CN111841598A - S-doped Co @ NC composite material with high oxygen evolution catalytic activity and preparation method thereof - Google Patents
S-doped Co @ NC composite material with high oxygen evolution catalytic activity and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 66
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 27
- 239000001301 oxygen Substances 0.000 title claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 42
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 60
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 37
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 34
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 24
- 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 claims description 22
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 abstract description 10
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 38
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
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- 239000010431 corundum Substances 0.000 description 11
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
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- 239000011248 coating agent Substances 0.000 description 8
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- 241000282414 Homo sapiens Species 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 239000002717 carbon nanostructure Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses an S-doped Co @ NC composite material with high oxygen evolution catalytic activity and a preparation method thereof, wherein the S-doped Co @ NC composite material with excellent electrocatalytic performance is obtained by regulating the specific surface area and the crystal structure of a metal organic framework, regulating the content of cobalt element active ingredients and the doping amount of sulfur element in a nitrogen-doped porous carbon material, and finding out the optimal crystal structure and S/N atomic ratio; on the other hand, the doping of S ions can improve the conductivity and the interface charge transfer efficiency of the composite material, so that the material has better OER characteristics.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to an S-doped Co @ NC composite material with high oxygen evolution catalytic activity and a preparation method thereof.
Background
The energy is the basis of national economy and social development, with the development of the national economy and society, the demand for the energy is continuously increased, the traditional fossil energy can generate a large amount of pollutants, destroy the ecological environment of the earth and cause serious ecological and environmental problems, thereby influencing the physical and mental health of human beings. Therefore, a novel renewable energy source is searched as a substitute of the traditional energy source, and the renewable energy source is a problem which is urgently needed to be solved in the energy field at present.
Among the numerous energy crisis solutions, electrocatalysis technology is considered as an energy conversion and storage mode with important application prospect, and the technology provides important guarantee for the utilization of renewable clean energy. The electrocatalyst with the oxygen reduction reaction, the oxygen evolution reaction and the hydrogen evolution reaction has important application prospect in the fields of clean energy such as metal-air batteries, fuel cells, hydrogen production by water splitting, oxygen production and the like. The high-efficiency electrocatalytic material with oxygen evolution catalytic activity (OER) plays an important role in the process of generating oxygen by decomposing water completely, electrocatalytic cracking water is highly dependent on the activity of an electrocatalyst in oxygen evolution reaction, and therefore, in order to improve the efficiency of electrocatalytic oxygen evolution, the electrocatalyst with high oxygen evolution reaction activity must be found. To date, iridium and ruthenium oxides have been considered as the best oxygen evolution catalysts, however, the high price and scarce reserves have limited the widespread use of such materials in industrial fields. Therefore, an electrocatalyst which is inexpensive, abundant in reserves, and has high oxygen evolution catalytic activity has been sought.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides an S-doped Co @ NC composite material with high oxygen evolution catalytic activity and a preparation method thereof.
The invention provides a preparation method of an S-doped Co @ NC composite material with high oxygen evolution catalytic activity, which comprises the following steps:
s1, dissolving cobalt nitrate hexahydrate, terephthalic acid and triethylene diamine in an organic solvent, stirring for 20-40min at 50-70 ℃, and heating for 20-30h at 100-140 ℃ to obtain the Co-MOF material, wherein the mass ratio of the cobalt nitrate hexahydrate, the terephthalic acid and the triethylene diamine is (1.5-2): (0.5-1): (0.2-0.25);
s2, calcining the Co-MOF material in a nitrogen atmosphere at the temperature of 700-900 ℃ for 1-3h to obtain a Co @ NC material;
s3, uniformly dispersing the Co @ NC material in an aqueous solution of thiourea, drying, and calcining at the temperature of 700-900 ℃ for 1-3h in a nitrogen atmosphere to obtain the S-doped Co @ NC composite material with high oxygen evolution catalytic activity, wherein the mass ratio of the Co @ NC material to the thiourea is 1: (0.5-2).
