CN113215610A - Porous channel nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal monoatomic atoms and preparation method and application thereof - Google Patents
Porous channel nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal monoatomic atoms and preparation method and application thereof Download PDFInfo
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- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 93
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 42
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- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
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- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a porous nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal single atoms, and a preparation method and application thereof, wherein the preparation method comprises the following steps: the preparation method comprises the following steps: preparing 3d transition metal/TEOS/PAN mixed sol; the 3d transition metal/TEOS/PAN mixed sol is subjected to electrostatic spinning, heat treatment under high-temperature inert atmosphere and alkali etching to generate SiO2And (3) obtaining the porous channel nitrogen-doped carbon nanofiber composite material loaded with the 3d transition metal single atom by using a hard template. Product forms prepared by the inventionThe carbon nanofiber has the characteristics of multiple active sites, low overpotential, good stability, a one-dimensional composite structure and the like, is an electrolytic hydro-electric catalyst material with great potential, and can be used for preparing an acidic hydrogen evolution reaction electro-catalyst.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts, and particularly relates to a porous nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal single atoms, and a preparation method and application thereof.
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 cathodic hydrogen evolution reaction in the electrolytic water reaction involves a higher reaction energy barrier and a larger overpotential, which severely affects the overall electrolytic water reaction kinetics rate. Therefore, it is of great significance to develop a high-efficiency hydrogen evolution electrocatalyst to reduce the reaction activation energy and energy barrier and to improve the reaction kinetic rate. At present, a commercial hydrogen evolution catalyst is a noble metal platinum carbon, 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 hydrogen evolution electrocatalyst is particularly critical.
The electrocatalytic reaction only reacts on the surface interface of the nano catalyst, so that the adsorption of reactants on the surface of the catalyst and the desorption of products on the surface of the catalyst determine the catalytic efficiency to a great extent, and the reaction kinetics in the catalytic reaction process can be effectively changed by regulating and controlling the size and the surface electronic structure of the nano catalyst, so that the hydrogen production performance of electrolyzed water is improved. Recent studies have shown that as the size of nanoparticles is reduced to sub-nanometer dimensions, the number of non-coordinated metal atoms increases dramatically, providing a greater abundance of catalytically active sites. Particularly, when stable metal monoatomic is formed, the atom utilization rate reaches the maximum and approaches to 100 percent. In recent years, some transition metal monatomic catalysts have attracted considerable attention in electrocatalytic reactions, and various transition metal monatomic catalysts supported on a base material such as a metal oxide, a metal nitride, porous carbon, or a molecular sieve have been developed. The substrate material not only can stabilize the transition metal single-atom catalyst and provide good conductivity, but also can regulate and control the electronic structure of transition metal atoms through the interface action with metal, thereby further improving the catalytic performance. The reported methods for preparing transition metal monatomic catalysts are mainly: thermal deposition, hydrothermal, electrodeposition, photoreduction, templating, and the like. These preparation methods are relatively cumbersome and not conducive to mass production, and some methods require harsh conditions, which limits their practical applications. The electrostatic spinning technology has attracted extensive attention due to the advantages of simple preparation, low cost, high efficiency and capability of preparing micro-nano fiber materials in batches. Although such research has been advanced to some extent, the monatomic catalyst has the characteristics of high surface free energy, easy agglomeration and sintering, and the electrolytic water performance of the monatomic catalyst still cannot meet the strict requirements of industrial production. Research results show that the active sites of the catalyst can be effectively dispersed by modifying or coating the metal monatomic active substance on the carbon material, so that a larger specific surface area is provided, more catalytic active centers are exposed, and the stability of active species is enhanced. Meanwhile, hetero atoms (such as N, P, S and the like) are doped into the carbon matrix, so that the hydrogen evolution performance can be effectively improved by adjusting the electronic structure of the nearby carbon atoms; on the other hand, the material can be used as a site for anchoring a monoatomic atom, and the coordination environment and the electronic structure of the monoatomic material are optimized. In structural design, compared with zero-dimensional and two-dimensional structures, the one-dimensional porous nano structure which is well designed usually has a highly open space structure due to the geometric advantages, so that more available surface active areas and high multi-interface specific surface areas are provided, and the adsorption and effective hydrogen escape of reaction intermediate products are improved, thereby remarkably improving the electrochemical reaction performance related to gas escape reaction. It is noteworthy that the cross-linking of the structural units of the one-dimensional carbon material into the three-dimensional carbon matrix maximizes the utilization rate of the catalyst and optimizes the electron transport path, and suppresses the stacking problem that may occur with adjacent carbon nanofibers. Therefore, combining these synergistic advantages, it is a sensible strategy to synthesize heteroatom-doped one-dimensional multi-channel carbon nanofiber anchored monatomic materials. 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: aiming at the problems in the prior art, the invention provides a preparation method of a porous channel nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal monoatomic atoms, the method realizes and prepares a nitrogen-doped carbon nanofiber anchoring 3d transition metal monoatomic material with a porous channel structure, the method is simple, easy and universal, and low in cost, and the prepared nitrogen-doped highly porous flexible carbon nanofiber material loaded with 3d transition metal monoatomic atoms shows excellent activity and stability as a hydrogen evolution electrocatalyst material, and mainly solves the problems of high preparation cost, complex flow and unsatisfactory activity and stability of the existing electrolytic water hydrogen evolution catalyst.
