CN111659439A - Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof - Google Patents
Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 58
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- 238000002156 mixing Methods 0.000 claims abstract description 5
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
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- 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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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B01J37/14—Oxidising with gases containing free oxygen
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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Abstract
The invention provides a nitrogen-doped carbon nano composite material loaded with an NiS/NiO heterojunction and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1 preparation of Ni2+a/PVP hybrid sol; s2, mixing the Ni2+Performing electrostatic spinning on the/PVP mixed sol to obtain a solid carbon fiber film; s3, pre-oxidizing the solid carbon fiber film in air atmosphere, and then sequentially carrying out heat treatment in inert atmosphere, oxidation treatment in air atmosphere and sulfide vapor deposition to obtain the NiS/NiO heterojunction-loaded nitrogen-doped carbon nano composite material. The PVP selected by the method is cheap and easy to obtain, and compared with the traditional method for preparing the electrolyzed water oxygen evolution electrocatalyst material, the method has the advantages of simple and feasible process, low cost, simple operation and capability of realizing large-scale production.
Description
Technical Field
The invention relates to a nitrogen-doped carbon nano composite material loaded with an NiS/NiO heterojunction and a preparation method and application thereof, belonging to the technical field of alkaline oxygen evolution reaction catalysts.
Background
With the rapid consumption of energy sources such as traditional fossil, coal and the like and the increasingly prominent problem of environmental pollution, the search for novel green and sustainable energy sources is urgent. Hydrogen energy is an important energy form for replacing fossil fuel due to zero emission and ultrahigh energy density (143 kJ.kg)-1) The advantages of environmental protection, sustainable utilization and the like are considered as a promising alternative energy carrier. Compared with the traditional hydrogen production mode, the hydrogen production by electrolyzing water is considered as a hydrogen production method with wide application prospect due to the advantages of being green, efficient, capable of realizing large-scale production and the like. However, the anode electrocatalytic oxygen evolution reaction in the electrolyzed water reaction has a high reaction energy barrier and a large overpotential, which seriously affects the overall electrolyzed water reaction kinetic rate. Therefore, efficient oxygen evolution electrocatalysts were developed to reduce the reaction activation energy and energy barrier and improve the reaction kineticsThe rate is of significance. At present, the commercial oxygen evolution high-efficiency catalyst is a noble metal catalyst such as iridium, ruthenium base and the like, but the large-scale practical application of the catalyst is severely limited due to the defects of rare reserves, high price and the like. Therefore, the development of a novel cheap and efficient non-noble metal oxygen evolution electrocatalyst is particularly critical.
A great deal of research is carried out on various non-noble metal oxygen evolution electrocatalysts, transition metal Ni-based materials, alloys thereof and compound materials thereof, such as carbides, phosphides, sulfides, nitrides and the like, due to the advantages of abundant reserves, more redox sites, good corrosion resistance and the like. Among them, NiO shows better oxygen evolution activity in current research due to its abundant oxygen vacancies, specific 3d electron type, specific eg orbital, and better binding energy with oxygen-containing species. Meanwhile, NiS obtains certain application in the field of water electrolysis due to the special 3d configuration and high conductivity (adv. Mater.2017,29,1701584; ACS Nano 2017,11, 11574-. Although such research has been advanced, the oxygen evolution performance of NiO catalysts has been difficult to meet the stringent requirements of commercial production. Research results show that the NiS and the NiO are compounded to form a heterojunction material, so that the surface electronic structure of the heterojunction material can be effectively adjusted, the conductivity of the heterojunction material is improved, the rapid transfer of charges is promoted, and the intrinsic activity of the heterojunction material is improved; meanwhile, the one-dimensional multi-stage nano carbon material is a feasible strategy in dynamics, the one-dimensional multi-stage nano carbon material can effectively improve the conductivity of the catalyst, provide a larger specific surface area, expose more catalytic sites and enhance the stability of active species. Meanwhile, the doping of hetero atoms (such as N, P, S and the like) into the carbon matrix can effectively improve the oxygen evolution performance by adjusting the electronic structure of the nearby carbon atoms. Therefore, combining these synergistic advantages, the synthesis of one-dimensional multi-stage carbon matrix-supported NiS/NiO heterojunctions doped with heteroatoms is a sensible strategy. However, in general, the preparation of such materials tends to be time-consuming, tedious, and low-yielding.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems, the invention aims to provide a nitrogen-doped carbon nanocomposite material loaded with an NiS/NiO heterojunction, and a preparation method and application thereof. The method is simple and universal, the cost is low, and the prepared nitrogen-doped carbon nano composite material loaded with the NiS/NiO heterojunction as an oxygen evolution electrocatalyst material has excellent activity and stability.
