CN109847778B - Cobalt disulfide/carbon nitrogen composite material for oxygen evolution by electrolyzing water and synthetic method thereof - Google Patents
Cobalt disulfide/carbon nitrogen composite material for oxygen evolution by electrolyzing water and synthetic method thereof Download PDFInfo
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Abstract
The invention relates to a cobalt disulfide/carbon nitrogen composite material for oxygen evolution by water electrolysis and a synthesis method thereof. The material is in a porous dodecahedral structure, CoS2The nanoparticles are coated with graphitic carbon and uniformly distributed on the dodecahedral carbon nitrogen framework. The catalyst has excellent activity and super-long-time stability in the electrolytic water oxygen evolution process, has excellent performance far exceeding the catalytic performance of noble metals Ru and Ir, has performance far better than that of non-noble metal catalysts obtained by other methods, and has great application prospect in the field of electrolytic water oxygen evolution.
Description
Technical Field
The invention belongs to the technical field of water electrolysis catalysts, and relates to a novel high-efficiency non-noble metal cobalt disulfide/carbon nitrogen composite material for an electrolysis water oxygen evolution catalyst and a preparation method thereof.
Background
With the increasing demand of people for energy, the development of a novel energy conversion system with high efficiency and stability becomes a research hotspot of the scientific community. The electrolytic water is a clean and sustainable large-scale hydrogen preparation method, and is an energy conversion system based on water, hydrogen and oxygen, so that a 'zero-emission' clean energy conversion system is obtained in the real sense. And designing a high-performance catalyst material is the core for improving the performance of the electrolytic water. In the water electrolysis process, because the oxygen evolution process is a four-electron process, higher overpotential is often needed to push the oxygen evolution process to proceed, thereby preventing the whole water electrolysis process from proceeding smoothly, and therefore, the search for a proper catalyst to reduce the overpotential of the oxygen evolution process has great significance. Although noble metal catalysts such as ruthenium (Ru) and iridium (Ir) have high catalytic activity for oxygen evolution, their low storage on earth and high price severely hinder the large-scale application of hydrogen production and oxygen production by electrolysis of water. Therefore, in recent years, the use of non-noble metal materials instead of noble metals for electrocatalytic oxygen evolution has also become the direction of much effort by researchers.
Due to its high efficiency intrinsic catalytic activity and abundant natural reserves, the 3d transition metals cobalt, nickel are considered to be the most promising materials to replace noble metal catalysts. However, conventional bulk or agglomerated cobalt and nickel metal nanoparticles are less competitive in electrochemical catalytic applications due to the smaller specific surface area and fewer catalytically active sites. In addition, bare cobalt and nickel metal nanoparticles are less stable in strongly alkaline solutions and at high overpotentials. However, the simple sulfurization treatment has disadvantages such as insufficient sulfurization, poor conductivity, insufficient active sites, and poor stability.
The metal organic framework compounds (MOFs) have the characteristics of large specific surface area, uniform pore channels, periodic element arrangement and the like, ZIF-67 is taken as one of the MOFs, and is a dodecahedron formed by bonding metal element cobalt and an organic ligand, and the prior art reports that: it is used as precursor and modified to raise catalytic performance, including forming LDH structure with the precursor, oxidizing, phosphorizing, sulfurizing and other steps. Jian-Rong Li et al (adv. energy mater.2017, 1602643) use ZIF-67 as a template for oxidation, sulfidation, and phosphating for catalytic oxygen evolution, but the performance needs to be improved.
Disclosure of Invention
The invention aims to provide a non-noble metal electro-catalysis oxygen evolution material for electrolyzing water to evolve oxygen, in particular to a cobalt disulfide/carbon nitrogen composite material and a synthetic method thereof.
A cobalt disulfide/carbon nitrogen composite material is provided, which is a porous dodecahedron structure, CoS2The nanoparticles are coated with graphitic carbon and uniformly distributed on the dodecahedral carbon nitrogen framework.
According to the scheme, the size of the cobalt disulfide/carbon nitrogen composite material is 0.1-1.5 mu m, and CoS2The particle size is between 5nm and 10 nm.
