CN113215607B - Sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material and preparation method thereof - Google Patents
Sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a sulfur-nitrogen Co-doped porous carbon supported ternary transition metal composite material with a chemical formula of (Co, Ni, Fe)9S8/NSCSs，(Co,Ni,Fe)9S8the/NSCSs are spindle-shaped and comprise the following elements in percentage by mass: n: 1-2 wt%, O: 3-5 wt%, S: 3-4 wt%, Fe: 3-5 wt%, Co: 4-5 wt%, Ni: 6-8 wt% and the balance of C. The invention also discloses a preparation method of the sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material. The ternary transition metal composite material prepared by the invention provides high active sites due to the unique electronic structure of metal-sulfur bonds, the synergistic effect among three components of CoNiFe and N and S heteroatom Co-doped carbon, so that (Co, Ni, Fe)9S8Ternary Metal sulfide ratio commercial RuO2The catalyst has better electrochemical performance.
Description
Technical Field
The invention relates to a ternary transition metal composite material and a preparation method thereof, in particular to a sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material and a preparation method thereof.
Background
Hydrogen production by electrolysis of water is considered a clean and efficient renewable energy approach to address the energy crisis and the severe environmental pollution caused by fossil fuels. The Oxygen Evolution Reaction (OER), one of the half reactions of water electrolysis, is too high in energy consumption in practical application due to its slow kinetics and high overpotential, and thus seriously hinders the commercial development of the water electrolysis hydrogen production technology. Electrocatalysts of high oxygen evolution activity have long been generally noble metals Ir, Ru-based materials. However, the scarcity of these two elements determines the urgency for developing abundant, low cost, high efficiency non-noble metal OER catalysts. For OER, in addition to oxides and hydroxides, transition metal sulfides are widely regarded as a novel non-noble metal catalyst with great development prospects due to their diverse valence states and high catalytic activity.
In recent years, mono-or binary transition metal sulfides have been developed as high performance OER electrocatalysts. Researches show that the electronic structure can be effectively improved by adding a third metal into the bimetal component, and the synergistic effect between the three metals can induce the formation of more oxygen vacancies and higher graphitization degree. Therefore, forming a multi-metal structure is a common strategy for improving the performance of the electrocatalyst, and combining the multi-metal structure with sulfide on the basis is an effective means for further improving the catalytic performance.
However, the reported catalysts have the disadvantages of complex preparation method, long synthesis period, low efficiency, use of toxic reagents and the like, and limit the industrial application. Therefore, how to obtain a high-efficiency OER catalyst by a simple preparation method is a problem which needs to be solved urgently.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention aims to provide the sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material with good stability and good catalytic effect.
The technical scheme is as follows: the invention relates to a sulfur-nitrogen Co-doped porous carbon supported ternary transition metal composite material with a chemical formula of (Co, Ni, Fe)9S8/NSCSs，(Co,Ni,Fe)9S8the/NSCSs are spindle-shaped and comprise the following elements in percentage by mass: n: 1-2 wt%, O: 3-5 wt%, S: 3-4 wt%, Fe: 3-5 wt%, Co: 4-5 wt%, Ni: 6-8 wt% and the balance of C.
Further, Co, Ni, Fe and sulfur element are formed together (Co, Ni, Fe)9S8The trimetallic sulfide nanoparticles are embedded into the nitrogen-sulfur co-doped spindle porous carbon frame, so that the Hofmann type metal organic frame nano spindle which is co-assembled by ternary metals and has a good appearance can be effectively obtained.
The preparation method of the sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material comprises the following steps:
dissolving an iron precursor and a cobalt precursor into a mixed solution;
dissolving the organic ligand and the surface modifier in the mixed solution, and performing ultrasonic dispersion;
dissolving potassium tetracyanonickelate in water;
step four, adding the solution obtained in the step two into the solution obtained in the step one under magnetic stirring;
step five, adding the solution obtained in the step three into the solution obtained in the step four, stirring, and reacting to obtain a CoNiFe trimetal Hofmann type metal-organic framework mixture;
step six, centrifugally washing the product obtained in the step five by water, removing supernatant, taking precipitate, and drying to obtain powder;
and seventhly, pyrolyzing the powder obtained in the sixth step under the protection of protective gas and at the temperature of 700-900 ℃ to obtain the sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material.
