CN114094125B - CoFe/CeO 2 Preparation method and application of-nitrogen-doped carbon nanotube composite electrode catalyst material - Google Patents
CoFe/CeO 2 Preparation method and application of-nitrogen-doped carbon nanotube composite electrode catalyst material Download PDFInfo
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Abstract
The invention belongs to the technical field of catalytic materials, and relates to CoFe/CeO 2 A preparation method and application of-NCNTs composite electrode catalyst material. The method comprises the following steps: adding cobalt nitrate hexahydrate and ferric trichloride into a mixed solution of ethanol and water, stirring, adding cerous nitrate hexahydrate to obtain a mixed solution, placing the mixed solution into sealed heating equipment with a microwave generator, adjusting power and temperature to carry out reaction, and obtaining a solid product after the reaction is finished; adding dicyanodiamine into a porcelain boat, placing the porcelain boat in a tubular furnace close to an air inlet end, uniformly grinding a solid product, adding the ground solid product into the porcelain boat, placing the porcelain boat in the tubular furnace close to an air outlet endCalcining the gas end, controlling the introduction rate of nitrogen, and calcining to obtain the final material. The method is simple and easy to implement, low in cost and high in yield; the obtained material is in a tubular structure, has large specific surface area, good conductivity and high nano particle dispersion degree, is suitable for a direct methanol fuel cell anode catalytic material, and has good methanol catalytic oxidation performance and catalytic stability.
Description
Technical Field
The invention belongs to the field of anode catalytic materials of direct methanol fuel cells, and relates to CoFe/CeO 2 Nitrogen-doped carbon nanotubes (CoFe/CeO) 2 -NCNTs) composite electrode catalyst material and its preparation method and application.
Technical Field
In recent years, more and more novel energy storage and conversion technologies begin to develop rapidly, and the requirement of related corollary equipment for efficient utilization of energy is growing day by day, so that the development of an efficient, environment-friendly and stable energy conversion device is urgent. The direct methanol fuel cell has the advantages of cleanness, no pollution and high energy conversion utilization rate, but the preparation of the anode catalyst for catalyzing the methanol oxidation needs Pt or other noble metals, the cost is high, the preparation process is more complicated, and the anode catalyst is easy to be poisoned and inactivated in the catalysis process and has poor stability, so that a plurality of research organizations are dedicated to developing the methanol oxidation catalyst with low cost, high activity and high stability. The 3d transition metal is widely used for preparing the electrocatalyst due to the abundant electrons and wide material sources, and has better stability and catalytic activity in the catalytic process, more and more advanced transition metal-based catalysts are developed, wherein the CoFe alloy has better stability and catalytic activity due to the special bimetal synergistic effect. However, the alloy particles aggregate during the cyclic operation, resulting in poor conductivity, and poor catalytic activity and stability, which requires the introduction of an appropriate support to avoid such a situation.
Rare earth semiconductor CeO 2 Because the Ce-III-IV-doped zinc oxide has rich oxygen defects, has higher activity and stability in the conversion of Ce (III) and Ce (IV), has excellent redox cycle performance and high-efficiency oxygen transfer capacity, and has great potential in the field of electrocatalysis. Adding CeO 2 Binding to the CoFe alloy will create a nano-interface between the active particles, promoting charge transfer and providing more opportunities for adsorption and desorption, optimizing the binding energy of the catalyst to the reactive sites.
The carbon nano tube can be widely applied to a carrier of an electrocatalyst due to the large specific surface area, high conductivity and excellent mechanical properties of the carbon nano tube, but the carbon nano tube has a smooth surface, and is difficult to load nano particles on the surface, and meanwhile, the process of functionalizing the surface of the carbon nano tube is very complicated, so that the design of a simple, convenient and efficient method for loading the required nano particles on the carbon nano tube is particularly important.
Disclosure of Invention
The invention provides a solution to the defects and the insufficient catalytic performance of the material in the prior art, such as: the carbon nano tube has the problems of low loading capacity, poor metal particle dispersibility, poor conductivity caused by easy aggregation in the catalytic process, unsatisfactory stability, unobvious catalytic performance of a simple alloy catalyst and the like.
In order to achieve the above purpose, the invention firstly provides CoFe/CeO 2 -NCNTs composite electrode catalyst material, the material is in a tubular structure, nitrogen-doped carbon nano tube and CoFe alloy particles which are formed by Co catalysis of dicyanodiamine, ceO 2 A nanoparticle composition; the diameter of the carbon nano tube is 80-100 nm, the tube wall is thin and has no agglomeration, and the nano particles are encapsulated at two ends of the carbon nano tube.