Preferably, the mass ratio of the cobalt nitrate hexahydrate to the terephthalic acid is 1.8: 0.7: 0.22.
preferably, the mass ratio of the Co @ NC material to thiourea is 1: 1.5.
Preferably, in the step S2, the nitrogen flow rate is 50-100 mL/min.
Preferably, in step S1, cobalt nitrate hexahydrate, terephthalic acid and triethylene diamine are dissolved in an organic solvent, stirred at 60 ℃ for 30min and then heated at 120 ℃ for 24 h.
Preferably, in the step S2, the Co-MOF material is calcined under nitrogen atmosphere at 800 ℃ for 2 h.
Preferably, in the step S3, the Co @ NC material is uniformly dispersed in an aqueous solution of thiourea, dried, and then calcined at 800 ℃ for 2 hours in a nitrogen atmosphere.
Preferably, the ratio of the mass of the cobalt nitrate hexahydrate to the volume of the organic solvent is (3-5) g: 100 mL; preferably, the ratio of the mass of the cobalt nitrate hexahydrate to the volume of the organic solvent is 3.6 g: 100 mL; preferably; the organic solvent is N, N-dimethylformamide.
Preferably, the concentration of the thiourea aqueous solution is 5-20 g/L; preferably, the concentration of the aqueous solution of thiourea is 15 g/L.
Preferably, in the step S2, heating to 700-900 ℃ at a heating rate of 5-15 ℃/min; preferably, in the step S2, the heating is performed at a heating rate of 10 ℃/min to 800 ℃.
Preferably, in the step S3, heating to 700-900 ℃ at a heating rate of 5-15 ℃/min; preferably, in the step S3, the heating is performed at a heating rate of 10 ℃/min to 800 ℃.
Preferably, in step S1, after heating, the method further includes cooling to room temperature, washing the product, and drying at 60 ℃ for 24 h.
Preferably, in the step S3, the drying temperature is 60 ℃ and the drying time is 12 h.
An S-doped Co @ NC composite material with high oxygen evolution catalytic activity is prepared by the preparation method.
The invention has the following beneficial effects:
according to the invention, the content of cobalt element active ingredients and the doping amount of sulfur element in the nitrogen-doped porous carbon material are adjusted by regulating the specific surface area and the crystal structure of the metal organic framework, and the optimal crystal structure and S/N atomic ratio are found out, so that the S-doped Co @ NC composite material with excellent electro-catalytic performance is obtained, and on one hand, the composite material has a small particle size, a core-shell structure and a large specific surface area, is beneficial to full exposure of active sites, and has more electrochemical reaction areas; on the other hand, the doping of S ions can improve the conductivity and the interface charge transfer efficiency of the composite material, so that the material has better OER characteristics. In addition, the method has the advantages of simple equipment, simple process, lower preparation cost and the like.
Drawings
Figure 1 is an XRD pattern of an S-doped Co @ NC composite prepared in example 1 of the present invention.
Figure 2 is an SEM image of an S-doped Co @ NC composite prepared in example 1 of the present invention.
Figure 3 is an XPS spectrum of an S-doped Co @ NC composite prepared in example 1 of the present invention.
FIG. 4 is a Raman spectrum of an S-doped Co @ NC composite material prepared in example 1 of the present invention.
