CN113764688A - Three-dimensional carbon structure supported GaN catalyst and preparation method thereof - Google Patents
Three-dimensional carbon structure supported GaN catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 238000000034 method Methods 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 4
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- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 31
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- 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
-
- 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
A three-dimensional carbon structure supported GaN catalyst and a preparation method thereof belong to the technical field of fuel cell catalysts. The method comprises the following steps: 1) obtaining three-dimensional carbon structure powder from the carbon-based materials with various structures through a pretreatment process; 2) carrying out plasma treatment on the three-dimensional structure carbon powder to obtain surface activated three-dimensional structure carbon powder; 3) preparing a GaN nano material by adopting a microwave plasma chemical vapor deposition system; 4) transferring the GaN nano material to the surface of a foamed nickel electrode, and performing electrostatic adsorption on the three-dimensional carbon structure in an aqueous solution; 5) and annealing the three-dimensional carbon structure adsorbing the GaN nano material to obtain the three-dimensional carbon structure supported GaN catalyst. The three-dimensional carbon structure supported GaN catalyst prepared by the invention has the mass activity of more than 100mA/mgGaN @0.9V, and after 10000 circles of aging test, the mass activity attenuation is less than 20%.
Description
Technical Field
The invention belongs to the technical field of fuel cell catalysts, and relates to a gallium nitride (GaN) supported catalyst with a three-dimensional carbon structure and a preparation method thereof.
Background
Proton exchange membrane fuel cells are one of the important ways of utilizing hydrogen energy, can realize high-efficiency energy conversion, are key technical means for replacing petroleum fuels, and the catalysts adopted by the current proton exchange membranes are mostly noble metal catalysts such as Pt and Ir, which greatly hinders the large-scale development and utilization of the hydrogen energy, so that high-performance non-noble metal catalysts become the hot spots of the current research. Non-noble metal catalysts suffer from the following major problems: 1. the activity of the non-noble metal catalyst is not high, and the catalytic efficiency is low; 2. the stability of the non-noble metal catalyst is poor; 3. the non-noble metal catalysts require higher energy consumption. GaN, one of the most important third-generation semiconductors, has characteristics of not only piezoelectric polarization (stress-induced polarization) but also spontaneous polarization generation (structural symmetry polarization), and has been widely used in photoelectric devices, communication chips, high-frequency and high-power semiconductor devices, and the like. In recent years, GaN has been successively found to have good catalytic properties, including in particular: 1) the appropriate energy band structure and chemical stability enable the photocatalyst to have good photocatalytic activity and catalytic stability; 2) the catalytic crystal face can be regulated to further regulate the catalytic performance; 3) the catalytic activity of the catalyst can be improved by the polarized surface induced electric field. According to the invention, the three-dimensional carbon structure is uniformly loaded with GaN and subjected to post-treatment, so that the catalytic activity and stability of the three-dimensional carbon structure loaded with GaN are improved, the impurity content of the three-dimensional carbon structure loaded with GaN is greatly reduced, and the catalyst has a long cycle life while maintaining high-efficiency catalysis.
Disclosure of Invention
The invention provides a three-dimensional carbon structure supported GaN catalyst and a preparation method thereof, in order to realize a non-noble metal catalyst of a fuel cell with high activity and high stability. The technical steps provided by the invention are as follows:
step 1: preparation and treatment of three-dimensional carbon structure carrier
Mixing 0.5-1.5 parts of zero-dimensional carbon material, 0.5-1.5 parts of one-dimensional carbon material, 0.5-1.5 parts of two-dimensional carbon material and 1-10 parts of carbon black according to parts by weight, dissolving in 20-100 parts of 10 wt% nitric acid solution, stirring for 5-10 hours at 60-80 ℃, washing and filtering the obtained mixture with water, drying for 5-10 hours at 60-80 ℃, and ball-milling the dried product for 1-2 hours at 250-400rpm to obtain three-dimensional carbon structure powder;
step 2: surface modification of three-dimensional carbon structure
Carrying out surface modification on the three-dimensional carbon powder in the step 1 by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) system, wherein the powder is contained in a rotatable ceramic crucible, the crucible is fixed by a rotating rod, and N is introduced2Or O2Gas, the radio frequency power is 150W, the heat preservation temperature is 100-;
and step 3: preparation of GaN nano material
Mixing 1 part of gallium oxide and 0.5-2 parts of activated carbon powder by mass to form uniform powder, placing the powder in a crucible of a microwave plasma chemical vapor deposition system, and preparing SiO with a surface sputtered Au catalyst in advance2the/Si substrate is arranged right above the crucible, and N of 5-10sccm is introduced2Maintaining the pressure of the cavity at 1-5Torr and the microwave power at 300W, growing for 20-60 minutes at the temperature of 850-3Stirring the mixture and a mixed solution of HF with the concentration of 50 wt% in a volume ratio of 2-10:1 for 30 minutes, and filtering to obtain a Ga-rich GaN nano material;
and 4, step 4: preparation of three-dimensional carbon structure loaded GaN material
Dispersing 1 part of the GaN nano material in the step 2 into 100 parts of ethanol by mass, performing ultrasonic treatment for 20 minutes, coating the mixture on the surface of a foamed nickel electrode, and placing 1 part of the surface modified three-dimensional carbon structure in the step 2, 20 parts of deionized water and ultrasonic dispersion for 30 minutes in an electrolytic cell for electrostatic adsorption;
and 5: three-dimensional carbon structure loaded GaN material post-treatment
Subjecting the product of step 5to 200sccm gas flow N2And (3) annealing at the temperature of 150-400 ℃ in a muffle furnace for 1-3 hours under protective gas to obtain the final product, namely the three-dimensional carbon structure supported GaN catalyst.