The invention also provides a CoFe/CeO 2 The preparation method of the-NCNTs composite electrode catalyst material specifically adopts the following technical scheme:
(1) Adding cobalt nitrate hexahydrate and ferric trichloride into a mixed solution of ethanol and water, and stirring by magnetic force to obtain a solution A;
(2) Adding cerous nitrate hexahydrate into the solution A, continuously stirring and mixing to obtain a mixed solution B,
(3) Placing the mixed solution B in sealed heating equipment with a microwave generator, starting the microwave generator to modulate to a certain power and temperature, and turning off the microwave generator after a period of treatment to obtain a solid mixture C;
(4) Adding dicyanodiamine into the porcelain boat A and placing the porcelain boat A at the air inlet end in the tubular furnace; grinding the mixture C obtained in the step (3), adding the ground mixture C into a porcelain boat B, and placing the porcelain boat B at the gas outlet end in a tube furnace; calcining the porcelain boat A and the porcelain boat B after the porcelain boats A and B are placed, controlling the nitrogen introducing rate, and calcining to obtain the CoFe/CeO 2 -NCNTs composite electrode catalyst material.
Preferably, in the step 1, the volume ratio of ethanol to water in the mixed solution of ethanol and water is 5:1; the molar ratio of the cobalt nitrate hexahydrate to the ferric trichloride is 1.25-2.5: 2, the dosage relation of the ferric trichloride and the mixed solution is 0.002M:60 ml.
Preferably, in step 2, the ratio of the number of moles of cobalt nitrate hexahydrate and ferric trichloride to the number of moles of cerium nitrate is 9:1 to 4.
Preferably, in step 3, the power of the microwave generator is 80-150W, the temperature is 150-220 ℃, and the processing time is 3-6 min.
Preferably, in the step 4, the molar ratio of dicyanodiamine to cobalt nitrate hexahydrate and ferric chloride in the mixture C is 4: 0.125-0.25: 2.
preferably, in the step 4, the calcining temperature in the tubular furnace is 900-950 ℃, the heating rate is 2 ℃/min, the calcining time is 4-6 h, and the nitrogen gas introduction rate is 40-60 ml/min.
Wherein, the porcelain boat A and the porcelain boat B are porcelain boats, and different letters are only distinguished on names.
The invention also provides a CoFe/CeO 2 Application of-NCNTs composite electrode catalyst material, namely CoFe/CeO 2 -NCNTs composite electrode catalyst material, ethanol, 5wt% nafion solutionTaking the mass ratio as 100:10:1, and dripping the obtained mixed solution on the surface of the glassy carbon electrode, and naturally airing to obtain the electrode containing the composite material. The electrode material is subjected to voltammetry test in the environment of 3M methanol and 1MKOH solution at 200mV s -1 The current density can reach 281mA cm at the voltage of 1V (V vs Ag/AgCl) under the sweeping speed 2 The material shows excellent catalytic oxidation activity of methanol, can still keep 83.1 percent of the initial value after 3600 seconds constant voltage test, and shows excellent stability.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a method for preparing CoFe/CeO 2 The method for synthesizing the NCNTs composite electrode catalyst material is simple and easy to implement, has low cost, is different from the traditional mode of using the carbon nano tube to load nano particles, forms the carbon nano tube by utilizing the catalytic action of Co on a carbon source and a nitrogen source provided by dicyanodiamine in the calcining process, directly encapsulates different nano particles, has obvious loading effect, can ensure that different nano particles are uniformly loaded, avoids the agglomeration of the nano particles, exposes more catalytic active sites, and simultaneously can greatly increase the conductivity of the material, thereby effectively promoting the implementation of interface catalytic reaction.
2. The invention prepares CoFe/CeO by a simple one-step calcination method 2 Compared with other common Co and Fe metal materials, the CoFe alloy has better stability and catalytic activity due to better bimetal synergistic effect, co in the CoFe alloy can catalyze dicyanodiamine to form a carbon nano tube carrier to disperse metal nano particles, and simultaneously added CeO 2 The catalyst has better oxidation-reduction cycle performance, can form a special interface with CoFe alloy, quickens the rapid conduction of charges between the interfaces, provides more opportunities for adsorption and desorption, and optimizes the binding energy of the catalyst and reactive sites. The carrier of the material is a carbon nano tube with a thin tube wall, has excellent conductivity, and the nano particles are mostly encapsulated at two ends of the nano tube, are uniformly dispersed by the carbon nano tube while being in better contact with methanol, and are exposed moreThe active site of (1).