FIG. 5 is an OER polarization curve, stability test curve and impedance spectrum thereof for the S-doped Co @ NC composite material prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Preparing an S-doped Co @ NC composite material:
s1, weighing 1.8g of cobalt nitrate hexahydrate, 0.7g of terephthalic acid and 0.22g of triethylene diamine, dissolving the cobalt nitrate hexahydrate, the terephthalic acid and the triethylene diamine in 50mL of N, N-dimethylformamide, stirring the mixture in a constant-temperature water bath kettle at the temperature of 60 ℃ for 30min, transferring the mixture into a 100mL high-pressure kettle, then placing the high-pressure kettle into a forced air drying oven to heat the mixture for 24h at the temperature of 120 ℃, respectively washing the product twice with DMF and ethanol, then placing the product into a vacuum drying oven, and drying the product for 24h at the temperature of 60 ℃ to obtain a Co-MOF material;
s2, placing the Co-MOF material in a corundum boat, heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, carrying out heat preservation and calcination for 2h, wherein the nitrogen flow is 80mL/min, and cooling to room temperature to obtain a Co @ NC material;
s3, dissolving 300mg of thiourea in 20mL of deionized water to obtain a thiourea aqueous solution with the concentration of 15g/L, adding 200mg of Co @ NC material into the thiourea aqueous solution, performing ultrasonic dispersion for 15min, uniformly dispersing the mixture in an air-blast drying oven, drying the mixture for 12h at the temperature of 60 ℃, heating the mixture to 800 ℃ in a corundum boat in a nitrogen atmosphere at the heating rate of 10 ℃/min, performing heat preservation and calcination for 2h, and cooling the mixture to room temperature to obtain the thiourea composite material.
Preparing a working electrode: mixing 10mg of the prepared S-doped Co @ NC composite material, 25 muL of DuPont membrane solution and 400 muL of isopropanol, performing ultrasonic treatment for 60min, and uniformly coating the obtained mixed solution on carbon paper (1.0 multiplied by 1.0cm), wherein the coating weight is 3mg/cm2And (4) drying the mixture in a constant temperature box at 60 ℃ for 10 hours per square centimeter to obtain the product.
The structure and properties of the S-doped Co @ NC composite material prepared in example 1 were characterized, with the following results:
fig. 1 is an XRD pattern of the S-doped Co @ NC composite material prepared in example 1, which can be seen to appear at 2 θ ═ 29.8 °,31.2 °,39.6 °,47.6 °,52.1 °,61.2 °,73.2 ° and 76.8 ° to Co9S8(311) Diffraction peaks corresponding to the (222), (331), (511), (440), (533), (731), and (800) crystal planes, and in addition, diffraction peaks corresponding to the CoS (100), (101), (102), and (110) crystal planes also appear at 2 θ of 30.5 °,35.2 °,46.9 °, and 54.3 °. Fig. 2 is an SEM image of the S-doped Co @ NC composite material prepared in example 1, and it can be seen that the composite material has a loose nano structure, and a large number of Co and S compound nano particles are wrapped or embedded on the loose nano structure, which helps to improve the catalytic activity of the material. FIG. 3 is a high resolution XPS spectra of Co2p and S2p for S doped Co @ NC composites prepared in example 1, wherein the XPS peaks at 162.1eV and 169.0eV correspond to S2p and S2p, respectively 2-S2 p of ion1/2Binding energy of and SO3 2-Or SO4 2-S2 p of1/2The binding energy of (1). XPS peaks centered at 781.9eV correspond to Co2+The binding energy of Co2p 3/2 of the ion is that the peak is located at 785.5eV, and is derived from Co2+And Co3+Ions. XPS peaks centered at 798.2eV correspond to Co2+The binding energy of Co2p1/2 of the ion is corresponding to that of the Co2p1/2, and the accompanying peak is located at 803.1eV2+And Co3+Ions. FIG. 4 is a schematic view ofRaman spectra of S-doped Co @ NC composite material prepared in example 1, as can be seen, were at 1345 and 1574cm-1Two Raman scattering peaks appear, which correspond to the D peak and the G peak of the carbon material respectively, and the result shows that graphitized carbon appears in the composite material.
FIG. 5a is the OER test results of the S-doped Co @ NC composite material obtained in example 1 under alkaline conditions, wherein the OER test employs a conventional three-electrode system, and the sample is tested for its LSV curve in a 1M KOH solution using an electrochemical workstation model CHI660E, with a sweep voltage of 1.3-1.8V (vs. reversible hydrogen electrode) and a sweep speed of 10mV S-1. As can be seen, the sample was at 10mA cm-2The overpotential at this time was 189mV (vs. rhe), which is much less than the overpotential of Co @ NC without S doping, indicating that S doping helps to improve its OER characteristics. Fig. 5b is a current density-time curve of the S-doped Co @ NC composite material obtained in example 1, and the result shows that the current density value of the curve does not fluctuate greatly, indicating that the material has stable OER characteristics. FIG. 5c is an impedance spectrum of the S-doped Co @ NC composite material obtained in example 1, and the curve is fitted according to an equivalent circuit model to obtain the charge transfer resistance (R) of the catalyst ct) Is 5.01X 10-6Ω, it can be seen that the charge transfer resistance is very small, indicating that the charge is relatively easy to cross the two-phase interface of the electrode and electrolyte.