The technical scheme is as follows: the invention is realized by the following technical scheme:
a preparation method of a nitrogen-doped carbon nano composite material loaded with a NiS/NiO heterojunction comprises the following steps:
s1 preparation of Ni2+a/PVP hybrid sol;
s2, mixing the Ni2+Performing electrostatic spinning on the/PVP mixed sol to obtain a solid carbon fiber film;
s3, pre-oxidizing the solid carbon fiber film in an air atmosphere, and then sequentially carrying out heat treatment in an inert atmosphere, oxidation treatment in the air atmosphere and sulfide vapor deposition to obtain the NiS/NiO heterojunction-loaded nitrogen-doped carbon nano composite material.
Preferably, the Ni is2+The preparation method of the/PVP mixed sol comprises the following steps:
dissolving PVP in a mixed solution of DMF and ethanol to obtain a PVP solution;
adding nickel nitrate into the PVP solution, and stirring and uniformly mixing to obtain the Ni2+the/PVP mixed sol.
Preferably, the mass fraction of PVP in the PVP solution is 5-10%.
Preferably, the Ni is2+In the mixed sol of/PVP, Ni2+The molar amount of (b) is 0.25 to 2.0 mmol.
As a preferable scheme:
in step S3, the pre-oxidation in the air atmosphere is performed at 200 to 300 ℃.
In step S3, the heat treatment is carried out in an inert atmosphere, wherein the temperature is raised to 400-1000 ℃ at the speed of 1-20 ℃/min, and the heat is preserved for 2-4 h. The inert atmosphere comprises at least one of nitrogen, argon, helium and carbon dioxide.
In step S3, the oxidation treatment in the air atmosphere is carried out by keeping the temperature at 200-500 ℃ for 0.5-3 h.
And in the step S3, performing vulcanization vapor deposition, wherein thiourea is used as a sulfur source for the product of the oxidation treatment in the air atmosphere, and the vulcanization vapor deposition is performed for 0.5-3 h at the temperature of 250-450 ℃.
The nitrogen-doped carbon nano composite material loaded with the NiS/NiO heterojunction, which is prepared by the preparation method, is provided.
The application of the nitrogen-doped carbon nano composite material loaded with the NiS/NiO heterojunction as an alkaline oxygen evolution reaction catalyst.
The reaction principle of the invention is as follows: nickel nitrate is used as a metal source, polyvinylpyrrolidone is used as a carbon-nitrogen source, and Ni is prepared in advance by an electrostatic spinning technology2+The one-dimensional carbon nanofiber and the NiS/NiO heterojunction material loaded by the carbon nanotube are prepared by utilizing the preoxidation of the/PVP composite fiber material in the air atmosphere and the carbonization and reduction of the/PVP composite fiber material in the high-temperature inert atmosphere, and through the oxidation treatment and the sulfide vapor deposition in the air atmosphere. The material has regular and uniform appearance, wherein the NiS/NiO heterojunction nano-particles have smaller sizes and are uniformly embedded in the carbon nano-fibers and the carbon nano-tubes. In addition, the carbon nanofiber and the carbon nanotube contain rich N elements, and due to the advantages of the carbon nanofiber, the components and the structure between the carbon nanotube and an active substance NiS/NiO heterojunction, the obtained material has high oxygen evolution activity and excellent stability.
The heterojunction is composed of two different substances, NiS and NiO.
