CN112054220B - Preparation method of flexible Pd/NiO nano particle @ carbon fiber catalyst - Google Patents
Preparation method of flexible Pd/NiO nano particle @ carbon fiber catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000835 fiber Substances 0.000 claims abstract description 57
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 19
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910002666 PdCl2 Inorganic materials 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 238000003763 carbonization Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 230000000877 morphologic effect Effects 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004917 carbon fiber Substances 0.000 abstract description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 72
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 7
- 101150003085 Pdcl gene Proteins 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000013305 flexible fiber Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/30—Fuel cells in portable systems, e.g. mobile phone, laptop
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a preparation method of a flexible Pd/NiO nano particle @ carbon fiber catalyst, which comprises the following steps: dissolving PAN powder in DMF, heating and stirring to prepare PAN/DMF spinning solution, and preparing PAN fiber by using an electrostatic spinning technology; collecting PAN fiber in Ni (NO)3)·6H2O and PdCl2Adding a NaOH solution into the mixed solution dropwise until the pH value of the mixed solution is 8-10, stirring, drying, and then placing in a muffle furnace for pre-oxidation to obtain a pre-oxidized precursor PAN fiber; and finally, sintering and carbonizing the pre-oxidized precursor PAN fiber in a vacuum tube furnace to obtain the flexible Pd/NiO nano particle @ carbon fiber catalyst. The flexible Pd/NiO nano particle @ carbon fiber catalyst prepared by the method has controllable components, nano particle size and carbon fiber diameter, and the loaded nano particle has strong binding force with a flexible carrier and high stability.
Description
Technical Field
The invention belongs to the technical field of preparation of catalytic materials, and particularly relates to a preparation method of a flexible Pd/NiO nano particle @ carbon fiber catalyst.
Background
The flexible wearable electronic equipment draws wide attention of researchers due to characteristics of portability, foldability and the like, so that the rapid development of a flexible energy storage technology is promoted, and a flexible energy device is produced and developed rapidly. The flexible Pd/NiO nano particle @ carbon fiber catalyst has many advantages as an indispensable important material in the flexible energy key technology, for example, the catalytic performance is not affected by folding, an additional electrode or a current collector is not needed, after the flexible Pd/NiO nano particle @ carbon fiber catalyst is woven into a textile, the flexible Pd/NiO nano particle @ carbon fiber catalyst not only has excellent flexibility and a 3D porous structure with high mechanical strength, but also has excellent conductivity, so that the catalyst is easy to install in reactors of different shapes while effectively reducing the use amount of Pd and reducing the cost, and has a large reaction site area, fast reaction kinetics and convenient recovery. The catalyst is loaded on the flexible fiber carrier, so that the limitation that the loaded catalyst is limited to hard and brittle carriers such as metal, oxide and the like is broken through, and the application range of the catalyst is expanded.
At present, the methods for preparing the flexible catalyst material mainly comprise a powder dispersion loading method, an in-situ growth method, a protofilament improvement method and the like. The powder dispersion loading method is simple in preparation process and easy to process, but the catalyst is easy to agglomerate seriously on the surface of the fabric under the action of a coupling agent or a binder, so that the catalytic activity of the catalyst is reduced. The flexible catalyst prepared by the protofilament improvement method has the characteristics of durability and the like, but the doped nano powder is easily embedded into the fiber, the catalytic performance of the catalyst cannot be fully exerted, the process is complex, the dosage of the reagent is large, and the problems of nano powder agglomeration, spinning broken ends and the like can occur in the blending spinning process.
Generally, when an in-situ growth method is used to prepare a flexible catalyst, the method is limited because most fiber fabrics are not resistant to high temperature. However, the problem does not exist when the in-situ growth method is used for preparing the flexible Pd/NiO nano-particle @ carbon fiber catalyst, and the method continuously performs preparation and finishing, so that the preparation process is simple and easy to control, the macro preparation is easy, the industrialization is easy to realize, and the production cost is effectively reduced; meanwhile, the size of the nano particles and the diameter of the carbon fiber can be accurately regulated and controlled by changing the preparation process parameters, so that the porosity, the specific surface area and the like of the woven textile can be regulated and controlled.
Disclosure of Invention
The invention aims to provide a preparation method of a flexible Pd/NiO nano particle @ carbon fiber catalyst, which improves the binding force and stability of nano particles and a flexible carrier.
