CN111841598B - 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 63
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 28
- 239000001301 oxygen Substances 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 46
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 52
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 38
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 26
- 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
- 238000001035 drying Methods 0.000 claims description 22
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- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 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 11
- 150000002500 ions Chemical class 0.000 abstract description 7
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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
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- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
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- 238000002441 X-ray diffraction Methods 0.000 description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
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- B01J35/33—Electric or magnetic properties
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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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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 producing oxygen by decomposing water completely, and electrocatalytic cracking water is highly dependent on the activity of an electrocatalyst in an oxygen evolution reaction, so that the electrocatalyst with high oxygen evolution reaction activity must be searched for in order to improve the efficiency of electrocatalytic oxygen evolution. 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 a Co-MOF material, wherein the mass ratio of the cobalt nitrate hexahydrate to the terephthalic acid to 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 700-900 ℃ for 1-3h in a heat preservation manner to obtain a Co @ NC material;
s3, uniformly dispersing the Co @ NC material in an aqueous solution of thiourea, drying, calcining at 700-900 ℃ for 1-3h in a nitrogen atmosphere at a constant temperature 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 1.5.
Preferably, in the step S2, the nitrogen flow is 50-100mL/min.
Preferably, in the step S1, cobalt nitrate hexahydrate, terephthalic acid and triethylene diamine are dissolved in an organic solvent, stirred for 30min at 60 ℃, and then heated for 24h at 120 ℃.
Preferably, in the step S2, the Co-MOF material is calcined under nitrogen atmosphere at 800 ℃ for 2h.
Preferably, in the step S3, the co @ nc material is uniformly dispersed in an aqueous solution of thiourea, and is calcined in a nitrogen atmosphere at 800 ℃ for 2 hours after being dried.
Preferably, the ratio of the mass of the cobalt nitrate hexahydrate to the volume of the organic solvent is (3-5) g:100mL; preferably, the ratio of the mass of the cobalt nitrate hexahydrate to the volume of the organic solvent is 3.6g:100mL; preferably; the organic solvent is N, N-dimethylformamide.
Preferably, the concentration of the thiourea aqueous solution is 5-20g/L; preferably, the concentration of the aqueous solution of thiourea is 15g/L.
Preferably, in the step S2, the mixture is heated to 700-900 ℃ at a heating speed of 5-15 ℃/min; preferably, in the step S2, the heating is carried out at a heating rate of 10 ℃/min to 800 ℃.
Preferably, in the step S3, the mixture is heated to 700-900 ℃ at a heating speed of 5-15 ℃/min; preferably, in the step S3, the heating is carried out at a heating rate of 10 ℃/min to 800 ℃.
Preferably, in the step S1, after heating, cooling to room temperature is further included, and the product is dried after being washed, wherein the drying temperature is 60 ℃, and the drying time is 24h.
Preferably, in the step S3, the drying temperature is 60 ℃ and the drying time is 12h.
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 smaller particle size, a core-shell structure and larger specific surface area, is beneficial to full exposure of active sites, and has more electrochemical reaction area; 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
FIG. 1 is an XRD pattern of an S-doped Co @ NC composite material prepared in example 1 of the present invention.
FIG. 2 is an SEM image of an S-doped Co @ NC composite material prepared in example 1 of the present invention.
FIG. 3 is an XPS spectrum of S-doped Co @ NC composite material prepared in example 1 of the present invention.
FIG. 4 is a Raman spectrum of 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 of 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 60 ℃ for 30min, transferring the mixture into a 100mL high-pressure kettle, then putting the high-pressure kettle into a forced air drying oven, heating the high-pressure kettle at 120 ℃ for 24h, respectively washing the product twice with DMF (dimethyl formamide) and ethanol, putting 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 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, placing 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 the nitrogen atmosphere, performing heat preservation and calcination for 2h, and cooling to room temperature to obtain the material.
Preparing a working electrode: mixing 10mg of the prepared S-doped Co @ NC composite material, 25. Mu.L of DuPont membrane solution and 400. Mu.L of isopropanol, performing ultrasonic treatment for 60min, and uniformly coating the obtained mixed solution on carbon paper (1.0 × 1.0 cm) with a coating weight of 3mg/cm 2 Per square centimeterAnd (4) drying the rice in a constant temperature oven at 60 ℃ for 10 hours to obtain the rice.