The cobalt disulfide/carbon nitrogen composite material is used as an electrolytic water anode oxygen evolution catalyst in the electrolytic water oxygen evolution.
The application method comprises the following steps: the cobalt disulfide/carbon nitrogen composite material is used as an active component to prepare an electrode, and then the electrode is used as a working electrode for anodic oxygen evolution of electrolyzed water.
The method comprises the following specific steps: preparing a dispersion liquid by using a Nafion solution, then loading the dispersion liquid on a foam nickel carrier and drying the dispersion liquid at normal temperature to obtain foam nickel containing active components of the cobalt disulfide/carbon nitrogen composite material, using the foam nickel as a working electrode, using a platinum sheet as a counter electrode, using Hg/HgO as a reference electrode, using KOH as an electrolyte, and electrolyzing water to carry out anodic oxygen evolution. It has good catalytic performance at 10mA cm-2The overpotential of the current density of (1) is only 205mV, and when the current density reaches 1000mA cm-2The overpotential was 327 mV. The catalyst has catalytic performance far exceeding that of noble metals Ru and Ir, and performance far better than that of non-noble metal catalysts obtained by other methods.
The synthesis method of the cobalt disulfide/carbon nitrogen composite material as the electrolytic water oxygen evolution catalyst is characterized by comprising the following steps of:
annealing ZIF-67 under inert gas in two steps, wherein the annealing in two steps is as follows: firstly, calcining ZIF-67 at 280-400 ℃ in an inert atmosphere, and then calcining at 600-1000 ℃ in an inert atmosphere;
and then fully grinding and mixing the annealed product and S powder, and annealing in an inert atmosphere to carry out a vulcanization reaction to obtain the cobalt disulfide/carbon nitrogen composite material.
According to the scheme, the calcination time of the first step at 280-400 ℃ is 1.5-3 h, the temperature in the first step calcination is more preferably 300 ℃, and the duration is preferably 2 h; the calcination time of the second step at 600-1000 ℃ is 3.5-5 h, the temperature of the second step calcination is preferably 800 ℃, and the duration is preferably 4 h.
According to the scheme, the mixing ratio of the annealed product to the S powder is 10: 1-1: 10 in mass ratio.
According to the scheme, the temperature of the vulcanization reaction is 280-350 ℃, the time is 10-15 h, the temperature is preferably 300 ℃, and the time duration is preferably 12 h.
According to the scheme, the preparation method of the ZIF-67 comprises the following steps:
(1) dissolving 2-methylimidazole in a mixed solvent consisting of methanol and ethanol to prepare a 2-methylimidazole solution, wherein the concentration of the 2-methylimidazole solution is 0.05-1M, and the volume ratio of the methanol to the ethanol is any ratio, preferably 1: 1;
(2) dissolving a cobalt source substance in a solvent obtained by mixing methanol and ethanol solution to prepare a cobalt source solution, wherein the concentration of the cobalt source solution is 0.01-0.2M, and the volume ratio of methanol to ethanol is any ratio, preferably 1: 1;
(3) and (3) quickly pouring the solution obtained in the step (1) into the solution obtained in the step (2) while stirring, continuously stirring for a period of time, standing to obtain a purple precipitate, alternately performing centrifugal washing and filtration by using organic solvents ethanol and methanol, and drying for 6-15 hours at 40-80 ℃.
According to the scheme, the temperature for stirring and mixing the two solutions in the step (3) is within the range of 0-50 ℃, preferably 25 ℃, the stirring time is within 5 s-1 h, preferably 10min, the standing temperature is within the range of 0-50 ℃, preferably 25 ℃, and the time is within 5-36 h, preferably 24 h.
