CN111834640A - Efficient and stable organic matter electrocatalytic oxidation catalyst and preparation method and application thereof - Google Patents
Efficient and stable organic matter electrocatalytic oxidation catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111834640A CN111834640A CN201910297551.1A CN201910297551A CN111834640A CN 111834640 A CN111834640 A CN 111834640A CN 201910297551 A CN201910297551 A CN 201910297551A CN 111834640 A CN111834640 A CN 111834640A
- Authority
- CN
- China
- Prior art keywords
- temperature
- catalyst
- oxidation catalyst
- electrocatalytic oxidation
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
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
- H01M4/9008—Organic or organo-metallic compounds
-
- 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
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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 an efficient and stable organic electro-catalytic oxidation catalyst, a preparation method and application thereof, wherein the molecular formula of the catalyst is HaMxRyYzN3Wherein M, R, Y is different transition metal, N is one element of oxygen, nitrogen, carbon, phosphorus and sulfur, a is 0-1, x + y + z is 1, and at most one value of x, y and z is 0. The organic electro-catalytic oxidation catalyst prepared by the method can avoid the use amount of noble metals, can realize the decomposition of small molecules by repeatedly utilizing waste heat generated by the fuel cell, and improves the comprehensive utilization efficiency of the fuel cell.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to an efficient and stable organic matter electrocatalytic oxidation catalyst, and a preparation method and application thereof.
Background
The hydrogen energy is the most ideal green energy in the 21 st century and has the characteristics of cleanness, high efficiency and high quality. C, H, N, O is smallThe molecular liquid organic matter is used as fuel, so that the problems of storage, transportation and safety of hydrogen in the hydrogen fuel cell can be solved. When the fuel cell works, C, H, N, O micromolecule liquid organic matters enter the flow channel from the anode flow field plate, then enter the anode catalyst through the anode diffusion layer, are oxidized under the action of the catalyst to release electrons and protons, and C, H, N, O micromolecule liquid organic matters after reaction are discharged from the anode. The electrons flow through an external circuit to do work, and the protons are transferred to the cathode through the solid electrolyte membrane. At the moment, oxygen or air enters the flow channel through the cathode flow field plate, enters the cathode catalyst layer through the cathode diffusion layer, and reacts with protons transferred from the anode in a combined manner to generate H2O, while consuming electrons transferred from the external circuit. Generation of H2O is discharged from the cathode in the form of water vapor or condensed water. At present, C, H, N, O the catalyst for electrocatalytic oxidation of small molecular organic matters is mainly made of noble metal materials such as Pd, Pt, Ru, Rh and the like, and is expensive and deficient in resources, so that the development of the C, H, N, O catalyst for electrocatalytic oxidation of small molecular organic matters with low cost and high efficiency becomes a research hotspot in the fields of energy, catalysis and materials.
Through long-term exploration and research, professor of Chenghangsong and teams thereof discover that a class of transition metal oxides has good addition/dehydrogenation performance and long cycle life, and the class of transition metal oxides becomes an electronic conductor after hydrogenation. The principle of electrocatalytic oxidation is similar to Hydrodeoxygenation (HDO), Hydrodenitrogenation (HDN) and Hydrodesulfurization (HDS), so that the material can be a high-efficiency and stable electrocatalytic oxidation catalyst.
Disclosure of Invention
The invention aims to provide an efficient and stable C, H, N, O micromolecular organic matter electrocatalytic oxidation catalyst, namely binary and ternary transition metals of oxygen, nitrogen, carbon, phosphorus and sulfide, aiming at the defects of the prior art, and a preparation method and application of the catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme: an efficient and stable organic electro-catalytic oxidation catalyst with molecular formula of HaMxRyYzN3Wherein said M, R, Y isIn the same transition metal, N is one element of oxygen, nitrogen, carbon, phosphorus and sulfur, a is 0-1, x + y + z is 1, and at most one of x, y and z is 0.
Further, the transition metal is vanadium, chromium, manganese, scandium, titanium, zirconium, niobium, molybdenum, rhodium, iron, cobalt, nickel, copper, zinc, osmium, tungsten, tantalum, iridium.