The technical scheme adopted by the invention is that the preparation method of the flexible Pd/NiO nano particle @ carbon fiber catalyst is implemented according to the following steps:
dissolving PAN powder in DMF, heating and stirring to prepare PAN/DMF spinning solution with a certain concentration, and preparing PAN fibers with different diameters, sizes and morphological characteristics by an electrostatic spinning technology;
step 2, collecting PAN fiber in Ni (NO) with a certain molar ratio3)2 ·6H2O and PdCl2Dropwise adding a NaOH solution into the mixed solution until the pH value of the mixed solution is 8-10, stirring and drying to obtain a precursor PAN fiber;
step 3, placing the precursor PAN fiber in a muffle furnace, and pre-oxidizing at a certain temperature to obtain a pre-oxidized precursor PAN fiber;
and 4, sintering and carbonizing the pre-oxidized precursor PAN fiber in a vacuum tube furnace to obtain the flexible Pd/NiO nano particle @ carbon fiber catalyst.
The present invention is also characterized in that,
in the step 1, the mass concentration of the PAN/DMF spinning solution is 5-30%, the voltage is 10-40kV during electrostatic spinning, and the temperature is 5-60 ℃.
In step 2, PdCl2And Ni (NO)3)2·6H2The molar ratio of O is 1: 1-20, and the loading amount of Pd is 1-10 wt%.
In the step 2, stirring for 1-5 h; the drying temperature is 50-90 ℃.
In the step 3, during pre-oxidation, the temperature of the muffle furnace is raised to 280-400 ℃ at the temperature raising rate of 5-20 ℃/min, and the temperature is preserved for 30-90min, and the muffle furnace is cooled along with the furnace.
In the step 4, during sintering and carbonization, the temperature of the vacuum tube furnace is increased to 750-1100 ℃ at the heating rate of 5-20 ℃/min, and the temperature is kept for 30-90min, and the furnace is cooled.
The beneficial effect of the invention is that,
the flexible Pd/NiO nano particle @ carbon fiber catalyst prepared by the method has controllable components, nano particle size and carbon fiber diameter, and the loaded nano particle has strong binding force with a flexible carrier and high stability; the preparation process is simple and easy to control, mass preparation is easy, industrialization is easy to realize, and the production cost is effectively reduced. Meanwhile, after the catalyst is woven into a textile, the catalyst not only has excellent flexibility and a controllable 3D porous structure with high mechanical strength, but also has excellent conductivity, so that the catalyst is easily installed in reactors of different shapes while the use amount of Pd is effectively reduced and the cost is reduced, has a large reaction site area, is quick in reaction kinetics, and is convenient to recover.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The preparation method of the flexible Pd/NiO nano particle @ carbon fiber catalyst is implemented according to the following steps:
step 1, dissolving Polyacrylonitrile (PAN) powder in N, N-Dimethylformamide (DMF), electromagnetically heating and stirring to prepare PAN/DMF spinning solution with a certain concentration, and carrying out electrostatic spinning to prepare PAN fibers with different diameter, size and appearance characteristics by adjusting the concentration, voltage and temperature of the solution;
wherein, the mass concentration of the PAN/DMF spinning solution is 5-30%, the voltage is 10-40kV during electrostatic spinning, and the temperature is 5-60 ℃;
step 2, collecting PAN fiber in Ni (NO) with a certain molar ratio3)2 ·6H2O and PdCl2Dropwise adding a NaOH solution into the mixed solution until the pH value of the mixed solution is 8-10, continuously and dynamically stirring for a period of time at room temperature, and then placing the mixed solution in a drying box for drying to obtain a precursor PAN fiber;
wherein PdCl is2And Ni (NO)3)2 ·6H2The molar ratio of O is 1: 1-20, wherein the load of Pd is 1-10 wt%; stirring for 1-5 h; the drying temperature is 50-90 ℃;
step 3, placing the precursor PAN fiber in a muffle furnace, and pre-oxidizing at a certain temperature to obtain a pre-oxidized precursor PAN fiber;
during pre-oxidation, the temperature of the muffle furnace is increased to 280-400 ℃ at the heating rate of 5-20 ℃/min, the temperature is kept for 30-90min, and the muffle furnace is cooled along with the furnace;
step 4, sintering and carbonizing the pre-oxidized precursor PAN fiber in a vacuum tube furnace to obtain a flexible Pd/NiO nano particle @ carbon fiber catalyst;
during sintering and carbonization, the temperature of the vacuum tube furnace is increased to 750-1100 ℃ at the heating rate of 5-20 ℃/min, and the temperature is preserved for 30-90min, and the furnace is cooled;
the invention discloses a preparation method of a flexible Pd/NiO nano particle @ carbon fiber catalyst for a fuel cell, which is characterized in that PAN fiber is obtained by utilizing an electrostatic spinning technology and collected in Ni (NO) with a certain molar ratio3)2 ·6H2O and PdCl2The dynamic NaOH aqueous solution is stirred for a period of time, a precursor PAN fiber is obtained after drying, the PAN fiber forms the carbon nanofiber through pre-oxidation and high-temperature sintering, meanwhile, the Pd/NiO nano particles are formed and grow on the surface of the carbon nanofiber in situ, and finally the flexible Pd/NiO nano particle @ carbon fiber catalyst is obtained.
