CN109772413B - Nitrogen-sulfur co-doped graphdiyne material, preparation method and application thereof, and oxygen evolution reaction catalyst containing nitrogen-sulfur co-doped graphdiyne material - Google Patents
Nitrogen-sulfur co-doped graphdiyne material, preparation method and application thereof, and oxygen evolution reaction catalyst containing nitrogen-sulfur co-doped graphdiyne material Download PDFInfo
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Abstract
The invention provides a nitrogen and sulfur co-doped graphyne material, a preparation method and application thereof, and an oxygen evolution reaction catalyst containing the same. The nitrogen and sulfur co-doped graphdine material provided by the invention has higher catalytic efficiency on oxygen evolution reaction in electrochemical reaction, wherein the current density is 25.5 (mA/cm)21.6V) or more, and at most 47.0 (mA/cm)21.6V) and the overpotential is as low as 300 mV.
Description
Technical Field
The invention belongs to the technical field of graphite alkyne, and relates to a nitrogen and sulfur co-doped graphite alkyne material, a preparation method and application thereof, and an oxygen evolution reaction catalyst containing the same.
Background
The oxygen evolution reaction is an important reaction in the electrochemical field and plays a key role in energy conversion. Although noble metal-based catalysts such as ruthenium dioxide and iridium dioxide have high catalytic activity for oxygen evolution reaction, their high price and poor stability limit the commercial application of noble metal-based catalysts. In general, the development of high-efficiency and low-cost non-metal-based catalysts is becoming a trend of catalysts, and especially, carbon materials with abundant raw materials and good stability have recently received much attention.
A wide variety of heteroatom-doped carbon materials have been extensively studied, and among them, diatom co-doped carbon materials, especially nitrogen and sulfur co-doped carbon materials, exhibit high oxygen evolution activity and long-term stability, which have attracted considerable attention from researchers (Zhang, j., Zhao, Z., Xia, Z., Dai, l.nat. nanotech.2015,10,444). CN106334501A discloses a three-dimensional N/S double-doped graphene aerogel and a preparation method and application thereof, which comprises the steps of carrying out hydrothermal reaction on graphene oxide, a nitrogen source, a sulfur simple substance and an alkaline compound at the temperature of 120-220 ℃, and then washing, freezing and drying to obtain the three-dimensional N/S double-doped graphene aerogel, wherein the doping amount of N/S can be accurately regulated and controlled, and the relative position relationship of nitrogen and sulfur is not involved. CN106207204A discloses a nitrogen-sulfur double-doped carbon material bifunctional catalyst, and a preparation method and application thereof, wherein the catalyst is prepared by double-doping electronegative nitrogen and sulfur by using marine polysaccharide sodium alginate as a carbon source and thiourea as a nitrogen and sulfur source and calcining at high temperature in an inert atmosphere to obtain the nitrogen-sulfur double-doped carbon material electrocatalyst. The catalyst has high catalytic activity of oxygen evolution and oxygen reduction, but the relative position relation of nitrogen and sulfur is not involved.
The graphyne as a novel carbon material is formed by alternately connecting diacetylene bonds and benzene rings. It has the characteristics of two-dimensional planar carbon network structure, large conjugated system, uniform pore distribution, adjustable electrical properties and the like, so that it can be used as a non-metal catalyst. However, the current chemically synthesized graphdine has a single structure and only contains carbon elements, which limits further improvement of the performance and limits the application field of the graphdine. CN104667953A discloses a nitrogen-doped graphdiyne, a preparation method and a use thereof, wherein nitrogen element is introduced in the form of nitrogen-containing gas. CN105645378A discloses a preparation method of hetero-atom doped graphyne, and reports of diatom doped graphyne are not found.
Therefore, a method for co-doping graphite alkyne with diatom is needed to be provided at present, and a new idea is provided for preparing a low-cost and high-activity nonmetal catalyst.
Disclosure of Invention
The invention aims to provide a nitrogen and sulfur co-doped graphite alkyne material, a preparation method and application thereof, and an oxygen evolution reaction catalyst containing the nitrogen and sulfur co-doped graphite alkyne material. The nitrogen and sulfur co-doped graphite alkyne material provided by the invention has higher catalytic efficiency on oxygen evolution reaction in electrochemical reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a nitrogen and sulfur co-doped graphyne material, wherein the nitrogen and sulfur co-doped graphyne material comprises a sulfur element doped on a benzene ring and a nitrogen element in an sp hybridization state.