Further, the mixed solution is a mixture of two or more of water, methanol, ethanol, and acetonitrile.
Further, in the first step, the iron precursor is any one of ferric tetrafluoroborate, ferrous sulfate, ferrous chloride and ferrous bromide, and the concentration is 0.0025-0.005 mol/L. The cobalt precursor is any one of cobalt nitrate, cobalt chloride and cobalt sulfate, and the concentration is 0.0025-0.005 mol/L. The concentration of the iron precursor and the cobalt precursor is lower than 0.0025mol/L, which is not beneficial to the synthesis of products and leads to the reduction of yield, and the concentration is higher than 0.005mol/L, which is not beneficial to the dispersion of the products.
Further, in the second step, the organic ligand is dipyridyl disulfide or dipyridyl sulfide, which has good structure and chemical properties and the concentration of 0.005-0.01 mol/L. The concentration of the organic ligand is lower than 0.005mol/L, a regular pore channel structure is not easy to form, the yield is reduced, and the product size is reduced to be unfavorable for forming a Hofmann type CoNiFe ternary metal organic framework due to the concentration of the organic ligand is higher than 0.01 mol/L. The surface modifier is polyvinylpyrrolidone or polyethylene glycol, can modify the surface of a product and prevent metal ions from being oxidized, and the concentration is 0.075-0.2 mol/L. The concentration of the surface modifier is lower than 0.1mol/L, so that the product is uneven in distribution and incomplete in appearance, the concentration is higher than 0.2mol/L, the product is not favorable for forming a metal frame, and the product is poor in dispersibility and even hardened.
Further, in the seventh step, the protective gas is nitrogen or argon. The heating rate of pyrolysis is 3-5 ℃/min, and the reaction time is 2-4 h.
The working principle is as follows: the metal raw material is inorganic salt, and the ligand is organic matter, so the mixed solution of organic solvent and water is selected as the solvent. In order to obtain the Hofmann type three-component CoNiFe metal organic framework nano spindle, a Ni metal precursor needs to be tetracyanonickelate, and a Fe metal precursor is ferrous salt. The spindle-shaped sulfur-nitrogen co-doped porous carbon loaded ternary transition metal composite material has larger active area due to the porous carbon substrate, can expose more active sites, can adjust the electronic structure through the synergistic effect of the three metal ions, and has better electrochemical performance than single metal sulfide and double metal sulfide under the same condition. Meanwhile, the metal-sulfur bond in the metal sulfide has more covalent characteristics, which is beneficial to the adjustment of an energy band structure near a conduction band/valence band and increases active sites in the electrochemical oxygen evolution reaction, thereby providing more favorable conditions for the catalytic reaction.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1. the metal-sulfur bond in the metal sulfide has unique electronic structure, the synergistic effect among three components of CoNiFe and N and S heteroatom Co-doped carbon improve the catalytic activity, so that (Co, Ni, Fe)9S8Ternary Metal sulfide ratio commercial RuO2The catalyst shows better electrochemical performance;
2. the nitrogen-sulfur heteroatom doped carbon substrate material has high conductivity, large specific surface area and excellent physical and structural stability; the porous structure derived from the Hofmann metal organic framework pore structure provides a larger active surface area;
3、(Co,Ni,Fe)9S8the nanoparticles enwrap the highly wrinkled carbon layer, which is beneficial for inhibiting (Co, Ni, Fe)9S8The aggregation of the nano particles in the electrocatalysis process further improves the activity and stability of the electrolytic water oxygen evolution reaction;
4. the preparation method is simple and convenient, easy to control, uniform in appearance and size, good in dispersity, and capable of introducing Ni metal precursor K2[Ni(CN)4]The CoNiFe ternary metal organic framework with good appearance and good Hofmann type can be successfully obtained; the metal atoms in the Hofmann metal organic framework and cyano groups (-CN) form a stable coordination structure and a regular pore channel structure, and under the influence of the coordination and the pore channel structure, atom aggregation can be effectively reduced in the pyrolysis process, and the atom utilization rate is improved.
Drawings
FIG. 1 is a scanning electron microscope image of a product obtained in example 1 of the present invention;
FIG. 2 is a transmission electron microscope image of a product obtained in example 1 of the present invention;
FIG. 3 is a spectrum of transmission energy of the product obtained in example 1 of the present invention;
FIG. 4 shows the product obtained in example 1 of the present invention and commercial RuO2The performance curve of the electrolytic water oxygen evolution reaction of the catalyst.
