CN111659439B - 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 PDF

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CN111659439B
CN111659439B CN202010488855.9A CN202010488855A CN111659439B CN 111659439 B CN111659439 B CN 111659439B CN 202010488855 A CN202010488855 A CN 202010488855A CN 111659439 B CN111659439 B CN 111659439B
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徐林
李同飞
刘千玉
李苏霖
殷静雯
李玉
孙冬梅
唐亚文
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Nanjing Normal University
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Abstract

The invention provides a nitrogen-doped carbon nano composite material loaded with a NiS/NiO heterojunction and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, preparing Ni 2+ a/PVP hybrid sol; s2, adding the Ni 2+ Performing electrostatic spinning on the/PVP mixed sol to obtain a solid carbon fiber film; and 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. 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

Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof
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 electrocatalytic oxygen evolution reaction of the anode in the electrolyzed water reaction has a higher reaction energy barrier and a larger overpotential, which seriously affects the overall electrolyzed water reaction kinetic rate. Therefore, it is of great significance to develop an efficient oxygen evolution electrocatalyst to reduce the reaction activation energy and energy barrier and to increase the reaction kinetic rate. 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 and compound materials thereof, such as carbides, phosphides, sulfides, nitrides and the like, because of the advantages of abundant reserves, more redox sites, good corrosion resistance and the like. Among them, niO shows a good oxygen evolution activity in current research because of its abundant oxygen vacancies, specific 3d electron type, specific eg orbital, and good binding energy with oxygen-containing species. Meanwhile, niS is applied to the field of electrolytic water to a certain extent due to the special 3d configuration and high conductivity (adv. Mater.2017,29, 1701584. 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 invention aims to: 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 Ni 2+ a/PVP hybrid sol;
s2, adding the Ni 2+ The mixed sol of PVP is processedCarrying out electrostatic spinning to obtain a solid carbon fiber film;
and 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 is 2+ 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 Ni 2+ the/PVP mixed sol.
More preferably, the mass fraction of PVP in the PVP solution is 5 to 10%.
Preferably, the Ni is 2+ In the mixed sol of/PVP, ni 2+ The molar weight of (b) is 0.25 to 2.0mmol.
As a preferable scheme:
in the step S3, the pre-oxidation is carried out in the air atmosphere at the temperature of 200-300 ℃.
In step S3, the heat treatment is carried out under the inert atmosphere, 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 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.
And in the step S3, performing vulcanization vapor deposition, namely performing vulcanization vapor deposition on a product subjected to oxidation treatment in an air atmosphere at 250-450 ℃ for 0.5-3 h by taking thiourea as a sulfur source.
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 nanocomposite material loaded with the NiS/NiO heterojunction as an alkaline oxygen evolution reaction catalyst.
The reaction principle of the invention is as follows: taking nickel nitrate as a metal source, polyvinylpyrrolidonePreparing Ni in advance by using alkanone as carbon-nitrogen source through electrostatic spinning technology 2+ 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 between the electrolyte and the catalyst, thereby being beneficial to the reaction;
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 carbon nanotube-supported NiS/NiO heterojunction material of a nitrogen-doped carbon nanofiber prepared according to example 1 of the invention;
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, carbon nanotube supported NiS/NiO heterojunction material, prepared according to example 1 of the present invention;
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 of the present invention and comparative examples 1 to 3.
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 concept 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)Ni 2+ preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C 2 H 5 OH solution, 1.5mmol of Ni (NO) was added 3 ) 2 ·6H 2 O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni 2+ A PVP sol;
2) Preparation of nitrogen-doped carbon nano composite material by electrostatic spinning methodLoading NiS/NiO heterojunction composite material: 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 pre-oxidized for 3 hours at 250 ℃ in the air, and then the solid carbon fiber film material is subjected to N 2 Heating 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. As can be seen from the XRD spectrum of FIG. 4, the diffraction peaks of the material are completely matched with the standard cards of NiO and NiS respectively (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 (figure 5) of the product D /I G The value of 0.93 indicates a higher degree of graphitization of the resulting carbon material. From the thermogravimetric spectrum (fig. 6), it was found that the carbon content of the material was 19.56wt%. 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 -2 The overpotential of this material at a current density of (d) is only 269mV. The Tafel plot (FIG. 8) shows that the Tafel slope of this material has a value of only 48.4mV dec -1 This is superior to most basic oxygen evolution electrocatalyst materials. Cycle Performance test (FIG. 9) at pass 300The LSV curves before and after 0 CV cycles almost coincide, indicating that the stability is better. 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 and a carbon nanotube loaded NiS/NiO heterojunction material comprises the following steps:
1)Ni 2+ preparation of PVP mixed sol: 0.8g PVP was weighed out with 6mL DMF and 6mL C 2 H 5 OH solution, 1.5mmol of Ni (NO) was added 3 ) 2 ·6H 2 O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni 2+ A PVP sol;
2) Preparing a nitrogen-doped carbon nano composite material loaded 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 N 2 Heating 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 3
A preparation method of a nitrogen-doped carbon nanofiber, namely a carbon nanotube-loaded NiS/NiO heterojunction material, comprises the following steps:
1)Ni 2+ preparation of PVP mixed sol: weigh 0.7g PVP with 6mL DMF and 6mL C 2 H 5 OH solution, 1.5mmol of Ni (NO) was added 3 ) 2 ·6H 2 O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni 2+ 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 N 2 Heating 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)Ni 2+ preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C 2 H 5 OH solution was mixed and 1.0mmol of Ni (NO) was added 3 ) 2 ·6H 2 O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni 2+ A PVP sol;
2) Preparing a nitrogen-doped carbon nano composite material load NiS/NiO heterojunction composite material by an electrostatic spinning method: the tawny 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 pre-oxidized for 3 hours at 250 ℃ in the air, and then the solid carbon fiber film material is subjected to N 2 Heating 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)Ni 2+ preparation of/PVP (polyvinyl pyrrolidone) mixed sol: weigh 1.0g PVP with 6mL DMF and 6mL C 2 H 5 OH solution was mixed and 0.5mmol of Ni (NO) was added 3 ) 2 ·6H 2 O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni 2+ 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 N 2 Heating 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)Ni 2+ preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C 2 H 5 OH solution was mixed and 0.25mmol of Ni (NO) was added 3 ) 2 ·6H 2 O solid metal nitrate; mechanically stirring for 12h at room temperature to obtain light green Ni 2+ 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 N 2 Heating 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)Ni 2+ preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C 2 H 5 OH solution, 1.5mmol of Ni (NO) was added 3 ) 2 ·6H 2 O solid metal nitrate; mechanically stirring for 12h at room temperature to obtain light green Ni 2+ 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 pre-oxidized for 3 hours at 250 ℃ in the air, and then the solid carbon fiber film material is subjected to N 2 Heating 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)Ni 2+ preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C 2 H 5 OH solution, 1.5mmol of Ni (NO) was added 3 ) 2 ·6H 2 O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni 2+ A PVP sol;
2) Preparing a nitrogen-doped carbon nano composite material loaded 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 N 2 At a rate of 5 deg.C/min under an atmosphereRaising the temperature to 600 ℃ at a heating rate, carrying out heat treatment, keeping the temperature for 3h, then cooling to room temperature, carrying out oxidation treatment at 300 ℃ in an air atmosphere, taking thiourea of which the mass is twenty times that of a sample as a sulfur source, and carrying out vulcanization vapor deposition at 350 ℃ for 1.0h 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)Ni 2+ preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C 2 H 5 OH solution was mixed and 1.5mmol of Ni (NO) was added 3 ) 2 ·6H 2 O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni 2+ 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 N 2 Heating 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 at 350 ℃ for 2.0h 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)Ni 2+ preparation of/PVP hybrid sol: weigh 1.0g PVP with 6mL DMF and 6mL C 2 H 5 OH solution, 1.5mmol of Ni (NO) was added 3 ) 2 ·6H 2 O solid metal nitrate; mechanically stirring at room temperature for 12h to obtain light green Ni 2+ A PVP sol;
2) Preparation of nitrogen-doped carbon nano-grade by electrostatic spinning methodThe composite material loads the NiS/NiO heterojunction composite material: 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 N 2 Heating 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 in 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 2h.
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 4h.
Comparative example 1
The comparative example is different from example 1 only in that it is subjected to the high temperature carbonization treatment at 600 ℃ and the other 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, the metal-free electrocatalytic material shows the most negative initial reduction potential and the smallest current density, showing 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 (7)

