CN113036165B - Nitrogen-sulfur doped defected carbon nano tube and preparation method thereof - Google Patents
Nitrogen-sulfur doped defected carbon nano tube and preparation method thereof Download PDFInfo
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- H01M4/90—Selection of catalytic material
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- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
The invention discloses a nitrogen-sulfur doped defected carbon nano tube, a preparation method thereof and a prepared defected carbon nano tubeCarbon nanotube materials have high efficiency electrocatalytic activity and durability. The method comprises the following steps: dicyandiamide as carbon/nitrogen source, Co (NO) 3 ) 2 ·6H 2 O is a metal source, by the sulfur-containing inorganic Salt Co (SCN) 2 Introducing heteroatom S, and carrying out primary heat treatment on the mixture precursor in an inert atmosphere to form N, S double-doped defected carbon nanotubes, wherein the defect is generated because the heteroatom S is diffused to a cobalt-containing region from a carbon region to form sulfide in the heat treatment process, so that abundant vacancies are left in a carbon skeleton, and the formation of pyridine nitrogen active sites is promoted. Thanks to the structural and compositional advantages, the N, S double-doped defected carbon nanotubes exhibit excellent ORR electrocatalytic activity and can be used as high-efficiency catalysts for fuel cells and zinc-air batteries.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a nitrogen-sulfur doped defected carbon nanotube and a preparation method thereof.
Background
Fuel cells have been considered as the most ideal energy storage devices, and zinc-air cells have become one of the most promising energy devices in the next-generation energy devices due to their advantages of low cost, environmental friendliness, high energy density, and convenient use. Currently, research on zinc-air batteries is mainly focused on an Oxygen Reduction Reaction (ORR) catalyst of a cathode, and a large amount of noble metal catalyst is required due to low efficiency of electrode reaction caused by slow kinetic process, however, the noble metal-based catalyst is expensive and poor in stability, so that the large-scale application of the zinc-air battery is greatly limited. Therefore, there is an increasing research effort to develop a non-noble metal catalyst with high activity and high stability to improve the electrode reaction efficiency of the above energy device.
Among many non-noble metal-based catalysts, carbon-based materials have the characteristics of good stability, low price, easy structure adjustment and the like, and are widely researched materials in the field of catalysis, however, among many carbon-based materials, carbon nanotubes have more obvious advantages, not only have high electron conductivity, but also can improve the activity thereof by doping heterogeneous elements, and in addition, the complete one-dimensional structure of the carbon nanotubes also ensures the chemical stability of the carbon nanotubes, so that the carbon nanotubes are excellent electrocatalysts. At present, most of carbon nanotubes doped with heterogeneous elements (P, S) are based on modification of commercial carbon nanotubes, sulfur doping often adopts an organic sulfur source, such as thiourea, trithiocyanuric acid, and the like, and related researches show that N, S doped carbon nanotubes can be obtained by introducing thiourea, melamine, and the like to modify the commercial carbon nanotubes. The ex-situ method has long steps, and because the atomic radius (0.102nm) of S is larger than that of C (0.077nm), the S element is difficult to be introduced into the pure carbon nanotube, and the doping effect is poor. Based on the above, in-situ rapid growth of N, S doped carbon nanotubes is a better choice. However, at present, many reports are made on carbon nanotubes doped with nitrogen in situ, and research on carbon nanotubes doped with elements such as P, S and the like grown by in situ catalysis is very little. In addition, the selection of the sulfur source is also important, and the organic sulfur source is mostly adopted to realize the doping of S in the research, but the inorganic sulfur source is cheaper, safe and environment-friendly.
Disclosure of Invention
The invention provides a nitrogen-sulfur doped defected carbon nanotube and a preparation method thereof, and the prepared carbon nanotube material not only has a stable structure and low price, but also has high-efficiency electrocatalytic activity and excellent durability.