Example 2
Preparing an S-doped Co @ NC composite material:
s1, weighing 1.8g of cobalt nitrate hexahydrate, 0.7g of terephthalic acid and 0.22g of triethylene diamine, dissolving the cobalt nitrate hexahydrate, the terephthalic acid and the triethylene diamine in 50mL of N, N-dimethylformamide, stirring the mixture in a constant-temperature water bath kettle at the temperature of 60 ℃ for 30min, transferring the mixture into a 100mL high-pressure kettle, then placing the high-pressure kettle into a forced air drying oven to heat the mixture for 24h at the temperature of 120 ℃, respectively washing the product twice with DMF and ethanol, then placing the product into a vacuum drying oven, and drying the product for 24h at the temperature of 60 ℃ to obtain a Co-MOF material;
s2, placing the Co-MOF material in a corundum boat, heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, carrying out heat preservation and calcination for 2h, wherein the nitrogen flow is 80mL/min, and cooling to room temperature to obtain a Co @ NC material;
s3, dissolving 400mg of thiourea in 20mL of deionized water to obtain a thiourea aqueous solution with the concentration of 15g/L, adding 200mg of Co @ NC material into the thiourea aqueous solution, performing ultrasonic dispersion for 15min, putting the mixture into a forced air drying oven, drying for 12h at the temperature of 60 ℃, then heating to 800 ℃ at the heating rate of 10 ℃/min in a corundum boat in a nitrogen atmosphere, performing heat preservation and calcination for 2h, and cooling to room temperature to obtain the thiourea composite material.
Preparing a working electrode: mixing 10mg of the prepared S-doped Co @ NC composite material, 25 muL of DuPont membrane solution and 400 muL of isopropanol, performing ultrasonic treatment for 60min, and uniformly coating the obtained mixed solution on carbon paper (1.0 multiplied by 1.0cm), wherein the coating weight is 3mg/cm2And (4) drying the mixture in a constant temperature box at 60 ℃ for 10 hours per square centimeter to obtain the product.
The structure and performance of the S-doped Co @ NC composite material prepared in example 2 were characterized, with the following results:
the XRD pattern obtained in example 2 was similar to that measured in example 1 and appeared to be similar to Co at 2 θ of 29.8 °,31.2 °,39.6 °,47.6 °,52.1 °,61.2 °,73.2 ° and 76.8 °9S8(311) Diffraction peaks corresponding to the (222), (331), (511), (440), (533), (731), and (800) crystal planes appear at 2 θ of 30.5 °,35.2 °,46.9 °, and 54.3 ° to correspond to the CoS (100), (101), (102), and (110) crystal planes. The composite material of example 2 also has a large number of nano-sized particles, but the dispersibility is poor, and the nano-structure may affect the catalytic activity thereof. The Raman spectrum of the S-doped Co @ NC composite material prepared in example 2 also showed at 1345 and 1574cm-1Two Raman scattering peaks appear, which correspond to the D peak and the G peak of the carbon material respectively, and the result shows that graphitized carbon appears in the composite material. OER results of the S-doped Co @ NC composite material obtained in example 2 under alkaline conditions showed that the sample was at 10mA cm -2The overpotential at this time was 299mV (vs. rhe), which is also less than the overpotential of Co @ NC without S doping, indicating that S doping helps to improve its OER characteristics. Fitting is carried out according to the impedance spectrum obtained in the embodiment of the equivalent circuit model to obtain the charge transfer resistance (R) of the catalystct) And 3.27 omega.