Detailed Description
The raw materials and the apparatus used in the following examples were purchased directly.
Example 1
A preparation method of a sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material comprises the following steps:
(1) at 25 ℃, 0.15mmol of ferric tetrafluoroborate Fe (BF) is added4)20.15mmol of cobalt nitrate Co (NO)3)2Dissolving the mixed solution in 40mL of mixed solution of methanol and water in a volume ratio of 1:1 to obtain mixed solution of which the concentrations of an iron precursor and a cobalt precursor are both 0.00375mol/L as solution A;
(2) dissolving 3mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.3mmol of organic ligand dipyridyl disulfide in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 2min to obtain mixed solution with ligand concentration of 0.0075mol/L as solution B;
(3) adding 0.3mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel precursor concentration of 0.03mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 3 hours to obtain a yellow solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying overnight at 50 ℃ to obtain yellow powder;
(7) and (3) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating to 800 ℃ at a heating rate of 5 ℃/min in a tubular furnace with nitrogen as protective gas, reacting for 2h, and naturally cooling to normal temperature to obtain the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material.
EDS analysis is carried out on the obtained spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material, and the composite material comprises the following elements: c: 74.41 wt%, N: 1.67 wt%, O: 4.57 wt%, S: 3.97 wt%, Fe: 3.44 wt%, Co: 4.69 wt%, Ni: 7.25 wt%.
Fig. 1 is a scanning electron microscope image of the spindle-shaped sulfur-nitrogen co-doped porous carbon-supported ternary transition metal composite material prepared in example 1, wherein the magnification is 10000, and it can be seen that the composite material has a nano spindle structure.
Fig. 2 is a transmission electron microscope image of the spindle-shaped sulfur-nitrogen co-doped porous carbon-supported ternary transition metal composite material prepared in example 1, and the magnification is 150000. As can be seen from the transmission electron microscope image in fig. 2, the spindle-shaped sulfur-nitrogen Co-doped porous carbon supported ternary transition metal composite material prepared in example 1 uses a carbon material as a substrate, and a metal nanocrystal formed by Fe, Co, and Ni metal alloys is loaded on the carbon material, so that the whole structure is spindle-shaped.
Fig. 3 is a transmission energy spectrum of the spindle-shaped sulfur-nitrogen Co-doped porous carbon-supported ternary transition metal composite material prepared in example 1, which shows that elements such as C, N, O, S, Fe, Co, and Ni are uniformly distributed in the spindle nanostructure. The magnification of fig. 3 is 180000.
Electrochemical performance tests are performed on the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material prepared in example 1, fig. 4 is a corresponding oxygen evolution reaction performance curve diagram, and as can be seen from fig. 4, the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material prepared in example 1 and commercial RuO are obtained2The overpotentials of the catalysts are 320mV (vs. RHE) and 370mV (vs. RHE), respectively, and thus it can be known that the oxygen evolution catalytic performance of the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material obtained in example 1 is superior to that of the commercial RuO2The catalyst shows that the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material has excellent catalytic performance for the electrolyzed water oxygen evolution reaction.
Example 2
A preparation method of a sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material comprises the following steps:
(1) at 25 deg.C, 0.1mmol of ferric tetrafluoroborate Fe (BF)4)2And 0.1mmol nitric acidCobalt Co (NO)3)2Dissolving the mixed solution in 40mL of mixed solution of methanol and water with the volume ratio of 1:1 to obtain mixed solution of iron precursor and cobalt precursor with the concentration of 0.0025mol/L as solution A;
(2) dissolving 4mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.2mmol of organic ligand dipyridyl disulfide in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 2min to obtain mixed solution with ligand concentration of 0.005mol/L as solution B;
(3) adding 0.2mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel precursor concentration of 0.02mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 2 hours to obtain a yellow solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying overnight at 50 ℃ to obtain yellow powder;
(7) and (3) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating to 750 ℃ at a heating rate of 5 ℃/min in a tubular furnace with argon as protective gas, reacting for 2h, and naturally cooling to normal temperature to obtain the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material.
EDS analysis is carried out on the obtained spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material, and the composite material comprises the following elements: c: 75.03 wt%, N: 1.62 wt%, O: 4.62 wt%, S: 3.85 wt%, Fe: 3.40 wt%, Co: 4.34 wt%, Ni: 7.11 wt%.