The ratio of the amount of the 2-methylimidazole substance to the amount of the cobalt source substance in the step (3) is 0.005-0.5: 1.
according to the scheme, the cobalt source substance in the step (3) is selected from Co (NO)3)2·6H2O、CoCl2·6H2O、CoSO4·6H2O、C15H21CoO6。
The invention creatively obtains the sulfur-rich electrocatalyst with high oxygen evolution performance, namely the CoS coated by graphite carbon, which is in nanoscale and uniform in appearance by a two-step calcination carbonization method and a one-step calcination vulcanization method for the first time2The nano particles are uniformly distributed on the electrolytic water oxygen evolution catalyst on a carbon and nitrogen frame obtained by taking a metal organic frame as a template. The conductive film has good conductivity and excellent hydrophilic capability, can effectively activate water molecules, and has abundant active sites, so that water can be efficiently decomposed to produce oxygen. The catalyst shows excellent activity and ultra-long time stability in the electrolytic water oxygen evolution as the electrolytic water anode oxygen evolution catalyst, and has excellent performance (at 10 mA-cm)-2The overpotential of the current density of (1) is only 205mV, and when the current density reaches 1000mA cm-2The overpotential was 327 mV. Far surpass the catalysis of noble metals Ru and IrThe performance and the performance are far better than those of non-noble metal catalysts obtained by other methods, and the catalyst has a great application prospect in the field of electrolytic water oxygen evolution.
Drawings
Fig. 1 shows an X-ray diffraction pattern (abbreviated as XRD) of a sample: (a) ZIF-67; (b) Co/NC: a cobalt/carbon nitrogen composite; CoS2NC: a cobalt disulfide/carbon nitrogen composite.
Fig. 2 is a scanning electron microscope image (SEM for short) of a sample: (a) ZIF-67 obtained in the step (3); (b) a cobalt/carbon nitrogen composite; (c) a cobalt disulfide/carbon nitrogen composite.
FIG. 3 is a Transmission Electron Micrograph (TEM) of a cobalt/carbon nitrogen composite; (a) (b) TEM at low magnification; (c) the image is an enlarged view of a box area in the image (b), and is a high-resolution transmission electron microscope image (HRTEM for short); (d) high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM for short) for cobalt/carbon nitrogen composite material; (e) and (f) and (g) are the C, N and Co element distribution diagrams, respectively.
FIG. 4 is a Transmission Electron Microscope (TEM) image of a cobalt disulfide/carbon nitrogen composite; (a) (b) TEM at low magnification; (c) the image is an enlarged view of a box area in the image (b), and is a high-resolution transmission electron microscope image (HRTEM for short); (d) high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM for short) of cobalt/carbon-nitrogen composite material; (e) (f), (g) and (h) are distribution diagrams of C, N, Co and S elements, respectively.
FIG. 5 shows samples ZIF-67, cobalt/carbon nitrogen composite (Co/NC), cobalt disulfide/carbon nitrogen composite (CoS)2/NC) Raman spectrum (Raman for short).
FIG. 6 is a graph of the catalytic performance of the samples: (a) sample nickel foam, ZIF-67, RuO2Linear Scanning Voltammogram (LSV) of cobalt/carbon nitrogen composite, cobalt disulfide/carbon nitrogen composite exhibiting the lowest overpotential; (b) is LSV diagram of the cobalt disulfide/carbon nitrogen composite material under high current density; (c) is a stability test chart of the cobalt disulfide/carbon nitrogen composite material.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
Example 1
(1) Weighing 1.746g Co (NO)3)2·6H2O in a mixed solvent of 40mL of ethanol and 40mL of methanol, stirring with a magnetic stirrer for 10min, and then sonicating for 10 min. Similarly, 1.97g of 2-methylimidazole was weighed in a mixed solvent of 40ml of ethanol and 40ml of methanol, stirred with a magnetic stirrer for 10min, and then sonicated for 10 min. And (3) rapidly pouring the organic solution into a salt solution while stirring, continuously stirring for 10min, standing at room temperature for 24h, alternately washing the obtained purple precipitate with ethanol and methanol, centrifuging, and drying at 60 ℃ for 12h to obtain the metal organic framework compound ZIF-67. FIG. 1(a) shows an XRD pattern of the prepared ZIF-67, in which characteristic peaks correspond one-to-one to fitted peaks, and an electron micrograph in FIG. 2(a) shows that ZIF-67 is a dodecahedral structure having a uniform size and a smooth appearance. The raman peaks of ZIFs in fig. 5 are also all peaks of the corresponding organic substance.
