oxygen reduction catalyst is less at present, and the mass production method is few.
Zhao et al prepared a nanowire with lead (Pd) as a core and platinum (Pt) and nickel (Ni) as a shell using a lead (Pd) wire template, and after 30000 potential cycles (0.6-1.1V, 100mV/s), the mass activity was still 16.5 times that of the commercial platinum carbon catalyst, but lead (Pd) was still an expensive metal, and the use of lead (Pd) as the core was not favorable for reducing the cost of the catalyst, and the nickel (Ni) on the surface layer still had the possibility of dissolving in the operating environment, and gradually reduced the activity of the catalyst, and therefore had a certain difficulty if it was used for a long time. Qiu et al report a porous alloy nanowire which can be produced in a large scale, a PtCuAu alloy porous nanowire with the diameter of 200-500 nm is prepared by dealloying, the activity of platinum can be effectively improved by forming an alloy structure, the specific surface area of a catalyst can be improved by the porous structure, the activity of the catalyst is further improved, and the stability of the catalyst can be effectively improved by forming a nanowire structure, so that the catalyst shows good electrochemical activity, but the radius of the catalyst is larger, and most of internal metal is not utilized.
Therefore, the development of a catalyst with simple preparation process, low cost, high platinum utilization rate and good activity and stability is a technical problem which needs to be solved urgently in the technical field.
Disclosure of Invention
The invention mainly aims to prepare the fuel cell catalyst with simple preparation process, low cost, high platinum utilization rate and better activity and stability.
In order to achieve the above purpose of the invention, the following technical scheme is adopted:
a carbon-loaded platinum-copper alloy porous nanowire catalyst for a fuel cell is composed of a carrier and an active component, and is characterized in that the active component is a platinum-copper alloy porous nanowire; the composite material comprises the following components in percentage by mass: carrier carbon: 70-80%, copper: 3-10%, platinum: 10 to 27 percent.
Preferably, the support carbon is commercial XC-72 carbon black.
Preferably, the diameter of the platinum-copper alloy porous nanowire is 15-25 nm, and preferably 20 nm.
Preferably, in the platinum-copper alloy porous nanowire, the molar ratio of platinum to copper is 3: 1-1: 3.
The invention also aims to provide a preparation method of the carbon-supported platinum-copper alloy porous nanowire catalyst for the fuel cell.
In order to achieve the above purpose of the invention, the following technical scheme is adopted:
a preparation method of a carbon-supported platinum-copper alloy porous nanowire catalyst for a fuel cell comprises the following steps:
(1) weighing copper chloride, hexadecylamine and glucose according to a proportion, adding the copper chloride, the hexadecylamine and the glucose into deionized water, stirring and mixing uniformly, introducing nitrogen into a mixed solution for 1-2 hours, heating to 100-120 ℃, and performing centrifugal cleaning for multiple times after reaction is finished to obtain copper wires (copper nanowires);
(2) dispersing the copper wire obtained in the step (1) in a cyclohexane solution to obtain a copper wire cyclohexane solution, adding a chloroplatinic acid cyclohexane solution to react at room temperature under an ultrasonic condition, adding ethanol after the reaction, centrifuging to obtain a platinum-copper alloy porous nanowire (PtCu PNWs), and dispersing in the cyclohexane solution to obtain a platinum-copper alloy porous nanowire cyclohexane solution;
(3) ultrasonically dispersing carbon black in cyclohexane to obtain a carbon black cyclohexane solution, adding the platinum-copper alloy porous nanowire cyclohexane solution prepared in the step (2) into the carbon black cyclohexane solution, stirring, performing centrifugal separation, drying the obtained solid, and grinding.
(4) And (3) adding the solid powder obtained in the step (3) into a mixed solution of ethanol and acetic acid, stirring at 50-70 ℃, washing off residual hexadecylamine on the surface of the catalyst, washing with deionized water, and drying to obtain a final product (PtCu PNWs/C).
Preferably, the carbon black in step (1) is a commercial XC-72 carbon black.
Preferably, the centrifugal washing in step (1) is as follows: adding the mixed solution of cyclohexane and ethanol, and performing centrifugal cleaning for many times.