The nitrogen-sulfur co-doped graphite alkyne material provided by the invention comprises most of sulfur elements and nitrogen elements with determined doping positions, wherein the sulfur elements are doped on a benzene ring, and part of the nitrogen elements are doped on an alkyne bond.
Preferably, in the nitrogen and sulfur co-doped graphyne material, the sulfur element doped on the benzene ring is 0.2-5% in mole percentage, such as 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, etc.
In the invention, because most of sulfur is doped on the benzene ring, the sulfur doped at other positions (such as defect positions) is extremely little, and the characterization can not be realized on XPS characterization, the amount of the sulfur element doped on the benzene ring is basically equal to the amount of the sulfur element in the nitrogen-sulfur co-doped graphite alkyne material.
In the nitrogen and sulfur co-doped graphyne material provided by the invention, except a small amount of sulfur elements doped in the edge defect part of the graphyne material, most of the sulfur elements are doped on a benzene ring.
In the nitrogen and sulfur co-doped graphdine material, the content of nitrogen element existing in sp hybridized state is 0.2-10% by mole, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% and the like.
In the nitrogen and sulfur co-doped graphdine material provided by the invention, not all nitrogen exists in an sp hybridized form, for example, part of nitrogen may substitute carbon elements on a benzene ring to obtain a structure similar to pyridine.
Preferably, in the nitrogen and sulfur co-doped graphdiyne material, the molar ratio of the nitrogen element to the sulfur element is (1-30: 1), such as 5:1, 8:1, 10:1, 12:1, 15:1, 18:1, 20:1, 22:1, 25:1, 28:1, and the like.
The molar ratio of nitrogen to sulfur in the invention refers to that all nitrogen elements (sp hybridized and sp) in the nitrogen and sulfur co-doped graphatine material2And sp3Hybrid) to the molar ratio of all sulfur elements.
In a second aspect, the invention provides a preparation method of the nitrogen and sulfur co-doped graphyne material according to the first aspect, which comprises the following steps: and calcining the nitrogen and sulfur source and the carbon source in the same protective atmosphere, or calcining the nitrogen source, the sulfur source and the carbon source in the same protective atmosphere to obtain the nitrogen and sulfur co-doped graphite alkyne material.
Preferably, the nitrogen-sulfur source is a chemical having both a carbon-nitrogen bond and a carbon-sulfur single bond and/or a carbon-sulfur double bond.
Preferably, the nitrogen source comprises a compound having a carbon-nitrogen double bond and/or a carbon-nitrogen triple bond.
Preferably, the sulfur source comprises a compound having a sulfur-sulfur bond and/or a carbon-sulfur bond.
The invention can lead the finally obtained material to have sp hybridized nitrogen element and sulfur element doped on the benzene ring by selecting the mutual matching of the nitrogen source or the nitrogen source with carbon-nitrogen double bond and/or carbon-nitrogen triple bond and the sulfur source with sulfur-sulfur bond and/or carbon-sulfur bond.
The same protective atmosphere in the invention means that the nitrogen source, the sulfur source and the carbon source are in the same environment, or the nitrogen source and the sulfur source are in the same environment, for example, when the calcination is carried out in a tube furnace, the two are in the same environment and atmosphere, and the two can be placed after being mixed or separately.
Preferably, the source of sulfur and nitrogen comprises any one of thiourea compounds, ammonium thiocyanate compounds or thiazole compounds or a combination of at least two thereof.
Preferably, the compound having a carbon-nitrogen double bond and/or a carbon-nitrogen triple bond includes any one of melamine, dicyandiamide, cyanamide, nitrile and guanidine or a combination of at least two thereof.
Preferably, the sulphur source comprises sublimed sulphur and/or dibenzylsulphur.
Preferably, the preparation method comprises the following steps:
and under the same protective atmosphere, separately placing a nitrogen source and a sulfur source at the upstream of the carbon source, or placing a nitrogen-sulfur source at the upstream of the carbon source under the same protective atmosphere, and then calcining to obtain the nitrogen-sulfur co-doped graphite alkyne material.