(2) And (2) putting the ZIF-67 in the step (1) in a magnetic boat, annealing for 2h at 300 ℃ in a tubular furnace under a nitrogen atmosphere, then annealing for 4h at 800 ℃, and cooling and taking out a sample to obtain the porous dodecahedral cobalt/carbon nitrogen composite material. The XRD pattern in fig. 1(b) shows that the cobalt/carbon nitrogen composite material retains only three distinct characteristic peaks of metallic cobalt, the electron micrograph in fig. 2(b) shows that the cobalt/carbon nitrogen composite material retains the original dodecahedron structure but the surface becomes rough, exposing cobalt particles, and the TEM in fig. 3 shows that after annealing, the cobalt/carbon nitrogen composite material changes from the original smooth surface to a porous structure, the metallic cobalt is coated with graphitic carbon, which is externally amorphous carbon nitrogen, and the cobalt particles are uniformly distributed throughout the dodecahedron, wherein d is 0.21nm corresponding to the lattice fringes of cobalt, d is 0.34nm corresponding to the lattice fringes of graphitic carbon, and the elemental distribution map shows that C, N, Co are uniformly dispersed throughout the dodecahedron. FIG. 5 shows ZIF-67, cobalt/carbon nitrogen composite (Co/NC), cobalt disulfide/carbon nitrogen composite (CoS)2Raman spectrum of/NC), wherein cobalt/carbon nitrogen composite (CoS)2NC) in the raman spectrum: the D peak represents a defect of the lattice of C atoms, and the G peak represents in-plane stretching vibration of the hybridization of C atoms sp 2.
(3) And (3) adding alcohol into the cobalt/carbon nitrogen composite material and the sulfur powder in the ratio of 1:3 in a mortar in the step (2), fully grinding and mixing by a wet method for multiple times, annealing for 12 hours in a magnetic boat at 300 ℃ in a tubular furnace under the nitrogen atmosphere, and cooling to obtain a collected sample, namely the cobalt disulfide/carbon nitrogen composite material as the efficient electrolytic water oxygen evolution catalyst. Fig. 1(b) shows that characteristic peaks of cobalt disulfide were detected in the cobalt disulfide/carbon nitrogen composite, and the electron micrograph of fig. 2(c) shows that the cobalt disulfide/carbon nitrogen composite retained the original dodecahedral structure and the surface became rougher. The TEM of fig. 4 shows that after sulfidation, the resulting cobalt disulfide is coated with graphitic carbon, which is an amorphous carbon-nitrogen structure on the outside, and the cobalt disulfide particles are uniformly distributed throughout the dodecahedron, wherein d-0.28 nm corresponds to the lattice fringes of cobalt disulfide, d-0.34 nm corresponds to the lattice fringes of graphitic carbon, and the elemental profile shows that C, N, Co, S are uniformly dispersed throughout the dodecahedron. The raman peaks of the cobalt disulfide/carbon nitrogen composite in figure 5 show the corresponding D, G peaks.
(4) Weighing the catalyst 5mg, adding into 400 μ L ethanol, performing ultrasonic treatment for 30min, adding 100 μ L isopropanol dropwise into the solution, performing ultrasonic treatment for 30min, adding 50 μ L commercially available 5 wt% Nafion solution dropwise, performing ultrasonic treatment for 30min, and uniformly adding into 1 × 1cm-2And drying the foamed nickel at normal temperature. Electrochemical tests were carried out with 1mol/L KOH as the electrolyte, foamed nickel containing the catalyst as the working electrode, a platinum sheet as the counter electrode, and Hg/HgO as the reference electrode. The results are shown in FIG. 6, where (a) shows: the cobalt disulfide/carbon nitrogen composite material shows absolute oxygen evolution activity by electrolyzing water at 10 mA-cm relative to other materials-2The overpotential needs only 205mV at the current density of (d). Far exceeds the precious metal RuO2The catalytic performance of (2). (b) The graph shows that when the current density reaches 1000mA cm-2The overpotential was only 327 mV.
(c) The current density of the graph is 10mA cm-2And 1000mA · cm-2After continuous electrolysis for 10h, the catalyst maintains good stability.
