CN113755858B - Preparation of porous carbon-supported metal molybdenum compound and application of porous carbon-supported metal molybdenum compound in hydrogen evolution - Google Patents
Preparation of porous carbon-supported metal molybdenum compound and application of porous carbon-supported metal molybdenum compound in hydrogen evolution Download PDFInfo
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Abstract
The invention relates to preparation of a porous carbon-supported metal molybdenum compound and application of hydrogen evolution, which comprises the following steps: the method comprises the following steps: carrying out ball milling and mixing on tribenzoic acid, 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone, and sintering in the air at 300-500 ℃ for 3-5h to prepare a carbon-supported molybdenum compound; step two: transferring the carbon-carried molybdenum compound into a nitrogen atmosphere furnace, carbonizing at 700-900 ℃ to obtain porous carbon-loaded molybdenum carbide; or, mixing the carbon-supported molybdenum compound and the ammonium hypophosphite compound, and carbonizing at 600-800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum phosphide; or mixing the carbon-supported molybdenum compound with thioacetamide, and carbonizing at 600-800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum disulfide. The method is simple to prepare, is suitable for preparing all metal molybdenum compounds, and has a good application prospect in the hydrogen evolution direction.
Description
Technical Field
The invention relates to preparation of a porous carbon-supported metal molybdenum compound and application of hydrogen evolution, belonging to the field of molybdenum compounds.
Background
The molybdenum metal has excellent performance and can be applied to the fields of chemical industry, steel, biology, electronics, medicine, agriculture and the like. With the development of the industrialization level, the application field of molybdenum is continuously expanded. Among them, the molybdenum-based catalyst has been widely used in the industrial fields of petroleum, medicine, etc., such as petroleum hydrodesulfurization, catalytic reforming, and acrylonitrile synthesis.
Hydrogen production by water electrolysis is of great interest due to its efficient and environmentally friendly operation, however, one of the most serious problems with water electrolysis techniques under alkaline conditions is the relatively slow Hydrogen Evolution Reaction (HER), even with Pt as a catalyst. Therefore, the development of basic HER catalysts with excellent activity, high stability and low price to replace expensive commercial Pt/C is one of the most urgent tasks in the field of hydrogen energy technology. Molybdenum carbide (Mo) in catalyst 2 C) Due to its platinum-like electronic configuration, good electronic conductivity and excellent resistance to water dissociationThe catalytic activity thus showed similar HER activity as the Pt catalyst under alkaline conditions. For further improvement of Mo-based 2 C catalyst HER activity, the prior art discloses doping molybdenum carbide nanorods with phosphorus to optimize Mo 2 Hydrogen adsorption energy of C to achieve an overpotential of 89 mV. However, mo 2 The synthesis of C usually requires a high temperature carbonization process, resulting in Mo 2 The small specific surface area of the C-based catalyst limits Mo due to the relatively few active sites exposed 2 HER activity of C-based catalysts.
Based on the shortcomings of the prior art, there is a need for improvements in existing molybdenum carbide-based catalysts.
Disclosure of Invention
The object of the present invention is to overcome the drawbacks of the prior art, provides a preparation method of the porous carbon-supported metal molybdenum compound and simultaneously provides application of the porous carbon-supported metal molybdenum compound.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
subject of the technology 1
A method for preparing a porous carbon-supported metal molybdenum compound, comprising the steps of:
the method comprises the following steps: pretreatment of
Carrying out ball milling and mixing on tribenzoic acid, 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone, and sintering in the air at 300-500 ℃ for 3-5h to prepare a carbon-supported molybdenum compound;
step (ii) of II, secondly: charring treatment
Transferring the carbon-loaded molybdenum compound into a nitrogen atmosphere furnace, and carbonizing at 700-900 ℃ to obtain porous carbon-loaded molybdenum carbide;
or, mixing the carbon-supported molybdenum compound and the ammonium hypophosphite compound, and carbonizing at 600-800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum phosphide;
or mixing the carbon-supported molybdenum compound with thioacetamide, and carbonizing at 600-800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum disulfide.
As some of the present invention in a preferred embodiment of the process according to the invention, the molybdenum salt is selected from at least one of ammonium molybdate, sodium molybdate, potassium molybdate, molybdenum pentachloride and molybdenum carbonate.
As some preferred embodiments of the present invention, the substance ratio of the tribenzoic acid, 2-aminobenzoic acid, ammonium chloride and molybdenum salt is (1-3): (0.2-1): (1-5): (0.1-1.5).