The invention also provides a porous channel nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal single atoms and prepared by the preparation method and application.
The technical scheme is as follows: in order to achieve the purpose, the invention provides a preparation method of a porous channel nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal single atoms, which comprises the following steps:
(1) dissolving a carbon nanofiber precursor, 3d transition metal salt and tetraethyl orthosilicate in N, N dimethylformamide to obtain uniformly mixed 3d transition metal/TEOS/PAN mixed sol;
(2) the mixed sol is subjected to electrostatic spinning and heat treatment under high-temperature inert atmosphere to generate SiO2Template and alkali etching to remove SiO2And (3) obtaining the porous channel nitrogen-doped carbon nanofiber composite material loaded with the 3d transition metal single atom by using a hard template.
Wherein, the carbon nanofiber precursor in the step (1) is one or more of polyacrylonitrile, polyvinylpyrrolidone and polyvinyl alcohol.
The 3d transition metal salt in the step (1) comprises one or more of Mo salt, V salt, Fe salt, Co salt, Ni salt, Cu salt and Mn salt, and the molar weight of the 3d transition metal salt is 0.1-1.0 mmol.
Preferably, the 3d transition metal salt in the step (1) is one or more of molybdenum acetylacetonate, ammonium molybdate and sodium molybdate.
Wherein the addition amount of the tetraethyl orthosilicate in the step (1) is 0.1-2.5 mL, the addition amount of the carbon nanofiber precursor is 0.5-1.5g, and the addition amount of the N, N-dimethylformamide is 6-15 mL.
Wherein, the electrostatic spinning in the step (2) has the following operation parameters: the spinning voltage is 10-30 kV, the distance from the receiving device to the spinning needle is 4-20 cm, and the solution flow rate is 0.01-1.0 mL/min.
The heat treatment method under the high-temperature inert atmosphere in the step (2) specifically comprises the following steps: in an inert atmosphere, heating to 600-1000 ℃ at the speed of 1-20 ℃/min, and preserving heat for 2-8 h.
Preferably, the inert atmosphere in step (2) comprises N2、Ar、N2/H2、Ar/H2、NH3、CO2At least one of (1).
Wherein the alkali etching in the step (2) is carried out by using 0.2-2.0M NaOH solution for water bath treatment.
The porous nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal single atoms is prepared by the preparation method.
The invention relates to application of a porous nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal single atoms in preparation of an acidic hydrogen evolution reaction electrocatalyst.
The carbon carrier consists of one-dimensional highly porous flexible carbon nano fiber, and the one-dimensional highly porous flexible carbon nano fiber is prepared by carbonizing a carbon nano fiber precursor such as polyacrylonitrile at high temperature and passing through SiO2And (4) template-assisted synthesis.
The reaction principle of the invention is as follows: using 3d transition metal salt such as molybdenum acetylacetonate as metal source, carbon nanofiber precursor such as Polyacrylonitrile (PAN) as carbon nitrogen source, and tetraethyl orthosilicate (Si (OC)2H5)4TEOS) as silicon source, preparing 3d transition metal/TEOS/PAN mixed sol in advance by electrostatic spinning, calcining at high temperature under inert atmosphere, and preparing SiO-coated by carbonization and reduction2Particles and 3d transition metal such as molybdenum monoatomic carbon nanofiber material, and finally etching redundant tetraethyl orthosilicate by alkali liquor to form SiO2And (4) carrying out particle preparation to obtain the nitrogen-doped carbon nanofiber anchoring 3d transition metal monoatomic material with a porous channel structure. Wherein, TEOS is converted into SiO in situ in the high-temperature calcination process2The material can be used as a hard template and a pore-forming agent, and is a necessary condition for forming a multi-pore channel and monatomic material, the material is regular and uniform in appearance, and the 3d transition metal such as Mo is uniformly embedded in the highly porous and flexible carbon nanofiber. In addition, the obtained highly porous flexible carbon nanofiber contains abundant N elements, and due to the composition and structure advantages between the one-dimensional highly porous flexible carbon nanofiber and the active metal 3d transition metal such as Mo monatomic, the obtained material has high catalytic activity of hydrogen evolution from electrolyzed water and excellent stability.