The NiS/NiO heterojunction material loaded by the one-dimensional carbon nanofiber and the carbon nanotube structure prepared by the method has the following advantages:
1) the NiS/NiO heterojunction active metal nano-particles with smaller particle sizes have excellent electrochemical activity and more catalytic active sites;
2) the catalyst material has a large specific surface area due to the composite structure of the one-dimensional carbon nanofibers and the carbon nanotubes, and meanwhile, the mesoporous structure of the carbon-based material can effectively promote the contact of the electrolyte and the catalyst, so that the reaction is facilitated;
3) the one-dimensional composite structure can directionally promote the rapid transmission of electrons and ions, improve the catalytic reaction rate, and promote the reaction of reactants and the rapid output of products;
4) the one-dimensional carbon matrix material can effectively anchor the NiS/NiO heterojunction of the active metal material, so that the active metal material is not easy to agglomerate and fall off in the reaction process, and the integrity of the one-dimensional composite structure is favorably maintained;
5) PVP with higher nitrogen content is selected as a carbon-nitrogen source, a carbon carrier with higher graphitization degree and better thermal stability is generated through high-temperature carbonization and reduction, and the conductivity of the carbon carrier can be effectively changed by doping nitrogen, so that the oxygen evolution performance of the material is improved.
The technical effects are as follows: compared with the prior art, the invention has the following advantages:
1) preparing carbon nano-fibers with a one-dimensional composite structure and a NiS/NiO heterojunction electrocatalyst material loaded by the carbon nano-tubes by an electrostatic spinning technology which is simple and convenient and can realize large-scale production and combining a high-temperature carbonization thermal reduction technology and a low-temperature vapor deposition technology;
2) the selected PVP is cheap and easy to obtain, and compared with the traditional method for preparing the electrolyzed water oxygen evolution electrocatalyst material, the method has the advantages of simple and feasible process, low cost and simple operation, and can realize large-scale production;
3) the prepared product has regular shape, and NiS/NiO heterojunction nano particles are uniformly loaded in the one-dimensional composite carbon nano material in size, so that the prepared material has the characteristics of more active sites, low overpotential, good stability, a one-dimensional composite structure and the like.
Drawings
FIG. 1 is a low power SEM image of nitrogen doped carbon nanofibers loaded with NiS/NiO heterojunction material prepared according to example 1 of the present invention;
FIG. 2 is an enlarged SEM image of a nitrogen-doped carbon nanofiber prepared according to example 1 of the present invention, wherein the carbon nanotube supports a NiS/NiO heterojunction material;
FIG. 3 is a TEM image of nitrogen-doped carbon nanofibers prepared according to example 1 of the present invention, carbon nanotubes supporting NiS/NiO heterojunction material;
FIG. 4 is an XRD pattern of a carbon nanotube-supported NiS/NiO heterojunction material of nitrogen-doped carbon nanofibers prepared according to example 1 of the present invention;
FIG. 5 is a Raman spectrum of a nitrogen-doped carbon nanofiber prepared according to example 1 of the present invention, the carbon nanotube supporting NiS/NiO heterojunction material;
FIG. 6 is a TG map of a nitrogen-doped carbon nanofiber prepared according to example 1 of the present invention, carbon nanotube supporting NiS/NiO heterojunction material;
FIG. 7 is a LSV curve of nitrogen-doped carbon nanofibers prepared according to example 1 of the present invention, carbon nanotubes supporting NiS/NiO heterojunction material;
FIG. 8 is Tafel curve of NiS/NiO heterojunction material loaded on carbon nanotubes of nitrogen-doped carbon nanofibers prepared according to example 1 of the present invention;
FIG. 9 is a comparison of LSV curves before and after cycle stability testing of carbon nanotube-loaded NiS/NiO heterojunction materials for nitrogen-doped carbon nanofibers prepared according to example 1 of the present invention;
FIG. 10 is a time-series current test curve of the carbon nanotube-supported NiS/NiO heterojunction material of nitrogen-doped carbon nanofibers prepared according to example 1 of the present invention;
FIG. 11 is a comparison of the LSV curves of the materials obtained in example 1 and comparative examples 1-3 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
A preparation method of a nitrogen-doped carbon nanofiber, namely a carbon nanotube-loaded NiS/NiO heterojunction material, comprises the following steps:
1)Ni2+preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C2H5OH solution was mixed and 1.5mmol of Ni (NO) was added3)2·6H2O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni2+A PVP sol;
2) preparing a nitrogen-doped carbon nano composite material load NiS/NiO heterojunction composite material by an electrostatic spinning method: the light green Ni prepared in the step 1)2+The PVP sol is treated by an electrostatic spinning technology to obtain a solid carbon fiber film material, the solid carbon fiber film material is firstly subjected to pre-oxidation treatment at 250 ℃ for 3h in the air, and then is subjected to N2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, then cooling to room temperature, carrying out oxidation treatment at 300 ℃ under the air atmosphere, taking thiourea as a sulfur source, wherein the mass of the thiourea is twenty times that of a sample, and carrying out vulcanization vapor deposition for 3h at 350 ℃ to obtain a final product.
