CN109888307B - A kind of cobalt-sulfur compound/nitrogen-sulfur-doped carbon composite catalyst and preparation method thereof - Google Patents
A kind of cobalt-sulfur compound/nitrogen-sulfur-doped carbon composite catalyst and preparation method thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 title abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 44
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- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
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- 229940011182 cobalt acetate Drugs 0.000 claims description 2
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- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 239000010411 electrocatalyst Substances 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 8
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
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- 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
- Y02E60/50—Fuel cells
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Abstract
本发明属于电催化材料领域，具体公开了一种钴硫化合物/氮硫掺杂碳复合催化剂及其制备方法。本发明以钴盐、硫脲和有机碳源为主要原料，采用一步固相反应法，在惰性气氛下进行热处理，实现钴硫化合物/氮硫掺杂碳催化剂材料的制备；所得钴硫化合物/氮硫掺杂碳复合催化材料结构稳定、导电性良好，可表现出优异的催化性能和高稳定性；且涉及的制备方法简单，反应条件温和，环境友好，产物组成可控，适合推广应用。The invention belongs to the field of electrocatalytic materials, and specifically discloses a cobalt-sulfur compound/nitrogen-sulfur-doped carbon composite catalyst and a preparation method thereof. The invention uses cobalt salt, thiourea and organic carbon source as main raw materials, adopts a one-step solid-phase reaction method, and conducts heat treatment in an inert atmosphere to realize the preparation of cobalt-sulfur compound/nitrogen-sulfur-doped carbon catalyst material; the obtained cobalt-sulfur compound/nitrogen-sulfur doped carbon catalyst material is The nitrogen-sulfur-doped carbon composite catalytic material has stable structure and good electrical conductivity, and can exhibit excellent catalytic performance and high stability; and the involved preparation method is simple, the reaction conditions are mild, the environment is friendly, and the product composition is controllable, which is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a cobalt-sulfur compound/nitrogen-sulfur doped carbon composite catalytic material and a preparation method thereof.
Background
Electrochemical energy storage and conversion devices are currently considered to be the cleanest, efficient, and environmentally friendly method of addressing energy crisis and environmental pollution issues. Among them, new energy devices (such as fuel cells, metal air cells, electrolytic water, etc.) in which oxidation and reduction reactions of oxygen are used as main electrode reactions have received much attention due to their high efficiency, high energy density, and low carbon dioxide emission. Currently, the noble metal platinum (Pt) and its composite materials are well-known ORR electrocatalysts with excellent performance; the noble metals ruthenium (Ru) and iridium (Ir) or oxides of both metals are considered to be OER electrocatalysts excellent in performance. However, the above materials have problems of high price, low reserves on the earth, easy inactivation and poisoning, etc., and are limited in the process of large-scale practical production and application. Therefore, the further development of non-noble metal electrocatalysts with low cost, high efficiency and high stability is an urgent problem to be solved for promoting the development of electrochemical renewable energy technology.
Transition metal sulfurThe family compounds have the characteristics of low price and rich resources, have high oxygen reduction catalytic activity and strong selectivity, and are an active research direction of non-noble metal catalysts. The cobalt-sulfur compound has the characteristics of good conductivity, better catalytic activity than sulfides such as iron, nickel and the like, is widely concerned, and is a catalyst with good development potential. In order to uniformly distribute the electrocatalyst on the electrode surface, researchers often support the catalyst on the surface of a suitable carbon material support, and the catalyst is more stable for a long time due to the high conductivity and high specific surface area of the carbon support. A large number of researches show that heteroatom doping carbon (such as boron, nitrogen, phosphorus, sulfur and the like) can increase electron conduction and active sites so as to effectively improve the catalytic performance. Therefore, some researchers have been working on the compounding of the cobalt sulfur compound with the carbon-based material to expect good catalytic activity. For example, Chen et al used hydrothermal plus subsequent calcination to add CoS2Loading the graphene on nitrogen and sulfur doped graphene to obtain CoS2the/N, S-coded graphene composite catalyst material shows good catalytic activity [ Journal of Power Sources,2018,389:178-]. Literature [ Nanotechnology,2019,30(7):075402]Hydrothermal synthesized CdS nano-wire is used as sacrificial template to be mixed with raw materials such as dopamine, cobalt nitrate hexahydrate and tromethamine, and Co is obtained by drying and calcining9S8the/N, S-CNTs composite catalyst material shows RuO2Similar OER activity. However, in the prior art, the preparation of cobalt-sulfur compounds and carbon-based composite materials is generally complicated, the precursor is expensive or is simply and directly mixed with a carbon material to improve the catalytic activity, and the problems of uneven catalyst distribution, weak bonding force between the transition metal compound and the carbon material, unstable adhesion and the like are often caused, so that the catalytic performance of the catalyst is not ideal, the stability is poor, and the large-scale commercial production of the catalyst is hindered.