As some preferred embodiments of the present invention, the polyvinylpyrrolidone in step one is used in an amount of 5 to 20 wt% of the molybdenum salt.
As some preferred embodiments of the invention, the amount of ammonium hypophosphite compound used in step two is 50 to 200 wt% of the molybdenum on carbon compound.
As some preferred embodiments of the present invention, the amount of thioacetamide used in step two is 10 to 100 wt% of the molybdenum on carbon compound.
As some of the preferred embodiments of the present invention, in the first step, the heating rate is 3-10 ℃/min.
As some preferred embodiments of the invention, the method specifically comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 1:1:5:0.1 of tribenzoic acid, 2-aminobenzoic acid, ammonium chloride and molybdenum salt are mixed with polyvinylpyrrolidone by ball milling, sintering the mixture for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the consumption of the polyvinylpyrrolidone is 10 wt percent of the molybdenum salt;
step two: charring treatment
Transferring the carbon-loaded molybdenum compound into a nitrogen atmosphere furnace, and carbonizing at 800 ℃ to obtain porous carbon-loaded molybdenum carbide;
or, after mixing the carbon-supported molybdenum compound and the ammonium hypophosphite compound, carbonizing the mixture in a nitrogen atmosphere furnace at 800 ℃, thus preparing the porous carbon-supported molybdenum phosphide, wherein the dosage of the ammonium hypophosphite compound is 100 wt percent of the carbon-supported molybdenum compound;
or mixing the carbon-supported molybdenum compound with thioacetamide, and carbonizing at 800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum disulfide, wherein the dosage of the thioacetamide is 50 wt percent of the carbon-supported molybdenum compound.
Subject matter two
In another aspect, the present invention provides a technical subject matter as described above the porous obtained by the method of (1) a carbon-supported metal molybdenum compound.
Subject three
In another aspect, the invention provides an application of the porous carbon-supported metal molybdenum compound of the second technical subject in the electrocatalytic hydrogen evolution direction.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
the preparation method of the porous carbon-supported molybdenum compound is simple in steps, raw materials in the preparation process are low in price, and the porous carbon-supported molybdenum carbide, the porous carbon-supported molybdenum phosphide and the porous carbon-supported molybdenum disulfide prepared by the preparation method are suitable for preparing all molybdenum compounds, show good hydrogen evolution performance in 1.0M KOH of alkaline electrolyte, and the lowest overpotential is only 75 mV.
The air sintering in the preparation process of the invention is used for initiating the initial polymerization of the material, and meanwhile, the oxygen in the air has the oxidation effect and can etch the material to form defects which are beneficial to the loading of the molybdenum compound; high-temperature carbonization in nitrogen is beneficial to forming of porous materials, and molybdenum carbide is formed at the same time, so that the conductivity of the materials is improved, and the electron transfer is facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a TEM image of a porous carbon-supported molybdenum carbide prepared in example 1;
FIG. 2 is a TEM image of the porous carbon-supported molybdenum phosphide prepared in example 2;
FIG. 3 is a TEM image of porous carbon-supported molybdenum disulfide prepared in example 3;
FIG. 4 is a defect signal diagram of example 1;
FIG. 5 is a defect signal diagram of example 2;
FIG. 6 is a defect signal diagram of example 3;
FIG. 7 is a comparative graph of the catalytic hydrogen production performance of the porous carbon supported molybdenum carbide prepared in example 1, comparative example 2 and comparative example 3 of the present invention, wherein a. Comparative example 1; b. comparative example 2; c. comparative example 3; d. example 1;
FIG. 8 is a graph comparing the hydrogen production performance of the porous carbon supported molybdenum phosphide prepared in example 2, comparative example 4, comparative example 5 and comparative example 6 of the present invention by catalysis, wherein a is compared with that of comparative example 4; b. comparative example 5; c. comparative example 6; d. example 2;
FIG. 9 is a graph comparing the catalytic hydrogen production performance of porous carbon supported molybdenum disulfide prepared in example 3, comparative example 7, comparative example 8 and comparative example 9 of the present invention, wherein a. Comparative example 7; b. comparative example 8; c. comparative example 9; d. example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail and fully with reference to the following embodiments.