Preferably, in the step (1), the adding amount of the copper chloride, the hexadecylamine and the glucose is 40-60 times of the mass of the hexadecylamine according to the mass ratio of (1-3) to (15-20) to (2-8) (preferably 2:18: 5).
Preferably, in the step (1), the stirring and mixing time is 5-6 h; the heating reaction time of the oil bath is 3-5 h.
Preferably, in the step (2), the concentration of the copper wire cyclohexane solution is 10-30 mmol/L; in the chloroplatinic acid cyclohexane solution, the concentration of platinum (Pt) ions is 0.01-0.1 mol/L.
Preferably, in the step (2), a cyclohexane solution containing 0.02 to 0.05mmol of chloroplatinic acid is added to a cyclohexane solution containing 0.12mmol of copper wire.
Preferably, in the step (2), the adopted ultrasonic frequency is 10-30 kHz; the reaction time is 10-30 min.
Preferably, in the step (3), the ultrasonic dispersion time of the carbon black is 1-2 h; the stirring time is 5-6 h.
Preferably, in the step (3), 20-30 mg of the platinum-copper alloy porous nanowire is added into 70-80 mg of the carbon black.
Preferably, in the step (4), the stirring time is 3-5 h.
The structural representation of the prepared product proves that the carbon nano-wire is uniformly dispersed on the surface of the carbon carrier by taking carbon as a carrier and taking an active component as a metal nano-wire, wherein the metal nano-wire is a platinum-copper alloy porous nano-wire material, the diameter of the nano-wire is about 20nm, and the nano-wire has a uniform pore structure on the surface and uniform diameter distribution through electron microscope observation.
The invention has the advantages that:
according to the invention, hexadecylamine is adopted as a structure directing agent, copper wires (copper nanowires) with small radius and high purity are successfully prepared in a water phase system, the copper wires are adopted as sacrificial templates, and the copper wires are used as a part of reactants and also play a role of templates prepared by a one-dimensional nano structure, so that a platinum-based nano wire structure alloy material (a platinum-copper alloy porous nano wire material) is effectively prepared; the cavitation of the ultrasonic wave is utilized to enable platinum ions and copper wires to form a porous alloy structure in the replacement process, and the accumulation of vacancies in the replacement process forms a pore structure, so that the contact area of active sites can be greatly increased, and the utilization rate of platinum is improved; the formation of an alloy structure is realized through atomic diffusion in the replacement process, and the electronic structure of platinum (Pt) can be adjusted, so that the activity of the catalyst is improved; the structure and the composition of the metal alloy nanowire (platinum-copper alloy porous nanowire) are controlled by controlling the addition of chloroplatinic acid, so that the porous alloy nanowire structure with a smaller diameter is formed.
The invention is further illustrated by the following figures and specific examples, which are not meant to limit the scope of the invention.
Drawings
Fig. 1 is an XRD pattern of a copper wire prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of the platinum-copper alloy porous nanowire (PtCu PNWs) prepared in example 1 of the present invention.
FIG. 3-1 is a transmission electron micrograph of a copper wire prepared in example 1 of the present invention.
FIG. 3-2 is a high resolution electron micrograph of a copper wire prepared according to example 1 of the present invention.
FIG. 4-1 is a transmission electron microscope image of a carbon-supported platinum-copper alloy porous nanowire (PtCu PNWs/C) prepared in example 1 of the present invention.
Fig. 4-2 is a high-resolution electron microscope image of the carbon-supported platinum-copper alloy porous nanowire (PtCu PNWs/C) prepared in example 1 of the present invention.
Detailed Description
The invention relates to a carbon-supported platinum-copper alloy porous nanowire catalyst for a fuel cell, which consists of a carrier and an active component, wherein the carrier is commercial XC-72 carbon black, the active component is a platinum-copper alloy porous nanowire, and the catalyst comprises the following raw materials in percentage by mass: carrier carbon: 70-80%, copper: 3-10%, platinum: 10 to 27 percent.
