CN112921352A - Preparation method of cobalt phosphide nano-particles - Google Patents
Preparation method of cobalt phosphide nano-particles Download PDFInfo
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- CN112921352A CN112921352A CN202110082442.5A CN202110082442A CN112921352A CN 112921352 A CN112921352 A CN 112921352A CN 202110082442 A CN202110082442 A CN 202110082442A CN 112921352 A CN112921352 A CN 112921352A
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- carbon cloth
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of cobalt phosphide nano particles, which takes sodium hypophosphite as a phosphorus source at the temperature of 300 ℃ by a low-temperature phosphorization method to successfully convert an elemental cobalt nano particle thin film which is tightly grown on carbon cloth into cobalt phosphide nano particles (CoPNPS/CC). CoPNPS/CC shows excellent activity and stability for catalyzing hydrogen evolution. CoP particles and CoP and carbon cloth fibers are tightly connected together, which is beneficial to the mutual transmission of electrons so as to accelerate the decomposition efficiency of water. In addition, the flexibility of the carbon cloth enables CoPNPS/CC to grow on the surface of the carbon cloth tightly to form a uniform nano particle film, and in addition, the conductivity of the carbon cloth is favorable for electrons to flow freely between the CoPNPs/CC so as to accelerate the reaction; the three-dimensional structure of the carbon cloth is beneficial to the generated hydrogen to be quickly separated out, and the covering of the active sites caused by the accumulation of bubbles on the surface of the catalyst is reduced.
Description
Technical Field
The invention relates to the technical field of preparation of hydrogen evolution catalysts, in particular to a preparation method of cobalt phosphide nanoparticles.
Background
The water electrolysis is one of the simplest methods for preparing high-purity hydrogen on a large scale, and the use of an electrocatalyst can obviously reduce the additional energy consumed by the water electrolysis. Since water electrolysis apparatuses based on proton exchange membrane technology need to be operated in strongly acidic electrolytes, it is essential to develop a hydrogen evolution catalyst that can be stably present in acidic electrolytes. At present, platinum group nano materials are still the catalysts with the highest catalytic performance in the acid electrolyte, but the high price caused by the scarcity of the platinum group nano materials severely restricts the application of the platinum group nano materials in water electrolysis and hydrogen evolution. Therefore, the development of the catalyst with high efficiency and low cost can effectively reduce the cost of hydrogen evolution. Initially, nickel-based materials were applied to hydrogen evolution catalysts under acidic conditions, and although nickel-based catalysts showed a certain catalytic activity, the materials were easily corroded in an acidic electrolyte and could not be used stably for a long period of time. After decades of intense research efforts, researchers have developed many stable and efficient acidic hydrogen evolution low-cost catalysts, including transition metal sulfides, carbides, nitrides, phosphides, and the like. Among a plurality of transition metal nano materials, the cobalt-based nano material has good application prospect. Phosphide is a high-efficiency hydrogen evolution catalyst developed in recent years, and a plurality of researchers try to prepare cobalt phosphide nano materials in consideration of the special electronic structure of cobalt element. For example, Schaak group prepared uniformly dispersed cobalt phosphide nanoparticles by heating and refluxing with trioctylphosphine as a phosphorus source with the aid of an organic reagent. In addition, the Sunxiaping group prepared carbon nanotube-supported phosphide-diamond nanoparticles by a low-temperature phosphating method and demonstrated good catalytic hydrogen evolution activity. The phosphorized diamond nano particles prepared by the method all need to use a polymer adhesive to fix the polymer adhesive on a conductive electrode to prepare a cathode of electrolyzed water for catalyzing hydrogen evolution, and the adhesive with relatively weak conductivity can possibly shield active sites to reduce mass transfer efficiency so as to influence the activity of the catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of cobalt phosphide nanoparticles, which solves the problem that a relatively weak-conductivity adhesive possibly shields active sites to reduce mass transfer efficiency so as to influence the activity of a catalyst.
In order to achieve the purpose, the invention is realized by the following technical scheme: a preparation method of cobalt phosphide nanoparticles specifically comprises the following steps:
s1, adding cobalt chloride hexahydrate and polyvinylpyrrolidone into N, N-dimethylformamide, and heating and stirring at 80 ℃ until the cobalt chloride hexahydrate and the polyvinylpyrrolidone are dissolved to obtain a viscous solution;
s2, soaking the carbon cloth into the viscous solution obtained in the step S1, and then drying the carbon cloth attached with the cobalt precursor at 80 ℃;
s3, putting the carbon cloth in a tubular furnace in a protective gas atmosphere, raising the temperature to a certain temperature at a speed of 10 ℃/min, and continuously maintaining for 2h to obtain simple substance cobalt nanoparticles (CoNPs/CC) uniformly growing on the surface of the carbon cloth;
s4, then, placing CoNPs/CC and a phosphorus source in a tubular furnace in a protective gas atmosphere, raising the temperature to a certain temperature at the speed of 2 ℃/min, and continuously maintaining for 2 h;
s5, finally, obtaining the cobalt phosphide nano particles (CoPNPS/CC) after the tube furnace is naturally cooled.