Disclosure of Invention
The invention mainly aims to provide a cobalt-sulfur compound/nitrogen-sulfur doped carbon composite catalytic material and a preparation method thereof aiming at the defects in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a cobalt-sulfur compound/nitrogen-sulfur doped carbon composite catalytic material comprises the following steps:
1) uniformly mixing cobalt salt, an organic carbon source and thiourea to obtain a mixed raw material;
2) and carrying out heat treatment on the obtained mixed raw materials under a protective atmosphere, and then washing and drying the obtained product to obtain the cobalt-sulfur compound/nitrogen-sulfur doped carbon composite catalytic material.
In the scheme, the cobalt salt can be selected from cobalt nitrate, cobalt acetate, cobalt sulfate and the like.
In the scheme, the organic carbon source can be selected from polyaniline, dopamine, polyaniline and the like.
In the scheme, the mass ratio of the cobalt salt, the organic carbon source and the thiourea is 1 (1.7-6.9) to 1-5.3.
Preferably, the mass ratio of the cobalt salt, the organic carbon source and the thiourea is 1 (3.4-5.2) to (2.6-3.1).
In the above scheme, the heat treatment process comprises: firstly heating to 160-200 ℃ for reaction for 4-12h, and then heating to 500-900 ℃ for reaction for 2-6 h.
Preferably, the heat treatment process comprises: firstly, the reaction is carried out for 4-6h at the temperature of 180 ℃ and 200 ℃, and then the reaction is carried out for 2-4h at the temperature of 700 ℃ and 900 ℃.
In the scheme, the washing step is washing with water and absolute ethyl alcohol for 2-3 times respectively.
In the scheme, the drying temperature is 60-80 ℃, and the drying time is 6-12 h; preferably, a vacuum drying process is used.
The cobalt-sulfur compound/nitrogen-sulfur doped carbon composite catalytic material prepared according to the scheme.
The principle of the invention is as follows:
the invention takes polyaniline as an organic carbon source, thiourea as a sulfur source and a nitrogen source and simultaneously used as a reactant to generate sulfide with a cobalt source, and after the sulfide is mixed with the cobalt source, the preparation of a sulfur-cobalt compound, the compounding of the sulfur-cobalt compound/the carbon material and the doping of sulfur and nitrogen heteroatoms are synchronously realized by adopting a one-step solid phase reaction method, so that the flaky carbon composite material with high specific surface area, high conductivity, high catalytic activity, uniform compounding and low cost is simply and effectively obtained.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, thiourea is used as a reactant and a nitrogen-sulfur dopant, so that raw materials are effectively saved, the introduction of redundant reactants can be reduced, the pollution of impurity ions is avoided, the use performance of the obtained composite material is ensured, and the thiourea thermally decomposes to generate gas in a solid-phase reaction and plays a role of a pore-forming agent, so that the specific surface area of the obtained composite material can be effectively increased, and the catalytic activity of the composite material is improved; in addition, the thiourea can realize the in-situ compounding of the cobalt sulfide compound/nitrogen sulfur doped carbon, which is beneficial to improving the bonding strength of the composite material and ensuring the high stability of the catalyst.
2) The invention takes an organic carbon source, thiourea and a cobalt source as main raw materials, adopts a one-step solid phase reaction method to prepare the sheet-shaped cobalt sulfide compound/nitrogen-sulfur doped carbon composite catalytic material, fully exerts the synergistic effect of the cobalt sulfide and the carbon material, has the advantages of high specific surface area, excellent electrical property, high stability and the like, and can show good ORR and OER dual-functional catalytic activity.
