CN112007673B - N-doped porous carbon-coated MoP nano rod material and preparation method and application thereof - Google Patents

N-doped porous carbon-coated MoP nano rod material and preparation method and application thereof Download PDF

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CN112007673B
CN112007673B CN202010939066.2A CN202010939066A CN112007673B CN 112007673 B CN112007673 B CN 112007673B CN 202010939066 A CN202010939066 A CN 202010939066A CN 112007673 B CN112007673 B CN 112007673B
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porous carbon
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doped porous
mop
moo
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CN112007673A (en
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耿保友
王晓丹
李文
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Anhui Normal University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
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    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/08—Other phosphides
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
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    • 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
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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    • 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 an N-doped porous carbon-coated MoP nano rod material and a preparation method and application thereof, wherein the preparation method of the N-doped porous carbon-coated MoP nano rod material comprises the following steps: 1) adding MoO3Carrying out contact reaction on the nano-rods, a surfactant, a zinc source and dimethyl imidazole in a solvent to prepare precursor powder; 2) and calcining and carbonizing the precursor powder under a protective gas, and then carrying out phosphating treatment on a calcined and carbonized product to obtain the N-doped porous carbon coated MoP nanorod material. The N-doped porous carbon-coated MoP nanorod material has excellent catalytic activity, can be applied to HER electrocatalysis, and has the advantages of simplicity in operation, uniform and controllable appearance.

Description

N-doped porous carbon-coated MoP nano rod material and preparation method and application thereof
Technical Field
The invention relates to a MoP nano material, in particular to an N-doped porous carbon-coated MoP nano rod material and a preparation method and application thereof.
Background
Hydrogen is considered one of the most promising energy carriers due to its clean, renewable and abundant natural resources. Among various hydrogen production methods, electrochemical hydrogen production methods are receiving much attention because of their advantages of high efficiency, sustainability, environmental protection, etc., and electrocatalysts play a crucial role in order to effectively obtain hydrogen and reduce overpotential in water electrolysis.
To date, platinum group noble metals have been considered as commercial HER electrocatalysts, exhibiting extremely low overpotentials. Unfortunately, their low abundance and high price limit their large-scale applications, and it is therefore inevitable to develop high-performance HER electrocatalysts that are earth-rich.
Over the past decades, many non-noble metal electrocatalysts have exhibited superior HER activity. Among the candidate catalytic materials, transition metal phosphides, in particular molybdenum-based phosphides, have attracted considerable interest due to their abundant resources, low cost, suitable electronic structure and chemical stability. However, their further applications are mainly limited by conductivity and lack of active sites. In order to improve the hydrogen evolution activity of molybdenum phosphide, the common methods include doping nonmetal, designing bimetallic phosphide, compounding with carbon-based materials and other strategies, so as to increase the active sites of the reaction and improve the catalytic activity of the reaction, and the common methods include C doping, N doping and the like. However, the problems of controlling the doping amount and maintaining the appearance are still solved, and the problems result in that the active sites of the doped material are reduced, and the activity of the catalytic hydrogen evolution reaction is reduced.
Disclosure of Invention
The invention aims to provide an N-doped porous carbon-coated MoP nanorod material, and a preparation method and application thereof.
In order to achieve the aim, the invention provides a preparation method of an N-doped porous carbon-coated MoP nanorod material, which comprises the following steps:
1) adding MoO3Carrying out contact reaction on the nano-rods, a surfactant, a zinc source and dimethyl imidazole in a solvent to prepare precursor powder;
2) and calcining and carbonizing the precursor powder under a protective gas, and then carrying out phosphating treatment on a calcined and carbonized product to obtain the N-doped porous carbon coated MoP nanorod material.
The invention also provides an N-doped porous carbon-coated MoP nano rod material, which is prepared according to the preparation method.
The invention further provides an application of the N-doped porous carbon-coated MoP nanorod material in HER electrocatalysis.
In the technical scheme, in the step 1),by mixing MoO3Combining the nano-rod and a metal organic framework material (obtained by the reaction of a zinc source and dimethylimidazole and used as a template) to obtain precursor powder, and then calcining and carbonizing in the step 2) to obtain the MoO coated with the porous carbon layer3And finally, carrying out phosphating treatment on the nano rod to obtain the N-doped porous carbon coated MoP nano rod material.