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 is seen to appear at 2 θ =29.8 °,31.2 °,39.6 °,47.6 °,52.1 °,61.2 °,73.2 ° and 76.8 ° to Co 9 S 8 (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 =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 of the S-doped Co @ NC composite material prepared in example 1, wherein the XPS peaks at 162.1eV and 169.0eV correspond to S 2- S2p of ion 1/2 Binding energy of and SO 3 2- Or SO 4 2- S2p of 1/2 The binding energy of (4). XPS peaks centered at 781.9eV correspond to Co 2+ The Co2p 3/2 binding energy of the ion is accompanied by a peak at 785.5eV, which is derived from Co 2+ And Co 3+ Ions. XPS peak centered at 798.2eV corresponds to Co 2+ The binding energy of Co2p1/2 of the ion is corresponding to that of the Co2p1/2, and the accompanying peak is located at 803.1eV 2+ And Co 3+ Ions. FIG. 4 is a Raman spectrum of the S-doped Co @ NC composite material prepared in example 1, as can be seen at 1345 and 1574cm -1 Two 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 result of the S-doped Co @ NC composite material obtained in example 1 under alkaline condition, wherein the OER test adopts a traditional three-electrode system, the LSV curve of the sample is tested in 1M KOH solution by using CHI660E type electrochemical workstation, and the electric potential is scannedThe pressure was 1.3-1.8V (relative to the reversible hydrogen electrode) and the scanning speed was 10mV s -1 . As can be seen, the sample is at 10mA cm -2 The overpotential in the case of the doping is 189mV (vs. RHE), which is far less than the overpotential of Co @ NC without doped S, which indicates that S doping is helpful for improving the OER characteristic of the doped S. 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 charge transfer resistance (R) of the catalyst was obtained by fitting the curve according to an equivalent circuit model ct ) Is 5.01X 10 -6 Ω, 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 60 ℃ for 30min, transferring the mixture into a 100mL high-pressure kettle, then putting the high-pressure kettle into a forced air drying oven, heating the high-pressure kettle at 120 ℃ for 24h, respectively washing the product twice with DMF (dimethyl formamide) and ethanol, putting 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 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, placing 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 the nitrogen atmosphere, performing heat preservation and calcination for 2h, and cooling to room temperature to obtain the material.
Preparing a working electrode: taking 10mg of the prepared S-doped Co @ NC composite material, 25 mu L of DuPont membrane solution and 400 mu L of iso-membraneMixing with propanol, ultrasonic treating for 60min, and uniformly coating the obtained mixed solution onto carbon paper (1.0 × 1.0 cm) with a coating amount of 3mg/cm 2 And (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 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 =29.8 °,31.2 °,39.6 °,47.6 °,52.1 °,61.2 °,73.2 ° and 76.8 ° 9 S 8 (311) Diffraction peaks corresponding to the (222), (331), (511), (440), (533), (731), and (800) crystal planes appear at 2 θ =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. Raman spectra of S-doped Co @ NC composite material prepared in example 2, also at 1345 and 1574cm -1 Two 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 -2 The overpotential at this time was 299mV (vs. RHE), which is also smaller than the overpotential of Co @ NC without S doping, indicating that S doping contributes to improving its OER characteristics. The impedance spectrum obtained in the embodiment of the equivalent circuit model is fitted to obtain the charge transfer resistance (R) of the catalyst ct ) And was 3.27 Ω.
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 60 ℃ for 30min, transferring the mixture into a 100mL high-pressure kettle, then putting the high-pressure kettle into a forced air drying oven, heating the high-pressure kettle at 120 ℃ for 24h, respectively washing the product twice with DMF (dimethyl formamide) and ethanol, putting 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 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, placing 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 the nitrogen atmosphere, performing heat preservation and calcination for 2h, and cooling to room temperature to obtain the material.