In order to realize the purpose, the invention adopts the following technical scheme:
a nitrogen-sulfur doped defected carbon nanotube is a N, S double-doped defected carbon nanotube, the carbon nanotube material is bamboo-like, the end part of a carbon nanotube is open and presents a hollow structure, and the end part of the carbon nanotube is closed with particles wrapped by a carbon layer; the pipe diameter of the carbon nano tube is 50-150 nm.
A preparation method of a nitrogen-sulfur doped defected carbon nano tube comprises the following steps:
(1) a certain amount of Co (NO) 3 ) 2 ·6H 2 Dissolving O in the mixed solvent of absolute ethyl alcohol and deionized water, dispersing dicyandiamide in the solution, and filteringCarrying out ultrasonic treatment to fully dissolve the mixed solution, and then violently stirring the mixed solution for 1 hour at room temperature to obtain a uniformly mixed solution;
(2) stirring and evaporating the mixed solution at 70-80 ℃ to dryness to obtain a single precursor;
(3) fully grinding the precursor prepared in the step (2) for later use;
(4) heating the precursor ground in the step (3) to 800-1100 ℃ under the protection of nitrogen atmosphere, wherein the heating rate is 6 ℃ for min -1 Setting the heat preservation time to be 2h, and then cooling to room temperature to obtain a carbonized product, namely Co @ N-CNTs;
(5) weighing Co (SCN) 2 By replacing part of Co (NO) 3 ) 2 ·6H 2 O, synthesizing to obtain Co @ N, S-CNTs-1 according to the preparation method of Co @ N-CNTs; weighing Co (SCN) 2 Complete substitution of Co (NO) 3 ) 2 ·6H 2 And preparing the Co @ N, S-CNTs-2 by using O.
In the above step, the amount of dicyandiamide and Co (NO) in step 1 3 ) 2 ·6H 2 The molar ratio of O is 10:1, and the volume ratio of absolute ethyl alcohol to deionized water in the mixed solvent is 2: 1;
when synthesizing Co @ N, S-CNTs-1 in step 5, Co (SCN) 2 By replacing part of Co (NO) 3 ) 2 ·6H 2 O，Co(SCN) 2 With Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 1: 1.
The nitrogen-sulfur doped carbon nanotubes can be used as a catalyst for fuel cells or zinc-air cells.
Has the beneficial effects that: the invention provides a nitrogen-sulfur doped defected carbon nano tube and a preparation method thereof, wherein inorganic cobalt thiocyanate is used as a sulfur source, and the defected carbon nano tube containing N, S double doping is grown through the in-situ catalysis of transition metal, so that the effective doping of a heterogeneous element S is realized, and the formation of carbon defects is caused by the introduction of S atoms, and the electrocatalytic activity of a carbon nano tube material is obviously improved. The formation of the carbon nano-tube comes from the catalytic action of metallic cobalt, and forms the carbon nano-tube with typical bamboo-like characteristics, the tube diameter of the carbon nano-tube is about 50-150nm, and some carbon nano-tubesThe ends are open, presenting a hollow structure, some carbon nanotubes are closed at the ends and have particles surrounded by a carbon layer. Since during the heat treatment the hetero atoms S tend to diffuse from the carbon region to the cobalt-containing region to form sulfides, leaving rich vacancies in the carbon skeleton, while also promoting the formation of pyridine nitrogen active sites, the half-wave potential of the synthetic catalyst is 0.86V (relative to RHE), superior to Pt/C (0.83V) thanks to this structural and compositional advantage. The carbon nano tube catalyst provided by the invention is applied to a zinc-air battery and shows higher power density (62.1mW cm) -2 ) Is superior to Pt/C (58.7mW cm) -2 ). The catalytic material with a stable structure, high efficiency and durability is prepared by a simple extensible method with low cost, a new thought is provided for the development of energy devices, and the development of clean energy can be assisted.
Drawings
FIG. 1 is an SEM image of Co @ N-CNTs in an example of the present invention;
FIG. 2 is an SEM image of Co @ N, S-CNTs-1 in an example of the present invention;
FIG. 3 is an SEM image of Co @ N, S-CNTs-2 in an example of the present invention;
FIG. 4 is a Raman spectrum of Co @ N-CNTs, Co @ N, S-CNTs-1, Co @ N, S-CNTs-2 according to the present invention.