A preparation method of an organic electro-catalytic oxidation catalyst comprises the following steps:
(1) weighing two or three transition metal acid ammonium salts, stirring and mixing the transition metal acid ammonium salts and polyethylene glycol, heating and stirring the mixed solution, and dropwise adding 10% dilute nitric acid after stirring to adjust the pH value of the solution to 1-3;
(2) filling the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction; after the reaction is finished, carrying out suction filtration, washing the reactant to be neutral by using ultrapure water and ethanol, and fully drying at 60 ℃;
(3) calcining the dried product at high temperature for 1-5 h to obtain a metal oxide product;
(4) putting the product into a high-temperature high-pressure reaction kettle, and heating for reaction to obtain HaMxRyYzO3；
(6) The product H is reacted withaMxRyYzO3And NH3、H2/CH4、NaH2PO2Or calcining the sulfur powder at the high temperature of 350-700 ℃ for 2 hours to respectively prepare nitrogen, carbon, phosphorus and sulfide.
Further, in the step 1, the mass ratio of the metal acid ammonium salt to the polyethylene glycol is 1: 2.
Further, the reaction conditions of the mixed solution in the step 1 are that the temperature is controlled to be 50-70 ℃, and the stirring time is controlled to be 24-72 hours.
Further, the calcining temperature in the step 3 is 100-300 ℃.
Further, the hydrothermal reaction conditions in the step 2 are as follows: the temperature is 150-250 ℃, and the reaction time is 48-62 h.
Further, the reaction conditions in step 4 are as follows: the temperature is 150-500 ℃, the hydrogen pressure is 3MPa, and the reaction time is 2-5 h.
An application of a catalyst in electrocatalytic oxidation reaction of small molecular organic matters.
The organic electro-catalytic oxidation catalyst prepared by the method can avoid the use amount of noble metals, can realize the decomposition of small molecules by repeatedly utilizing waste heat generated by the fuel cell, and improves the comprehensive utilization efficiency of the fuel cell.
Drawings
FIG. 1 is a diagram showing the construction of a test system according to example 3.
FIG. 2 is a graph of I-V curves for the catalyst of example 3.
Detailed Description
In order to make the technical solutions better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only partial embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It is noted that the description and claims of the present application and the drawings described above
The terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
(1) Weighing 10g of cobalt nitrate and 10.8g of nickel nitrate, then stirring and mixing with polyethylene glycol, and stirring for 48h at 60 ℃; after stirring, dropwise adding dilute nitric acid with the mass ratio of 10% to adjust the pH of the solution to 2;
(2) filling the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 48 hours at the temperature of 200 ℃;
(3) after the hydrothermal reaction is finished, carrying out suction filtration, washing the reactant to be neutral by using ultrapure water and ethanol, and fully drying at 60 ℃;
(4) calcining the dried substance at high temperature for 5h to obtain a bimetal oxide product;
(5) putting the product into a high-temperature high-pressure reaction kettle, heating and reacting for 5 hours at the temperature of 150 ℃ and the hydrogen pressure of 3MPa to obtain H0.15Ni0.6Co0.4O3。
Example 2
(1) Weighing 10g of ammonium metatungstate, 10.8g of cobalt nitrate and 7.8g of nickel nitrate, then stirring and mixing with polyethylene glycol, and stirring for 48 hours at 60 ℃; after stirring, dropwise adding dilute nitric acid with the mass ratio of 10% to adjust the pH of the solution to 2;
(2) filling the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 48 hours at the temperature of 200 ℃;
(3) after the hydrothermal reaction is finished, carrying out suction filtration, washing the reactant to be neutral by using ultrapure water and ethanol, and fully drying at 60 ℃;
(4) calcining the dried substance at high temperature for 5h to obtain a trimetal oxide product;
(5) putting the product into a high-temperature high-pressure reaction kettle, heating and reacting for 5 hours at the temperature of 150 ℃ and the hydrogen pressure of 3MPa to obtain H0.15Ni0.29Co0.42W0.29O3。
Example 3
1.H0.15Ni0.29Co0.42W0.29O3Method for preparing catalyst solution
9.4mg of H are weighed out0.15Ni0.29Co0.42W0.29O3The catalyst (hereinafter referred to as catalyst) is dispersed in the mixed solution of 4mL of absolute ethyl alcohol and 1mL of deionized water, 1.6mg of conductive carbon black is added, and the mixture is subjected to ultrasonic treatment for 1 hour to uniformly disperse the catalyst.
2. Method for spraying electrode
(1) And (3) carbon paper treatment: cutting 2.0cm by 2.0cm carbon paper, and blowing off contaminants such as impurities on the carbon paper by using an ear washing ball.