The invention focuses on the SiO generated in situ by taking tetraethyl orthosilicate as a silicon source2As a hard template, a monatomic catalyst and a porous channel structure are formed, if no tetraethyl orthosilicate is used as a silicon source, the SiO is generated2The introduction of (2) cannot form a monoatomic and porous channel structure. The single-atom catalyst has very obvious advantages: the atom utilization rate is close to 100 percent, the intrinsic activity is high, the porous channel is favorable for the contact of the catalyst and the electrolyte, and the dynamic reaction rate of the catalyst is improved.
The 3d transition metal monatomic material loaded by the one-dimensional highly-porous flexible carbon nanofiber structure prepared by the invention has the following advantages:
1) the 3d transition active metal with atom size, such as Mo, has excellent electrochemical activity and more catalytic active sites;
2) the composite structure of the one-dimensional highly-porous flexible carbon nanofiber enables the catalyst material to have a large specific surface area, and meanwhile, the porous structure of the carbon fiber material can effectively promote the contact of electrolyte and the catalyst, so that the generation of hydrogen evolution reaction is facilitated;
3) the three-dimensional network structure assembled by 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 nanofiber material can effectively anchor active 3d transition metal materials such as Mo monoatomic atoms, so that the active 3d transition metal materials are not easy to agglomerate and fall off in the reaction process, and the integrity of the one-dimensional composite structure is maintained;
5) PAN with higher nitrogen content is selected as a nitrogen and phosphorus source, and a carbon carrier with higher graphitization degree and better thermal stability is doped through high-temperature carbonization and reduction, and the conductivity of the carbon carrier can be effectively changed by doping nitrogen, so that the hydrogen evolution performance of the material is improved.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1) the 3d transition metal monatomic electrocatalyst material which is of a one-dimensional composite structure and is loaded by the highly porous flexible carbon nanofiber is prepared by simple and convenient electrostatic spinning and high-temperature carbonization thermal reduction, and large-scale production can be realized;
2) the carbon nitrogen source is selected from Polyacrylonitrile (PAN)) As sources of 3d transition metals, e.g. molybdenum (C) acetylacetonate10H14MoO6) And SiO with Tetraethylorthosilicate (TEOS) as a hard template and porogen2The silicon source is cheap and easy to obtain, and compared with the traditional method for preparing the electrolytic water electrocatalyst material, the method has the advantages of simple and easy process, low cost, simple operation and capability of realizing large-scale production;
3) the prepared product has regular shape, and 3d transition metal monoatomic atoms are uniformly loaded in the one-dimensional composite highly porous flexible carbon nano fibers, so that the prepared material has the characteristics of more active sites, low overpotential, good stability and the like. The material prepared by the invention is an electrolytic water hydrogen evolution electrocatalyst material with great potential, can be used for preparing an electrocatalyst for acidic electrolytic water reaction, and is expected to have wide application prospect in the future energy industry.
Drawings
Fig. 1 is a low power SEM image of a nitrogen-doped carbon nanofiber anchored Mo monoatomic material of a multi-channel structure prepared according to example 1 of the present invention;
fig. 2 is an enlarged SEM image of a nitrogen-doped carbon nanofiber anchored Mo monoatomic material of a multi-channel structure prepared according to example 1 of the present invention;
fig. 3 is a TEM spectrum of a nitrogen-doped carbon nanofiber anchored Mo monoatomic material of a multi-channel structure prepared according to example 1 of the present invention;
fig. 4 is a STEM-HAADF map of a nitrogen-doped carbon nanofiber anchored Mo monoatomic material of a multi-channel structure prepared according to example 1 of the present invention;
fig. 5 is an XRD pattern of the nitrogen-doped carbon nanofiber anchored Mo monoatomic material of the porous channel structure prepared according to example 1 of the present invention;
fig. 6 is a Raman spectrum of a nitrogen-doped carbon nanofiber anchored Mo monoatomic material of a multi-channel structure prepared according to example 1 of the present invention;
fig. 7 is an isothermal adsorption and desorption curve of a nitrogen-doped carbon nanofiber anchored Mo monoatomic material of a multi-channel structure prepared according to example 1 of the present invention;
fig. 8 is a hydrogen evolution LSV curve of a nitrogen-doped carbon nanofiber anchored Mo monoatomic material of a multi-channel structure prepared according to example 1 of the present invention;
fig. 9 is a hydrogen evolution Tafel curve of a nitrogen-doped carbon nanofiber anchored Mo monoatomic material with a multi-channel structure prepared according to example 1 of the present invention;
fig. 10 is an LSV curve after 3000 previous and subsequent tests of a nitrogen-doped carbon nanofiber anchored Mo monoatomic material of a multi-channel structure prepared according to example 1 of the present invention;
FIG. 11 is a comparison of LSV curves of the hydrogen evolution reactions of the materials obtained in example 1 and comparative examples 1-2 of the present invention.