Further, the zero-dimensional carbon material comprises nano diamond and fullerene; the one-dimensional carbon material comprises carbon nano tubes and carbon nano fibers; the two-dimensional carbon material comprises graphene;
further, the rotatable crucible is of a square hollow barrel-shaped structure, the thickness of the powder to be placed is not higher than 2mm, and the rotating speed is 1-10 rpm;
further, N is introduced2Gas flow of 5-15sccm, cavity pressure of 10-20Pa, and introduction of O2The gas flow is 20-30sccm, and the cavity pressure is 20-40 Pa;
further, the anode of the electrolytic cell is a foam nickel electrode coated with Ga-rich GaN nano material, the cathode is a carbon rod electrode, the external circuit voltage is 0.5-1V, the pressurizing time is 0.5-3 hours, and magnetic stirring is carried out at 30-60rpm in the electrostatic adsorption process.
The invention has the following advantages and benefits:
(1) according to the invention, the three-dimensional carbon structure supported GaN catalyst is prepared by adopting an aqueous solution electrostatic adsorption method, the bonding force of GaN and a carbon material is improved by a thermal annealing method, and the stability of the material is improved;
(2) furthermore, the invention provides a preparation idea of the non-noble metal catalyst, and provides a new development idea and technical approach for researching and developing a new generation of high-performance non-noble metal electrocatalyst;
(3) furthermore, the invention adopts a plasma treatment mode to construct the three-dimensional carbon structure powder with electronegativity, thereby providing necessary conditions for the electrostatic adsorption process;
(4) furthermore, the invention provides a preparation method of Ga-rich GaN, which utilizes the polarization characteristics of the surface and the interface to obviously improve the performance of the electrocatalyst.
Drawings
FIG. 1 is a schematic view of plasma processing (1 is a radio frequency coil, 2 is a crucible holder, 3 is a rotating rod, 4 is a reaction chamber, and 5 is a rotatable crucible)
FIG. 2 is a sectional view of the crucible (6 is plasma, 7 is powder to be processed)
FIG. 3GaN nanomaterial
Detailed Description
The following examples are given to more specifically explain the production process and principle of the present invention. The examples are given solely for the purpose of illustration and description and are not intended to limit the scope of the invention.