Detailed Description
The invention is described in detail below with reference to the following figures and specific examples:
embodiments relate to reagent and equipment sources:
Co(NO 3 ) 2 ·6H 2 o, available from alatin reagent, inc;
Co(SCN) 2 from Shanghai Maxin Biotechnology, Inc.;
dicyandiamide, available from carbofuran technologies ltd;
absolute ethanol is analytically pure AR, purchased from Nanjing chemical reagents, Inc.;
an electrochemical workstation: shanghai Chenghua instruments, Inc., CHI 760E;
scanning electron microscope: hitachi, Japan S-4800, acceleration voltage 10 kV;
raman spectrum: horiba Scientific LabRAM HR Evolution
Example 1
A preparation method of nitrogen-sulfur doped defected carbon nano-tubes comprises the following steps:
(1) accurately weighing 4mmol Co (NO) 3 ) 2 ·6H 2 O, and dissolved in a mixed solvent of absolute ethanol (50ml) and deionized water (25 ml). 40mmol of dicyandiamide was dispersed in the above solution and sufficiently dissolved by ultrasonic treatment. Then, the mixed solution is stirred vigorously for 1 hour at room temperature;
(2) transferring the mixed solution to a water bath kettle, stirring and evaporating at 80 ℃ to dryness to obtain a single precursor;
(3) fully grinding the precursor prepared in the step (2) for later use;
(4) putting the sample ground in the step (3) into a porcelain boat, heating to 800-1100 ℃ under the protection of nitrogen atmosphere, wherein the heating rate is 6 ℃ for min -1 . The heat preservation time is set to be 2h, and the carbonized product, namely Co @ N-CNTs, is obtained after the carbonized product is cooled to the room temperature.
Example 2
A preparation method of a nitrogen-sulfur doped defected carbon nano tube comprises the following steps:
(1) accurately weighing 2mmol Co (NO) 3 ) 2 ·6H 2 O and 2mmol Co (SCN) 2 And dissolved in a mixed solvent of absolute ethanol (50ml) and deionized water (25 ml). Then, 40mmol of dicyandiamide was dispersed in the above solution and sufficiently dissolved by ultrasonic treatment. The mixed solution is stirred vigorously for 1h at room temperature;
(2) transferring the mixed solution to a water bath kettle, stirring and evaporating at 80 ℃ to dryness to obtain a single precursor;
(3) fully grinding the precursor prepared in the step (2) for later use;
(4) putting the sample ground in the step (3) into a porcelain boat, heating to 800-1100 ℃ under the protection of nitrogen atmosphere, wherein the heating rate is 6 ℃ for min -1 . The holding time is set to be 2h, and a carbonized product is obtained after cooling to the room temperature, namelyIs Co @ N, S-CNTs-1.
Example 3
A preparation method of nitrogen-sulfur doped defected carbon nano-tubes comprises the following steps:
(1) accurately weigh 4mmol Co (SCN) 2 And dissolved in a mixed solvent of absolute ethanol (50ml) and deionized water (25 ml). 40mmol of dicyandiamide was dispersed in the above solution and sufficiently dissolved by ultrasonic treatment. Then the mixed solution is stirred vigorously for 1 hour at room temperature;
(2) transferring the mixed solution to a water bath kettle, stirring and evaporating at 80 ℃ to dryness to obtain a single precursor;
(3) fully grinding the precursor prepared in the step (2) for later use;
(4) putting the sample ground in the step (3) into a porcelain boat, heating to 800-1100 ℃ under the protection of nitrogen atmosphere, wherein the heating rate is 6 ℃ for min -1 . The heat preservation time is set to be 2h, and a carbonized product, namely Co @ N, S-CNTs-2, is obtained after the carbonized product is cooled to the room temperature.