In the invention, the introduction direction of the protective gas is taken as the standard, the upstream is the position close to the introduction of the protective gas, and the nitrogen source and the sulfur source or the nitrogen-sulfur source are arranged at the upstream of the carbon source, so that the doping source can be fully contacted with the carbon source.
The preparation method provided by the invention has the characteristics of simple operation, low cost and environmental friendliness.
In the present invention, the calcination may be carried out in a tube furnace.
Preferably, the mass ratio of the nitrogen source, the sulfur source and the carbon source is (1-100): 1-200):1, 5,10, 20, 30, 40, 50, 60, 70, 80, 90 and the like can be selected from 1-100, and 5,10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 150, 180, 190 and the like can be selected from 1-200.
Preferably, the mass ratio of the nitrogen-sulfur source and the carbon source in the step (1) is (1-100):1, such as 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, and the like.
The invention can regulate the doping amount of nitrogen and sulfur elements in the finally obtained material and the doping proportion of the nitrogen and sulfur elements by regulating the mass ratio of the nitrogen source, the sulfur source and the carbon source or the mass ratio of the nitrogen and sulfur source and the carbon source.
Preferably, the carbon source is a graphite alkyne material, and any graphite alkyne material can be used for preparing a nitrogen and sulfur co-doped graphite alkyne material.
Preferably, the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
Preferably, the calcination temperature is 700-1000 ℃, such as 800 ℃, 850 ℃, 900 ℃, 950 ℃ and the like, and the holding time is 0.5-8h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h and the like.
Preferably, during calcination, the temperature rise rate is 1-10 deg.C/min, such as 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min, etc.
In a third aspect, the invention provides the application of the nitrogen and sulfur co-doped graphite alkyne material in the catalyst.
Preferably, the catalyst is an electrochemical catalyst.
Preferably, the electrochemical catalyst is an oxygen evolution reaction catalyst.
The nitrogen and sulfur co-doped graphite alkyne material provided by the invention can efficiently catalyze the oxygen evolution reaction and can be used as a catalyst for the oxygen evolution reaction.
In a fourth aspect, the present invention provides an oxygen evolution reaction catalyst, which comprises the nitrogen and sulfur co-doped graphyne material described in the first aspect.
Preferably, the oxygen evolution reaction catalyst is the nitrogen and sulfur co-doped graphyne material described in the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nitrogen-sulfur co-doped graphite alkyne material provided by the invention comprises most of sulfur elements and nitrogen elements with determined doping positions, wherein the sulfur elements are doped on a benzene ring, and part of the nitrogen elements are doped on an alkyne bond.
(2) The nitrogen and sulfur co-doped graphdine material provided by the invention has higher catalytic efficiency on oxygen evolution reaction in electrochemical reaction, wherein the current density is 25.5 (mA/cm)21.6V) or more, and at most 47.0 (mA/cm)21.6V) and the overpotential is as low as 300 mV.
Drawings
FIG. 1A is a graph of synchrotron radiation results (photon energy 390-410eV) for the materials provided in example 1 and comparative example 1.
FIG. 1B is a graph of synchrotron radiation results (photon energy 160-185eV) for the materials provided in example 1 and comparative example 1.
FIG. 2A is an X-ray photoelectron spectrum (binding energy 395-407eV) of the materials provided in example 1 and comparative example 1.
FIG. 2B is an X-ray photoelectron spectrum (binding energy 160-171eV) of the materials provided in example 1 and comparative example 1.
Fig. 3 is a structural schematic diagram of the nitrogen and sulfur co-doped graphyne material provided by the invention.
Fig. 4 is a plot of linear sweep voltammetry tests for the materials provided in example 1 and comparative examples 1-3.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A nitrogen and sulfur co-doped graphite alkyne material is prepared by the following steps:
placing a sulfur source and a nitrogen source at the upstream of the tubular furnace, and placing a carbon source at the center of the tubular furnace; heating to 900 ℃ at the speed of 10 ℃/min, and keeping the temperature for 2.5 hours for calcination to obtain a nitrogen and sulfur co-doped graphite alkyne material;
wherein the mass ratio of the nitrogen source, the sulfur source and the carbon source is 100:200:1, the nitrogen source is melamine, the sulfur source is dibenzyl sulfur, and the carbon source is a graphite alkyne material.