Example 1
The preparation method of the flexible Pd/NiO nano particle @ carbon fiber catalyst is specifically implemented according to the following steps:
step 1, dissolving Polyacrylonitrile (PAN) powder in N, N-Dimethylformamide (DMF), electromagnetically heating and stirring to prepare PAN/DMF spinning solution with a certain concentration, and carrying out electrostatic spinning to prepare PAN fibers with different diameter, size and appearance characteristics by adjusting the concentration, voltage and temperature of the solution;
wherein the mass concentration of the PAN/DMF spinning solution is 8 percent, and during electrostatic spinning, the voltage is 28kV and the temperature is 30 ℃;
step 2, collecting PAN fiber in Ni (NO) with a certain molar ratio3)2 ·6H2O and PdCl2Adding a NaOH solution into the mixed solution dropwise until the pH value of the mixed solution is 9, continuously and dynamically stirring the mixed solution for a period of time at room temperature, and then placing the mixed solution in a drying box for drying to obtain a precursor PAN fiber;
wherein PdCl is2And Ni (NO)3)2 ·6H2The molar ratio of O is 1: 10; stirring for 4 h; the drying temperature is 50 ℃;
step 3, placing the precursor PAN fiber in a muffle furnace, and pre-oxidizing at a certain temperature to obtain a pre-oxidized precursor PAN fiber;
during pre-oxidation, the temperature of the muffle furnace is increased to 280 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 30min, and the muffle furnace is cooled along with the furnace;
step 4, sintering and carbonizing the pre-oxidized precursor PAN fiber in a vacuum tube furnace to obtain a flexible Pd/NiO nano particle @ carbon fiber catalyst;
and during sintering and carbonization, heating the vacuum tube furnace to 800 ℃ at the heating rate of 5 ℃/min, preserving the heat for 60min, and cooling along with the furnace.
Example 2
The preparation method of the flexible Pd/NiO nano particle @ carbon fiber catalyst is implemented according to the following steps:
step 1, dissolving Polyacrylonitrile (PAN) powder in N, N-Dimethylformamide (DMF), electromagnetically heating and stirring to prepare PAN/DMF spinning solution with a certain concentration, and carrying out electrostatic spinning to prepare PAN fibers with different diameter, size and appearance characteristics by adjusting the concentration, voltage and temperature of the solution;
wherein, the mass concentration of the PAN/DMF spinning solution is 10 percent, and during electrostatic spinning, the voltage is 25kV and the temperature is 20 ℃;
step 2, collecting PAN fiber in Ni (NO) with a certain molar ratio3)2 ·6H2O and PdCl2Adding a NaOH solution into the mixed solution dropwise until the pH value of the mixed solution is 10, continuously and dynamically stirring the mixed solution for a period of time at room temperature, and then placing the mixed solution in a drying box for drying to obtain a precursor PAN fiber;
wherein PdCl is2And Ni (NO)3)2 ·6H2The molar ratio of O is 1: 15; the stirring time is 2 h; the drying temperature is 50 ℃;
step 3, placing the precursor PAN fiber in a muffle furnace, and pre-oxidizing at a certain temperature to obtain a pre-oxidized precursor PAN fiber;
during pre-oxidation, the temperature of the muffle furnace is increased to 300 ℃ at the heating rate of 15 ℃/min, the temperature is kept for 60min, and the muffle furnace is cooled along with the furnace;
step 4, sintering and carbonizing the pre-oxidized precursor PAN fiber in a vacuum tube furnace to obtain a flexible Pd/NiO nano particle @ carbon fiber catalyst;
during sintering and carbonization, heating the vacuum tube furnace to 750 ℃ at the heating rate of 10 ℃/min, preserving the heat for 90min, and cooling along with the furnace;
example 3
The preparation method of the flexible Pd/NiO nano particle @ carbon fiber catalyst is implemented according to the following steps:
step 1, dissolving Polyacrylonitrile (PAN) powder in N, N-Dimethylformamide (DMF), electromagnetically heating and stirring to prepare PAN/DMF spinning solution with a certain concentration, and carrying out electrostatic spinning to prepare PAN fibers with different diameter, size and appearance characteristics by adjusting the concentration, voltage and temperature of the solution;
wherein, the mass concentration of the PAN/DMF spinning solution is 5 percent, and during electrostatic spinning, the voltage is 30kV and the temperature is 25 ℃;
step 2, collecting PAN fiber in Ni (NO) with a certain molar ratio3)2 ·6H2O and PdCl2Adding a NaOH solution into the mixed solution dropwise until the pH value of the mixed solution is 10, continuously and dynamically stirring the mixed solution for a period of time at room temperature, and then placing the mixed solution in a drying box for drying to obtain a precursor PAN fiber;