(2) Spraying of an electrode: and (3) placing the carbon paper in the step (1) on a sample table of an electrostatic spraying instrument, pouring the uniformly dispersed catalyst solution into a syringe, placing the syringe in a sample chamber, and adjusting the spraying voltage and the spraying flow rate to enable the carbon paper to be sprayed in a mist shape and uniformly sprayed on each part of the carbon paper. And naturally drying the prepared carbon paper for subsequent testing. The spraying of the catalyst of the anode and the cathode is respectively carried out by the method.
3. Electrocatalytic oxidation performance test
(1) Building a single battery test system: the single cell testing system mainly comprises a single cell system, a fuel feeding and discharging system, an oxygen or air feeding and discharging system, a temperature control system, a software control system and the like, and the structure of the single cell testing system is shown in figure 1.
(2) Testing the performance of the fuel cell: the fuel cell testing platform software control system is used for enabling the electronic load to work in a constant current mode, the load current is continuously changed to measure the output voltage value of the single cell under different current densities, and then the I-V curve of the single cell can be obtained through data processing and drawing. In the experimental process, the battery is heated through a temperature control system, the cyclohexane micromolecule liquid organic matter is heated through an oven, and the I-V curve test is carried out when the cyclohexane micromolecule liquid organic matter is heated to a set value. Setting the fuel flow to be 2mL/min, the oxygen flow to be 0.6mL/min, setting the current initial value to be 0A, setting the current final value based on the output voltage value to be 0.1V, setting each group of load current to correspond to the test time to be about 3min, stabilizing for 10s under the current load, and taking one group of data every 2 s. Selecting current density as gradient change according to polarization curve characteristics, sequentially increasing load current value until the voltage of a single cell is reduced to about 0.1V, and finishing to obtain an I-V curve as shown in figure 2, wherein the output power of the battery is increased when the temperature of the catalyst is 80 ℃ and the power of the battery reaches 5mW cm-2(ii) a And after the experiment is finished, closing the test platform, discharging the cyclohexane micromolecule organic solution in the pipeline, introducing nitrogen into the cathode of the single cell for purging, and closing the nitrogen after the cell is cooled to room temperature.
Although the present invention has been described with reference to the preferred embodiments, the embodiments and drawings are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be defined by the claims of the present application.
Claims (9)
1. An efficient and stable organic matter electrocatalytic oxidation catalyst is characterized in that: the molecular formula of the catalyst is HaMxRyYzN3Wherein M, R, Y is different transition metal, N is one element of oxygen, nitrogen, carbon, phosphorus and sulfur, a is 0-1, x + y + z is 1, and at most one value of x, y and z is 0.
2. The efficient and stable electrocatalytic oxidation catalyst for organic matter as set forth in claim 1, wherein: the transition metal is vanadium, chromium, manganese, scandium, titanium, zirconium, niobium, molybdenum, rhodium, iron, cobalt, nickel, copper, zinc, osmium, tungsten, tantalum and iridium.
3. A method for preparing an electrocatalytic oxidation catalyst for organic matter according to claim 1 or 2, characterized by comprising the steps of:
(1) weighing two or three transition metal acid ammonium salts, stirring and mixing the transition metal acid ammonium salts and polyethylene glycol, heating and stirring the mixed solution, and dropwise adding 10% dilute nitric acid after stirring to adjust the pH value of the solution to 1-3;
(2) filling the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction; after the reaction is finished, carrying out suction filtration, washing the reactant to be neutral by using ultrapure water and ethanol, and fully drying at 60 ℃;
(3) calcining the dried product at high temperature for 1-5 h to obtain a metal oxide product;
(4) putting the product into a high-temperature high-pressure reaction kettle, and heating for reaction to obtain HaMxRyYzO3；
(6) The product H is reacted withaMxRyYzO3And NH3、H2/CH4、NaH2PO2Or calcining the sulfur powder at the high temperature of 350-700 ℃ for 2 hours to respectively prepare nitrogen, carbon, phosphorus and sulfide.
4. The production method according to claim 3, characterized in that: in the step 1, the mass ratio of the metal acid ammonium salt to the polyethylene glycol is 1: 2.
5. The production method according to claim 3, characterized in that: the reaction conditions of the mixed solution in the step 1 are that the temperature is controlled to be 50-70 ℃, and the stirring time is controlled to be 24-72 hours.
6. The production method according to claim 3, characterized in that: the hydrothermal reaction conditions in the step 2 are as follows: the temperature is 150-250 ℃, and the reaction time is 48-62 h.
7. The production method according to claim 3, characterized in that: the calcining temperature in the step 3 is 100-300 ℃.