3. The invention uses CoFe/CeO 2 -NCNTs composite electrode catalyst material, ethanol, 5% wt nafion solution in a mass ratio of 100:10:1, and dripping the mixture on the surface of a glassy carbon electrode, and naturally airing to obtain the electrode containing the composite material. The electrode material is tested in a voltammetric test in a 3M methanol and 1M KOH solution environment and shows that the voltage is 200mV s -1 The current density can reach 281mA cm at the sweep speed and the voltage of 1V (V vs Ag/AgCl) 2 The material can still keep 83.1 percent of the initial value after 3600 seconds constant voltage test, and shows very good stability.
Drawings
FIG. 1 shows CoFe/CeO prepared in example 1 of the present invention 2 -XRD pattern of NCNTs composite electrode catalyst material;
FIG. 2 shows CoFe/CeO prepared in example 1 of the present invention 2 -scanning electron micrographs of NCNTs composite electrode catalyst material;
FIG. 3 shows CoFe/CeO prepared in example 2 of the present invention 2 -scanning electron micrographs of NCNTs composite electrode catalyst material;
FIG. 4 shows CoFe/CeO prepared in example 3 of the present invention 2 -cyclic voltammograms of NCNTs composite electrode catalyst material at different sweep rates;
FIG. 5 shows CoFe/CeO prepared in example 4 of the present invention 2 -cyclic voltammogram of NCNTs composite electrode catalyst material in 1M KOH solution with or without methanol;
FIG. 6 shows CoFe/CeO prepared in example 5 of the present invention 2 Chronoamperometry of NCNTs composite electrode catalyst material.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples.
Example 1:
(1) 0.3675g cobalt nitrate hexahydrate (0.00125M), 0.3244 ferric chloride (0.002M) were added to a mixed solution of ethanol and water (V) Ethanol ：V Water (W) = 5: 1) in total 60mL, and solution a was obtained by magnetic stirring;
(2) Adding 0.21753g cerous nitrate hexahydrate (0.0005M) into the solution A, and continuously stirring and mixing to obtain a mixed solution B;
(3) And (3) placing the mixed solution B in sealed heating equipment with a microwave generator, starting the microwave generator, regulating the power to 80W, regulating the temperature to 150 ℃, treating for 3min, and then closing the microwave generator to obtain a solid mixture C.
(4) 3.365g dicyanodiamine (0.04M) was added to the porcelain boat and placed at the inlet end of the tube furnace (near the inlet end); grinding the mixture C uniformly, adding the mixture C into another porcelain boat, placing the porcelain boat at the gas outlet end (close to the gas outlet end) of the tube furnace, calcining the porcelain boat after the porcelain boat is placed, introducing nitrogen at a rate of 40ml/min, calcining at a temperature of 900 ℃, heating at a rate of 2 ℃/min, keeping the temperature for 4h, and calcining to obtain CoFe/CeO 2 -NCNTs composite electrode catalyst material.
As shown in FIG. 1, coFe/CeO obtained in this example 2 The diffraction peaks of the NCNTs composite electrode catalyst material at 44.87 degrees, 65.31 degrees and 82.74 degrees of 2 theta respectively correspond to the (110), (211) and (200) crystal planes of the CoFe alloy, and the diffraction peaks at 28.55 degrees, 33.08 degrees, 47.48 degrees, 56.34 degrees, 76.70 degrees and 88.43 degrees respectively correspond to CeO 2 The (111), (200), (220), (311), (331), and (422) crystal planes of (A). They were in agreement with standard comparison cards PDF #49-1568 and PDF #34-0394, respectively, demonstrating CoFe/CeO 2 NCNTs nanomaterials were successfully prepared in this experiment;
as shown in FIG. 2, coFe/CeO prepared by the invention 2 the-NCNTs nano material is in a tubular structure, the diameter of the carbon nano tube is 80-100 nm, the tube wall is thin, the agglomeration phenomenon is avoided, and CoFe alloy particles and CeO 2 The nanoparticles are encapsulated at both ends of the carbon nanotubes.