The preparation method of the carbon-supported platinum-copper alloy porous nanowire catalyst for the fuel cell mainly comprises three steps, firstly, hexadecylamine is used as a structure directing agent, and copper nanowires with uniform structures and smaller diameters are prepared by controlling reaction temperature, time and oxygen content in a solution; then, under the ultrasonic condition, adding chloroplatinic acid solution into the obtained copper nanowire, preparing a platinum-copper alloy nanowire by utilizing the difference of reduction potentials of platinum and copper, and controlling the reaction condition to prepare porous nanowire structures with different appearances; and finally, loading the prepared platinum-copper alloy porous nanowire on carbon powder, and removing residual hexadecylamine by acid washing to obtain the final platinum-copper alloy porous nanowire.
Example 1
The preparation method of the carbon-supported platinum-copper alloy porous nanowire catalyst for the fuel cell comprises the following steps:
(1) weighing 21mg of copper chloride, 180mg of hexadecylamine and 50mg of glucose, placing the copper chloride, the hexadecylamine and the glucose into a round-bottom flask, adding 10mL of deionized water, and stirring at room temperature for 5-6 hours to uniformly disperse reactants; introducing nitrogen into the reaction solution for 1-2 hours under the stirring condition, expelling oxygen in the reaction solution, screwing a glass plug, heating the reaction solution in an oil bath to 120 ℃, and reacting for 4 hours to obtain a copper wire; centrifuging and precipitating the product at 12000rpm, adding a mixed solution of cyclohexane and ethanol for cleaning, and cleaning hexadecylamine on the surface of a copper wire to obtain a copper wire (copper nanowire);
(2) ultrasonically dispersing the copper wire (copper nanowire) prepared in the step (1) in a cyclohexane solution, wherein the concentration is 12mmol/L, so as to obtain the cyclohexane solution of the copper wire (copper nanowire); 20mg of chloroplatinic acid (H) was weighed out2PtCl6·6H2O), dissolving the platinum-copper alloy porous nanowire in 1mL of cyclohexane solution, adding the solution into 10mL of copper wire cyclohexane solution under the conditions of 20kHz ultrasound and nitrogen introduction, reacting for 20min, then adding ethanol, centrifugally separating out the platinum-copper alloy porous nanowire under the condition of 12000rpm to obtain a platinum-copper alloy porous nanowire, and then dispersing the platinum-copper alloy porous nanowire in the cyclohexane solution to obtain a platinum-copper alloy porous nanowire cyclohexane solution with the concentration of 2 mg/mL;
(3) weighing 80mg of carbon powder (XC-72 carbon black, the same below) in a beaker, adding 40mL of cyclohexane, performing ultrasonic treatment for 1-2 h at room temperature to uniformly disperse the carbon powder in the cyclohexane to obtain a carbon powder cyclohexane solution, dropwise adding 10mL of platinum-copper alloy porous nanowire cyclohexane solution into the carbon powder cyclohexane solution under the stirring condition, further stirring for 5-6 h to uniformly load the platinum-copper alloy porous nanowire on the carbon powder, performing centrifugal separation at 12000rpm, washing with ethanol for multiple times, drying the obtained solid in an oven at 60 ℃ for 24h, and grinding;
(4) and (3) weighing 100mg of solid powder obtained in the step (3), putting the solid powder into a round-bottom flask, adding a mixed solution of 20mL of ethanol and 20mL of acetic acid, ultrasonically dispersing for 20min, heating to 60 ℃, reacting for 4h, cleaning with deionized water, and drying in an oven at 60 ℃ for 24h to obtain the product, namely the carbon-supported platinum-copper alloy porous nanowire (PtCu PNWs/C).