wherein PdCl is2And Ni (NO)3)2 ·6H2The molar ratio of O is 1: 8; the stirring time is 3 hours; the drying temperature is 70 ℃;
step 3, placing the precursor PAN fiber in a muffle furnace, and pre-oxidizing at a certain temperature to obtain a pre-oxidized precursor PAN fiber;
during pre-oxidation, the temperature of the muffle furnace is increased to 320 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 40min, and the muffle furnace is cooled along with the furnace;
step 4, sintering and carbonizing the pre-oxidized precursor PAN fiber in a vacuum tube furnace to obtain a flexible Pd/NiO nano particle @ carbon fiber catalyst;
during sintering and carbonization, heating the vacuum tube furnace to 900 ℃ at the heating rate of 10 ℃/min, preserving the heat for 40min, and cooling along with the furnace;
example 4
The preparation method of the flexible Pd/NiO nano particle @ carbon fiber catalyst is implemented according to the following steps:
step 1, dissolving Polyacrylonitrile (PAN) powder in N, N-Dimethylformamide (DMF), electromagnetically heating and stirring to prepare PAN/DMF spinning solution with a certain concentration, and carrying out electrostatic spinning to prepare PAN fibers with different diameter, size and appearance characteristics by adjusting the concentration, voltage and temperature of the solution;
wherein the mass concentration of the PAN/DMF spinning solution is 25 percent, the voltage is 35kV, and the temperature is 35 ℃ during electrostatic spinning;
step 2, collecting PAN fiber in Ni (NO) with a certain molar ratio3)2 ·6H2O and PdCl2Adding a NaOH solution into the mixed solution dropwise until the pH value of the mixed solution is 11, continuously and dynamically stirring the mixed solution for a period of time at room temperature, and then placing the mixed solution in a drying box for drying to obtain a precursor PAN fiber;
wherein PdCl is2And Ni (NO)3)2 ·6H2The molar ratio of O is 1: 15; stirring for 4 h; the drying temperature is 80 ℃;
step 3, placing the precursor PAN fiber in a muffle furnace, and pre-oxidizing at a certain temperature to obtain a pre-oxidized precursor PAN fiber;
during pre-oxidation, the temperature of the muffle furnace is increased to 350 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 70min, and the muffle furnace is cooled along with the furnace;
step 4, sintering and carbonizing the pre-oxidized precursor PAN fiber in a vacuum tube furnace to obtain a flexible Pd/NiO nano particle @ carbon fiber catalyst;
during sintering and carbonization, the temperature of the vacuum tube furnace is increased to 1000 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 30min, and the furnace is cooled;
example 5
The preparation method of the flexible Pd/NiO nano particle @ carbon fiber catalyst is specifically implemented according to the following steps:
step 1, dissolving Polyacrylonitrile (PAN) powder in N, N-Dimethylformamide (DMF), electromagnetically heating and stirring to prepare PAN/DMF spinning solution with a certain concentration, and carrying out electrostatic spinning to prepare PAN fibers with different diameter, size and appearance characteristics by adjusting the concentration, voltage and temperature of the solution;
wherein the mass concentration of the PAN/DMF spinning solution is 28 percent, and during electrostatic spinning, the voltage is 40kV and the temperature is 60 ℃;
step 2, collecting PAN fiber in Ni (NO) with a certain molar ratio3)2 ·6H2O and PdCl2Adding a NaOH solution into the mixed solution dropwise until the pH value of the mixed solution is 10, continuously and dynamically stirring the mixed solution for a period of time at room temperature, and then placing the mixed solution in a drying box for drying to obtain a precursor PAN fiber;
wherein PdCl is2And Ni (NO)3)2·6H2The molar ratio of O is 1: 20; stirring for 5 h; the drying temperature is 90 ℃;
step 3, placing the precursor PAN fiber in a muffle furnace, and pre-oxidizing at a certain temperature to obtain a pre-oxidized precursor PAN fiber;
during pre-oxidation, the temperature of the muffle furnace is increased to 350 ℃ at the heating rate of 20 ℃/min, the temperature is kept for 90min, and the muffle furnace is cooled along with the furnace;
step 4, sintering and carbonizing the pre-oxidized precursor PAN fiber in a vacuum tube furnace to obtain a flexible Pd/NiO nano particle @ carbon fiber catalyst;
and during sintering and carbonization, heating the vacuum tube furnace to 1100 ℃ at the heating rate of 20 ℃/min, preserving the temperature for 90min, and cooling along with the furnace.