Examples 2 to 5
The only difference from example 1 is that in this example, the mass ratio of the nitrogen source, sulfur source and carbon source was 100:100:1 (example 2), 100:50:1 (example 3), 50:50:1 (example 4) and 1:1:1 (example 5).
Example 6
The difference from example 1 is that in this example, the nitrogen source is cyanamide and the sulphur source is sublimed sulphur.
Example 7
A nitrogen and sulfur co-doped graphite alkyne material is prepared by the following steps:
placing a sulfur source and a nitrogen source at the upstream of the tubular furnace, and placing a carbon source at the center of the tubular furnace; heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 5h for calcination to obtain a nitrogen and sulfur co-doped graphite alkyne material;
wherein the mass ratio of the nitrogen source, the sulfur source and the carbon source is 20:20:1, the nitrogen source is dicyandiamide, the sulfur source is sublimed sulfur, and the carbon source is a graphdine material.
Example 8
A nitrogen and sulfur co-doped graphite alkyne material is prepared by the following steps:
placing a nitrogen-sulfur source at the upstream of the tubular furnace, and placing a carbon source at the center of the tubular furnace; heating to 1000 ℃ at the speed of 2 ℃/min, and keeping the temperature for 1h for calcination to obtain a nitrogen-sulfur co-doped graphite alkyne material;
wherein the mass ratio of the nitrogen-sulfur source to the carbon source is 50:1, the nitrogen-sulfur source is thiourea, and the carbon source is a graphite alkyne material.
Comparative example 1
The only difference from example 1 is that in this comparative example, no sulphur source was added.
Comparative example 2
The only difference from example 1 is that, in this comparative example, no nitrogen source was added.
Comparative example 3
The difference from example 1 is that in this comparative example, the carbon source was directly calcined in the same manner as in example 1.
Performance testing
The doped graphdine materials provided in examples 1-8 and comparative examples 1-3 were tested for performance by the following method:
(1) synchrotron radiation experiment: soft X-ray near-edge absorption spectra (XANES) of K-edge of N and L-edge of sulfur were acquired at room temperature in a magnetic circular dichroism experimental station (BL12B-a) in a full electron yield mode (TEY) with an energy step of 0.2 eV;
fig. 1A and 1B are graphs showing the results of synchrotron radiation of the materials provided in example 1 and comparative example 1, and as can be seen from fig. 1A, in the nitrogen configuration obtained by doping, the binding energy of graphyne shifts to a low wavenumber (>0.2eV), and is classified as sp hybridized nitrogen on the alkyne bond; as shown in FIG. 1B, 162-168eV is the sulfur atom doped on the benzene ring.
Namely, the finally obtained nitrogen-sulfur co-doped graphyne material has sulfur elements doped in benzene rings and sp hybridized nitrogen elements.
(2) X-ray photoelectron spectroscopy: the test is carried out by an ESCLAb 220i-XL electron spectrometer under the condition of 300-W Al K alpha;
FIGS. 2A and 2B are X for the materials provided in example 1 and comparative example 1A ray photoelectron spectrum, and the peak (ca.397.6eV) at the low binding energy is attributed to sp hybridized nitrogen as shown by the peak fitting of the X-ray photoelectron spectrum in the figure 2A; as shown by the peak-splitting fitting of the X-ray photoelectron spectrum in FIG. 2B, 163.8eV and 165.0eV are assigned to S-C and S ═ C, and 168.3eV is assigned to C-SO2-C。
In the XPS chart, sulfur elements other than the sulfur element doped on the benzene ring are not observed, indicating that most of the sulfur elements are doped on the benzene ring. As for C-SO2The presence of-C, which is also doped on the benzene ring, but ends up as SO due to the small amount of oxygen contained in the graphatidyne2Exist in the form of (1).
Namely, the finally obtained nitrogen-sulfur co-doped graphyne material has sulfur elements doped in benzene rings and sp hybridized nitrogen elements.