Detailed Description
The invention will be further described with reference to specific embodiments and the accompanying drawings.
The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Polyacrylonitrile, Sigma-Aldrich, Mw 150000
Polyvinylpyrrolidone, Sigma-Aldrich, Mw 1300000
Polyvinyl alcohol Sigma-Aldrich, Mw 13000 ═ Mw
Example 1
A preparation method of a Mo monoatomic supported porous nitrogen-doped carbon nanofiber composite material comprises the following steps:
1)Mo6+preparation of/TEOS/PAN Mixed Sol: weighing 0.5mmol of molybdenum acetylacetonate, 1.0g of PAN polyacrylonitrile, 2.0mL of TEOS and 12mL of N, N dimethylformamide solution, and uniformly mixing for 12h under the condition of stirring at normal temperature to obtain mixed sol, namely Mo6+TEOS/PAN mixed sol;
2) preparing a nitrogen-doped multi-channel flexible carbon nanofiber loaded Mo monoatomic composite material by electrostatic spinning: mo prepared in the step 1)6+TEOS/PAN, the flexible carbon nanofiber membrane material is obtained through electrostatic spinning treatment, and the operating parameters of electrostatic spinning are as follows: the spinning voltage is 20kV, the distance from the receiving device to the spinning needle is 18cm, and the solution flow rate is 0.6 mL/min. Then in N2Heating to 900 ℃ at a heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, cooling to room temperature, treating the obtained solid product in 2.0M NaOH aqueous solution in 60 ℃ water bath for 8h, respectively centrifuging and washing for three times under the conditions of water and ethanol, and drying for 12h at 40 ℃ in an oven to obtain the final product, namely the nitrogen-doped porous carbon nanofiber load Mo monatomic composite material (SA-Mo @ NMCNFs).
Physical characterization was performed on the nitrogen-doped multi-channel flexible carbon nanofiber supported Mo single-atom composite material prepared in example 1 by using TEM, SEM, XRD, Raman, EDX and other approaches. From the low power SEM (as shown in fig. 1), it can be seen that the highly porous and flexible one-dimensional carbon nanofibers are cross-linked to form a three-dimensional network structure, and meanwhile, it can be clearly seen that no significant Mo nanoparticles exist on the flexible one-dimensional porous carbon nanofibers (mainly because of the small size of the monoatomic atom, which cannot be observed by a common electron microscope), and from the further enlarged SEM image (as shown in fig. 2), it can be seen that the diameter of the prepared material is about 150nm, and meanwhile, a porous channel structure exists inside the carbon nanofibers. The TEM spectrum (as shown in FIG. 3) shows that no Mo nano particles are obviously embedded in the flexible porous carbon nano fiber, and a multi-pore channel structure exists, which is consistent with the result of SEM and can be preliminarily proved to be in a monoatomic morphology. As shown in FIG. 4, in a dark field environment, a spherical aberration electron microscope image of a sample shows that a white bright point in the image is Mo, and the brightness of the white bright point is higher than that of a C and N substrate, so that a monoatomic form is formed, and the existence of Mo monoatomic can be directly proved. As can be seen from an XRD pattern (as shown in figure 5), diffraction peaks of the material correspond to C (002) crystal faces and C (111) crystal faces at 26 degrees and 44 degrees respectively, and the successful preparation of Mo monoatomic atoms is proved. Calculating I of the sample according to Raman spectrum (shown in FIG. 6) of the productD/IGThe value is 1.23, which indicates that the obtained carbon material anchoring Mo monoatomic atoms has higher defect degree and is beneficial to the promotion of the electrocatalytic activity. The nitrogen isothermal adsorption and desorption curve test (as shown in figure 7) shows that the pore diameter is a mesoporous structure, and the BET specific surface area is 274.4 m2 g-1And the specific surface area is large.
At 0.5M H2SO4In medium at 5mV s-1The material prepared in example 1 was tested for its hydrogen evolution performance, resulting in an LSV profile. From FIG. 8, it can be seen that the current density is 10mA cm-2The overpotential of this material at current density of (a) is only 66 mV. The Tafel curve (as shown in FIG. 9) shows that the Tafel slope of the material has a value of only 48.9mV dec-1This is superior to most acidic hydrogen evolution electrocatalyst materials, Co-Mo, under the same test conditions2C (Adv.Funct.Mater.,2020,30,2000561),NV-Fe2N-350(adv. mater.,2020,32, 1904346). Meanwhile, when the material is subjected to cyclic voltammetry curves of 3000 circles before and after scanning, the LSV of the material is hardly changed before and after the cyclic voltammetry curves, and the material is also shown to have excellent catalytic stability. The results show that the material has good application prospect as the acidic electrolyzed water hydrogen evolution electrocatalyst material.