Example 2
The preparation method of the carbon-supported platinum-copper alloy porous nanowire catalyst for the fuel cell comprises the following steps:
(1) weighing 21mg of copper chloride, 180mg of hexadecylamine and 50mg of glucose, placing the copper chloride, the hexadecylamine and the glucose into a round-bottom flask, adding 10mL of deionized water, and stirring at room temperature for 5-6 hours to uniformly disperse reactants; introducing nitrogen for 1-2 h under the condition of stirring into the reaction solution, expelling oxygen in the reaction solution, screwing a glass plug, heating the reaction solution in an oil bath to 120 ℃, and reacting for 4h to obtain a copper wire; centrifuging and precipitating the product at 12000rpm, adding a mixed solution of cyclohexane and ethanol for cleaning, and cleaning hexadecylamine on the surface of a copper wire to obtain a copper wire (copper nanowire);
(2) ultrasonically dispersing the copper wire (copper nanowire) prepared in the step (1) in a cyclohexane solution, wherein the concentration is 12mmol/L, so as to obtain the cyclohexane solution of the copper wire (copper nanowire); 20mg of chloroplatinic acid (H) was weighed out2PtCl6·6H2O), dissolving in 1mL of cyclohexane solution, adding into 10mL of copper wire cyclohexane solution under the conditions of 20kHz ultrasound and nitrogen introduction, reacting for 20min, then adding ethanol, and centrifugally separating out the platinum-copper alloy porous nanowire under the condition of 12000rpm to obtain the platinum-copper alloy porous nanowire; then, dispersing the platinum-copper alloy porous nanowire in a cyclohexane solution to obtain a platinum-copper alloy porous nanowire cyclohexane solution with the concentration of 2 mg/mL;
(3) weighing 70mg of carbon powder (XC-72 carbon black, the same below) in a beaker, adding 40mL of cyclohexane, performing ultrasonic treatment for 1-2 h at room temperature to uniformly disperse the carbon powder in the cyclohexane to obtain a carbon powder cyclohexane solution, dropwise adding 15mL of platinum-copper alloy porous nanowire cyclohexane solution into the carbon powder cyclohexane solution under the stirring condition, further stirring for 5-6 h to uniformly load the platinum-copper alloy porous nanowire on the carbon powder, performing centrifugal separation at 12000rpm, washing with ethanol for multiple times, drying the obtained solid in an oven at 60 ℃ for 24h, and grinding;
(4) and (3) weighing 100mg of solid powder obtained in the step (3), putting the solid powder into a round-bottom flask, adding a mixed solution of 20mL of ethanol and 20mL of acetic acid, ultrasonically dispersing for 20min, heating to 60 ℃, reacting for 4h, cleaning with deionized water, and drying in an oven at 60 ℃ for 24h to obtain the product, namely the carbon-supported platinum-copper alloy porous nanowire (PtCu PNWs/C).
Example 3
The preparation method of the carbon-supported platinum-copper alloy porous nanowire catalyst for the fuel cell comprises the following steps:
(1) weighing 21mg of copper chloride, 180mg of hexadecylamine and 50mg of glucose, placing the copper chloride, the hexadecylamine and the glucose into a round-bottom flask, adding 10mL of deionized water, and stirring at room temperature for 5-6 hours to uniformly disperse reactants; introducing nitrogen into the reaction solution for 1-2 h under the condition of stirring, expelling oxygen in the reaction solution, screwing a glass plug, heating the reaction solution to 120 ℃, and reacting for 4h to obtain a copper wire; centrifuging and precipitating the product at 12000rpm, adding a mixed solution of cyclohexane and ethanol for cleaning, and cleaning hexadecylamine on the surface of a copper wire to obtain a copper wire (copper nanowire);
(2) ultrasonically dispersing the copper wire (copper nanowire) prepared in the step (1) in a cyclohexane solution, wherein the concentration is 12mmol/L, so as to obtain the cyclohexane solution of the copper wire (copper nanowire); 26mg of chloroplatinic acid (H) are weighed out2PtCl6·6H2O), dissolving the platinum-copper alloy porous nanowire in 1.3mL of cyclohexane solution, adding the cyclohexane solution into 10mL of copper wire cyclohexane solution under the conditions of 20kHz ultrasound and nitrogen introduction, reacting for 20min, then adding ethanol, centrifugally separating out the platinum-copper alloy porous nanowire under the condition of 12000rpm to obtain a platinum-copper alloy porous nanowire, and then dispersing the platinum-copper alloy porous nanowire in the cyclohexane solution to obtain a platinum-copper alloy porous nanowire cyclohexane solution with the concentration of 2 mg/mL;
(3) weighing 80mg of carbon powder (XC-72 carbon black, the same below) in a beaker, adding 40mL of cyclohexane, performing ultrasonic treatment for 1-2 h at room temperature to uniformly disperse the carbon powder in the cyclohexane to obtain a carbon powder cyclohexane solution, dropwise adding 10mL of platinum-copper alloy porous nanowire cyclohexane solution into the carbon powder cyclohexane solution under the stirring condition, further stirring for 5-6 h to uniformly load the platinum-copper alloy porous nanowire on the carbon powder, performing centrifugal separation at 12000rpm, washing with ethanol for multiple times, drying the obtained solid in an oven at 60 ℃ for 24h, and grinding;
(4) and (3) weighing 100mg of solid powder obtained in the step (3), putting the solid powder into a round-bottom flask, adding a mixed solution of 20mL of ethanol and 20mL of acetic acid, ultrasonically dispersing for 20min, heating to 60 ℃, reacting for 4h, cleaning with deionized water, and drying in an oven at 60 ℃ for 24h to obtain the product, namely the carbon-supported platinum-copper alloy porous nanowire (PtCu PNWs/C).