Physical characterization is carried out on the NiS/NiO heterojunction nano material loaded by the one-dimensional composite structure of the nitrogen-doped carbon nanofiber and the carbon nanotube prepared in the embodiment by adopting the ways of TEM, SEM, XRD, Raman, TG and the like. From the low power SEM (figure 1), it can be seen that more carbon nanotubes are distributed on the one-dimensional carbon nanofibers, the one-dimensional structures of the carbon nanofibers and the carbon nanotubes are crosslinked with each other to form a three-dimensional network structure, meanwhile, NiS/NiO heterojunction nanoparticles are uniformly distributed on the carbon nanofibers and the carbon nanotubes, and the further enlarged SEM image (figure 2) can be seen that the prepared material is of the structure, and the diameter of the carbon nanofibers is about 200 nm. The TEM spectrum (FIG. 3) shows that NiS/NiO heterojunction nanoparticles are embedded inside the carbon nanofibers and carbon nanotubes, and the structure is consistent with the results of SEM. From FIG. 4, XRD spectrum shows that the diffraction peaks of the material are respectively matched with the standard cards of NiO and NiSThe sheets are completely coincided (JCPDS card, 47-1049; 65-3419), which proves the successful preparation of the NiS/NiO heterojunction, and simultaneously the (002) crystal face corresponds to the diffraction peak of graphitized carbon. Calculating to obtain I of the sample according to Raman spectrum (FIG. 5) of the productD/IGThe value of 0.93 indicates that the degree of graphitization of the resulting carbon material is high. From the thermogravimetric spectrum (fig. 6), it was found that the carbon content of the material was 19.56 wt%. Fig. 7 is a graph of LSV obtained by subjecting the material to an oxygen evolution performance test. From the graph, it can be seen that the current density is 10mA cm-2The overpotential of this material at a current density of (d) is only 269 mV. The Tafel plot (FIG. 8) shows that the Tafel slope of this material has a value of only 48.4mV dec-1This is superior to most basic oxygen evolution electrocatalyst materials. The LSV curves before and after 3000 CV cycles almost coincide, indicating better stability, from the cycle performance test (fig. 9). Fig. 10 is a chronoamperometric curve of the material, and the current density of the sample has little decay after a long time test of 25000s, which also shows that the material has excellent cycle stability. The results show that the material has good application prospect as an alkaline oxygen evolution electrocatalyst material.
Example 2
A preparation method of a nitrogen-doped carbon nanofiber, namely a carbon nanotube-loaded NiS/NiO heterojunction material, comprises the following steps:
1)Ni2+preparation of/PVP hybrid sol: 0.8g PVP was weighed out with 6mL DMF and 6mL C2H5OH solution was mixed and 1.5mmol of Ni (NO) was added3)2·6H2O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni2+A PVP sol;
2) preparing a nitrogen-doped carbon nano composite material load NiS/NiO heterojunction composite material by an electrostatic spinning method: the light green Ni prepared in the step 1)2+The PVP sol is treated by an electrostatic spinning technology to obtain a solid carbon fiber film material, the solid carbon fiber film material is firstly subjected to pre-oxidation treatment at 250 ℃ for 3h in the air, and then is subjected to N2Heating to 600 deg.C at a heating rate of 5 deg.C/min under air atmosphere, maintaining at the temperature for 3 hr, cooling to room temperature, and treating under air atmosphere for 30 deg.COxidizing at 0 ℃, taking thiourea with twenty times of the mass of the sample as a sulfur source, and carrying out vulcanization vapor deposition at 350 ℃ for 3h to obtain the final product.