8. The production method according to claim 3, characterized in that: the reaction conditions in the step 4 are as follows: the temperature is 150-500 ℃, the hydrogen pressure is 3MPa, and the reaction time is 2-5 h.
9. Use of a catalyst according to any one of claims 1 or 2 in electrocatalytic oxidation of small organic molecules.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910297551.1A CN111834640A (en) | 2019-04-15 | 2019-04-15 | Efficient and stable organic matter electrocatalytic oxidation catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910297551.1A CN111834640A (en) | 2019-04-15 | 2019-04-15 | Efficient and stable organic matter electrocatalytic oxidation catalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111834640A true CN111834640A (en) | 2020-10-27 |
Family
ID=72914538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910297551.1A Pending CN111834640A (en) | 2019-04-15 | 2019-04-15 | Efficient and stable organic matter electrocatalytic oxidation catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111834640A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107482232A (en) * | 2017-08-25 | 2017-12-15 | 河南师范大学 | A kind of fuel cell oxygen reduction electrocatalyst phosphorus, the preparation method of nitrogen co-doped carbon material |
| CN107519879A (en) * | 2017-09-01 | 2017-12-29 | 武汉氢阳能源有限公司 | A kind of binary, ternary transition metal hydride and its preparation method and application |
-
2019
- 2019-04-15 CN CN201910297551.1A patent/CN111834640A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107482232A (en) * | 2017-08-25 | 2017-12-15 | 河南师范大学 | A kind of fuel cell oxygen reduction electrocatalyst phosphorus, the preparation method of nitrogen co-doped carbon material |
| CN107519879A (en) * | 2017-09-01 | 2017-12-29 | 武汉氢阳能源有限公司 | A kind of binary, ternary transition metal hydride and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Song et al. | Direct methanol fuel cells: The effect of electrode fabrication procedure on MEAs structural properties and cell performance | |
| CN109713321A (en) | A kind of adjustable membrane electrode of pore structure and preparation method thereof | |
| JP6275730B2 (en) | Non-PGM catalyst for thermal decomposition multi-complex compound system ORR | |
| CN110611105B (en) | Preparation method of ORR catalyst | |
| CN104218250A (en) | PtM/C electrocatalyst for fuel cell and preparation method of PtM/C electrocatalyst for fuel cell | |
| CN113277573B (en) | PEM (proton exchange membrane) electrolyzed water anode catalyst and preparation method thereof | |
| CN102104157A (en) | Preparation method for carbon dry gel | |
| KR101148830B1 (en) | Supported catalyst for fuel cell, manufacturing method thereof, and fuel cell using the same | |
| Wang et al. | Formic acid electrooxidation catalyzed by Pd/SmOx-C hybrid catalyst in fuel cells | |
| KR101327894B1 (en) | Method for preparing platinum-cobalt-based electrocatalysts for fuel cells | |
| Lobato et al. | Study of different bimetallic anodic catalysts supported on carbon for a high temperature polybenzimidazole-based direct ethanol fuel cell | |
| CN110729489B (en) | Alkaline fuel cell and preparation method of molybdenum-nickel alloy nano material | |
| CN111834642B (en) | Organic matter electrocatalytic oxidation catalyst and preparation method and application thereof | |
| CN109950558B (en) | Preparation method and application of efficient and stable bifunctional catalyst | |
| CN111640953A (en) | Air electrode catalyst of aluminum-air battery and preparation method thereof | |
| CN111834640A (en) | Efficient and stable organic matter electrocatalytic oxidation catalyst and preparation method and application thereof | |
| CN101414684A (en) | Electric catalyst for fuel battery cathode with proton exchange film and preparation thereof | |
| CN109167091A (en) | A method of membrane electrode is prepared using carbon periosteum as carrier | |
| CN112310421B (en) | Electrode for fuel cell, membrane electrode assembly, chip, catalyst layer, catalyst dispersion, and method for producing same | |
| CN109301266B (en) | Oxygen reduction catalyst, preparation method and application thereof | |
| US20240055641A1 (en) | Proton conductor and manufacturing method thereof | |
| KR102632222B1 (en) | Electrode for polymer electrolyte membrane fuel cell comprising antioxidant and membrane-electrode assembly comprising the same | |
| KR102468470B1 (en) | Method for producing a platinum-based alloy catalyst | |
| Nakamura et al. | Nonprecious metal electrocatalysts for alkaline fuel cells | |
| KR20110032395A (en) | Method for preparing cathode ptfe/c catalysts for fuel cells having an improved activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201027 |