TABLE 1 data of the catalytic activity of the electrocatalytic oxidation of methanol in lye of typical case samples
| Sample (I) | Preparation conditions | Activity of |
| Pd/NiO nano particle @ carbon fiber catalyst-1 | Example 1 | 85.2mA·mg-1 |
| Pd/NiO nano particle @ carbon fiber catalyst-2 | Example 2 | 96.9mA·mg-1 |
| Pd/NiO nano particle @ carbon fiber catalyst-3 | Example 3 | 58.4mA·mg-1 |
| Pd/NiO nano particle @ carbon fiber catalyst-4 | Example 4 | 48.3mA·mg-1 |
| Pd/NiO nano particle @ carbon fiber catalyst-5 | Example 5 | 32.2mA·mg-1 |
In view of the low price and high energy density of methanol, which is considered to be a good fuel, the electrocatalytic performance of the sample of the invention on methanol is firstly tested to evaluate the application prospect in the direct methanol fuel cell. The sample of the invention is in 0.5M KOH +0.5M methanol solution, and the scanning speed is 20 mV.s-1The peak-to-peak current densities of the oxidation current in the forward scan direction of the cyclic voltammogram measured under the conditions are shown in table 1 below. The data result of trial tests shows that the samples prepared under different preparation process conditions have larger difference in catalytic performance, but the catalytic activity of the samples can be obviously improved after the preparation process conditions of the samples are effectively and reasonably adjusted, and the samples are expected to reach or even exceed the current commercial Pd/C or Pt/C catalyst.
Claims (3)
1. The preparation method of the flexible Pd/NiO nano particle @ carbon fiber catalyst is characterized by comprising the following steps:
dissolving PAN powder in DMF, heating and stirring to prepare PAN/DMF spinning solution with a certain concentration, and preparing PAN fibers with different diameters, sizes and morphological characteristics by an electrostatic spinning technology;
step 2, collecting PAN fiber in Ni (NO) with a certain molar ratio3)2·6H2O and PdCl2Adding a NaOH solution into the mixed solution dropwise until the pH value of the mixed solution is 8-10, stirring, and drying to obtain a precursor PAN fiber;
PdCl2and Ni (NO)3)2·6H2The molar ratio of O is 1: 1-20, wherein the load of Pd is 1-10 wt%;
step 3, placing the precursor PAN fiber in a muffle furnace, and pre-oxidizing at a certain temperature to obtain a pre-oxidized precursor PAN fiber;
during pre-oxidation, the temperature of the muffle furnace is increased to 280-400 ℃ at the heating rate of 5-20 ℃/min, the temperature is kept for 30-90min, and the muffle furnace is cooled along with the furnace;
step 4, sintering and carbonizing the pre-oxidized precursor PAN fiber in a vacuum tube furnace to obtain a flexible Pd/NiO nano particle @ carbon fiber catalyst;
during sintering and carbonization, the temperature of the vacuum tube furnace is raised to 750-1100 ℃ at the heating rate of 5-20 ℃/min, and the temperature is preserved for 30-90min, and the furnace is cooled.
2. The preparation method of the flexible Pd/NiO nano-particle @ carbon fiber catalyst as claimed in claim 1, wherein in the step 1, the mass concentration of the PAN/DMF spinning solution is 5-30%, the voltage is 10-40kV during electrostatic spinning, and the temperature is 5-60 ℃.
3. The method for preparing the flexible Pd/NiO nano-particle @ carbon fiber catalyst as claimed in claim 1, wherein in the step 2, the stirring time is 1-5 h; the drying temperature is 50-90 ℃.
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