Example 3
A preparation method of a sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material comprises the following steps:
(1) at 25 ℃, 0.2mmol of ferric tetrafluoroborate Fe (BF) is added4)2And 0.2mmol of cobalt nitrate Co (NO)3)2Dissolving in 40mL of mixed solution of methanol and water at a volume ratio of 1:1 to obtain ironA mixed solution of the precursor and the cobalt precursor with the concentration of 0.005mol/L is used as a solution A;
(2) dissolving 8mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.4mmol of organic ligand dipyridyl disulfide in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 2min to obtain mixed solution with ligand concentration of 0.01mol/L as solution B;
(3) adding 0.4mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel precursor concentration of 0.04mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 3 hours to obtain a yellow solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying overnight at 50 ℃ to obtain yellow powder;
(7) and (3) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating to 900 ℃ at a heating rate of 5 ℃/min in a tubular furnace with argon as protective gas, reacting for 3h, and naturally cooling to normal temperature to obtain the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material.
EDS analysis is carried out on the obtained spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material, and the composite material comprises the following elements: c: 73.93 wt%, N: 1.94 wt%, O: 4.15 wt%, S: 3.92 wt%, Fe: 3.80 wt%, Co: 4.76 wt%, Ni: 7.50 wt%.
Example 4
A preparation method of a sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material comprises the following steps:
(1) at 10 ℃, 0.15mmol of ferrous sulfate (FeSO)4) And 0.15mmol of cobalt sulfate (CoSO)4) Dissolving the mixed solution in 40mL of mixed solution of methanol and water with the volume ratio of 1:1 to obtain mixed solution of iron precursor and cobalt precursor with the concentration of 0.00375mol/L as solution A;
(2) dissolving 6mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.3mmol of organic ligand dipyridyl sulfide in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 1min to obtain mixed solution with a ligand concentration of 0.0075mol/L as solution B;
(3) adding 0.3mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel precursor concentration of 0.03mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 4 hours to obtain a yellow solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying overnight at 50 ℃ to obtain yellow powder;
(7) and (3) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating to 850 ℃ at the heating rate of 5 ℃/min in a tubular furnace with nitrogen as protective gas, reacting for 2h, and naturally cooling to normal temperature to obtain the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material.
EDS analysis is carried out on the obtained spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material, and the composite material comprises the following elements: c: 76.12 wt%, N: 1.88 wt%, O: 3.43 wt%, S: 3.12 wt%, Fe: 4.17 wt%, Co: 4.02 wt%, Ni: 7.26 wt%.
Example 5
A preparation method of a sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material comprises the following steps:
(1) at 60 ℃, 0.2mmol of ferric tetrafluoroborate Fe (BF) is added4)2And 0.2mmol of cobalt nitrate hexahydrate Co (NO)3)2·6H2Dissolving O in 40mL of mixed solution of methanol and water in a volume ratio of 1:1 to obtain mixed solution of an iron precursor and a cobalt precursor with the concentration of 0.005mol/L as solution A;
(2) dissolving 8mmol of surfactant polyethylene glycol and 0.4mmol of organic ligand dipyridyl disulfide in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 2min to obtain mixed solution with ligand concentration of 0.01mol/L as solution B;
(3) adding 0.4mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel precursor concentration of 0.04mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 2 hours to obtain a yellow solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying overnight at 50 ℃ to obtain yellow powder;
(7) and (3) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating to 800 ℃ at a heating rate of 5 ℃/min in a tubular furnace with nitrogen as protective gas, reacting for 4h, and naturally cooling to normal temperature to obtain the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material.
EDS analysis is carried out on the obtained spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material, and the composite material comprises the following elements: c: 75.42 wt%, N: 1.68 wt%, O: 4.21 wt%, S: 3.02 wt%, Fe: 4.87 wt%, Co: 4.34 wt%, Ni: 6.46 wt%.