The metal organic framework of the porous carbon layer in the N-doped porous carbon-coated MoP nano rod material is porous and has a large specific surface area, so that a larger contact area is provided for a catalyst, more active sites are exposed, and the hydrogen evolution catalytic activity can be effectively improved. The preparation method is simple to operate, uniform and controllable in appearance and high in active site number, and solves the problems of difficulty in appearance control, low yield and high preparation cost in the prior art, so that the preparation method can be better applied to cathode catalyst materials for electrolytic water hydrogen evolution reaction.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is MoO in preparation example 13Scanning and transmission images (SEM image on the left side and TEM image on the right side) of the nano-rods and the precursor powder;
FIG. 2 is a TEM image of the products of examples 4-5 and an SEM image of the product of preparation 2.
FIG. 3 is a scanning and transmission image (SEM image on the left side and TEM image on the right side) of example 1, example 8, and comparative examples 1-2;
FIG. 4 is an XRD spectrum of the product of example 1;
fig. 5a and 5b are LSV plots of HER performance in application example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of an N-doped porous carbon-coated MoP nano rod material, which comprises the following steps:
1) adding MoO3Carrying out contact reaction on the nano-rods, a surfactant, a zinc source and dimethyl imidazole in a solvent to prepare precursor powder;
2) and calcining and carbonizing the precursor powder under a protective gas, and then carrying out phosphating treatment on a calcined and carbonized product to obtain the N-doped porous carbon coated MoP nanorod material.
In step 1), the amount of each material may be selected within a wide range, but in order to increase the catalytic activity of the resulting MoP nanorod material, preferably, in step 1), MoO is used3The dosage ratio of the nano rod, the surfactant, the zinc source and the dimethyl imidazole is 0.1 g: 0.2-0.5 g: 1-4 mmol: 10-30 mmol.
In step 1), the amount of solvent may be selected within a wide range, but in order to increase the catalytic activity of the resulting MoP nanorod material, preferably, in step 1), MoO is used3The dosage ratio of the nano rod to the solvent is 0.1 g: 50-100 mL.
In step 1), the conditions of the contact reaction may be selected within a wide range, but in order to increase the catalytic activity of the resulting MoP nanorod material, it is preferable that in step 1), the contact reaction at least satisfies the following conditions: the reaction temperature is 15-35 ℃, and the reaction time is 2-4 h.
In step 1), MoO3The size of the nanorods can be selected within a wide range, but in order to increase the catalytic activity of the resulting MoP nanorod material, preferably, in step 1)Medium, MoO3The nano-rods at least meet the following conditions: the length is 5-10 μm and the diameter is 200-500 nm.
In step 1), the kind of the zinc source may be selected within a wide range, but in order to improve the catalytic activity of the resulting MoP nanorod material, it is preferable that in step 1), the zinc source is selected from at least one of zinc nitrate, zinc chloride, and zinc sulfate.
In step 1), the kind of the surfactant may be selected within a wide range, but in order to improve the catalytic activity of the resulting MoP nanorod material, it is preferable that in step 1), the surfactant is selected from at least one of polyvinylpyrrolidone PVP, cetyltrimethylammonium bromide CTAB, and sodium dodecylbenzenesulfonate.
In step 1), the kind of the solvent may be selected within a wide range, but in order to improve the catalytic activity of the resulting MoP nanorod material, it is preferable that in step 1), the solvent is selected from at least one of water, ethanol, and methanol.
In step 1), the charging sequence may be selected within a wide range, but in order to improve the catalytic activity of the resulting MoP nanorod material, preferably, the charging sequence of step 1) is: now will MoO3The nanorods, surfactant, zinc source, and solvent were mixed, followed by the addition of dimethylimidazole.
In step 1), in order to further improve the purity of the precursor powder, preferably, after the contact reaction, step 1) further comprises washing the reaction product, and then drying at 50-80 ℃ for 36-60 h.
In step 2), the conditions for calcination and carbonization can be selected within a wide range, but in order to improve the catalytic activity of the resulting MoP nanorod material, it is preferable that in step 2), calcination and carbonization satisfy at least the following conditions: the reaction temperature is 700-900 ℃, and the reaction time is 1-2 h; more preferably, in step 2), the calcination carbonization at least satisfies the following condition: at Ar/H2Under the mixed atmosphere, the temperature is raised from 15-25 ℃ to 700-900 ℃ at the speed of 2-4 ℃/min, the temperature is kept for 1-2h, and then the temperature is lowered to 15-25 ℃ at the speed of 2-4 ℃/min.