Example 2
(1) Weighing 1.746g Co (NO)3)2·6H2O in a mixed solvent of 40ml of ethanol and 40ml of methanol, stirring for 10min with a magnetic stirrer, and then performing ultrasonic treatment for 10 min. Similarly, 1.97g of 2-methylimidazole was weighed in a mixed solvent of 40ml of ethanol and 40ml of methanol, stirred with a magnetic stirrer for 10min, and then sonicated for 10 min. And (3) rapidly pouring the organic solution into a salt solution while stirring, continuously stirring for 5min, standing at room temperature for 18h, alternately washing the obtained purple precipitate with ethanol and methanol, centrifuging, and drying at 60 ℃ for 12h to obtain the metal organic framework ZIF-67.
(2) And (2) putting the ZIF-67 in the step (1) in a magnetic boat, annealing for 2h at 300 ℃ in a tubular furnace under the nitrogen atmosphere, then annealing for 3.5h at 1000 ℃, and cooling and taking out a sample to obtain the porous dodecahedral cobalt/carbon nitrogen composite material.
(3) And (3) adding alcohol into the cobalt/carbon nitrogen composite material and the sulfur powder in the ratio of 3:1 in a mortar in the step (2), fully grinding and mixing the materials by a wet method for many times, annealing the materials in a magnetic boat at 350 ℃ in a tubular furnace in a nitrogen atmosphere for 10 hours, and cooling the materials to obtain a collected sample, namely the cobalt disulfide/carbon nitrogen composite material as the efficient electrolytic water oxygen evolution catalyst.
(4) Weighing the catalyst 5mg, adding the catalyst into 400 mu L of ethanol, performing ultrasonic treatment for 30min, dropwise adding 100 mu L of isopropanol into the solution, performing ultrasonic treatment for 30min, dropwise adding 50 mu L of commercially available 5 wt% Nafion solution, performing ultrasonic treatment for 30min, and uniformly dropwise adding the Nafion solution at a concentration of 1X 1cm-2The foamed nickel is dried at normal temperature. Electrochemical tests were carried out with 1mol/L KOH as the electrolyte, foamed nickel containing the catalyst as the working electrode, a platinum sheet as the counter electrode, and Hg/HgO as the reference electrode. When the current density is 10mA cm-2And 100mA · cm-2See table 1 for overpotentials at time, respectively.
Example 3
(1) Weighing 1.746g Co (NO)3)2·6H2O in a mixed solvent of 40ml of ethanol and 40ml of methanol, stirring with a magnetic stirrer for 10min, and then sonicating for 10 min. Similarly, 1.97g of 2-methylimidazole was weighed in a mixed solvent of 50ml of ethanol and 40ml of methanol, stirred with a magnetic stirrer for 10min, and then sonicated for 10 min. Rapidly pouring the organic solution into the salt solution while stirring, continuously stirring for 20min, standing at room temperature for 24 hr, and mixingAnd washing the obtained purple precipitate with ethanol and methanol alternately, centrifuging, and drying at 60 ℃ for 12h to obtain the metal organic framework ZIF-67.
(2) And (2) putting the ZIF-67 in the step (1) in a magnetic boat, annealing for 2h at 300 ℃ in a tubular furnace under a nitrogen atmosphere, then annealing for 4h at 800 ℃, and cooling and taking out a sample to obtain the porous dodecahedral cobalt/carbon nitrogen composite material.
(3) And (3) adding alcohol into the cobalt/carbon nitrogen composite material and the sulfur powder in the ratio of 1:6 in the mortar in the step (2), fully grinding and mixing the materials by a wet method for multiple times, annealing the materials in a magnetic boat at 280 ℃ in a tubular furnace under the nitrogen atmosphere for 15 hours, and cooling the materials to obtain a collected sample, namely the cobalt disulfide/carbon nitrogen composite material as the efficient electrolytic water oxygen evolution catalyst.