3) The synthesis process is simple, the controllable adjustment of the cobalt-sulfur compound product in the obtained composite material can be realized by simply adjusting the heat treatment conditions and the like, and a brand new thought can be provided for the preparation and performance optimization research of the cobalt-sulfur compound and carbon-based composite material.
4) The invention has the advantages of cheap and easily obtained raw materials, short reaction period, low temperature, low energy consumption, environmental friendliness and low equipment requirement, is suitable for large-scale industrial production, can promote the practical application of the electrode material for oxygen reduction and oxygen precipitation, and realizes industrial large-scale production.
Drawings
FIG. 1 shows CoS obtained in example 1 of the present invention2The XRD pattern of the @ N/S-C composite electro-catalytic material.
FIG. 2 is an XRD pattern of the CoS @ N/S-C composite electrocatalytic material obtained in example 2 of the present invention.
FIG. 3 shows Co obtained in example 4 of the present invention9S8The XRD pattern of the @ N/S-C-700 composite electrocatalytic material.
FIG. 4 shows Co obtained in example 4 of the present invention9S8SEM picture of @ N/S-C-700 composite catalyst.
FIG. 5 shows the results of Co obtained in example 4 of the present invention9S8XPS plot of @ N/S-C-700 hybrid catalyst.
FIG. 6 shows Co obtained in example 4 of the present invention and comparative examples 1 and 29S8@N/S-C-700、Co9S8ORR electrocatalytic performance profiles for N/S-C and commercial Pt/C electrocatalytic materials.
FIG. 7 shows Co obtained in example 4 of the present invention and comparative examples 1 and 29S8@N/S-C-700、Co9S8OER electrocatalytic performance plots for N/S-C and commercial Pt/C electrocatalytic materials.
FIG. 8 shows Co obtained in example 4 of the present invention9S8The anti-methanol stability plots for @ N/S-C-700 and commercial Pt/C electrocatalytic materials.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A cobalt-sulfur compound/nitrogen-sulfur doped carbon composite catalytic material is prepared by the following steps:
1) weighing 0.001mol of cobalt nitrate, 0.004mol of thiourea and 0.5g of polyaniline, mixing, and ball-milling for 2h under the condition of 180rmp to obtain a mixed raw material;
2) transferring the mixed raw material obtained in the step 1) into a crucible, firstly heating to 200 ℃ for reaction for 4h in Ar atmosphere, then heating to 500 ℃ for reaction for 2h, cooling to room temperature along with the furnace, washing 3 times respectively by deionized water and absolute ethyl alcohol (the washing process is realized by centrifuging at 8000rpm for 3min), and putting the washed product into a vacuum drying oven for drying for 12h at 80 ℃ to obtain the cobalt sulfide/nitrogen sulfur doped carbon composite catalytic material (cobalt disulfide/nitrogen sulfur doped carbon composite electrocatalytic material).
Example 2
A cobalt-sulfur compound/nitrogen-sulfur doped carbon composite catalytic material is prepared by the following steps:
1) weighing 0.001mol of cobalt nitrate, 0.004mol of thiourea and 0.5g of polyaniline, mixing, and ball-milling for 2h under the condition of 180rmp to obtain a mixed raw material;
2) transferring the mixed raw material obtained in the step 1) into a crucible, firstly heating to 200 ℃ for reaction for 4h in Ar atmosphere, then heating to 600 ℃ for reaction for 2h, cooling to room temperature along with the furnace, washing 3 times respectively by deionized water and absolute ethyl alcohol (the washing process is realized by centrifuging at 8000rpm for 3min), and putting the washed product into a vacuum drying oven for drying for 12h at 80 ℃ to obtain the cobalt sulfide/nitrogen sulfur doped carbon composite catalytic material (cobalt sulfide/nitrogen sulfur doped carbon composite electrocatalytic material).