Example 3
Preparing an S-doped Co @ NC composite material:
s1, weighing 1.8g of cobalt nitrate hexahydrate, 0.7g of terephthalic acid and 0.22g of triethylene diamine, dissolving the cobalt nitrate hexahydrate, the terephthalic acid and the triethylene diamine in 50mL of N, N-dimethylformamide, stirring the mixture in a constant-temperature water bath kettle at the temperature of 60 ℃ for 30min, transferring the mixture into a 100mL high-pressure kettle, then placing the high-pressure kettle into a forced air drying oven to heat the mixture for 24h at the temperature of 120 ℃, respectively washing the product twice with DMF and ethanol, then placing the product into a vacuum drying oven, and drying the product for 24h at the temperature of 60 ℃ to obtain a Co-MOF material;
s2, placing the Co-MOF material in a corundum boat, heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, carrying out heat preservation and calcination for 2h, wherein the nitrogen flow is 80mL/min, and cooling to room temperature to obtain a Co @ NC material;
s3, dissolving 100mg of thiourea in 20mL of deionized water to obtain a thiourea aqueous solution with the concentration of 15g/L, adding 200mg of Co @ NC material into the thiourea aqueous solution, performing ultrasonic dispersion for 15min, uniformly dispersing the mixture in an air-blast drying oven, drying the mixture for 12h at the temperature of 60 ℃, heating the mixture to 800 ℃ in a corundum boat in a nitrogen atmosphere at the heating rate of 10 ℃/min, performing heat preservation and calcination for 2h, and cooling the mixture to room temperature to obtain the thiourea composite material.
Preparing a working electrode: mixing 10mg of the prepared S-doped Co @ NC composite material, 25 muL of DuPont membrane solution and 400 muL of isopropanol, performing ultrasonic treatment for 60min, and uniformly coating the obtained mixed solution on carbon paper (1.0 multiplied by 1.0cm), wherein the coating weight is 3mg/cm2And (4) drying the mixture in a constant temperature box at 60 ℃ for 10 hours per square centimeter to obtain the product.
The structure and properties of the S-doped Co @ NC composite material prepared in example 3 were characterized, with the following results:
in contrast to example 1, the X-ray diffraction spectrum obtained in example 3 appeared at 29.8 °,31.2 °,47.6 °,52.1 ° and 76.8 ° with Co, 2 θ9S8(311) Diffraction peaks corresponding to the (222), (511), (440) and (800) crystal planes, and no diffraction peak associated with CoS was observed. The composite material obtained in example 3 is also composed of a large number of nano-sized particles, but with poor dispersion, and the nano-structure may affect its catalytic activity. Still at 1345 and 1574cm-1Two placesRaman characteristic peaks were observed, corresponding to the D and G peaks, respectively, of the carbon material, indicating the presence of graphitized carbon in the composite material. OER test results of the composite obtained in example 3 under alkaline conditions showed that the sample was at 10mA cm-2The overpotential at 275mV (vs. RHE), which is also less than the overpotential of Co @ NC with no S incorporation, indicates that S doping helps to improve its OER characteristics. Fitting is carried out according to the impedance spectrum obtained in the embodiment of the equivalent circuit model to obtain the charge transfer resistance (R) of the catalyst ct) Is 0.302 omega.