In examples 1 to 3, the scanning electron microscope observation results of the carbon nanotubes are shown in fig. 1 to 3, all the carbon nanotubes exhibit a typical bamboo-like structure, part of the ends of the carbon nanotubes are closed and particles coated by the carbon layer are formed, and part of the ends of the carbon nanotubes are open and present a hollow structure. The pipe diameter of the carbon nano-tube is about 50-150 nm.
Raman spectra for the samples prepared in examples 1-3 are shown in FIG. 4, with nitrogen-doped Co @ N-CNTs alone having D, G, 2D peaks representing the typical structure of carbon nanotubes, whereas in Co @ N, S-CNTs-1 and Co @ N, S-CNTs-2, the 2D peak disappeared at 675cm -1 A peak of sulfide appears, and I D /I G The ratio of (a) to (b) increases in turn, which indicates that an increase in the sulfur content leads to a significant increase in the degree of defectivity.
The above description is only for the purpose of illustrating the preferred embodiments and applications of the present invention, and should not be construed as limiting the present invention, and the present invention is not intended to be limited to the embodiments and applications, but rather to be construed as the invention in all aspects, and as long as the invention is achieved by other modifications, substitutions and alterations based on the technical spirit of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the invention, and these changes and modifications are to be considered as within the scope of the invention.
Claims (6)
1. A preparation method of a nitrogen-sulfur doped defected carbon nanotube is characterized by comprising the following steps:
(1) adopting inorganic sulfur Salt Co (SCN) 2 As a sulfur source, a certain amount of Co (SCN) 2 And Co (NO) 3 ) 2 ·6H 2 Mixtures of O or Co (SCN) 2 Dissolving in a mixed solvent of absolute ethyl alcohol and deionized water, dispersing dicyandiamide in the solution, performing ultrasonic treatment to fully dissolve the dicyandiamide, and then violently stirring the mixed solution at room temperature for 1 hour to obtain a uniformly mixed solution;
(2) stirring and evaporating the mixed solution at 70-80 ℃ to dryness to obtain a single precursor;
(3) fully grinding the precursor prepared in the step (2) for later use;
(4) heating the precursor ground in the step (3) to 800-1100 ℃ under the protection of nitrogen atmosphere, wherein the heating rate is 6 ℃ for min -1 The heat preservation time is set to be 2h, in the heat treatment process, heterogeneous atoms S are diffused from the carbon region to the cobalt-containing region to form sulfides, rich vacant sites are left in the carbon skeleton, the formation of pyridine nitrogen active sites is promoted, and then the mixture is cooled to room temperature to obtain a carbonized product, namely Co @ N, S-CNTs-1 or Co @ N, S-CNTs-2.
2. The method of claim 1, wherein the dicyandiamide in step 1 is mixed with Co (SCN) 2 And Co (NO) 3 ) 2 ·6H 2 O mixtures or Co (SCN) 2 The molar ratio of (1) to (2) is 10:1, and the volume ratio of the absolute ethyl alcohol to the deionized water in the mixed solvent is 2: 1.
3. The method of claim 1 or 2, wherein the Co (SCN) 2 And Co (NO) 3 ) 2 ·6H 2 Co in mixture (SCN) 2 With Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 1: 1.
4. The nitrogen-sulfur doped defected carbon nanotube prepared by the method of any one of claims 1 to 3, wherein the carbon nanotube is N, S double-doped defected carbon nanotube, has pyridine nitrogen active sites, has abundant vacancies in a carbon skeleton, is bamboo-like, has a hollow structure with a part of carbon nanotube ends open, and has a particle with a part of carbon nanotube ends closed and wrapped by a carbon layer.
5. The nitrogen-sulfur doped defected carbon nanotubes of claim 4, wherein the tube diameter of the carbon nanotubes is 50-150 nm.
6. The nitrogen-sulfur doped defective carbon nanotubes of any of claims 4 or 5 used in a catalyst for a fuel cell or a zinc-air cell.
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| AU2020101504A4 (en) * | 2019-10-23 | 2020-09-10 | Hunan University Of Science And Technology | Preparation of nitrogen-cobalt-phosphorus co-doped hollow carbon sphere composite and product and use thereof |
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