In step 2), the amount of each material may be selected within a wide range, but in order to improve the catalytic activity of the resulting MoP nanorod material, it is preferable that the calcined carbonized product, the phosphorus source, be used in the phosphating treatment of step 2) in a weight ratio of 10 mg: 40-100 mg.
In step 2), the mode of the phosphating treatment can be selected in a wide range, but in order to improve the catalytic activity of the prepared MoP nanorod material, the phosphating treatment is preferably as follows: the method is carried out by adopting a gas-solid conversion method, wherein a phosphorus source is positioned at an air inlet, a calcined carbonized product is positioned at an air outlet, and the calcination is carried out in the presence of protective gas.
In step 2), the conditions of the phosphating treatment can be selected within a wide range, but in order to improve the catalytic activity of the resulting MoP nanorod material, it is preferable that in step 2), the phosphating treatment at least satisfies the following conditions: the calcination temperature is 750-850 ℃, and the calcination time is 1-2 h; more preferably, in step 2), the phosphating treatment satisfies at least the following conditions: at Ar/H2Under the mixed atmosphere, the temperature is raised from 15-25 ℃ to 750-850 ℃ at the speed of 4-6 ℃/min, the temperature is kept for 1-2h, and then the temperature is lowered to 15-25 ℃ at the speed of 4-6 ℃/min.
In step 2), the kind of the phosphorus source may be selected within a wide range, but in order to improve the catalytic activity of the resulting MoP nanorod material, it is preferable that in step 2), the phosphorus source is selected from at least one of diammonium hydrogen phosphate, dipotassium hydrogen phosphate, and disodium hydrogen phosphate.
In the present invention, MoO3The nano-rod can be a commercially available product or can be prepared by self to ensure MoO3Purity of the nanorods, preferably, MoO3The nano-rod is prepared by the following method: carrying out hydrothermal reaction on a molybdenum source, concentrated nitric acid and water, and then washing and drying.
In the above-mentioned MoO3In the preparation method of the nano-rod, the dosage of each material can be selected in a wide range, but the MoO can be controlled3Yield of nanorods, preferably, the ratio of the molybdenum source, concentrated nitric acid and water is 5 mmol: 3-8 mL: 22 to 27mL, and the concentration of the concentrated nitric acid is 60 to 70 weight percent.
In the above-mentioned MoO3In the preparation method of the nano-rod, the conditions of the hydrothermal reactionCan be selected within a wide range, but for controlling MoO3Yield of nanorods, preferably, the hydrothermal reaction at least satisfies the following conditions: the reaction temperature is 180 ℃ and 200 ℃, and the reaction time is 10-16 h.
In the above-mentioned MoO3In the method for preparing nanorods, it is preferable that MoO is added to improve the drying effect3The drying in the nanorod preparation process at least meets the following conditions: the drying temperature is 50-80 deg.C, and the drying time is 36-60 h.
In the above-mentioned MoO3In the method for preparing the nanorods, the specific kind of the molybdenum source may be selected within a wide range, but it is preferable that the molybdenum source is selected from at least one of ammonium molybdate, sodium molybdate, and ammonium heptamolybdate from the viewpoint of cost and water solubility.
The invention also provides an N-doped porous carbon-coated MoP nano rod material, which is prepared according to the preparation method.
In order to further improve the catalytic effect of the MoP nanorod material, the MoP nanorod material coated with the N-doped porous carbon preferably satisfies the following conditions: the length is 5-10 μm and the diameter is 200-500 nm.
The invention further provides an application of the N-doped porous carbon-coated MoP nanorod material in HER electrocatalysis.
The present invention will be described in detail below by way of examples. In the following examples, the drugs and medicaments are all conventional commercial products.
Preparation example 1
MoO3Preparing the nano-rods:
weighing 1.05g of ammonium molybdate, dissolving the ammonium molybdate in 30ml of mixed solution of concentrated nitric acid and water (consisting of 60-70 wt% of concentrated nitric acid and water in a volume ratio of 1: 5), stirring for 30min, transferring the mixed solution to a 50ml reaction kettle, then putting the reaction kettle into an oven, and reacting for 20h at 200 ℃; then washed three times with deionized water and absolute ethyl alcohol respectively, and then dried in an oven at 60 ℃ for 48 hours to obtain MoO3The nanorods, as shown in a, b in FIG. 1, can be seen to be MoO3The specification of the nano-rod is as follows: length of 5-10 μm and diameter200-500 nm.