Example 1
The preparation method of the porous carbon-supported molybdenum carbide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 1:1:5:0.1 of tribenzoic acid, 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone are subjected to ball milling and mixing, and are sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 10 wt% of the molybdenum salt, and the first step is at a heating rate of 8 ℃/min;
step two: charring treatment
And transferring the carbon-loaded molybdenum compound into a nitrogen atmosphere furnace, and carbonizing at 800 ℃ to obtain the porous carbon-loaded molybdenum carbide.
Example 2
The preparation method of the porous carbon-supported molybdenum phosphide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 1:1:5:0.1 of tribenzoic acid, 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone are subjected to ball milling and mixing, and are sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 10 wt% of the molybdenum salt, and the first step is at a heating rate of 8 ℃/min;
step two: charring treatment
And mixing the carbon-supported molybdenum compound and an ammonium hypophosphite compound, and carbonizing at 800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum phosphide, wherein the using amount of the ammonium hypophosphite compound is 100 wt percent of the carbon-supported molybdenum compound.
Example 3
The preparation method of the porous carbon-supported molybdenum disulfide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the substances is 1:1:5:0.1 of tribenzoic acid, 2-aminobenzoic acid, ammonium chloride and molybdenum salt are mixed with polyvinylpyrrolidone by ball milling, sintered for 5 hours at 500 ℃ in air, preparing the carbon-supported molybdenum compound, wherein the dosage of polyvinylpyrrolidone is 10 wt% of molybdenum salt, and the first step is at a heating rate of 8 ℃/min;
step two: charring treatment
And mixing the carbon-supported molybdenum compound with thioacetamide, and carbonizing at 800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum disulfide, wherein the dosage of the thioacetamide is 50 wt percent of the carbon-supported molybdenum compound.
Example 4
The preparation method of the porous carbon-supported molybdenum carbide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 3:0.2:1:1.5, carrying out ball milling and mixing on tribenzoic acid, 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone, sintering for 3h at 300 ℃ in the air, and preparing the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 5 wt% of the molybdenum salt, and the first step is carried out at the heating rate of 10 ℃/min;
step two: charring treatment
And transferring the carbon-loaded molybdenum compound into a nitrogen atmosphere furnace, and carbonizing at 900 ℃ to obtain the porous carbon-loaded molybdenum carbide.
Example 5
The preparation method of the porous carbon-supported molybdenum phosphide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 2:0.5:3:1, carrying out ball milling and mixing on tribenzoic acid, 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone, sintering for 4 hours at 400 ℃ in the air, and preparing the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 10 wt% of the molybdenum salt, and the first step is carried out at the heating rate of 3 ℃/min;
step two: carbonizing treatment
And mixing the carbon-supported molybdenum compound and an ammonium hypophosphite compound, and carbonizing at 600 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum phosphide, wherein the using amount of the ammonium hypophosphite compound is 200 wt percent of the carbon-supported molybdenum compound.
Example 6
The preparation method of the porous carbon-supported molybdenum disulfide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 1:1:2:0.5 of tribenzoic acid, 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone are subjected to ball milling and mixing, and are sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 10 wt% of the molybdenum salt, and the first step is at the heating rate of 10 ℃/min;
step two: carbonizing treatment
And mixing the carbon-supported molybdenum compound with thioacetamide, and carbonizing at 700 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum disulfide, wherein the dosage of the thioacetamide is 100 wt percent of the carbon-supported molybdenum compound.
Comparative example 1
The preparation method of the porous carbon-supported molybdenum carbide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 2:5:0.1 of 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone are subjected to ball milling and mixing, and are sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 10 wt% of the molybdenum salt, and the first step is at a heating rate of 8 ℃/min;
step two: charring treatment
And transferring the carbon-loaded molybdenum compound into a nitrogen atmosphere furnace, and carbonizing at 800 ℃ to obtain the porous carbon-loaded molybdenum carbide.
Comparative example 2
The preparation method of the porous carbon-supported molybdenum carbide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 2:5:0.1 of tribenzoic acid, ammonium chloride and molybdenum salt are mixed with polyvinylpyrrolidone by ball milling, and the mixture is sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 10 wt percent of the molybdenum salt, and the first step is that the heating rate is 8 ℃/min;
step two: charring treatment
And transferring the carbon-loaded molybdenum compound into a nitrogen atmosphere furnace, and carbonizing at 800 ℃ to obtain the porous carbon-loaded molybdenum carbide.