Example 2:
(1) 0.441g of cobalt nitrate hexahydrate (0.0015M), 0.3244 ferric chloride (0.002M) were added to a mixed solution of ethanol and water (V) Ethanol ：V Water (W) = 5: 1) in total 60mL, and solution a was obtained by magnetic stirring;
(2) Adding 0.3263g cerous nitrate hexahydrate (0.00075M) into the solution A, and continuously stirring and mixing to obtain a mixed solution B;
(3) Placing the mixed solution B in a sealed heating device with a microwave generator, starting the microwave generator to adjust the power to 85W, adjusting the temperature to 170 ℃, and after treating for 4min, closing the microwave generator to obtain a solid mixture C;
(4) 3.365g dicyanodiamine (0.04M) was added to the porcelain boat and placed in the tube furnace at (near) the inlet end; grinding the mixture C uniformly, adding the mixture C into another porcelain boat, placing the porcelain boat at the gas outlet end (close to the gas outlet end) of the tube furnace, calcining the porcelain boat after the porcelain boat is placed, wherein the nitrogen introducing speed is 45ml/min, the calcining temperature is 910 ℃, the heating rate is 2 ℃/min, the heat preservation time is 4.5h, and the CoFe/CeO is obtained after calcining 2 -NCNTs composite electrode catalyst material.
(5) Taking the CoFe/CeO of the invention 2 -NCNTs composite electrode catalyst material 4mg, ethanol 1mL, 5% wt nafion solution 1uL mixing ultrasound, dripping on the surface of glassy carbon electrode active area, and air drying naturally to obtain the composite material-containing electrode. The electrode material was subjected to voltammetry testing in an environment of 3M methanol and 1M koh solution.
(6) The material and catalytic activity of the catalyst are characterized by an X-ray diffractometer (XRD), a Scanning Electron Microscope (SEM) and an electrochemical workstation.
As shown in FIG. 3, coFe/CeO prepared by the invention 2 The NCNTs composite electrode catalyst material is of a tubular structure, the diameter of the tube is 80-100 nm, the wall of the tube is thin, and the nano particles are encapsulated at two ends of the carbon nano tube. The reason for the formation of the structure is that the metal Co absorbs the carbon source and the nitrogen source provided by dicyanodiamine in the calcining process, precipitates a carbon cap after the absorption saturation and then orderly grows into the carbon nano tube in flowing nitrogen.
Example 3:
(1) 0.5145g cobalt nitrate hexahydrate (0.00175M), 0.3244 ferric chloride (0.002M) were added to a mixed solution of ethanol and water (V) Ethanol ：V Water (W) = 5: 1) in total 60mL, and solution a was obtained by magnetic stirring;
(2) Adding 0.43506g cerous nitrate hexahydrate (0.0005M) into the solution A, and continuously stirring and mixing to obtain a mixed solution B;
(3) Placing the mixed solution B in a sealed heating device with a microwave generator, starting the microwave generator, regulating the power to 90W, regulating the temperature to 180 ℃, treating for 5min, and then closing the microwave generator to obtain a solid mixture C;
(4) 3.365g dicyanodiamine (0.04M) was added to the porcelain boat and placed in the tube furnace at (near) the inlet end; grinding the mixture C uniformly, adding the mixture C into another porcelain boat, placing the porcelain boat at the gas outlet end (close to the gas outlet end) of the tube furnace, calcining the porcelain boat after the porcelain boat is placed, wherein the nitrogen introducing speed is 50ml/min, the calcining temperature is 920 ℃, the heating rate is 2 ℃/min, the heat preservation time is 4.5h, and obtaining CoFe/CeO after calcining 2 -NCNTs composite electrode catalyst material.
(5) Taking the CoFe/CeO of the invention 2 Mixing NCNTs composite electrode catalyst material 4mg, ethanol 1mL, 5wt% nafion solution 1uL, performing ultrasonic mixing, dripping on the surface of the glassy carbon electrode active area, and naturally airing to obtain the electrode containing the composite material. The electrode material was voltammetric tested in a solution of 3M methanol +1MKOH in 1 MKOH.
(6) The materials and catalytic activity of the catalyst are characterized by an X-ray diffractometer (XRD), a Scanning Electron Microscope (SEM) and an electrochemical workstation.