Example 4
The preparation method of the carbon-supported platinum-copper alloy porous nanowire catalyst for the fuel cell comprises the following steps:
(1) weighing 21mg of copper chloride, 180mg of hexadecylamine and 50mg of glucose, placing the copper chloride, the hexadecylamine and the glucose into a round-bottom flask, adding 10mL of deionized water, and stirring at room temperature for 5-6 hours to uniformly disperse reactants; introducing nitrogen into the reaction solution for 1-2 hours under the condition of stirring, expelling oxygen in the reaction solution, screwing a glass plug, heating the reaction solution to 120 ℃, and reacting for 4 hours to obtain a copper wire; centrifuging and precipitating the product at 12000rpm, adding a mixed solution of cyclohexane and ethanol for cleaning, and cleaning hexadecylamine on the surface of a copper wire to obtain a copper wire (copper nanowire);
(2) ultrasonically dispersing the copper wire (copper nanowire) prepared in the step (1) in a cyclohexane solution, wherein the concentration is 12mmol/L, so as to obtain the cyclohexane solution of the copper wire (copper nanowire); weighing 12mg of chloroplatinic acid (H)2PtCl6·6H2O), dissolving the platinum-copper alloy porous nanowire in 0.6mL of cyclohexane, adding the cyclohexane into 10mL of copper wire cyclohexane solution under the conditions of 20kHz ultrasound and nitrogen introduction, reacting for 20min, then adding ethanol, centrifugally separating out the platinum-copper alloy porous nanowire under the condition of 12000rpm to obtain a platinum-copper alloy porous nanowire, and then dispersing the platinum-copper alloy porous nanowire in the cyclohexane solution to obtain a platinum-copper alloy porous nanowire cyclohexane solution with the concentration of 2 mg/mL;
(3) weighing 80mg of carbon powder (XC-72 carbon black, the same below) in a beaker, adding 40mL of cyclohexane, performing ultrasonic treatment for 1-2 h at room temperature to uniformly disperse the carbon powder in the cyclohexane to obtain a carbon powder cyclohexane solution, dropwise adding 10mL of platinum-copper alloy porous nanowire cyclohexane solution into the carbon powder cyclohexane solution under the stirring condition, further stirring for 5-6 h to uniformly load the platinum-copper alloy porous nanowire on the carbon powder, performing centrifugal separation at 12000rpm, washing with ethanol for multiple times, drying the obtained solid in an oven at 60 ℃ for 24h, and grinding;
(4) and (3) weighing 100mg of solid powder obtained in the step (3), putting the solid powder into a round-bottom flask, adding a mixed solution of 20mL of ethanol and 20mL of acetic acid, ultrasonically dispersing for 20min, heating to 60 ℃, reacting for 4h, cleaning with deionized water, and drying in an oven at 60 ℃ for 24h to obtain the product, namely the carbon-supported platinum-copper alloy porous nanowire (PtCu PNWs/C).
And (3) product verification:
the structural characterization of the products prepared in examples 1 to 4 proves that the products are prepared by using carbon as a carrier and loading active metal on the surface of the carbon, wherein the active metal is a platinum-copper alloy porous nanowire material with the diameter of about 20nm, and the diameter distribution is uniform through electron microscope observation.