Preparation example 2
Preparation of MoP
Adding MoO3The nano rod is heated to 800 ℃ from 20 ℃ at the speed of 3 ℃/min and is kept warm for 2H under the mixed atmosphere of Ar/H2, and then the temperature is reduced to 20 ℃ at the speed of 3 ℃/min to obtain a carbonized product.
And then carrying out phosphating treatment: under Ar/H2 mixed atmosphere, the upstream of the quartz boat is 50mg of diammonium hydrogen phosphate, and the downstream is 10mg of carbonized product; raising the temperature from 20 ℃ to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 2h, and then reducing the temperature to 20 ℃ at the speed of 5 ℃/min to obtain MoP, as shown in c and d in figure 2.
Example 1
1) 0.1g of MoO3The nanorods, 0.35g PVP (polyvinylpyrrolidone) and 0.7437g zinc nitrate hexahydrate were dissolved in 30ml anhydrous methanol, and after stirring for 3h, 30ml 1.5mol.L-1Slowly adding the dimethyl imidazole solution into the solution, stirring for 30min, washing with anhydrous methanol for three times, and drying in an oven at 60 ℃ for 48h to obtain precursor powder, wherein the precursor powder is shown as c and d in figure 1.
2) Calcining and carbonizing: precursor powder is put in Ar/H2Under the mixed atmosphere, the temperature is raised to 800 ℃ from 20 ℃ at the speed of 3 ℃/min and is kept for 2h, and then the temperature is lowered to 20 ℃ at the speed of 3 ℃/min to obtain a carbonized product.
And (3) phosphating treatment: and (3) carrying out phosphating treatment on the carbonized product: under Ar/H2 mixed atmosphere, the upstream of the quartz boat is 50mg of diammonium hydrogen phosphate, and the downstream is 10mg of carbonized product; and (3) heating from 20 ℃ to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 2h, and then cooling to 20 ℃ at the speed of 5 ℃/min to obtain the N-doped porous carbon-coated MoP nanorod material, wherein the product is marked as 800-P, and as shown in e and f in figure 3, the length of the product is 5-10 mu m, and the diameter of the product is 200-500 nm.
Example 2
An N-doped porous carbon-coated MoP nanorod material was prepared according to the method of example 1, except that the mass of diammonium hydrogen phosphate in the phosphatizing calcination of step 2) was 100 mg.
Example 3
An N-doped porous carbon-coated MoP nanorod material was prepared according to the method of example 1, except that the mass of diammonium hydrogen phosphate in the phosphatizing calcination of step 2) was 40 mg.
Example 4
An N-doped porous carbon-coated MoP nanorod material was prepared according to the method of example 1, except that the temperature of the phosphorization calcination in step 3) was increased from 15 ℃ to 750 ℃ at a rate of 6 ℃/min and kept for 2h, and then the temperature was decreased to 15 ℃ at a rate of 6 ℃/min, and the product is shown as a in fig. 2.
Example 5
An N-doped porous carbon-coated MoP nanorod material was prepared according to the method of example 1, except that the temperature of the phosphorization calcination in step 3) was increased from 25 ℃ to 850 ℃ at a rate of 4 ℃/min and kept for 1h, and then the temperature was decreased to 25 ℃ at a rate of 4 ℃/min, and the product was as shown in b in fig. 2.
Example 6
An N-doped porous carbon-coated MoP nanorod material was prepared according to the method of example 1, except that zinc nitrate was changed to zinc chloride and PVP was changed to CTAB in step 2).
Example 7
An N-doped porous carbon-coated MoP nanorod material was prepared according to the method of example 1, except that zinc nitrate was changed to zinc sulfate and PVP was changed to sodium dodecylbenzenesulfonate in step 2).
Example 8
An N-doped porous carbon-coated MoP nanorod material was prepared as in example 1, except that in step 3), the carbonization calcination was carried out at a rate of 2 ℃/min from 15 ℃ to 700 ℃ and the temperature was maintained for 1h, and then the temperature was reduced at a rate of 2 ℃/min to 15 ℃, and the product was designated as 700-P, as shown in c and d in FIG. 3.
Comparative example 1
An N-doped porous carbon-coated MoP nanorod material was prepared according to the method of example 1, except that "800 ℃ and heat preservation for 2 h" in the carbonization calcination in step 3) was changed to "600 ℃ and heat preservation for 2 h", and the product was recorded as 600-P, as shown in a and b in FIG. 3.