As shown in FIG. 4, coFe/CeO was measured by cyclic voltammetry 2 Electrocatalytic performance of NCNTs nanomaterials on methanol, 200mV s -1 The material has no current response in a voltage range of a large area in a 1MKOH solution, while the current density of the same sweep-rate material in a solution of 3M methanol +1MKOH solution is slowly increased in 0-0.5V (vs Ag/AgCl) and is remarkably increased in 0.5-1V (vs Ag/AgCl), and the material shows excellent methanol catalytic oxidation performance. This is facilitated by the CoFe alloy and CeO 2 The nano interface created between the nano particles promotes charge transfer, provides more adsorption and desorption opportunities, optimizes the combination energy of the catalyst and the reaction active site, and simultaneously, the thinner carbon nano tube is also beneficial to the faster transmission of electrons.
Example 4:
(1) 0.588g of cobalt nitrate hexahydrate (0.002M), 0.3244 ferric chloride (0.002M) were added to a mixed solution of ethanol and water (V) Ethanol ：V Water (W) = 5: 1) in total 60mL, and solution a was obtained by magnetic stirring;
(2) Adding 0.5438g of cerous nitrate hexahydrate (0.00125M) into the solution A, and continuously stirring and mixing to obtain a mixed solution B;
(3) Placing the mixed solution B in a sealed heating device with a microwave generator, starting the microwave generator, regulating the power to 120W, regulating the temperature to 2000 ℃, treating for 6min, and then closing the microwave generator to obtain a solid mixture C;
(4) 3.365g dicyanodiamine (0.04M) was added to the porcelain boat and placed in the tube furnace at (near) the inlet end; grinding the mixture C uniformly, adding the mixture C into another porcelain boat, placing the porcelain boat at the gas outlet end (close to the gas outlet end) of the tube furnace, calcining the porcelain boat after the porcelain boat is placed, introducing nitrogen at the rate of 55ml/min, calcining at the temperature of 930 ℃, heating at the rate of 2 ℃/min, keeping the temperature for 6h, and calcining to obtain CoFe/CeO 2 -NCNTs composite electrode catalyst material.
(5) Taking the CoFe/CeO of the invention 2 -NCNTs composite electrode catalyst material 4mg, ethanol 1mL, 5% wt nafion solution 1uL mixing ultrasound, dripping on the surface of glassy carbon electrode active area, and air drying naturally to obtain the composite material-containing electrode. The electrode material was subjected to voltammetry testing in an environment of 3M methanol and 1M koh solution.
(6) The material and catalytic activity of the catalyst are characterized by an X-ray diffractometer (XRD), a Scanning Electron Microscope (SEM) and an electrochemical workstation.
As shown in FIG. 5, the catalyst has different catalytic oxidation effects on methanol at different sweep rates, and CoFe/CeO was measured by cyclic voltammetry 2 The electrocatalytic performance of NCNTs nano material to methanol is small in current response with the increase of voltage at a lower sweep speed, and the current slightly fluctuates when the voltage reaches over 0.8V (vs Ag/AgCl), the initial potential is small and the current response is very obvious at a higher sweep speed, and the current density reaches 281 cm mA at the voltage of 1V (vs Ag/AgCl) -2 The material has high methanol catalytic oxidation performance and stable catalytic effect at a high sweep rate.
Example 5:
(1) 0.735g of cobalt nitrate hexahydrate (0.0025M), 0.3244 ferric chloride (0.002M) was added to the mixed solution of ethanol and water (R) ((R))V Ethanol ：V Water (W) = 5: 1) in total 60mL, and solution a was obtained by magnetic stirring;
(2) Adding 0.8701g cerous nitrate hexahydrate (0.002M) into the solution A, and continuously stirring and mixing to obtain a mixed solution B;
(3) And (3) placing the mixed solution B in sealed heating equipment with a microwave generator, starting the microwave generator, regulating the power to 150W, regulating the temperature to 220 ℃, treating for 6min, and then closing the microwave generator to obtain a solid mixture C.
(4) 3.365g dicyanodiamine (0.04M) was added to the porcelain boat and placed in the tube furnace at (near) the inlet end; grinding the mixture C uniformly, adding the mixture C into another porcelain boat, placing the porcelain boat at the gas outlet end (close to the gas outlet end) of the tube furnace, calcining the porcelain boat after the porcelain boat is placed, wherein the nitrogen introducing speed is 60ml/min, the calcining temperature is 950 ℃, the heating rate is 2 ℃/min, the heat preservation time is 4h, and obtaining CoFe/CeO after calcining 2 -NCNTs composite electrode catalyst material.