(1) X-ray diffraction analysis
The samples of the copper wire and the platinum-copper alloy porous nanowire prepared by the method are respectively subjected to X-ray diffraction characterization, and diffraction patterns of the samples are analyzed.
As shown in fig. 1, is an XRD pattern of the copper wire prepared in example 1 of the present invention; in fig. 1, peaks appearing near 43.3 °, 50.4 ° and 74.1 ° 2 θ belong to characteristic peaks of (111), (200) and (220) crystal plane diffraction of the copper face-centered cubic (fcc) crystal form, respectively; the observation shows that: the characteristic peak of copper is strong and obvious, which shows that the crystal form of the particles of the sample is complete, and no miscellaneous peak of other oxides is found, which shows that the purity of the prepared copper wire is high and the copper wire is not oxidized, thus providing necessary conditions for the subsequent replacement reaction.
As shown in fig. 2, an XRD pattern of the platinum-copper alloy porous nanowire (PtCu PNWs) prepared in example 1 of the present invention is an XRD pattern of the platinum-copper alloy porous nanowire prepared after the substitution reaction in step (2), and peaks appearing near 41.1, 48.0, 70.7 and 85.8 ° 2 θ respectively belong to (111), (200), (220) and (222) crystallographic planes of a face-centered cubic (fcc) crystal form, and by comparing with a standard PDF card, the peaks belong to characteristic peaks of a platinum-copper (Pt-Cu) alloy, which are shifted up from the characteristic peak of platinum (Pt), which indicates that copper with a smaller particle size enters the platinum lattice, and the platinum lattice shrinks, and no elemental peaks of platinum (Pt) and copper (Cu) are found in the spectrogram, thus proving that a platinum-copper (Pt-Cu) alloy structure is completely formed.
(2) High resolution transmission electron microscopy analysis
The copper wire and the carbon-supported platinum-copper alloy porous nanowire prepared by the method are subjected to electron microscope analysis:
as shown in FIG. 3-1, which is a transmission electron micrograph of the copper wire prepared in example 1 of the present invention, it can be seen that the copper wire prepared has a uniform shape distribution and a diameter of about 18 nm.
As shown in fig. 3-2, which is a high resolution electron microscope image of the copper wire prepared in example 1 of the present invention, it can be seen from the figure that the clear lattice stripes are measured to find that the lattice stripe spacing is 0.209nm, which is close to the (111) interplanar spacing (0.2088nm) of Cu, indicating that the prepared nanowire is a pure copper nanowire.
FIG. 4-1 shows a transmission electron microscope image of a carbon-supported platinum-copper alloy porous nanowire (PtCu PNWs/C) prepared in example 1 of the present invention; it can be found that after the replacement, the surface of the nanowire is changed from smooth to rough and porous, the shape distribution is more uniform, and the diameter of the nanowire is slightly expanded compared with that of a copper wire because the structure is more loose due to the formation of the pore structure; the existence of the pores is beneficial to improving mass transfer in the catalytic process, and can also improve the specific surface area of the catalyst, thereby increasing the contact area of the active sites and the electrolyte.
As shown in fig. 4-2, which is a high resolution electron microscope image of the carbon-supported platinum copper porous nanowire (PtCu PNWs/C) prepared in example 1 of the present invention, it can be seen that many clear lattice stripes appear, and it is found by measurement that the lattice spacing is about 0.219nm and is close to the (111) lattice spacing (0.2191nm) of the platinum-copper (Pt-Cu) phase, further illustrating that copper is successfully doped into the platinum lattice to form a platinum-copper (Pt-Cu) alloy structure.
The method adopts copper wires as sacrificial templates, utilizes the difference of platinum-copper reduction potentials to perform a displacement reaction, adopts an ultrasonic preparation method, and promotes the formation of a uniform porous platinum-copper alloy nanowire structure by the cavitation action of ultrasonic.
The porous nano-wire structure catalyst prepared by the invention has the advantages of low platinum loading capacity, high catalytic activity, good chemical stability and the like, and is beneficial to promoting the further development of fuel cells.