Comparative example 2
An N-doped porous carbon-coated MoP nanorod material was prepared according to the method of example 1, except that "800 ℃ and heat preservation for 2 h" in the carbonization calcination in step 3) was changed to "900 ℃ and heat preservation for 2 h", and the product was recorded as 900-P, as shown in g and h in FIG. 3.
MoO can be seen from a and b in FIG. 13The nanorods were synthesized successfully, approximately 0.34 microns wide and approximately 9 microns long; the surface of the nanorods is clearly seen in the scan and transmission images to be relatively smooth. MoO can be seen in c and d in FIG. 13The surface of the nanorod is obviously rough, which is caused by the fact that the outer layer ZIF-8 single crystal is tightly packed on the surface, and the thickness of the carbon layer is about 100-200 nm; ZIF-8 was not observed in the free form in the scan and transmission patterns due to the addition of surfactant during the synthesis.
The scanning and transmission profiles of the products of examples 2-3, 6-7 substantially correspond to the scanning and transmission profile of the product of example 1.
As can be seen from FIG. 2, the morphology did not change before and after the phosphating calcination.
As can be seen from FIG. 3, as the carbonization calcination temperature is increased, the surface ZIF-8 single crystal is carbonized, and a carbon layer with a certain thickness is derived on the surface of the nanorod. When the carbonization temperature is 600 ℃, the surface is still smooth due to low temperature, and the appearance is not damaged; when the carbonization temperature reaches 700 ℃, the thickness of the carbon layer is obviously reduced, and meanwhile, the original nano rods begin to become thin, the surface also begins to become rough, and a plurality of mesopores begin to appear; when the temperature reaches 800 ℃, the surface is rougher and more holes are formed; when the temperature reaches 900 ℃, the original appearance of the nano-rod is destroyed, and obvious holes appear.
FIG. 4 is an XRD spectrum of the N-doped porous carbon-coated MoP nanorod material prepared in example 1, which corresponds to standard card MoP (PDF # 24-0771).
Application example 1
The performance of the N-doped porous carbon-coated MoP nanorod material prepared by the invention as an electrocatalyst is tested.
2mg of the catalyst (product in example or comparative example) and 1mg of carbon black were added to a mixed solution of 650uL of deionized water and 330uL of DMF, 20uL of a 5% by mass Nafion solution was added, and the mixture was ultrasonically dispersed for 30min to obtain a uniformly mixed catalyst ink. 7uL of ink was dropped onto the surface of the treated clean glassy carbon electrode (d: 3mm), and dried to obtain a working electrode.
The electrocatalysis performance test adopts a three-electrode system, a silver-silver chloride (Ag/AgCl) electrode is used as a reference electrode, a graphite rod is used as a counter electrode, and the volume of the electrode is 1mol.L-1The results of using the aqueous potassium hydroxide solution as an electrolyte are shown in FIG. 5.
As shown in FIG. 5a (the curves from left to right represent 600-P, 700-P, 900-P and 800-P, respectively), the product properties of different carbonization and calcination temperatures are different, and when the carbonization temperature and the phosphorization temperature are both 800 ℃, the material has a lower overpotential of only 165 mv.
It can also be seen from FIG. 5b (left to right curves representing the carbonized product, MoP, N/C/MoP and Pt/C, respectively), that the N/C/MoP nanorod material in example 1 compared to the MoP in preparation 2, and the carbonized product (Mo) in example 1 before phosphating2N/Mo/C), current density of 10mAcm in 1.0MKOH-2The overpotential is much lower and is closer to that of commercial platinum-carbon electrode materials (overpotential is 45 mv).
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (25)

1. A preparation method of an N-doped porous carbon-coated MoP nanorod material is characterized by comprising the following steps:
1) adding MoO3Carrying out contact reaction on the nano-rods, a surfactant, a zinc source and dimethyl imidazole in a solvent to prepare precursor powder;
2) and calcining and carbonizing the precursor powder under a protective gas, and then carrying out phosphating treatment on a calcined and carbonized product to obtain the N-doped porous carbon coated MoP nanorod material.
2. The method of claim 1, wherein, in step 1), the MoO is3The dosage ratio of the nano rod, the surfactant, the zinc source and the dimethyl imidazole is 0.1 g: 0.2-0.5 g: 1-4 mmol: 10-30 mmol.
3. The method of claim 2, wherein, in step 1), the MoO is3The dosage ratio of the nano rod to the solvent is 0.1 g: 50-100 mL.