Example 3
A preparation method of a nitrogen-doped carbon nanofiber, namely a carbon nanotube-loaded NiS/NiO heterojunction material, comprises the following steps:
1)Ni2+preparation of/PVP hybrid sol: 0.7g PVP was weighed out with 6mL DMF and 6mL C2H5OH solution was mixed and 1.5mmol of Ni (NO) was added3)2·6H2O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni2+A PVP sol;
2) preparing a nitrogen-doped carbon nano composite material load NiS/NiO heterojunction composite material by an electrostatic spinning method: the light green Ni prepared in the step 1)2+The PVP sol is treated by an electrostatic spinning technology to obtain a solid carbon fiber film material, the solid carbon fiber film material is firstly subjected to pre-oxidation treatment at 250 ℃ for 3h in the air, and then is subjected to N2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, then cooling to room temperature, carrying out oxidation treatment at 300 ℃ under the air atmosphere, taking thiourea as a sulfur source, wherein the mass of the thiourea is twenty times that of a sample, and carrying out vulcanization vapor deposition for 3h at 350 ℃ to obtain a final product.
Example 4
A preparation method of a nitrogen-doped carbon nanofiber, namely a carbon nanotube-loaded NiS/NiO heterojunction material, comprises the following steps:
1)Ni2+preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C2H5OH solution was mixed and 1.0mmol of Ni (NO) was added3)2·6H2O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni2+A PVP sol;
2) preparing a nitrogen-doped carbon nano composite material load NiS/NiO heterojunction composite material by an electrostatic spinning method: the yellow brown Ni prepared in the step 1)2+/PVP sol through electrostatic spinning technologyTreating to obtain solid carbon fiber film material, pre-oxidizing at 250 deg.c for 3 hr in air, and N treating2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, then cooling to room temperature, carrying out oxidation treatment at 300 ℃ under the air atmosphere, taking thiourea as a sulfur source, wherein the mass of the thiourea is twenty times that of a sample, and carrying out vulcanization vapor deposition for 3h at 350 ℃ to obtain a final product.
Example 5
A preparation method of a nitrogen-doped carbon nanofiber, namely a carbon nanotube-loaded NiS/NiO heterojunction material, comprises the following steps:
1)Ni2+preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C2H5OH solution was mixed and 0.5mmol of Ni (NO) was added3)2·6H2O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni2+A PVP sol;
2) preparing a nitrogen-doped carbon nano composite material load NiS/NiO heterojunction composite material by an electrostatic spinning method: the light green Ni prepared in the step 1)2+The PVP sol is treated by an electrostatic spinning technology to obtain a solid carbon fiber film material, the solid carbon fiber film material is firstly subjected to pre-oxidation treatment at 250 ℃ for 3h in the air, and then is subjected to N2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, then cooling to room temperature, carrying out oxidation treatment at 300 ℃ under the air atmosphere, taking thiourea as a sulfur source, wherein the mass of the thiourea is twenty times that of a sample, and carrying out vulcanization vapor deposition for 3h at 350 ℃ to obtain a final product.
Example 6
A preparation method of a nitrogen-doped carbon nanofiber, namely a carbon nanotube-loaded NiS/NiO heterojunction material, comprises the following steps:
1)Ni2+preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C2H5OH solution was mixed and 0.25mmol of Ni (NO) was added3)2·6H2O solid metal nitrate; mechanically stirring at room temperature for 12h to mixMixing uniformly to obtain light green Ni2+A PVP sol;
2) preparing a nitrogen-doped carbon nano composite material load NiS/NiO heterojunction composite material by an electrostatic spinning method: the light green Ni prepared in the step 1)2+The PVP sol is treated by an electrostatic spinning technology to obtain a solid carbon fiber film material, the solid carbon fiber film material is firstly subjected to pre-oxidation treatment at 250 ℃ for 3h in the air, and then is subjected to N2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, then cooling to room temperature, carrying out oxidation treatment at 300 ℃ under the air atmosphere, taking thiourea as a sulfur source, wherein the mass of the thiourea is twenty times that of a sample, and carrying out vulcanization vapor deposition for 3h at 350 ℃ to obtain a final product.