Example 2
A preparation method of a Mo monoatomic supported porous nitrogen-doped carbon nanofiber composite material comprises the following steps:
1)Mo6+preparation of/TEOS/PAN Mixed Sol: weighing 0.3mmol of molybdenum acetylacetonate, 1.0g of PAN, 2.0mL of TEOS and 12mL of N, N dimethylformamide solution, and uniformly mixing for 12h under the condition of stirring at normal temperature to obtain mixed sol, namely Mo6+TEOS/PAN mixed sol;
2) preparing a nitrogen-doped multi-channel flexible carbon nanofiber load Mo monoatomic composite material by using an electrostatic spinning technology: mo prepared in the step 1)6+TEOS/PAN, the flexible carbon nanofiber membrane material is obtained through electrostatic spinning treatment, and the operating parameters of electrostatic spinning are as follows: the spinning voltage is 20kV, the distance from the receiving device to the spinning needle is 18cm, and the solution flow rate is 0.6 mL/min. Then in N2Under the atmosphere, the temperature rise rate is 5 ℃/minAnd (3) heating to 900 ℃ for heat treatment, keeping the temperature for 3h, cooling to room temperature, treating the obtained solid product in 2.0M NaOH aqueous solution in a water bath at 60 ℃ for 8h, finally, respectively centrifugally washing for three times under the conditions of water and ethanol, and drying for 12h in an oven at 40 ℃ to obtain the final product, namely the nitrogen-doped porous carbon nanofiber loaded Mo monoatomic composite material.
Example 3
A preparation method of a Mo monoatomic supported porous nitrogen-doped carbon nanofiber composite material comprises the following steps:
1)Mo6+preparation of/TEOS/PAN Mixed Sol: weighing 0.8mmol of molybdenum acetylacetonate, 1.0g of PAN, 2.0mL of TEOS and 12mL of N, N dimethylformamide solution, and uniformly mixing for 12h under the condition of stirring at normal temperature to obtain mixed sol, namely Mo6+TEOS/PAN mixed sol;
2) preparing a nitrogen-doped multi-channel flexible carbon nanofiber load Mo monoatomic composite material by using an electrostatic spinning technology: mo prepared in the step 1)6+TEOS/PAN, the flexible carbon nanofiber membrane material is obtained through electrostatic spinning treatment, and the operating parameters of electrostatic spinning are as follows: the spinning voltage is 20kV, the distance from the receiving device to the spinning needle is 18cm, and the solution flow rate is 0.6 mL/min. Then in N2Heating to 900 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, cooling to room temperature, treating the obtained solid product in 2.0M NaOH aqueous solution in 60 ℃ water bath for 8h, respectively centrifugally washing for three times under the conditions of water and ethanol, and drying for 12h at the temperature of 40 ℃ in an oven to obtain the final product, namely the nitrogen-doped porous carbon nanofiber loaded Mo monatomic composite material.
Example 4
A preparation method of a Mo monoatomic supported porous nitrogen-doped carbon nanofiber composite material comprises the following steps:
1)Mo6+preparation of/TEOS/PAN Mixed Sol: weighing 0.5mmol of molybdenum acetylacetonate, 1.0g of PAN, 1.0mL of TEOS and 12mL of N, N dimethylformamide solution, and uniformly mixing for 12h under the condition of stirring at normal temperature to obtain a mixtureSynthetic sols, i.e. Mo6+TEOS/PAN mixed sol;
2) preparing a nitrogen-doped multi-channel flexible carbon nanofiber load Mo monoatomic composite material by using an electrostatic spinning technology: mo prepared in the step 1)6+TEOS/PAN, the flexible carbon nanofiber membrane material is obtained through electrostatic spinning treatment, and the operating parameters of electrostatic spinning are as follows: the spinning voltage is 20kV, the distance from the receiving device to the spinning needle is 18cm, and the solution flow rate is 0.6 mL/min. Then in N2Heating to 900 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, cooling to room temperature, treating the obtained solid product in 2.0M NaOH aqueous solution in 60 ℃ water bath for 8h, respectively centrifugally washing for three times under the conditions of water and ethanol, and drying for 12h at the temperature of 40 ℃ in an oven to obtain the final product, namely the nitrogen-doped porous carbon nanofiber loaded Mo monatomic composite material.