Example 3
A cobalt-sulfur compound/nitrogen-sulfur doped carbon composite catalytic material is prepared by the following steps:
1) weighing 0.001mol of cobalt nitrate, 0.012mol of thiourea and 1.5g of polyaniline, mixing and ball-milling for 2h under the condition of 180rmp to obtain a mixed raw material;
2) transferring the mixed raw material obtained in the step 1) into a crucible, firstly heating to 180 ℃ for reaction for 6h under Ar atmosphere, then heating to 900 ℃ for reaction for 4h, cooling to room temperature along with the furnace, washing for 2 times respectively by deionized water and absolute ethyl alcohol (the washing process is realized by centrifuging at 8000rpm for 3min), and putting the washed product into a vacuum drying oven for drying for 6h at 80 ℃ to obtain the cobalt-sulfur compound/nitrogen-sulfur doped carbon composite electro-catalytic material (the octa-sulfide nonacobalt/nitrogen-sulfur doped carbon composite electro-catalytic material).
Example 4
A cobalt-sulfur compound/nitrogen-sulfur doped carbon composite catalytic material is prepared by the following steps:
1) weighing 0.001mol of cobalt nitrate, 0.01mol of thiourea and 1g of polyaniline, mixing, and ball-milling for 2h under the condition of 180rmp to obtain a mixed raw material;
2) transferring the mixed raw material obtained in the step 1) into a crucible, firstly heating to 180 ℃ for reaction for 4h in Ar atmosphere, then heating to 700 ℃ for reaction for 2h, cooling to room temperature along with the furnace, washing 3 times respectively by deionized water and absolute ethyl alcohol (the washing process is realized by centrifuging at 8000rpm for 3min), and putting the washed product into a vacuum drying oven for drying for 8h at 80 ℃ to obtain the cobalt-sulfur compound/nitrogen-sulfur doped carbon composite catalytic material (the octa-sulfide nonacobalt/nitrogen-sulfur doped carbon composite electrocatalytic material).
Comparative example 1
The preparation method of the cobalt disulfide electrocatalytic material comprises the following steps:
1) weighing 0.001mol of cobalt nitrate hexahydrate and 0.01mol of thiourea, mixing, and ball-milling for 2h under the condition of 180rmp to obtain a mixed raw material;
2) and transferring the obtained mixed raw materials into a crucible, firstly heating to 200 ℃ for reaction for 4h under Ar atmosphere, then heating to 700 ℃ for reaction for 2h, cooling to room temperature along with the furnace, washing for 3 times respectively by deionized water and absolute ethyl alcohol (centrifuging for 3min at 8000 rpm), and putting the washed product into a vacuum drying oven for drying for 12h at 80 ℃ to obtain the nonacobalt octasulfide electrocatalytic material.
Comparative example 2
A preparation method of a nitrogen-sulfur-doped carbon composite electrocatalytic material comprises the following steps:
1) weighing 0.01mol of thiourea and 1g of polyaniline, mixing and ball-milling for 2h under the condition of 180rmp to obtain a mixed raw material;
2) transferring the mixed raw material obtained in the step 1) into a crucible, firstly heating to 200 ℃ for reaction for 4h under Ar atmosphere, then heating to 700 ℃ for reaction for 2h, cooling to room temperature along with the furnace, washing 3 times respectively by deionized water and absolute ethyl alcohol (realized by centrifuging at 8000rpm for 3min), and putting the washed substance into a vacuum drying oven for drying for 12h at 80 ℃ to obtain the nitrogen-sulfur doped carbon composite electro-catalytic material.
In order to further understand the performance of the cobalt-sulfur compound/nitrogen-sulfur doped carbon composite catalyst material obtained in the invention, the products obtained in examples 1-4 and comparative examples 1-2 were respectively subjected to relevant tests, which specifically include the following steps:
1) XRD test
Example 1(CoS2@ N/S-C) and example 2(CoS @ N/S-C), example 4 (Co)9S8@ N/S-C-700) were separately subjected to XRD testing, the results being shown. As can be seen from FIGS. 1, 2 and 3, the cobalt disulfide-doped carbon composite catalyst (example 1), the cobalt monosulfide-doped carbon composite catalyst (example 2) and the nine cobalt octasulfide composite catalyst (example 4) are respectively matched with the standard diffraction peaks of cobalt disulfide (JCPDS: 01-083-1455), cobalt monosulfide (JCPDS: 01-075-0605) and nine cobalt octasulfide (JCPDS: 03-065-6801), no any impurity peak occurs, and a broadening peak exists in the 20-30 DEG diffraction angle range, which indicates that the carbon material is introduced after the heat treatment.