Preparing a working electrode: mixing 10mg of the prepared S-doped Co @ NC composite material, 25. Mu.L of DuPont membrane solution and 400. Mu.L of isopropanol, performing ultrasonic treatment for 60min, and uniformly coating the obtained mixed solution on carbon paper (1.0 × 1.0 cm) with a coating weight of 3mg/cm 2 And (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 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 2 θ =29.8 °,31.2 °,47.6 °,52.1 ° and 76.8 ° to Co 9 S 8 (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 the dispersibility is poor, and the nano-structure may affect the catalytic activity thereof. Still at 1345 and 1574cm -1 Raman characteristic peaks corresponding to the D peak and the G peak of the carbon material were observed at two places, respectively, and this result indicates that graphitized carbon occurred 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 -2 The overpotential at this time was 275mV (vs. RHE), which is also smaller than the overpotential of Co @ NC without S doping, indicating that S doping contributes to improving 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 ) And 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 putting 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, putting the product into a vacuum drying oven, and drying the product at 60 ℃ for 24h to obtain a Co-MOF material;
s2, putting 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 5g/L thiourea aqueous solution, adding 200mg of Co @ NC material into the thiourea aqueous solution, performing ultrasonic dispersion for 15min, placing the mixture into a forced air drying oven, drying for 12h at 60 ℃, then heating to 700 ℃ in a corundum boat in a nitrogen atmosphere at a heating rate of 5 ℃/min, performing heat preservation and calcination for 1h, and cooling to room temperature to obtain the 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 cleaning the product twice with DMF 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, putting 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 a 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.
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 60 ℃ for 30min, transferring the mixture into a 100mL high-pressure kettle, then putting the high-pressure kettle into a forced air drying oven, heating the high-pressure kettle at 120 ℃ for 24h, respectively washing the product twice with DMF (dimethyl formamide) and ethanol, putting 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 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 above prepared Co @ NC composite material, 25. Mu.L of DuPont membrane solution and 400. Mu.L of isopropanol, subjecting to ultrasonic treatment for 60min, and uniformly coating the obtained mixture on carbon paper (1.0 × 1.0 cm) at a coating weight of 3mg/cm 2 And (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 results of the X-ray diffraction spectrum showed that the sample appeared at 2 θ =29.8 °,52.1 ° and 76.8 ° with Co 9 S 8 (311) Diffraction peaks corresponding to (440) and (800) crystal planes appeared at 2 θ =44.2 °,51.6 ° and 75.9 ° corresponding to Co (111), (200) and (220) crystal planes, and no diffraction peak associated with CoS was observed. Samples were at 1345 and 1574cm -1 Raman 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, has a loose nano structure, and is compounded by a large number of CoThe nano-particles are coated with loose carbon nanostructures. The results of OER testing of the composite obtained in this example under alkaline conditions show that the sample is at 10mA cm -2 The 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 model ct ) Is 2.68X 10 9 Ω。
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 (9)
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 a Co-MOF material, wherein the mass ratio of the cobalt nitrate hexahydrate to the terephthalic acid to 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 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 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 preparation method of the S-doped Co @ NC composite material with high oxygen evolution catalytic activity according to claim 1, wherein the mass ratio of the cobalt nitrate hexahydrate, the terephthalic acid and the triethylene diamine 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 1.5.
4. 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 ratio of the mass of the cobalt nitrate hexahydrate to the volume of the organic solvent is (3-5) g:100mL.
5. 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 organic solvent is N, N-dimethylformamide.
6. 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 in the step S2, the nitrogen flow is 50-100mL/min.
7. The preparation method of the S-doped Co @ NC composite material with high oxygen evolution catalytic activity according to claim 1 or 2, characterized in that the concentration of the thiourea aqueous solution is 5-20g/L.
8. 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, in the step S2, the S-doped Co @ NC composite material is heated to 700-900 ℃ at a heating speed of 5-15 ℃/min; in the step S3, the mixture is heated to 700-900 ℃ at a heating speed of 5-15 ℃/min.
9. An S-doped Co @ NC composite material with high oxygen evolution catalytic activity, which is characterized by being prepared by the preparation method of any one of claims 1-8.
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