Example 5
A preparation method of a Mo monoatomic supported porous nitrogen-doped carbon nanofiber composite material comprises the following steps:
1)Mo6+preparation of/TEOS/PAN Mixed Sol: weighing 0.5mmol of molybdenum acetylacetonate, 1.0g of PAN, 2.5mL of TEOS and 12mL of N, N dimethylformamide solution, and uniformly mixing for 12h under the condition of stirring at normal temperature to obtain mixed sol, namely Mo6+TEOS/PAN mixed sol;
2) preparing a nitrogen-doped multi-channel flexible carbon nanofiber load Mo monoatomic composite material by using an electrostatic spinning technology: mo prepared in the step 1)6+TEOS/PAN, the flexible carbon nanofiber membrane material is obtained through electrostatic spinning treatment, and the operating parameters of electrostatic spinning are as follows: the spinning voltage is 20kV, the distance from the receiving device to the spinning needle is 18cm, and the solution flow rate is 0.6 mL/min. Then in N2Heating to 900 ℃ at a heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, cooling to room temperature, treating the obtained solid product in 2.0M NaOH aqueous solution in 60 ℃ water bath for 8h, respectively centrifuging and washing for three times under the conditions of water and ethanol, and drying in an oven at 40 ℃ for 12h to obtain the final product, namely the nitrogen-doped productThe heterogeneous porous carbon nanofiber loads Mo monoatomic composites.
Example 6
A preparation method of a Mo monoatomic supported porous nitrogen-doped carbon nanofiber composite material comprises the following steps:
1)Mo6+preparation of/TEOS/PAN Mixed Sol: weighing 0.5mmol of molybdenum acetylacetonate, 1.0g of PAN, 2.0mL of TEOS and 12mL of N, N dimethylformamide solution, and uniformly mixing for 12h under the condition of stirring at normal temperature to obtain mixed sol, namely Mo6+TEOS/PAN mixed sol;
2) preparing a nitrogen-doped multi-channel flexible carbon nanofiber load Mo monoatomic composite material by using an electrostatic spinning technology: mo prepared in the step 1)6+TEOS/PAN, the flexible carbon nanofiber membrane material is obtained through electrostatic spinning treatment, and the operating parameters of electrostatic spinning are as follows: the spinning voltage is 20kV, the distance from the receiving device to the spinning needle is 18cm, and the solution flow rate is 0.6 mL/min. Then in N2Heating to 800 ℃ at a heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, cooling to room temperature, treating the obtained solid product in 2.0M NaOH aqueous solution in 60 ℃ water bath for 8h, respectively centrifugally washing for three times under the conditions of water and ethanol, and drying for 12h at 40 ℃ in an oven to obtain the final product, namely the nitrogen-doped porous carbon nanofiber loaded Mo monatomic composite material.
Example 7
A preparation method of a Mo monoatomic supported porous nitrogen-doped carbon nanofiber composite material comprises the following steps:
1)Mo6+preparation of/TEOS/PAN Mixed Sol: weighing 0.5mmol of molybdenum acetylacetonate, 1.0g of PAN, 2.0mL of TEOS and 12mL of N, N dimethylformamide solution, and uniformly mixing for 12h under the condition of stirring at normal temperature to obtain mixed sol, namely Mo6+TEOS/PAN mixed sol;
2) preparing a nitrogen-doped multi-channel flexible carbon nanofiber load Mo monoatomic composite material by using an electrostatic spinning technology: mo prepared in the step 1)6+TEOS/PAN, and flexible carbon nano is obtained through electrostatic spinning treatmentThe rice fiber membrane material has the following electrostatic spinning operation parameters: the spinning voltage is 20kV, the distance from the receiving device to the spinning needle is 18cm, and the solution flow rate is 0.6 mL/min. Then in N2Heating to 700 ℃ at a heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, cooling to room temperature, treating the obtained solid product in 2.0M NaOH aqueous solution in 60 ℃ water bath for 8h, respectively centrifugally washing for three times under the conditions of water and ethanol, and drying for 12h at 40 ℃ in an oven to obtain the final product, namely the nitrogen-doped porous carbon nanofiber loaded Mo monatomic composite material.
Example 8
A preparation method of a Mo monoatomic supported porous nitrogen-doped carbon nanofiber composite material comprises the following steps:
1)Mo6+preparation of/TEOS/PAN Mixed Sol: weighing 0.5mmol of molybdenum acetylacetonate, 1.0g of PAN, 2.0mL of TEOS and 12mL of N, N dimethylformamide solution, and uniformly mixing for 12h under the condition of stirring at normal temperature to obtain mixed sol, namely Mo6+TEOS/PAN mixed sol;
2) preparing a nitrogen-doped multi-channel flexible carbon nanofiber load Mo monoatomic composite material by using an electrostatic spinning technology: mo prepared in the step 1)6+TEOS/PAN, the flexible carbon nanofiber membrane material is obtained through electrostatic spinning treatment, and the operating parameters of electrostatic spinning are as follows: the spinning voltage is 20kV, the distance from the receiving device to the spinning needle is 18cm, and the solution flow rate is 0.6 mL/min. Then in N2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, cooling to room temperature, treating the obtained solid product in 2.0M NaOH aqueous solution in 60 ℃ water bath for 8h, respectively centrifugally washing for three times under the conditions of water and ethanol, and drying for 12h at the temperature of 40 ℃ in an oven to obtain the final product, namely the nitrogen-doped porous carbon nanofiber loaded Mo monatomic composite material.