Example 7
A preparation method of a nitrogen-doped carbon nanofiber, namely a carbon nanotube-loaded NiS/NiO heterojunction material, comprises the following steps:
1)Ni2+preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C2H5OH solution was mixed and 1.5mmol of Ni (NO) was added3)2·6H2O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni2+A PVP sol;
2) preparing a nitrogen-doped carbon nano composite material load NiS/NiO heterojunction composite material by an electrostatic spinning method: the light green Ni prepared in the step 1)2+The PVP sol is treated by an electrostatic spinning technology to obtain a solid carbon fiber film material, the solid carbon fiber film material is firstly subjected to pre-oxidation treatment at 250 ℃ for 3h in the air, and then is subjected to N2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, then cooling to room temperature, carrying out oxidation treatment at 300 ℃ under the air atmosphere, taking thiourea as a sulfur source, wherein the mass of the thiourea is twenty times that of a sample, and carrying out vulcanization vapor deposition for 0.5h at 350 ℃ to obtain a final product.
Example 8
A preparation method of a nitrogen-doped carbon nanofiber, namely a carbon nanotube-loaded NiS/NiO heterojunction material, comprises the following steps:
1)Ni2+preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C2H5OH solution was mixed and 1.5mmol of Ni (NO) was added3)2·6H2O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni2+A PVP sol;
2) preparing a nitrogen-doped carbon nano composite material load NiS/NiO heterojunction composite material by an electrostatic spinning method: the light green Ni prepared in the step 1)2+The PVP sol is treated by an electrostatic spinning technology to obtain a solid carbon fiber film material, the solid carbon fiber film material is firstly subjected to pre-oxidation treatment at 200 ℃ for 3h in the air, and then is subjected to N2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, then cooling to room temperature, carrying out oxidation treatment at 300 ℃ under the air atmosphere, taking thiourea as a sulfur source, wherein the mass of the thiourea is twenty times that of a sample, and carrying out vulcanization vapor deposition for 1.0h at 350 ℃ to obtain a final product.
Example 9
A preparation method of a nitrogen-doped carbon nanofiber, namely a carbon nanotube-loaded NiS/NiO heterojunction material, comprises the following steps:
1)Ni2+preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C2H5OH solution was mixed and 1.5mmol of Ni (NO) was added3)2·6H2O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni2+A PVP sol;
2) preparing a nitrogen-doped carbon nano composite material load NiS/NiO heterojunction composite material by an electrostatic spinning method: the light green Ni prepared in the step 1)2+The PVP sol is treated by an electrostatic spinning technology to obtain a solid carbon fiber film material, the solid carbon fiber film material is firstly subjected to pre-oxidation treatment at 300 ℃ for 3h in the air, and then is subjected to N2Heating to 600 deg.C at a temperature rise rate of 5 deg.C/min under atmosphere, maintaining at the temperature for 3 hr, cooling to room temperature, oxidizing at 300 deg.C under air atmosphere, using thiourea as sulfur source in twenty times of sample mass, and heating at 3 deg.CAnd (3) carrying out vulcanization vapor deposition for 2.0h at the temperature of 50 ℃ to obtain a final product.
Example 10
A preparation method of a nitrogen-doped carbon nanofiber, namely a carbon nanotube-loaded NiS/NiO heterojunction material, comprises the following steps:
1)Ni2+preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C2H5OH solution was mixed and 1.5mmol of Ni (NO) was added3)2·6H2O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni2+A PVP sol;
2) preparing a nitrogen-doped carbon nano composite material load NiS/NiO heterojunction composite material by an electrostatic spinning method: the light green Ni prepared in the step 1)2+The PVP sol is treated by an electrostatic spinning technology to obtain a solid carbon fiber film material, the solid carbon fiber film material is firstly subjected to pre-oxidation treatment at 250 ℃ for 3h in the air, and then is subjected to N2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, then cooling to room temperature, carrying out oxidation treatment at 300 ℃ under the air atmosphere, taking thiourea as a sulfur source, wherein the mass of the thiourea is twenty times that of a sample, and carrying out vulcanization vapor deposition for 4.0h at 400 ℃ to obtain a final product.
Example 11
The same as example 1, except that:
in the prepared PVP solution, the mass fraction of PVP is 5 percent; the temperature rising rate of the temperature programming is 1 ℃/min, the heat treatment temperature is 400 ℃, and the time is 2 h.