Fig. 3 is a schematic structural diagram of the nitrogen and sulfur co-doped graphyne material provided by the present invention, and fig. 1A, fig. 1B, fig. 2A, and fig. 2B show that the nitrogen and sulfur co-doped graphyne material provided by the present invention has a sulfur element doped in a benzene ring and a nitrogen element in an sp hybridization state.
(3) Oxygen evolution performance test:
and (3) testing conditions are as follows: the solution was 1.0M KOH, saturated by passing oxygen at least 30min, the scanning rate was 10mV/s, and the rotation speed of the disk electrode was 1600 rpm.
FIG. 4 is a plot of the linear sweep voltammetry tests for the materials provided in example 1 and comparative examples 1-3; as can be seen from FIG. 3, the ratio of the total amount of the catalyst to that of comparative example 1(29.5 mA/cm)21.6V), comparative example 2(1.8 mA/cm)21.6V) and comparative example 3(0.4 mA/cm)21.6V), the nitrogen and sulfur co-doped graphyne material provided by the invention has more excellent current density (47.0 mA/cm)21.6V) and is superior to commercial RuO2Catalyst (33.5 mA/cm)21.6V). The current density is data directly proving the catalytic capability of the catalyst, and the larger the current density is, the better the catalytic effect is.
Overpotential is current density of 10mA/cm2The corresponding potential value was further subtracted by 1.23V to obtain an overpotential of 300mV for example 1 and 310mV for comparative example 3, sinceComparative examples 2 and 3 the current density was less than 10mA/cm in the range determined2Therefore, the overpotential cannot be calculated, but as can be seen from the figure, it should be larger than that of example 1; while a lower overpotential indicates that the evolution of oxygen is efficiently catalyzed at a lower voltage.
The results of the tests on the other examples and comparative examples are shown in table 1:
table 1:
as can be seen from the examples and performance tests, the graphdine material with the sulfur element doped on the benzene ring and the nitrogen element in the sp hybridization state is successfully obtained, and the obtained material has higher current density for oxygen evolution reaction and lower overpotential and Tafel slope, wherein the current density is 25.5 (mA/cm)21.6V), and the overpotential is as low as 300mV, namely the catalytic efficiency is higher. It is understood from the comparison between example 1 and comparative examples 1 to 3 that the catalytic efficiency of graphyne can be improved by doping sulfur and nitrogen simultaneously in graphyne.
The applicant states that the nitrogen and sulfur co-doped graphyne material, the preparation method and the application thereof, and the oxygen evolution reaction catalyst containing the same are illustrated by the above examples, but the present invention is not limited to the above process steps, i.e., it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (21)
1. The nitrogen-sulfur co-doped graphdiyne material is characterized in that a sulfur element doped on a benzene ring and a sp hybridized nitrogen element are contained in the nitrogen-sulfur co-doped graphdiyne material;
in the nitrogen and sulfur co-doped graphdine material, the mol percentage content of the sulfur element doped on the benzene ring is 0.5-5%;
in the nitrogen and sulfur co-doped graphdine material, the mol percentage content of nitrogen element existing in sp hybridized state is 1-10%;
the nitrogen and sulfur co-doped graphdiyne material is prepared by the following preparation method: calcining a nitrogen-sulfur source and a carbon source in the same protective atmosphere, or calcining the nitrogen source, the sulfur source and the carbon source in the same protective atmosphere to obtain the nitrogen-sulfur co-doped graphite alkyne material;
the nitrogen-sulfur source is a chemical compound which has a carbon-nitrogen bond and a carbon-sulfur single bond and/or a carbon-sulfur double bond;
the nitrogen source includes compounds having a carbon-nitrogen double bond and/or a carbon-nitrogen triple bond;
the sulfur source includes a compound having a sulfur-sulfur bond and/or a carbon-sulfur bond.
2. The nitrogen-sulfur-codoped graphdiyne material according to claim 1, wherein the molar ratio of nitrogen element to sulfur element in the nitrogen-sulfur-codoped graphdiyne material is (1-30): 1.
3. The preparation method of the nitrogen and sulfur co-doped graphdiyne material according to claim 1 or 2, which comprises the following steps: and calcining the nitrogen and sulfur source and the carbon source in the same protective atmosphere, or calcining the nitrogen source, the sulfur source and the carbon source in the same protective atmosphere to obtain the nitrogen and sulfur co-doped graphite alkyne material.