Example 9
A preparation method of a Mo monoatomic supported porous nitrogen-doped carbon nanofiber composite material comprises the following steps:
1)Mo6+preparation of/TEOS/PAN Mixed Sol: weighing 0.5mmol of molybdenum acetylacetonate, 1.0g of PAN, 2.0mL of TEOS and 12mL of N, N dimethylformamide solution, and uniformly mixing for 12h under the condition of stirring at normal temperature to obtain mixed sol, namely Mo6+TEOS/PAN mixed sol;
2) preparing a nitrogen-doped multi-channel flexible carbon nanofiber load Mo monoatomic composite material by using an electrostatic spinning technology: mo prepared in the step 1)6+TEOS/PAN, the flexible carbon nanofiber membrane material is obtained through electrostatic spinning treatment, and the operating parameters of electrostatic spinning are as follows: the spinning voltage is 20kV, the distance from the receiving device to the spinning needle is 18cm, and the solution flow rate is 0.6 mL/min. Then in N2Heating to 1000 ℃ at a heating rate of 5 ℃/min under the atmosphere, carrying out heat treatment, keeping the temperature for 3h, cooling to room temperature, treating the obtained solid product in 2.0M NaOH aqueous solution in 60 ℃ water bath for 8h, respectively carrying out centrifugal washing for three times under the conditions of water and ethanol, and drying for 12h at 40 ℃ in an oven to obtain the final product, namely the nitrogen-doped porous carbon nanofiber loaded Mo monoatomic composite material.
Example 10
A preparation method of a Mo monoatomic supported porous nitrogen-doped carbon nanofiber composite material comprises the following steps:
1)Mo6+preparation of/TEOS/PAN Mixed Sol: weighing 0.5mmol of molybdenum acetylacetonate, 1.0g of PAN, 2.0mL of TEOS and 12mL of N, N dimethylformamide solution, and uniformly mixing for 12h under the condition of stirring at normal temperature to obtain mixed sol, namely Mo6+TEOS/PAN mixed sol;
2) preparing a nitrogen-doped multi-channel flexible carbon nanofiber load Mo monoatomic composite material by using an electrostatic spinning technology: mo prepared in the step 1)6+TEOS/PAN, the flexible carbon nanofiber membrane material is obtained through electrostatic spinning treatment, and the operating parameters of electrostatic spinning are as follows: the spinning voltage is 20kV, the distance from the receiving device to the spinning needle is 18cm, and the solution flow rate is 0.6 mL/min. Then in NH3Heating to 900 deg.C at a heating rate of 5 deg.C/min under atmosphere, maintaining at the temperature for 3 hr, and coolingCooling to room temperature, treating the obtained solid product in 2.0M NaOH aqueous solution in water bath at 60 ℃ for 8h, finally, respectively centrifugally washing for three times under the conditions of water and ethanol, and drying for 12h in an oven at 40 ℃ to obtain the final product, namely the nitrogen-doped porous carbon nanofiber loaded Mo monoatomic composite material.
Example 11
The same as example 1, except that: polyvinyl pyrrolidone is used to replace polyacrylonitrile; the molybdenum salt is ammonium molybdate; 0.1mmol of molybdenum acetylacetonate, 0.1mL of tetraethyl orthosilicate, 0.5g of polyvinylpyrrolidone and 6mL of N, N-dimethylformamide. The operating parameters of electrostatic spinning are as follows: the spinning voltage is 10kV, the distance from the receiving device to the spinning needle is 4cm, and the solution flow rate is 0.01 mL/min. In N2Under the atmosphere, the temperature rising rate of the programmed temperature rise is 5 ℃/min, the heat treatment temperature is 600 ℃, and the time is 8 h.
Example 12
The same as example 1, except that: polyvinyl pyrrolidone is used for replacing polyvinyl alcohol; the molybdenum salt is sodium molybdate; 1.0mmol of molybdenum acetylacetonate, 2.5mL of tetraethyl orthosilicate, 1.5g of polyvinylpyrrolidone and 15mL of N, N-dimethylformamide. The operating parameters of electrostatic spinning are as follows: the spinning voltage is 30kV, the distance from the receiving device to the spinning needle is 20cm, and the solution flow rate is 1.0 mL/min. At NH3Under the atmosphere, the temperature rising rate of the programmed temperature rise is 5 ℃/min, the heat treatment temperature is 1000 ℃, and the time is 2 h.
Example 13
The same as example 1, except that: molybdenum acetylacetonate was replaced by vanadyl acetylacetonate.
Example 14
The same as example 1, except that: molybdenum acetylacetonate was replaced by iron acetylacetonate.
Example 15
The same as example 1, except that: molybdenum acetylacetonate was replaced by cobalt acetylacetonate.