Preferably, the shielding gas in steps S4 and S3 includes one or more of nitrogen, helium, neon and argon.
Preferably, the certain temperature in step S3 is 600 ℃.
Preferably, the phosphorus source in step S4 is sodium hypophosphite.
Preferably, the certain temperature in step S4 is 300 ℃.
Advantageous effects
The invention provides a preparation method of cobalt phosphide nanoparticles. Compared with the prior art, the method has the following beneficial effects: according to the preparation method of the cobalt phosphide nano-particle, the Co NPs/CC is successfully converted into the CoP NPs/CC by taking sodium hypophosphite as a phosphorus source and adopting a low-temperature phosphating method at 300 ℃. As a self-supporting membrane electrode, CoP NPs/CC shows excellent activity and stability for catalyzing hydrogen evolution. Besides good catalytic activity of the CoP NPs, the special structure of the CoP NPs/CC also contributes greatly to the overall catalytic performance of the electrode. Firstly, CoP particles and CoP and carbon cloth fibers are tightly connected, and the interconnected structure is beneficial to the mutual transmission of electrons in the electrochemical test process so as to accelerate the decomposition efficiency of water. In addition, the carbon cloth substrate mainly has the following two functions: 1) the flexibility of the carbon cloth enables CoP NPs/CC to grow on the surface of the carbon cloth tightly to form a uniform nano particle film, and in addition, the conductivity of the carbon cloth is favorable for electrons to flow freely between the CoP NPs/CC so as to accelerate the reaction; 2) the three-dimensional structure of the carbon cloth is beneficial to the generated hydrogen to be quickly separated out, and the covering of the active sites caused by the accumulation of bubbles on the surface of the catalyst is reduced.
Drawings
FIG. 1 is a scanning electron microscope image of the Co NPs/CC and CoPNPs/CC of the present invention at different magnifications;
FIG. 2 is an X-ray diffraction pattern of Co NPs/CC and CoPNPs/CC of the present invention;
FIG. 3 is the total spectrum of X-ray photoelectron spectroscopy of CoPNPs/CC of the present invention;
FIG. 4 is an energy dispersive element spectrum of CoPNPs/CC according to the present invention;
FIG. 5 is a polarization curve diagram of CoP NPs/CC electrodes loaded by different CoPNPs according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 invention.
Referring to fig. 1-5, the embodiment of the present invention provides three technical solutions: a preparation method of cobalt phosphide nanoparticles specifically comprises the following steps:
example 1
S1, adding 6.3g of cobalt chloride hexahydrate and 1g of polyvinylpyrrolidone into 8ml of N, N-dimethylformamide, and heating and stirring at 80 ℃ until the cobalt chloride hexahydrate and the polyvinylpyrrolidone are dissolved to obtain a viscous solution;
s2, soaking a carbon cloth with the thickness of 1cm multiplied by 1cm into the viscous solution in the step S1, and then drying the carbon cloth attached with the cobalt precursor at 80 ℃;
s3, putting the carbon cloth in a tube furnace in a protective gas atmosphere, raising the temperature to 600 ℃ at a speed of 10 ℃/min, and continuously maintaining for 2h to obtain simple substance cobalt nanoparticles (CoNPs/CC) uniformly growing on the surface of the carbon cloth;
s4, then, placing CoNPs/CC and sodium hypophosphite in a tubular furnace in a protective gas atmosphere, raising the temperature to 300 ℃ at the speed of 2 ℃/min, and continuously maintaining for 2 h;
s5, finally, obtaining the cobalt phosphide nano-particles (CoP NPS/CC) after the tube furnace is naturally cooled.
Example 2
S1, adding 4g of cobalt chloride hexahydrate and 0.5g of polyvinylpyrrolidone into 5ml of N, N-dimethylformamide, and heating and stirring at 80 ℃ until the cobalt chloride hexahydrate and the polyvinylpyrrolidone are dissolved to obtain a viscous solution;
s2, soaking a carbon cloth with the thickness of 1cm multiplied by 1cm into the viscous solution in the step S1, and then drying the carbon cloth attached with the cobalt precursor at 80 ℃;
s3, putting the carbon cloth in a tube furnace in a protective gas atmosphere, raising the temperature to 600 ℃ at a speed of 10 ℃/min, and continuously maintaining for 2h to obtain simple substance cobalt nanoparticles (CoNPs/CC) uniformly growing on the surface of the carbon cloth;
s4, then, placing CoNPs/CC and sodium hypophosphite in a tubular furnace in a protective gas atmosphere, raising the temperature to 300 ℃ at the speed of 2 ℃/min, and continuously maintaining for 2 h;
s5, finally, obtaining the cobalt phosphide nano-particles (CoP NPS/CC) after the tube furnace is naturally cooled.