(4) Weighing the catalyst 5mg, adding into 400 μ L ethanol, performing ultrasonic treatment for 30min, adding 100 μ L isopropanol dropwise into the solution, performing ultrasonic treatment for 30min, adding 50 μ L5 wt% Nafion solution, performing ultrasonic treatment for 30min, and uniformly adding into 1 × 1cm-2And drying the foamed nickel at normal temperature. Electrochemical tests were carried out with 1mol/L KOH as the electrolyte, foamed nickel containing the catalyst as the working electrode, a platinum sheet as the counter electrode, and Hg/HgO as the reference electrode. When the current density is 10mA cm-2And 100mA · cm-2See table 1 for overpotentials at time, respectively.
Example 4
(1) Weighing 1.746g Co (NO)3)2·6H2O in a mixed solvent of 40ml of ethanol and 40ml of methanol, stirring with a magnetic stirrer for 10min, and then sonicating for 10 min. Similarly, 1.97g of 2-methylimidazole was weighed in a mixed solvent of 40ml of ethanol and 40ml of methanol, stirred with a magnetic stirrer for 10min, and then sonicated for 10 min. And (3) rapidly pouring the organic solution into a salt solution while stirring, continuously stirring for 30min, standing at room temperature for 24h, alternately washing the obtained purple precipitate with ethanol and methanol, centrifuging, and drying at 60 ℃ for 12h to obtain the metal organic framework ZIF-67.
(2) And (2) putting the ZIF-67 in the step (1) in a magnetic boat, annealing for 3h at 280 ℃ in a tubular furnace under the nitrogen atmosphere, then annealing for 5h at 600 ℃, and cooling and taking out a sample to obtain the porous dodecahedral cobalt/carbon nitrogen composite material.
(3) And (3) adding alcohol into the cobalt/carbon nitrogen composite material and the sulfur powder in the ratio of 1:3 in a mortar in the step (2), fully grinding and mixing by a wet method for multiple times, annealing for 12 hours in a magnetic boat at 300 ℃ in a tubular furnace under the nitrogen atmosphere, and cooling and collecting a sample, namely the cobalt disulfide/carbon nitrogen composite material as the efficient electrolytic water oxygen evolution catalyst.
(4) Weighing the catalyst 5mg, adding into 400 μ L ethanol, performing ultrasonic treatment for 30min, adding 100 μ L isopropanol dropwise into the solution, performing ultrasonic treatment for 30min, adding 50 μ L5 wt% Nafion solution, performing ultrasonic treatment for 30min, and uniformly adding into 1 × 1cm-2And drying the foamed nickel at normal temperature. Electrochemical tests are carried out by taking 1mol/L KOH as electrolyte, foamed nickel containing a catalyst as a working electrode, a platinum sheet as a counter electrode and Hg/HgO as a reference electrode. When the current density is 10mA cm-2And 100mA · cm-2See table 1 for overpotentials at time, respectively.
Example 5
(1) Weighing 1.746g Co (NO)3)2·6H2O in a mixed solvent of 30ml of ethanol and 40ml of methanol, stirring with a magnetic stirrer for 10min, and then sonicating for 10 min. Similarly, 1.97g of 2-methylimidazole was weighed in a mixed solvent of 30ml of ethanol and 40ml of methanol, stirred with a magnetic stirrer for 10min, and then sonicated for 10 min. And (3) rapidly pouring the organic solution into a salt solution while stirring, continuously stirring for 1h, standing at room temperature for 24h, alternately washing the obtained purple precipitate with ethanol and methanol, centrifuging, and drying at 60 ℃ for 12h to obtain the metal organic framework ZIF-67.
(2) And (2) putting the ZIF-67 in the step (1) in a magnetic boat, annealing for 2h at 300 ℃ in a tubular furnace under the nitrogen atmosphere, then annealing for 3.5h at 1000 ℃, and cooling and taking out a sample to obtain the porous dodecahedral cobalt/carbon nitrogen composite material.
(3) And (3) adding alcohol into the cobalt/carbon nitrogen composite material and the sulfur powder in the ratio of 1:3 in a mortar in the step (2), fully grinding and mixing by a wet method for multiple times, annealing for 12 hours in a magnetic boat at 350 ℃ in a tubular furnace under the nitrogen atmosphere, and cooling and collecting a sample, namely the cobalt disulfide/carbon nitrogen composite material as the efficient electrolytic water oxygen evolution catalyst.