Example 16
The same as example 1, except that: molybdenum acetylacetonate was replaced by nickel acetylacetonate.
Example 17
The same as example 1, except that: molybdenum acetylacetonate was replaced by copper acetylacetonate.
Comparative example 1
The comparative example differs from example 1 only in that no metal molybdenum acetylacetonate was added, the material obtained being designated as NMCNFs, the remaining operating conditions remaining unchanged.
Comparative example 2
This comparative example differs from example 1 only in that no TEOS was added and the material obtained was named Mo2C @ N-CNFs, and the rest of implementation conditions are unchanged.
The LSV test results of the hydrogen evolution reaction correspondingly tested according to the method of example 1 are shown in fig. 11, respectively, and the metal-free electrocatalytic material (comparative example 1) showed a poor initial reduction potential and a small current density, showing the worst hydrogen evolution performance; no SiO2Electrocatalytic material (Mo) prepared by template2C @ N-CNFs) all showed relatively SiO2The poor hydrogen evolution performance of the obtained material is assisted by the template. Comparison of the Total Hydrogen evolution Performance shows SA-Mo @ NMCNFs>Mo2C@N-CNFs>Order of NMCNFs. The one-dimensional porous flexible carbon nanofiber can effectively prevent Mo single atoms from agglomerating and falling off, and meanwhile, a fast channel for electrons and mass transfer is provided, so that the one-dimensional porous flexible carbon nanofiber is beneficial to solid-liquid-gas three-phase interface reaction of hydrogen evolution. The doping of N can change the neutral electronic structure of adjacent carbon, and is beneficial to changing the adsorption energy of hydrogen evolution reaction. In conclusion, based on the above structural and component advantages, the composite material prepared by the invention has excellent performance of hydrogen evolution by electrolyzing water.
Claims (10)
1. A preparation method of a porous channel nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal single atoms is characterized by comprising the following steps:
(1) dissolving a carbon nanofiber precursor, 3d transition metal salt and tetraethyl orthosilicate in N, N dimethylformamide to obtain uniformly mixed 3d transition metal/TEOS/PAN mixed sol;
(2) and (3) carrying out electrostatic spinning, heat treatment under high-temperature inert atmosphere and alkali etching on the mixed sol to obtain the porous nitrogen-doped carbon nanofiber composite material loaded with the 3d transition metal monoatomic atoms.
2. The 3d transition metal monoatomic-supported multi-channel nitrogen-doped carbon nanofiber composite material according to claim 1, wherein the carbon nanofiber precursor in the step (1) is one or more of polyacrylonitrile, polyvinylpyrrolidone and polyvinyl alcohol.
3. The porous nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal monoatomic ions according to claim 1, wherein the 3d transition metal salt in the step (1) preferably comprises one or more of Mo salt, V salt, Fe salt, Co salt, Ni salt, Cu salt and Mn salt, and the molar amount of the 3d transition metal salt is 0.1-1.0 mmol.
4. The porous nitrogen-doped carbon nanofiber composite supporting 3d transition metal monoatomic ions according to any one of claims 1 to 3, wherein the 3d transition metal salt in the step (1) is one or more of molybdenum acetylacetonate, ammonium molybdate and sodium molybdate.
5. The 3d transition metal monoatomic supported porous nitrogen-doped carbon nanofiber composite material according to claim 1, wherein the addition amount of tetraethyl orthosilicate in the step (1) is 0.1-2.5 mL, the addition amount of a carbon nanofiber precursor is 0.5-1.5g, and the addition amount of N, N-dimethylformamide is 6-15 mL.
6. The preparation method of the porous nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal monoatomic ions according to claim 1, wherein the electrostatic spinning in the step (2) has the following operation parameters: the spinning voltage is 10-30 kV, the distance from the receiving device to the spinning needle is 4-20 cm, and the solution flow rate is 0.01-1.0 mL/min.
7. The preparation method of the Mo monoatomic supported porous nitrogen-doped carbon nanofiber composite material according to claim 1, wherein the heat treatment method in the high-temperature inert atmosphere in the step (2) is specifically as follows: in an inert atmosphere, heating to 600-1000 ℃ at the speed of 1-20 ℃/min, and preserving heat for 2-8 h.
8. The method for preparing a porous nitrogen-doped carbon nanofiber composite carrying Mo monoatomic atoms according to claim 1, wherein the alkali etching in the step (2) is a water bath treatment using a 0.2-2.0M NaOH solution.
9. The porous nitrogen-doped carbon nanofiber composite material loaded with 3d transition metal single atoms and prepared by the preparation method of claim 1.
10. Use of the 3d transition metal monoatomic supported multi-pore nitrogen-doped carbon nanofiber composite material as claimed in claim 9 in preparation of an acidic hydrogen evolution reaction electrocatalyst.
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