Comparative example 3
The preparation method of the porous carbon-supported molybdenum carbide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 5:0.1 of ammonium chloride, molybdenum salt and polyvinylpyrrolidone are subjected to ball milling and mixing, and are sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 10 wt percent of the molybdenum salt, and the first step is that the heating rate is 8 ℃/min;
step two: charring treatment
And transferring the carbon-loaded molybdenum compound into a nitrogen atmosphere furnace, and carbonizing at 800 ℃ to obtain the porous carbon-loaded molybdenum carbide.
Comparative example 4
The preparation method of the porous carbon-supported molybdenum phosphide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 2:5:0.1 of 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone are subjected to ball milling and mixing, and are sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the consumption of the polyvinylpyrrolidone is 10 wt% of the molybdenum salt, and the first step is at the heating rate of 8 ℃/min;
step two: charring treatment
And mixing the carbon-supported molybdenum compound and the ammonium hypophosphite compound, and carbonizing at 800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum phosphide, wherein the dosage of the ammonium hypophosphite compound is 100 wt percent of the carbon-supported molybdenum compound.
Comparative example 5
The preparation method of the porous carbon-supported molybdenum phosphide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 2:5:0.1 of tribenzoic acid, ammonium chloride and molybdenum salt are mixed with polyvinylpyrrolidone by ball milling, and the mixture is sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 10 wt percent of the molybdenum salt, and the first step of the temperature rise rate is 8 ℃/min;
step two: charring treatment
And mixing the carbon-supported molybdenum compound and an ammonium hypophosphite compound, and carbonizing at 800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum phosphide, wherein the using amount of the ammonium hypophosphite compound is 100 wt percent of the carbon-supported molybdenum compound.
Comparative example 6
The preparation method of the porous carbon-supported molybdenum phosphide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 5:0.1 of ammonium chloride, molybdenum salt and polyvinylpyrrolidone are subjected to ball milling and mixing, and are sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the consumption of the polyvinylpyrrolidone is 10 wt percent of the molybdenum salt, and the first step is carried out at the heating rate of 8 ℃/min;
step two: charring treatment
And mixing the carbon-supported molybdenum compound and the ammonium hypophosphite compound, and carbonizing at 800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum phosphide, wherein the dosage of the ammonium hypophosphite compound is 100 wt percent of the carbon-supported molybdenum compound.
Comparative example 7
The preparation method of the porous carbon-supported molybdenum disulfide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 2:5:0.1 of 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone are subjected to ball milling and mixing, and are sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 10 wt% of the molybdenum salt, and the first step is at a heating rate of 8 ℃/min;
step two: carbonizing treatment
And mixing the carbon-supported molybdenum compound with thioacetamide, and carbonizing at 800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum disulfide, wherein the dosage of the thioacetamide is 50 wt percent of the carbon-supported molybdenum compound.
Comparative example 8
The preparation method of the porous carbon-supported molybdenum disulfide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 1:1:5:0.1 of tribenzoic acid, ammonium chloride and molybdenum salt are mixed with polyvinylpyrrolidone by ball milling, and the mixture is sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 10 wt percent of the molybdenum salt, and the first step of the temperature rise rate is 8 ℃/min;
step two: charring treatment
And mixing the carbon-supported molybdenum compound with thioacetamide, and carbonizing at 800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum disulfide, wherein the dosage of the thioacetamide is 50 wt percent of the carbon-supported molybdenum compound.
Comparative example 9
The preparation method of the porous carbon-supported molybdenum disulfide comprises the following steps:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 5:0.1 of ammonium chloride, molybdenum salt and polyvinylpyrrolidone are subjected to ball milling and mixing, and are sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the consumption of the polyvinylpyrrolidone is 10 wt percent of the molybdenum salt, and the first step is carried out at the heating rate of 8 ℃/min;
step two: charring treatment
And mixing the carbon-supported molybdenum compound with thioacetamide, and carbonizing at 800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum disulfide, wherein the dosage of the thioacetamide is 50 wt percent of the carbon-supported molybdenum compound.
TEM characterization was performed on the porous carbon-supported molybdenum carbide obtained in example 1, the porous carbon-supported molybdenum phosphide obtained in example 2, and the porous carbon-supported molybdenum disulfide obtained in example 3, as shown in fig. 1-3, in particular, from which the pore structure is clearly seen.
The specific surface areas of the porous carbon-supported metal molybdenum compounds prepared in examples 1 to 6 and comparative examples 1 to 9 were measured, and the current density in an alkaline electrolyte solution of 1.0M KOH was measured at 10mA cm -2 The results are shown in table 1 below.