(4) The catalyst was weighed in 5mgAdding into 400 μ L ethanol, performing ultrasonic treatment for 30min, adding 100 μ L isopropanol into the solution, performing ultrasonic treatment for 30min, adding 50 μ L5 wt% Nafion solution, performing ultrasonic treatment for 30min, and uniformly adding into 1 × 1cm-2And drying the foamed nickel at normal temperature. Electrochemical tests were carried out with 1mol/L KOH as the electrolyte, foamed nickel containing the catalyst as the working electrode, a platinum sheet as the counter electrode, and Hg/HgO as the reference electrode. When the current density is 10mA cm-2And 100mA · cm-2See table 1 for overpotentials at time, respectively.
Example 6
(1) Weighing 1.746g Co (NO)3)2·6H2O in a mixed solvent of 40ml of ethanol and 40ml of methanol, stirring with a magnetic stirrer for 10min, and then sonicating for 10 min. Similarly, 1.97g of 2-methylimidazole was weighed in a mixed solvent of 40ml of ethanol and 20ml of methanol, stirred with a magnetic stirrer for 10min, and then sonicated for 10 min. And (3) rapidly pouring the organic solution into a salt solution while stirring, continuously stirring for 10s, standing at room temperature for 24h, alternately washing the obtained purple precipitate with ethanol and methanol, centrifuging, and drying at 60 ℃ for 18h to obtain the metal organic framework ZIF-67.
(2) And (2) putting the ZIF-67 in the step (1) in a magnetic boat, annealing for 2h at 400 ℃ in a tubular furnace in a nitrogen atmosphere, then annealing for 4h at 800 ℃, and cooling and taking out a sample to obtain the porous dodecahedral cobalt/carbon nitrogen composite material.
(3) And (3) adding alcohol into the cobalt/carbon nitrogen composite material and the sulfur powder in the ratio of 1:3 in a mortar in the step (2), fully grinding and mixing by a wet method for multiple times, annealing for 12 hours at 280 ℃ in a tube furnace in a nitrogen atmosphere in a magnetic boat, and cooling and collecting a sample, namely the cobalt disulfide/carbon nitrogen composite material as the efficient electrolytic water oxygen evolution catalyst.
(4) Weighing the catalyst 5mg, adding into 400 μ L ethanol, performing ultrasonic treatment for 30min, adding 100 μ L isopropanol dropwise into the solution, performing ultrasonic treatment for 30min, adding 50 μ L commercially available 5 wt% Nafion solution dropwise, performing ultrasonic treatment for 30min, and uniformly adding into 1 × 1cm-2And drying the foamed nickel at normal temperature. Using 1mol/L KOH as electrolyte, using foamed nickel containing catalyst as working electrode, platinum sheet as counter electrode and Hg/HgO as reference electrodeAnd (4) performing electrochemical test. When the current density is 10mA cm-2And 100mA · cm-2See table 1 for overpotentials at time, respectively.
TABLE 1
Claims (7)
1. The application of the cobalt disulfide/carbon nitrogen composite material as an electrolyzed water anode oxygen evolution catalyst in electrolyzed water oxygen evolution is characterized in that: the cobalt disulfide/carbon nitrogen composite material is used as an active component to prepare an electrode, and then the electrode is used as a working electrode for anodic oxygen evolution of electrolyzed water, wherein the cobalt disulfide/carbon nitrogen composite material is in a porous dodecahedron structure, CoS2The nano particles are coated by graphite carbon and are uniformly distributed on the dodecahedron carbon nitrogen frame, the size of the cobalt disulfide/carbon nitrogen composite material is 0.1-1.5 mu m, and CoS2The particle size is between 5nm and 10nm, and the preparation method comprises the following steps: annealing ZIF-67 under inert gas in two steps, wherein the annealing in two steps is as follows: firstly, calcining ZIF-67 at 280-400 ℃ in an inert atmosphere, and then calcining at 600-1000 ℃ in an inert atmosphere; and then fully grinding and mixing the annealed product and S powder, and annealing in an inert atmosphere for a vulcanization reaction to obtain the cobalt disulfide/carbon nitrogen composite material.