(5) Taking the CoFe/CeO of the invention 2 Mixing NCNTs composite electrode catalyst material 4mg, ethanol 1mL, 5wt% nafion solution 1uL, performing ultrasonic mixing, dripping on the surface of the glassy carbon electrode active area, and naturally airing to obtain the electrode containing the composite material. The electrode material was subjected to voltammetry testing in an environment of 3M methanol and 1M koh solution.
(6) The material and catalytic activity of the catalyst are characterized by an X-ray diffractometer (XRD), a Scanning Electron Microscope (SEM) and an electrochemical workstation.
As shown in FIG. 6, coFe/CeO was paired using an electrochemical workstation 2 -NCNTs nano-material is subjected to stability test, and shows that the current density of the material is 281mA cm from the initial value in 3600s test -2 Down to 233mA cm -2 It becomes 83% of the initial value, and has excellent durability and sustained stability. This is due to the stable mosaic of the catalytic nanoparticles in the carbon nanotubes, avoiding the agglomeration of the nanoparticles during long-term catalysis.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. CoFe/CeO 2 The preparation method of the nitrogen-doped carbon nanotube composite electrode catalyst material is characterized by comprising the following steps of:
(1) Adding cobalt nitrate hexahydrate and ferric trichloride into a mixed solution of ethanol and water, and stirring by magnetic force to obtain a solution A;
(2) Adding cerous nitrate hexahydrate into the solution A, continuously stirring and mixing to obtain a mixed solution B,
(3) Placing the mixed solution B in sealed heating equipment with a microwave generator, starting the microwave generator to regulate the power to be 80-150W and the temperature to be 150-220 ℃, treating for 3-6min, and then closing the microwave generator to obtain a solid mixture C;
(4) Adding dicyanodiamine into the porcelain boat A and placing the porcelain boat A at the air inlet end in the tubular furnace; grinding the mixture C obtained in the step (3), adding the ground mixture C into a porcelain boat B, and placing the porcelain boat B at the gas outlet end in a tube furnace; calcining the porcelain boat A and the porcelain boat B after the porcelain boat A and the porcelain boat B are placed, and controlling the nitrogen introduction rate; wherein the calcining temperature in the tubular furnace is 900-950 ℃, the heating rate is 2 ℃/min, the calcining time is 4-6 h, and the nitrogen introduction rate is 40-60ml/min; calcining to obtain CoFe/CeO 2 -NCNTs composite electrode catalyst material, the obtained material is in a tubular structure, and nitrogen-doped carbon nano-tubes, coFe alloy particles and CeO which are formed by Co catalysis of dicyanodiamine 2 Nano particles; the diameter of the carbon nanotube is 80 to 100nm, the CoFe alloy particles and CeO 2 The nanoparticles are encapsulated at both ends of the carbon nanotubes.
2. CoFe/CeO according to claim 1 2 The preparation method of the nitrogen-doped carbon nanotube composite electrode catalyst material is characterized in that in the step 1, ethanol and the nitrogen-doped carbon nanotube composite electrode catalyst material are mixedThe volume ratio of ethanol to water in the mixed solution formed by water is 5:1.
3. CoFe/CeO according to claim 1 2 The preparation method of the nitrogen-doped carbon nanotube composite electrode catalyst material comprises the following steps of 1, wherein the dosage relation of ferric trichloride and a mixed solution is 0.002M:60ml; the molar ratio of the cobalt nitrate hexahydrate to the ferric trichloride is 1.25 to 2.5:2.
4. CoFe/CeO according to claim 1 2 In step 2, the ratio of the sum of the mole numbers of the cobalt nitrate hexahydrate and the ferric trichloride to the mole number of the cerium nitrate is 9:1~4.
5. CoFe/CeO according to claim 1 2 The preparation method of the nitrogen-doped carbon nanotube composite electrode catalyst material is characterized in that in the step 4, the molar ratio of dicyanodiamine to cobalt nitrate hexahydrate and ferric trichloride in the mixture C is 4:0.125 to 0.25:2.
6. the method of any one of claims 1~5 to produce CoFe/CeO 2 The application of the nitrogen-doped carbon nanotube composite electrode catalyst material in a direct methanol fuel cell as an anode catalyst.
7. Use according to claim 6, characterized in that the specific operations are: subjecting the CoFe/CeO 2 -NCNTs composite nanomaterial, ethanol, 5wt% nafion solution in a mass ratio of 100:10:1, and dripping the obtained mixed solution on the surface of the glassy carbon electrode, and naturally airing to obtain the electrode containing the composite material.
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