Example 3
S1, adding 2.4g of cobalt chloride hexahydrate and 0.2g of polyvinylpyrrolidone into 4ml of N, N-dimethylformamide, and heating and stirring at 80 ℃ until the cobalt chloride hexahydrate and the polyvinylpyrrolidone are dissolved to obtain a viscous solution;
s2, soaking a carbon cloth with the thickness of 1cm multiplied by 1cm into the viscous solution in the step S1, and then drying the carbon cloth attached with the cobalt precursor at 80 ℃;
s3, putting the carbon cloth in a tube furnace in a protective gas atmosphere, raising the temperature to 600 ℃ at a speed of 10 ℃/min, and continuously maintaining for 2h to obtain simple substance cobalt nanoparticles (CoNPs/CC) uniformly growing on the surface of the carbon cloth;
s4, then, placing CoNPs/CC and sodium hypophosphite in a tubular furnace in a protective gas atmosphere, raising the temperature to 300 ℃ at the speed of 2 ℃/min, and continuously maintaining for 2 h;
s5, finally, obtaining the cobalt phosphide nano-particles (CoP NPS/CC) after the tube furnace is naturally cooled.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A method for preparing cobalt phosphide nanoparticles is characterized in that: the method specifically comprises the following steps:
s1, adding cobalt chloride hexahydrate and polyvinylpyrrolidone into N, N-dimethylformamide, and heating and stirring at 80 ℃ until the cobalt chloride hexahydrate and the polyvinylpyrrolidone are dissolved to obtain a viscous solution;
s2, soaking the carbon cloth into the viscous solution obtained in the step S1, and then drying the carbon cloth attached with the cobalt precursor at 80 ℃;
s3, putting the carbon cloth in a tubular furnace in a protective gas atmosphere, raising the temperature to a certain temperature at a speed of 10 ℃/min, and continuously maintaining for 2h to obtain simple substance cobalt nanoparticles (CoNPs/CC) uniformly growing on the surface of the carbon cloth;
s4, then, placing CoNPs/CC and a phosphorus source in a tubular furnace in a protective gas atmosphere, raising the temperature to a certain temperature at the speed of 2 ℃/min, and continuously maintaining for 2 h;
s5, finally, obtaining the cobalt phosphide nano-particles (CoP NPS/CC) after the tube furnace is naturally cooled.
2. The PVD coating method for the cutting edge of a circle shear blade sheared by a high-strength steel plate as claimed in claim 1, is characterized in that: the shielding gas in the steps S4 and S3 comprises one or more of nitrogen, helium, neon and argon.
3. The method for preparing cobalt phosphide nanoparticles according to claim 1, wherein the method comprises the following steps: the certain temperature in step S3 is 600 ℃.
4. The method for preparing cobalt phosphide nanoparticles according to claim 1, wherein the method comprises the following steps: the phosphorus source in step S4 is sodium hypophosphite.
5. The method for preparing cobalt phosphide nanoparticles according to claim 1, wherein the method comprises the following steps: the constant temperature in step S4 is 300 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114497574A (en) * | 2021-12-02 | 2022-05-13 | 太原理工大学 | Self-supporting transition metal phosphide-doped porous carbon membrane hydrogen evolution electro-catalytic material |
Citations (3)
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| CN104941674A (en) * | 2015-06-18 | 2015-09-30 | 西南大学 | Catalyst for loading cobalt phosphide on activated carbon as well as preparation and application of catalyst |
| CN105803580A (en) * | 2016-04-15 | 2016-07-27 | 东华大学 | Preparation method of cobalt phosphide hollow nano-fiber material |
| CN111804317A (en) * | 2020-06-22 | 2020-10-23 | 肇庆市华师大光电产业研究院 | Method for directly growing high-density cobalt phosphide nano-wire electrocatalyst on conductive substrate and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941674A (en) * | 2015-06-18 | 2015-09-30 | 西南大学 | Catalyst for loading cobalt phosphide on activated carbon as well as preparation and application of catalyst |
| CN105803580A (en) * | 2016-04-15 | 2016-07-27 | 东华大学 | Preparation method of cobalt phosphide hollow nano-fiber material |
| CN111804317A (en) * | 2020-06-22 | 2020-10-23 | 肇庆市华师大光电产业研究院 | Method for directly growing high-density cobalt phosphide nano-wire electrocatalyst on conductive substrate and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| QUN LI等: ""Cobalt phosphide nanoparticles film growth on carbon cloth：A high-performance cathode for electrochemical hydrogen evolution"，Qun Li等，international journal of hydrogen energy，第39卷，第16806 -16811页，20140910", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114497574A (en) * | 2021-12-02 | 2022-05-13 | 太原理工大学 | Self-supporting transition metal phosphide-doped porous carbon membrane hydrogen evolution electro-catalytic material |
| CN114497574B (en) * | 2021-12-02 | 2024-02-13 | 太原理工大学 | Self-supporting transition metal phosphide doped porous carbon film hydrogen evolution electrocatalytic material |
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