Example 12
The same as example 1, except that:
in the prepared PVP solution, the mass fraction of PVP is 10 percent; the temperature raising rate of the temperature programming is 20 ℃/min, the heat treatment temperature is 1000 ℃, and the time is 4 h.
Comparative example 1
The comparative example is different from the example 1 only in that the high-temperature carbonization treatment at 600 ℃ is carried out, and the rest of the implementation conditions are not changed.
Comparative example 2
The comparative example is different from example 1 only in that the high temperature carbonization treatment at 600 ℃ and the oxidation treatment at 300 ℃ in the air atmosphere are carried out, and the rest of the implementation conditions are not changed.
Comparative example 3
This comparative example differs from example 1 only in that no transition metal is used and the remaining operating conditions are unchanged.
LSV test results of oxygen evolution reactions of the respective tests are shown in fig. 11, where the metal-free electrocatalytic material exhibits the most negative initial reduction potential and the smallest current density, exhibiting the worst oxygen evolution performance; the electrocatalytic material prepared from metal Ni or NiO shows poorer oxygen evolution performance than the S-doped NiO material. The overall performance comparison shows the order of NiS/NiO > Ni > C, with comparative example 2 having better performance than comparative example 1.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A preparation method of a nitrogen-doped carbon nano composite material loaded with an NiS/NiO heterojunction is characterized by comprising the following steps:
s1 preparation of Ni2+a/PVP hybrid sol;
s2, mixing the Ni2+Performing electrostatic spinning on the/PVP mixed sol to obtain a solid carbon fiber film;
s3, pre-oxidizing the solid carbon fiber film in air atmosphere, and then sequentially carrying out heat treatment in inert atmosphere, oxidation treatment in air atmosphere and sulfide vapor deposition to obtain the NiS/NiO heterojunction-loaded nitrogen-doped carbon nano composite material.
2. The method for preparing the NiS/NiO heterojunction-supported nitrogen-doped carbon nanocomposite material as claimed in claim 1, wherein the Ni is2+The preparation method of the/PVP mixed sol comprises the following steps:
dissolving PVP in a mixed solution of DMF and ethanol to obtain a PVP solution;
adding nickel nitrate into the PVP solution, and stirring and uniformly mixing to obtain the Ni2+the/PVP mixed sol.
3. The method for preparing the NiS/NiO heterojunction-supported nitrogen-doped carbon nanocomposite material as claimed in claim 2, wherein the mass fraction of PVP in the PVP solution is 5-10%.
4. The method for preparing the NiS/NiO heterojunction-supported nitrogen-doped carbon nanocomposite material as claimed in claim 1, wherein the Ni is2+In the mixed sol of/PVP, Ni2+The molar amount of (b) is 0.25 to 2.0 mmol.
5. The method for preparing the NiS/NiO heterojunction-supported nitrogen-doped carbon nanocomposite material as claimed in claim 1, wherein in the step S3, the pre-oxidation in the air atmosphere is performed at 200-300 ℃.
6. The method for preparing the NiS/NiO heterojunction-supported nitrogen-doped carbon nanocomposite material as claimed in claim 1, wherein in the step S3, the temperature is raised to 400-1000 ℃ at a rate of 1-20 ℃/min and is kept for 2-4 h by performing heat treatment in an inert atmosphere.
7. The method for preparing the NiS/NiO heterojunction-supported nitrogen-doped carbon nanocomposite material as claimed in claim 1, wherein in the step S3, the oxidation treatment in the air atmosphere is carried out by keeping the temperature at 200-500 ℃ for 0.5-3 h.
8. The method for preparing the NiS/NiO heterojunction-supported nitrogen-doped carbon nanocomposite material as claimed in claim 1, wherein in step S3, sulfide vapor deposition is performed, and thiourea is used as a sulfur source for the oxidation treatment product in the air atmosphere, and the sulfide vapor deposition is performed at 250-450 ℃ for 0.5-3 h.
9. The NiS/NiO heterojunction-supported nitrogen-doped carbon nanocomposite prepared by the preparation method of any one of claims 1 to 8.
10. Use of the NiS/NiO heterojunction-supported nitrogen-doped carbon nanocomposite material of claim 9 as a catalyst for basic oxygen evolution reaction.
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