2) SEM test
FIG. 4 is an SEM image of the nonacobalt octasulfide/N-S doped carbon composite electrocatalyst material obtained in example 4; the obtained electrocatalytic material can be seen from the figure, and nine cobalt octasulfide nanoparticles are loaded on a nitrogen-sulfur co-doped carbon sheet.
3) XPS test
Fig. 5 shows the XPS test results of the octasulfide nonacobalt/nitrogen sulfur doped carbon composite electrocatalyst material obtained in example 4, and the characteristic peaks of Co2p, N1S, S2p and C1S can be seen from the full spectrum diagram, which indicates that the sample obtained in this example contains Co, N, S and C elements. Further peak fitting was performed on the characteristic peaks of S2p and N1S, and the peak of S2p was observed at binding energies 163.83eV, 165.02eV and 168.10eV, corresponding to S2p 3/2 thiophenethiol, S2p 1/2 thiophenethiol, -C-SOXThe carbon in the composite catalyst is nitrogen-sulfur doped carbon, which is indicated by the fact that N1s can be divided into four peaks respectively corresponding to pyridine nitrogen, pyrrole nitrogen, graphite nitrogen and oxidizing nitrogen at binding energies of 398.38eV, 399.71eV, 400.97eV and 404.50 eV.
3) Electrocatalytic performance test
Example 4 (Co) was weighed separately9S8@ N/S-C-700), comparative example 1(Co9S8) The catalyst material obtained in comparative example 2(N/S-C) and the commercial electrocatalyst Pt/C were 1.5mg each, and were mixed with 3.5mg of SuperP in a centrifuge tube, and 800. mu.l of deionized water, 200. mu.l of isopropanol, and 40. mu.l of Nafion solution (5 wt%) were added dropwise, respectively; then ultrasonically dispersing for 30min to obtain uniform dispersionAnd (3) homogenizing ink, namely dripping 5ul of ink on the surface of the glassy carbon electrode with the diameter of 3mm, and drying the electrode at room temperature to respectively obtain the glassy carbon electrode modified by the electrocatalyst material.
The performance of the modified electrode is characterized by adopting a three-electrode system (auxiliary electrode, reference electrode and working electrode) and is 0.1mol L-1Testing in a potassium hydroxide solution; FIG. 6 shows different electrodes at O2Saturated 0.1mol L-1Linear scan curve for oxygen reduction in potassium hydroxide system. It can be seen from the figure that Co obtained in example 49S8The half-wave potential in the oxygen reduction reaction of @ N/S-C-700 is 0.807V vs RHE, the initial potential is 1.07V vs RHE, and the limiting current density is 6.7mA cm-2Shows superior to Co9S8And the oxygen reduction catalytic performance of N/S-C and commercial Pt/C.
FIG. 7 shows different electrodes at O2Saturated 0.1mol L-1Linear scanning curve of oxygen evolution reaction in potassium hydroxide system; it can be seen that the current density is 10mA cm-2When is Co9S8@N/S-C-700、Co9S8The overpotential of (A) is 1.545V vs RHE and 1.64V vs RHE, respectively, while the current density of N/S-C and Pt/C at the voltage cut-off is not up to 10mAcm-2Showing extremely poor OER electrocatalytic performance. Co9S8The @ N/S-C-700 composite catalyst has the advantages of being superior to Co9S8And ORR, OER dual-function catalytic activity of N/S-C and commercial Pt/C.
FIG. 8 is a graph showing Co test by chronoamperometry9S8The stability of the @ N/S-C-700 composite catalyst and the commercial Pt/C catalyst in methanol resistance can be seen from the figure that after methanol is added into the electrolyte at about 300S, the current of the Pt/C electrode is obviously reduced, and Co is obviously reduced9S8The current change of the @ N/S-C-700 electrode is almost negligible, indicating that Co9S8The @ N/S-C-700 composite catalyst has excellent stability against methanol.
The invention can be realized by all the listed raw materials, and the invention can be realized by the upper and lower limit values and interval values of all the raw materials; the examples are not to be construed as limiting the scope of the invention. The upper and lower limit values and interval values of the process parameters can realize the invention, and the embodiments are not listed.
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