TABLE 1
Effect example 1
Experiments show that the 2-aminobenzoic acid is partially replaced by tribenzoic acid to prepare the porous carbon-supported metal molybdenum compound, so that the catalytic performance of the porous carbon-supported metal molybdenum compound material is greatly improved, and better catalytic kinetics are achieved, and the comparison of the catalytic hydrogen production performance of the materials obtained in examples 1-3 and comparative examples 1-9 is specifically shown in fig. 7, 8 and 9.
Test example 1 examination of raw materials
In order to clarify the influence of the raw materials on the performance effect of the invention, the applicant examined the raw materials, and measuring the hydrogen production performance of the obtained material, and measuring the current density of each material in 1.0M KOH and 10mA cm -2 The amounts of other raw materials and the preparation methods of the test examples 1-1 to 1-13 were the same as those of example 1, and are shown in Table 2.
Table 2 examination results of raw materials
Test example 2 pairs investigation of temperature
In order to clarify the influence of temperature on the performance effect of the invention, the applicant examined the temperature, and measuring the hydrogen production performance of the obtained material, and measuring the current density of each material in 1.0M KOH and 10mA cm -2 The amounts of other raw materials and the preparation methods of test examples 2-1 to 2-6 were the same as those of example 1, and are shown in Table 3.
TABLE 3 examination of temperature
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. The preparation method of the porous carbon-supported metal molybdenum compound is characterized by comprising the following steps:
the method comprises the following steps: pretreatment of
Carrying out ball milling and mixing on tribenzoic acid, 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone, and sintering in the air at 300-500 ℃ for 3-5h to prepare a carbon-supported molybdenum compound;
step two: charring treatment
Mixing a carbon-supported molybdenum compound and an ammonium hypophosphite compound, and carbonizing at 600-800 ℃ in a nitrogen atmosphere furnace to obtain porous carbon-supported molybdenum phosphide;
or, mixing the carbon-supported molybdenum compound with thioacetamide, and carbonizing at 600-800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum disulfide;
the mass ratio of the tribenzoic acid, the 2-aminobenzoic acid, the ammonium chloride and the molybdenum salt is (1-3): (0.2-1): (1-5): (0.1-1.5);
the dosage of the polyvinylpyrrolidone in the first step is 5-20 wt% of molybdenum salt;
the dosage of the ammonium hypophosphite compound in the second step is 50-200 wt percent of the carbon-supported molybdenum compound;
the dosage of the thioacetamide in the step II is 10-100 wt percent of the carbon-supported molybdenum compound.
2. The method of claim 1, wherein the molybdenum salt is at least one selected from the group consisting of ammonium molybdate, sodium molybdate, potassium molybdate, molybdenum pentachloride, and molybdenum carbonate.
3. The method of claim 1, wherein the first temperature rise rate is 3-10 ℃/min.
4. The method of claim 1, further comprising the steps of:
the method comprises the following steps: pretreatment of
The mass ratio of the materials is 1:1:5:0.1 of tribenzoic acid, 2-aminobenzoic acid, ammonium chloride, molybdenum salt and polyvinylpyrrolidone are subjected to ball milling and mixing, and are sintered for 5 hours at 500 ℃ in the air to prepare the carbon-supported molybdenum compound, wherein the dosage of the polyvinylpyrrolidone is 10 wt% of the molybdenum salt;
step two: charring treatment
Transferring the carbon-loaded molybdenum compound into a nitrogen atmosphere furnace, and carbonizing at 800 ℃ to obtain porous carbon-loaded molybdenum carbide;
or mixing the carbon-supported molybdenum compound and an ammonium hypophosphite compound, and carbonizing at 800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum phosphide, wherein the using amount of the ammonium hypophosphite compound is 100 wt% of the carbon-supported molybdenum compound;
or mixing the carbon-supported molybdenum compound with thioacetamide, and carbonizing at 800 ℃ in a nitrogen atmosphere furnace to obtain the porous carbon-supported molybdenum disulfide, wherein the dosage of the thioacetamide is 50 wt percent of the carbon-supported molybdenum compound.
5. A porous metal molybdenum on carbon compound obtainable by the process as claimed in any one of claims 1 to 4.
6. Use of the porous molybdenum on carbon compound as defined in claim 5 for electrocatalytic hydrogen evolution.
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