Example 1
Weighing 0.5g of three-dimensional carbon structure raw material carbon nano tube, 0.5g of graphene, 0.5g of fullerene and 1g of carbon black to prepare uniformly mixed powder, adding 10g of 10 wt% nitric acid solution into the powder, stirring for 5 hours at 60 ℃, washing and filtering the obtained mixture with water, drying for 5 hours at 60 ℃, and ball-milling the dried product for 1 hour at 250rpm to obtain three-dimensional carbon structure powder; placing the powder in a rotatable ceramic crucible of a plasma enhanced chemical vapor deposition system, wherein the thickness of the powder is 1mm, the rotating speed of the crucible is 1rpm, and introducing N2Gas flow 5sccm, RF power 1Carrying out plasma treatment for 1 hour at the heat preservation temperature of 100 ℃ and 50W; weighing 1g of gallium oxide powder and 0.5g of activated carbon powder to prepare mixed powder, placing the mixed powder in a crucible of a microwave plasma chemical vapor deposition system, and preparing SiO with the surface sputtered with Au catalyst in advance2the/Si substrate is arranged right above the crucible, and N with the flow rate of 5sccm is introduced2Keeping the pressure of the cavity at 5Torr and the microwave power at 300W, and growing for 20 minutes at 850 ℃, wherein the yellow substance on the surface of the substrate is the obtained Ga-rich GaN nanowire material; measuring 20mL of HNO with the concentration of 70 wt%3And 10mL of HF with a concentration of 50 wt% was prepared as a mixed solution to etch SiO2Obtaining a dispersed Ga-rich GaN nanowire material after a/Si substrate, weighing 1mg of the Ga-rich GaN nanowire material, dispersing the Ga-rich GaN nanowire material into 100mg of ethanol, performing ultrasonic treatment for 20 minutes, coating the Ga-rich GaN nanowire material on the surface of a foamed nickel electrode, and volatilizing the ethanol for later use; weighing 1g of plasma-treated three-dimensional carbon powder and 20g of deionized water, placing the powder in an electrolytic cell after ultrasonic dispersion for 30 minutes, selecting a foamed nickel electrode coated with a Ga-rich GaN nano material as an anode, selecting a carbon rod electrode as a cathode, wherein the external circuit voltage is 0.5V, the pressurization time is 0.5 hour, and performing magnetic stirring at 30rpm in the electrostatic adsorption process; after the adsorption was completed, the solution was filtered, and the filtered material was placed at a flow rate of 200sccm N2And (4) annealing for 1 hour at a high temperature in a muffle furnace at 150 ℃ under protective gas. The prepared three-dimensional carbon structure supported GaN catalyst has the mass activity of 81mA/mg, and after 10000 circles of aging test, the mass activity is attenuated by 24.7%.
Example 2
Only the proportion of the three-dimensional carbon structure raw materials in the step 1 is changed into: 1.5g of carbon nano tube, 1.5g of graphene, 1.5g of fullerene and 10g of carbon black are prepared into uniform mixed powder, other conditions are unchanged, the mass activity of the prepared three-dimensional carbon structure supported GaN catalyst is 87.4mA/mg in the same way as example 1, and after 10000 circles of aging test, the mass activity is attenuated by 23.9%.
Example 3
Only the process in the step 1 is changed into the following steps: 10g of 10 wt% nitric acid solution is added into the powder, the mixture is stirred for 10 hours at 80 ℃, the obtained mixture is washed with water, filtered and dried for 10 hours at 80 ℃, the dried product is ball-milled for 2 hours at 400rpm, other conditions are not changed, the mass activity of the prepared three-dimensional carbon structure supported GaN catalyst is 90mA/mg as in example 1, and the mass activity is attenuated to 24.6% after 10000 circles of aging test.
Example 4
Only the process in the step 2 is changed into: the thickness of the powder is 1mm, the crucible rotation speed is 10rpm, and O is introduced2The mass activity of the prepared three-dimensional carbon structure supported GaN catalyst is 112mA/mg, and after 10000 circles of aging test, the mass activity is attenuated by 22.4 percent.
Example 4
Only the process in the step 3 is changed into: weighing 1g of gallium oxide powder and 2g of activated carbon powder to prepare mixed powder, and introducing N with the flow rate of 10sccm2The cavity pressure was kept at 1Torr and the microwave power was kept at 300W, the growth was carried out at 900 ℃ for 60 minutes while the other conditions were unchanged, the mass activity of the prepared three-dimensional carbon structure supported GaN catalyst was 94mA/mg as in example 1, and after 10000 cycles of aging test, the mass activity was attenuated by 20.1%.
Example 5
Only the process in the step 4 is changed into: the external circuit voltage is 1V, the pressurizing time is 3 hours, magnetic stirring is carried out at 60rpm in the electrostatic adsorption process, other conditions are not changed, the mass activity of the prepared three-dimensional carbon structure supported GaN catalyst is 104.2mA/mg in the same way as in example 1, and the mass activity is attenuated by 24.8% after 10000 circles of aging test.
Example 6
Except that the process in the step 5 is changed into: the muffle furnace temperature is 400 ℃, the high-temperature annealing is carried out for 3 hours, other conditions are unchanged, the mass activity of the prepared three-dimensional carbon structure supported GaN catalyst is 107.5mA/mg in the same way as in example 1, and after 10000 circles of aging test, the mass activity is attenuated by 18.4%.