4. The method according to claim 3, wherein the nitrogen-sulfur source is a chemical having both a carbon-nitrogen bond and a carbon-sulfur single bond and/or a carbon-sulfur double bond.
5. The method according to claim 3, wherein the nitrogen source comprises a compound having a carbon-nitrogen double bond and/or a carbon-nitrogen triple bond.
6. The production method according to claim 3, wherein the sulfur source comprises a compound having a sulfur-sulfur bond and/or a carbon-sulfur bond.
7. The method according to claim 4, wherein the nitrogen-sulfur source comprises any one of thiourea compounds, ammonium thiocyanate compounds or thiazole compounds or a combination of at least two thereof.
8. The method according to claim 5, wherein the compound having a carbon-nitrogen double bond and/or a carbon-nitrogen triple bond comprises any one of melamine, dicyandiamide, cyanamide, nitrile and guanidine or a combination of at least two thereof.
9. The method of claim 6, wherein the sulfur source comprises sublimed sulfur and/or dibenzyl sulfur.
10. The method of claim 3, comprising the steps of:
and under the same protective atmosphere, separately placing a nitrogen source and a sulfur source at the upstream of the carbon source, or placing a nitrogen-sulfur source at the upstream of the carbon source under the same protective atmosphere, and then calcining to obtain the nitrogen-sulfur co-doped graphite alkyne material.
11. The method according to claim 10, wherein the mass ratio of the nitrogen source, the sulfur source and the carbon source is (1-100): 1-200): 1.
12. The method according to claim 10, wherein the mass ratio of the nitrogen-sulfur source to the carbon source is (1-100): 1.
13. The method of claim 10, wherein the carbon source is a graphdiyne material.
14. The method according to claim 10, wherein the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
15. The method as claimed in claim 10, wherein the calcination temperature is 700-1000 ℃ and the holding time is 0.5-8 h.
16. The method according to claim 10, wherein the temperature increase rate during the calcination is 1 to 10 ℃/min.
17. The use of the nitrogen and sulfur co-doped graphdiyne material of claim 1 or 2 in a catalyst.
18. Use according to claim 17, wherein the catalyst is an electrochemical catalyst.
19. Use according to claim 18, wherein the electrochemical catalyst is an oxygen evolution reaction catalyst.
20. An oxygen evolution reaction catalyst comprising the nitrogen and sulfur co-doped graphdiyne material of claim 1 or 2.
21. The oxygen evolution reaction catalyst of claim 20, wherein the oxygen evolution reaction catalyst is the nitrogen and sulfur co-doped graphyne material of claim 1 or 2.
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| CN105645378A (en) * | 2015-12-31 | 2016-06-08 | 中国科学院青岛生物能源与过程研究所 | Preparation method of hetero-atom-doped graphyne |
| CN106207204A (en) * | 2016-09-19 | 2016-12-07 | 青岛科技大学 | Nitrogen sulfur difunctional VPO catalysts of codope material with carbon element and its preparation method and application |
| CN107321379A (en) * | 2017-08-10 | 2017-11-07 | 南京大学 | A kind of three-dimensional porous nickel oxide and nitrogen-doped graphene quantum dot compound and its preparation method and purposes |
| CN108455593A (en) * | 2018-05-07 | 2018-08-28 | 中国科学院过程工程研究所 | A kind of N doping graphite alkene material and its preparation method and application |
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| CN105645378A (en) * | 2015-12-31 | 2016-06-08 | 中国科学院青岛生物能源与过程研究所 | Preparation method of hetero-atom-doped graphyne |
| CN106207204A (en) * | 2016-09-19 | 2016-12-07 | 青岛科技大学 | Nitrogen sulfur difunctional VPO catalysts of codope material with carbon element and its preparation method and application |
| CN107321379A (en) * | 2017-08-10 | 2017-11-07 | 南京大学 | A kind of three-dimensional porous nickel oxide and nitrogen-doped graphene quantum dot compound and its preparation method and purposes |
| CN108455593A (en) * | 2018-05-07 | 2018-08-28 | 中国科学院过程工程研究所 | A kind of N doping graphite alkene material and its preparation method and application |
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