2. The application of claim 1, wherein the application method comprises: preparing a dispersion liquid by using a Nafion solution, then loading the dispersion liquid on a foam nickel carrier and drying the dispersion liquid at normal temperature to obtain foam nickel containing active components of the cobalt disulfide/carbon nitrogen composite material, using the foam nickel as a working electrode, using a platinum sheet as a counter electrode, using Hg/HgO as a reference electrode, using KOH as an electrolyte, and electrolyzing water to carry out anodic oxygen evolution.
3. Use according to claim 1, characterized in that: the calcination time of the first step at 280-400 ℃ is 1.5-3 h; and the calcining time of the second step at 600-1000 ℃ is 3.5-5 h.
4. Use according to claim 1, characterized in that: the mixing ratio of the annealed product to the S powder is 10: 1-1: 10 in mass ratio.
5. Use according to claim 1, characterized in that: the vulcanization reaction temperature is 280-350 ℃, and the time is 10-15 h.
6. Use according to claim 1, characterized in that: the preparation method of the ZIF-67 comprises the following steps:
(1) dissolving 2-methylimidazole in a mixed solvent consisting of methanol and ethanol to prepare a 2-methylimidazole solution with the concentration of 0.05-1M;
(2) dissolving a cobalt source substance in a solvent obtained by mixing methanol and an ethanol solution to prepare a cobalt source solution with the concentration of 0.01-0.2M;
(3) and (3) quickly pouring the solution obtained in the step (1) into the solution obtained in the step (2) while stirring, continuously stirring for a period of time, standing to obtain a purple precipitate, alternately performing centrifugal washing and filtration by using organic solvents ethanol and methanol, and drying for 6-15 hours at 40-80 ℃.
7. Use according to claim 6, characterized in that: in the step (3), the temperature for stirring and mixing the two solutions is within the range of 0-50 ℃, the stirring time is within 5 s-1 h, the standing temperature is within the range of 0-50 ℃, and the time is within 5-36 h; the ratio of the amount of the 2-methylimidazole substance to the amount of the cobalt source substance in the step (3) is 0.005-0.5: 1; the cobalt source material in the step (3) is selected from Co (NO)3)2·6H2O、CoCl2·6H2O、CoSO4·6H2O、C15H21CoO6。
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| CN110813334B (en) * | 2019-10-16 | 2023-01-10 | 武汉工程大学 | Preparation method and application of foam nickel loaded iron-nickel based composite material |
| CN110697782A (en) * | 2019-11-01 | 2020-01-17 | 宁波大学 | Co3S4@MoS2Preparation method and application of core-shell structure nanosheet array material |
| CN111155145B (en) * | 2020-01-15 | 2021-02-19 | 浙江农林大学 | Bifunctional electrolytic water electrode with super-wettability and preparation method thereof |
| CN111370707B (en) * | 2020-03-17 | 2021-04-27 | 东北大学秦皇岛分校 | Cobalt sulfide-based composite material and preparation method and application thereof |
| CN111697213B (en) * | 2020-05-06 | 2021-07-13 | 广州大学 | Cobalt disulfide-tin disulfide composite particle and preparation method and application thereof |
| CN111389430B (en) * | 2020-05-15 | 2022-10-25 | 郑州大学 | Catalyst CoP for hydrogen production by water electrolysis x S y MWCNTs and preparation method thereof |
| CN111468165B (en) * | 2020-05-22 | 2021-10-22 | 丁道其 | Nitrogen-doped nano CoS2Preparation method and application of graphene photocatalytic material |
| CN111841598B (en) * | 2020-06-23 | 2022-10-04 | 合肥师范学院 | S-doped Co @ NC composite material with high oxygen evolution catalytic activity and preparation method thereof |
| CN112403503B (en) * | 2020-11-27 | 2021-08-03 | 电子科技大学 | Preparation method of nitrogen-doped MOF structure modified two-phase sulfide material |
| CN113471455B (en) * | 2021-07-01 | 2022-10-28 | 湖南理工学院 | Cobalt disulfide/nitrogen and sulfur co-doped mesoporous carbon composite catalyst for zinc-air battery and preparation method thereof |
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