Claims (9)
1. A carbon-loaded platinum-copper alloy porous nanowire catalyst for a fuel cell is composed of a carrier and an active component, and is characterized in that the active component is a platinum-copper alloy porous nanowire; the composite material comprises the following components in percentage by mass: carrier carbon: 70-80%, copper: 3-10%, platinum: 10 to 27 percent.
2. The platinum-copper alloy on carbon porous nanowire catalyst for a fuel cell according to claim 1, characterized in that: the support carbon was commercial XC-72 carbon black.
3. The platinum-copper alloy on carbon porous nanowire catalyst for a fuel cell according to claim 1, characterized in that: the diameter of the platinum-copper alloy porous nanowire is 15-25 nm.
4. The platinum-copper alloy on carbon porous nanowire catalyst for a fuel cell according to claim 1, characterized in that: the diameter of the platinum-copper alloy porous nanowire is that the molar ratio of platinum to copper in the platinum-copper alloy porous nanowire is 3: 1-1: 3.
5. A preparation method of a carbon-supported platinum-copper alloy porous nanowire catalyst for a fuel cell comprises the following steps:
(1) weighing copper chloride, hexadecylamine and glucose according to a proportion, adding the copper chloride, the hexadecylamine and the glucose into deionized water, stirring and mixing uniformly, introducing nitrogen into a mixed solution for 1-2 hours, heating to 100-120 ℃, and performing centrifugal cleaning for multiple times after reaction is finished to obtain copper wires (copper nanowires);
(2) dispersing the copper wire obtained in the step (1) in a cyclohexane solution to obtain a copper wire cyclohexane solution, adding a chloroplatinic acid cyclohexane solution to react at room temperature under an ultrasonic condition, adding ethanol after the reaction, centrifuging to obtain a platinum-copper alloy porous nanowire, and dispersing the platinum-copper alloy porous nanowire in the cyclohexane solution to obtain a platinum-copper alloy porous nanowire cyclohexane solution;
(3) ultrasonically dispersing carbon black in cyclohexane to obtain a carbon black cyclohexane solution, adding the platinum-copper alloy porous nanowire cyclohexane solution prepared in the step (2) into the carbon black cyclohexane solution, stirring, performing centrifugal separation, drying the obtained solid, and grinding;
(4) and (4) adding the solid powder obtained in the step (3) into a mixed solution of ethanol and acetic acid, stirring at 50-70 ℃, washing off residual hexadecylamine on the surface of the catalyst, washing with deionized water, and drying to obtain a final product.
6. The method for preparing a carbon-supported platinum-copper alloy porous nanowire catalyst for a fuel cell according to claim 5, characterized in that: in step (1), the carbon black is a commercial XC-72 carbon black; the centrifugal cleaning comprises the following specific steps: adding a mixed solution of cyclohexane and ethanol, and performing centrifugal cleaning for many times; the adding amount of the copper chloride, the hexadecylamine and the glucose is 40-60 times of the mass of the hexadecylamine according to the mass ratio of (1-3) to (15-20) to (2-8); the stirring and mixing time is 5-6 h; the heating reaction time of the oil bath is 3-5 h.
7. The method for preparing a carbon-supported platinum-copper alloy porous nanowire catalyst for a fuel cell according to claim 6, characterized in that: in the step (2), the concentration of the copper wire cyclohexane solution is 10-30 mmol/L; in the chloroplatinic acid cyclohexane solution, the concentration of platinum (Pt) ions is 0.01-0.1 mol/L; adding a cyclohexane solution containing 0.02-0.05 mmol of chloroplatinic acid into a cyclohexane solution containing 0.12mmol of copper wires; the adopted ultrasonic frequency is 10-30 kHz; the reaction time is 10-30 min.
8. The method for preparing a carbon-supported platinum-copper alloy porous nanowire catalyst for a fuel cell according to claim 7, characterized in that: in the step (3), the ultrasonic dispersion time of the carbon black is 1-2 h; stirring for 5-6 h; and adding 20-30 mg of the platinum-copper alloy porous nanowire into 70-80 mg of carbon black.
9. The method for preparing a carbon-supported platinum-copper alloy porous nanowire catalyst for a fuel cell according to claim 8, characterized in that: in the step (4), the stirring time is 3-5 h.
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