Example 4
Preparing an S-doped Co @ NC composite material:
s1, weighing 1.5g of cobalt nitrate hexahydrate, 0.5g of terephthalic acid and 0.2g of triethylene diamine, dissolving the cobalt nitrate hexahydrate, the terephthalic acid and the triethylene diamine in 50mL of N, N-dimethylformamide, stirring the mixture in a constant-temperature water bath kettle at 50 ℃ for 20min, transferring the mixture into a 100mL high-pressure kettle, then placing the high-pressure kettle into a forced air drying oven, heating the high-pressure kettle at 100 ℃ for 20h, respectively washing the product twice with DMF (dimethyl formamide) and ethanol, then placing the product into a vacuum drying oven, and drying the product at 60 ℃ for 24h to obtain a Co-MOF material;
s2, placing the Co-MOF material in a corundum boat, heating to 700 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, carrying out heat preservation and calcination for 1h, wherein the nitrogen flow is 50mL/min, and cooling to room temperature to obtain a Co @ NC material;
s3, dissolving 100mg of thiourea in 20mL of deionized water to obtain a thiourea aqueous solution with the concentration of 5g/L, adding 200mg of Co @ NC material into the thiourea aqueous solution, performing ultrasonic dispersion for 15min, uniformly dispersing the mixture in an air-blast drying oven, drying the mixture for 12h at the temperature of 60 ℃, heating the mixture to 700 ℃ in a corundum boat in a nitrogen atmosphere at the heating rate of 5 ℃/min, performing heat preservation and calcination for 1h, and cooling the mixture to room temperature to obtain the thiourea composite material.
Example 5
Preparing an S-doped Co @ NC composite material:
S1, weighing 2g of cobalt nitrate hexahydrate, 1g of terephthalic acid and 0.25g of triethylene diamine, dissolving the cobalt nitrate hexahydrate, the terephthalic acid and the 0.25g of triethylene diamine in 40mL of N, N-dimethylformamide, stirring the mixture in a constant-temperature water bath kettle at 70 ℃ for 40min, transferring the mixture into a 100mL high-pressure kettle, then placing the high-pressure kettle into a forced air drying oven to heat the mixture for 30h at 140 ℃, respectively washing the product twice with DMF (dimethyl formamide) and ethanol, then placing the product into a vacuum drying oven, and drying the product for 24h at 60 ℃ to obtain a Co-MOF material;
s2, placing the Co-MOF material in a corundum boat, heating to 900 ℃ at a heating rate of 15 ℃/min in a nitrogen atmosphere, carrying out heat preservation and calcination for 3h, wherein the nitrogen flow is 100mL/min, and cooling to room temperature to obtain a Co @ NC material;
s3, dissolving 100mg of thiourea in 20mL of deionized water to obtain a thiourea aqueous solution with the concentration of 15g/L, adding 200mg of Co @ NC material into the thiourea aqueous solution, performing ultrasonic dispersion for 15min, uniformly dispersing the mixture in an air-blast drying oven, drying the mixture for 12h at the temperature of 60 ℃, heating the mixture to 900 ℃ in a corundum boat in a nitrogen atmosphere at the heating rate of 15 ℃/min, performing heat preservation and calcination for 3h, and cooling the mixture to room temperature to obtain the thiourea composite material.
Comparative example 1
Preparing an S-doped Co @ NC composite material:
s1, weighing 1.8g of cobalt nitrate hexahydrate, 0.7g of terephthalic acid and 0.22g of triethylene diamine, dissolving the cobalt nitrate hexahydrate, the terephthalic acid and the triethylene diamine in 50mL of N, N-dimethylformamide, stirring the mixture in a constant-temperature water bath kettle at the temperature of 60 ℃ for 30min, transferring the mixture into a 100mL high-pressure kettle, then placing the high-pressure kettle into a forced air drying oven to heat the mixture for 24h at the temperature of 120 ℃, respectively washing the product twice with DMF and ethanol, then placing the product into a vacuum drying oven, and drying the product for 24h at the temperature of 60 ℃ to obtain a Co-MOF material;
S2, placing the Co-MOF material in a corundum boat, heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, carrying out heat preservation and calcination for 2h, wherein the nitrogen flow is 80mL/min, and cooling to room temperature to obtain the Co @ NC composite material.
Preparing a working electrode: mixing 10mg of the Co @ NC composite material prepared above, 25 muL of DuPont film solution and 400 muL of isopropanol, performing ultrasonic treatment for 60min, and uniformly coating the obtained mixed solution on carbon paper (1.0 multiplied by 1.0cm), wherein the coating weight is 3mg/cm2And (4) drying the mixture in a constant temperature box at 60 ℃ for 10 hours per square centimeter to obtain the product.