4. The production method according to claim 2, wherein, in step 1), the contact reaction satisfies at least the following condition: the reaction temperature is 15-35 ℃, and the reaction time is 2-4 h.
5. The method of claim 1, wherein, in step 1), the MoO is3The nano-rods at least meet the following conditions: the length is 5-10 μm and the diameter is 200-500 nm.
6. The production method according to claim 5, wherein, in step 1), the zinc source is selected from at least one of zinc nitrate, zinc chloride, and zinc sulfate.
7. The production method according to claim 5, wherein in step 1), the surfactant is selected from at least one of polyvinylpyrrolidone PVP, cetyltrimethylammonium bromide CTAB, and sodium dodecylbenzenesulfonate.
8. The production method according to claim 5, wherein, in step 1), the solvent is selected from at least one of water, ethanol, and methanol.
9. The preparation method according to claim 1, wherein the charging sequence of step 1) is: now the MoO3The nanorods, surfactant, zinc source, and solvent are mixed, and then the dimethyl imidazole is added.
10. The preparation method according to claim 9, wherein, after the contact reaction, the step 1) further comprises washing the reaction product and then drying at 50-80 ℃ for 36-60 h.
11. The production method according to claim 1, wherein, in step 2), the calcination and carbonization satisfy at least the following condition: the reaction temperature is 700 ℃ and 850 ℃, and the reaction time is 1-2 h.
12. The production method according to claim 11, wherein, in step 2), the calcination and carbonization satisfy at least the following condition: at Ar/H2Under the mixed atmosphere, the temperature is raised from 15-25 ℃ to 700-850 ℃ at the speed of 2-4 ℃/min, the temperature is kept for 1-2h, and then the temperature is lowered to 15-25 ℃ at the speed of 2-4 ℃/min.
13. The production method according to claim 1, wherein, in the phosphating treatment of step 2), the calcined carbonized product and the phosphorus source are used in a weight ratio of 10 mg: 40-100 mg.
14. The production method according to claim 13, wherein the phosphating treatment is: the method is carried out by adopting a gas-solid conversion method, wherein the phosphorus source is positioned at the air inlet, the calcined carbonized product is positioned at the air outlet, and the calcination is carried out in the presence of protective gas.
15. The production method according to claim 13, wherein, in step 2), the phosphating treatment satisfies at least the following condition: the calcination temperature is 750-850 ℃, and the calcination time is 1-2 h.
16. The production method according to claim 13, wherein, in step 2), the phosphating treatment satisfies at least the following condition: at Ar/H2Under the mixed atmosphere, the temperature is raised from 15-25 ℃ to 750-850 ℃ at the speed of 4-6 ℃/min, the temperature is kept for 1-2h, and then the temperature is lowered to 15-25 ℃ at the speed of 4-6 ℃/min.
17. The production method according to claim 13, wherein, in step 2), the phosphorus source is selected from at least one of diammonium hydrogen phosphate, dipotassium hydrogen phosphate, and disodium hydrogen phosphate.
18. The method of claim 1, wherein the MoO3The nano-rod is prepared by the following method: carrying out hydrothermal reaction on a molybdenum source, concentrated nitric acid and water, and then washing and drying.
19. The method of claim 18, wherein the molybdenum source, concentrated nitric acid, and water are used in a ratio of 5 mmol: 3-8 mL: 22-27mL, and the concentration of the concentrated nitric acid is 60-70 wt%.
20. The preparation method according to claim 18, wherein the hydrothermal reaction satisfies at least the following condition: the reaction temperature is 180 ℃ and 200 ℃, and the reaction time is 10-16 h.
21. The method of claim 18, wherein the MoO3The drying in the nanorod preparation process at least meets the following conditions: the drying temperature is 50-80 deg.C, and the drying time is 36-60 h.
22. The method of claim 18, wherein the molybdenum source is selected from at least one of ammonium molybdate, sodium molybdate, and ammonium heptamolybdate.
23. An N-doped porous carbon-coated MoP nanorod material, characterized in that the N-doped porous carbon-coated MoP nanorod material is prepared according to the preparation method of any one of claims 1-22.
24. The N-doped porous carbon-coated MoP nanorod material of claim 23, wherein the N-doped porous carbon-coated MoP nanorod material meets the following condition: the length is 5-10 μm and the diameter is 200-500 nm.
25. Use of the N-doped porous carbon-coated MoP nanorod material of claim 23 in HER electrocatalysis.
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