Claims (6)
1. A preparation method of a three-dimensional carbon structure supported GaN catalyst is characterized by comprising the following steps:
step 1: preparation and treatment of three-dimensional carbon structure carrier
Mixing 0.5-1.5 parts of zero-dimensional carbon material, 0.5-1.5 parts of one-dimensional carbon material, 0.5-1.5 parts of two-dimensional carbon material and 1-10 parts of carbon black according to parts by weight, dissolving in 20-100 parts of 10 wt% nitric acid solution, stirring for 5-10 hours at 60-80 ℃, washing and filtering the obtained mixture with water, drying for 5-10 hours at 60-80 ℃, and ball-milling the dried product for 1-2 hours at 250-400rpm to obtain three-dimensional carbon structure powder;
step 2: surface modification of three-dimensional carbon structure
Carrying out surface modification on the three-dimensional carbon powder in the step 1 by adopting a plasma enhanced chemical vapor deposition system, wherein the powder is contained in a rotatable ceramic crucible, the crucible is fixed by a rotating rod, and N is introduced2Or O2Gas, the radio frequency power is 150W, the heat preservation temperature is 100-;
and step 3: preparation of GaN nano material
Mixing 1 part of gallium oxide and 0.5-2 parts of activated carbon powder by mass to form uniform powder, placing the powder in a crucible of a microwave plasma chemical vapor deposition system, and preparing SiO with a surface sputtered Au catalyst in advance2the/Si substrate is arranged right above the crucible, and N of 5-10sccm is introduced2Maintaining the pressure of the cavity at 1-5Torr and the microwave power at 300W, growing for 20-60 minutes at the temperature of 850-3Stirring the mixture and a mixed solution of HF with the concentration of 50 wt% in a volume ratio of 2-10:1 for 30 minutes, and filtering to obtain a Ga-rich GaN nano material;
and 4, step 4: preparation of three-dimensional carbon structure loaded GaN material
Dispersing 1 part of the GaN nano material in the step 2 into 100 parts of ethanol by mass, performing ultrasonic treatment for 20 minutes, coating the mixture on the surface of a foamed nickel electrode, and placing 1 part of the surface modified three-dimensional carbon structure in the step 2, 20 parts of deionized water and ultrasonic dispersion for 30 minutes in an electrolytic cell for electrostatic adsorption;
and 5: three-dimensional carbon structure loaded GaN material post-treatment
Subjecting the product of step 5to 200sccm gas flow N2Placing the mixture in a muffle furnace at the temperature of 150-400 ℃ under protective gas for high-temperature annealing for 1to 3 hours, wherein the final product is the three-dimensional carbon junctionAnd forming a supported GaN catalyst.
2. The method according to claim 1, wherein the zero-dimensional carbon material is nanodiamond or fullerene; the one-dimensional carbon material is carbon nano tube and carbon nano fiber; the two-dimensional carbon material is graphene.
3. The method according to claim 1, wherein the rotatable crucible has a square hollow barrel-shaped structure, the thickness of the powder placed therein is not more than 2mm, and the rotation speed is 1-10 rpm.
4. The method of claim 1, wherein N is introduced in step 22Gas flow of 5-15sccm, cavity pressure of 10-20Pa, and introduction of O2The air flow is 20-30sccm, and the cavity pressure is 20-40Pa 5.
5. The method according to claim 1, wherein the anode of the electrolytic cell is a foam nickel electrode coated with Ga-rich GaN nanomaterial, the cathode is a carbon rod electrode, the external circuit voltage is 0.5-1V, the pressurizing time is 0.5-3 hours, and magnetic stirring is performed at 30-60rpm during electrostatic adsorption.
6. A catalyst prepared by the process according to claim 1.
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| US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
| US11633785B2 (en) | 2019-04-30 | 2023-04-25 | 6K Inc. | Mechanically alloyed powder feedstock |
| US11717886B2 (en) | 2019-11-18 | 2023-08-08 | 6K Inc. | Unique feedstocks for spherical powders and methods of manufacturing |
| US11839919B2 (en) | 2015-12-16 | 2023-12-12 | 6K Inc. | Spheroidal dehydrogenated metals and metal alloy particles |
| US11855278B2 (en) | 2020-06-25 | 2023-12-26 | 6K, Inc. | Microcomposite alloy structure |
| US11919071B2 (en) | 2020-10-30 | 2024-03-05 | 6K Inc. | Systems and methods for synthesis of spheroidized metal powders |
| US11963287B2 (en) | 2020-09-24 | 2024-04-16 | 6K Inc. | Systems, devices, and methods for starting plasma |
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