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, preparing Ni 2+ a/PVP hybrid sol;
s2, mixing the Ni 2+ 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;
the Ni 2+ 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 Ni 2+ a/PVP hybrid sol;
in the step S3, the pre-oxidation is carried out in the air atmosphere under the condition of 200 to 300 ℃; the heat treatment under the inert atmosphere is 1 to 20 o Raising the temperature to 600 to 1000 ℃ at the speed of C/min, and preserving the heat for 2 to 4 hours.
2. The method for preparing the NiS/NiO heterojunction-loaded nitrogen-doped carbon nanocomposite material as claimed in claim 1, wherein the mass fraction of PVP in the PVP solution is 5-10%.
3. The method for preparing the NiS/NiO heterojunction-supported nitrogen-doped carbon nanocomposite material as claimed in claim 1, wherein the method is characterized in thatNi 2+ In the mixed sol of/PVP, ni 2+ The molar weight of (b) is 0.25 to 2.0mmol.
4. The method for preparing the NiS/NiO heterojunction-loaded 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 at 200 to 500 ℃ for 0.5 to 3 hours.
5. The method for preparing the NiS/NiO heterojunction-loaded nitrogen-doped carbon nanocomposite material as claimed in claim 1, wherein in the step S3, the sulfide vapor deposition is carried out, and thiourea is used as a sulfur source for a product of oxidation treatment in an air atmosphere, and the sulfide vapor deposition is carried out for 0.5 to 3 hours at the temperature of 250 to 450 ℃.
6. A nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction, which is prepared by the preparation method of any one of claims 1 to 5.
7. Use of the NiS/NiO heterojunction-supported nitrogen-doped carbon nanocomposite material of claim 6 as a catalyst for basic oxygen evolution reaction.
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