The structure and performance of the Co @ NC composite material prepared in comparative example 1 were characterized, and the results were as follows:
the test result of X-ray diffraction spectrum shows that the sample has 2 theta-2At 9.8 °,52.1 ° and 76.8 ° with Co9S8(311) Diffraction peaks corresponding to the (440) and (800) crystal planes appeared at 44.2 °,51.6 ° and 75.9 ° with respect to 2 θ, and no diffraction peak associated with CoS was observed. Samples were at 1345 and 1574cm-1Raman characteristic peaks are observed at two positions and respectively correspond to a D peak and a G peak of the carbon material, but the peak intensity is relatively weaker, which indicates that the graphitization degree of the carbon in the composite material is weaker. The composite material is composed of a large number of nano particles and has a loose nano structure, and a large number of Co compound nano particles are coated by the loose carbon nano structure. The results of OER testing of the composite obtained in this example under alkaline conditions show that the sample is at 10mA cm -2The overpotential at that time was 323mV (vs. rhe), and the charge transfer resistance (R) of the catalyst was obtained by fitting the impedance spectrum obtained in this example of the equivalent circuit modelct) Is 2.68X 109Ω。
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A preparation method of an S-doped Co @ NC composite material with high oxygen evolution catalytic activity is characterized by comprising the following steps:
s1, dissolving cobalt nitrate hexahydrate, terephthalic acid and triethylene diamine in an organic solvent, stirring for 20-40min at 50-70 ℃, and heating for 20-30h at 100-140 ℃ to obtain the Co-MOF material, wherein the mass ratio of the cobalt nitrate hexahydrate, the terephthalic acid and the triethylene diamine is (1.5-2): (0.5-1): (0.2-0.25);
s2, calcining the Co-MOF material in a nitrogen atmosphere at the temperature of 700-900 ℃ for 1-3h to obtain a Co @ NC material;
s3, uniformly dispersing the Co @ NC material in an aqueous solution of thiourea, drying, and calcining at the temperature of 700-900 ℃ for 1-3h in a nitrogen atmosphere to obtain the S-doped Co @ NC composite material with high oxygen evolution catalytic activity, wherein the mass ratio of the Co @ NC material to the thiourea is 1: (0.5-2).
2. The method for preparing an S-doped Co @ NC composite material with high oxygen evolution catalytic activity as claimed in claim 1, wherein the mass ratio of the cobalt nitrate hexahydrate, the terephthalic acid and the terephthalic acid is 1.8: 0.7: 0.22.
3. the preparation method of the S-doped Co @ NC composite material with high oxygen evolution catalytic activity as claimed in claim 1 or 2, characterized in that the mass ratio of the Co @ NC material to thiourea is 1: 1.5.
4. A method of preparing an S-doped Co @ NC composite material with high oxygen evolution catalytic activity according to any of claims 1-3, characterized in that the ratio of the mass of the cobalt nitrate hexahydrate to the volume of organic solvent is (3-5) g: 100 mL; preferably, the organic solvent is N, N-dimethylformamide.
5. The preparation method of the S-doped Co @ NC composite material with high oxygen evolution catalytic activity as claimed in any one of claims 1 to 4, characterized in that in the step S2, the nitrogen flow rate is 50-100 mL/min.
6. The process for the preparation of an S-doped Co @ NC composite material with high oxygen evolution catalytic activity according to any of claims 1 to 5, characterized in that the concentration of the aqueous solution of thiourea is 5 to 20 g/L.
7. The method for preparing S-doped Co @ NC composite material with high oxygen evolution catalytic activity as claimed in any one of claims 1 to 6, wherein in the step S2, heating is carried out at a heating rate of 5-15 ℃/min to 700-900 ℃; in the step S3, the heating rate is 5-15 ℃/min to 700-900 ℃.
8. An S-doped Co @ NC composite material with high oxygen evolution catalytic activity, characterized by being prepared by the preparation method of any one of claims 1 to 7.
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