Example 6
A preparation method of a sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material comprises the following steps:
(1) at 60 ℃, 0.1mmol of ferrous bromide (FeBr)2) And 0.1mmol of cobalt nitrate Co (NO)3)2Dissolving the mixed solution in 40mL of ethanol and water at a volume ratio of 1:1 to obtain a mixed solution with the concentration of the iron precursor and the cobalt precursor of 0.0025mol/L as a solution A;
(2) dissolving 8mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.2mmol of organic ligand dipyridyl disulfide in 40mL of mixed solution of ethanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 2min to obtain mixed solution with ligand concentration of 0.005mol/L as solution B;
(3) adding 0.2mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel precursor concentration of 0.02mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 4 hours to obtain a yellow solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying overnight at 50 ℃ to obtain yellow powder;
(7) and (3) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating to 900 ℃ at the heating rate of 3 ℃/min in a tubular furnace with nitrogen as protective gas, reacting for 2h, and naturally cooling to normal temperature to obtain the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material.
EDS analysis is carried out on the obtained spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material, and the composite material comprises the following elements: c: 74.72 wt%, N: 1.48 wt%, O: 3.21 wt%, S: 3.54 wt%, Fe: 4.87 wt%, Co: 4.22 wt%, Ni: 7.96 wt%.
Example 7
A preparation method of a sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material comprises the following steps:
(1) at 25 ℃, 0.15mmol of ferrous chloride (FeCl)2) And 0.15mmol of cobalt chloride (CoCl)2) Dissolving the mixed solution in 40mL of mixed solution of acetonitrile and water in a volume ratio of 1:1 to obtain mixed solution of an iron precursor and a cobalt precursor with the concentration of 0.00375mol/L as solution A;
(2) dissolving 6mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.3mmol of organic ligand dipyridyl disulfide in 40mL of mixed solution of acetonitrile and water in a volume ratio of 1:1, and performing ultrasonic treatment for 2min to obtain mixed solution with ligand concentration of 0.0075mol/L as solution B;
(3) adding 0.3mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtainTaking an aqueous solution with the nickel precursor concentration of 0.03mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 2 hours to obtain a yellow solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying overnight at 50 ℃ to obtain yellow powder;
(7) and (3) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating to 700 ℃ at a heating rate of 5 ℃/min in a tubular furnace with nitrogen as protective gas, reacting for 2h, and naturally cooling to normal temperature to obtain the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material.
EDS analysis is carried out on the obtained spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material, and the composite material comprises the following elements: c: 73.02 wt%, N: 1.78 wt%, O: 4.49 wt%, S: 3.52 wt%, Fe: 4.35 wt%, Co: 4.87 wt%, Ni: 7.97 wt%.
Example 8
A preparation method of a sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material comprises the following steps:
(1) at 10 ℃, 0.15mmol of ferrous sulfate (FeSO)4) And 0.15mmol of cobalt nitrate Co (NO)3)2Dissolving the mixed solution in 40mL of ethanol and water at a volume ratio of 1:1 to obtain a mixed solution of an iron precursor and a cobalt precursor with the concentration of 0.00375mol/L as a solution A;
(2) dissolving 6mmol of surfactant polyethylene glycol (PEG-2000) and 0.3mmol of organic ligand dipyridyl sulfide in 40mL of mixed solution of ethanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 1-2 min to obtain mixed solution with a ligand concentration of 0.0075mol/L as solution B;
(3) adding 0.3mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel precursor concentration of 0.03mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 3 hours to obtain a yellow solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying overnight at 50 ℃ to obtain yellow powder;
(7) and (3) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating to 900 ℃ at the heating rate of 4 ℃/min in a tubular furnace with argon as protective gas, reacting for 2h, and naturally cooling to normal temperature to obtain the spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material.
EDS analysis is carried out on the obtained spindle-shaped sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material, and the composite material comprises the following elements: c: 75.42 wt%, N: 1.35 wt%, O: 3.08 wt%, S: 3.31 wt%, Fe: 4.58 wt%, Co: 4.62 wt%, Ni: 7.64 wt%.
Claims (6)
1. The preparation method of the sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material is characterized by comprising the following steps of:
dissolving an iron precursor and a cobalt precursor into a mixed solution;
dissolving the organic ligand and the surface modifier in the mixed solution, and performing ultrasonic dispersion;
dissolving potassium tetracyanonickelate in water;
step four, adding the solution obtained in the step two into the solution obtained in the step one under magnetic stirring;
step five, adding the solution obtained in the step three into the solution obtained in the step four, stirring, and reacting to obtain a CoNiFe trimetal Hofmann type metal-organic framework mixture;
step six, centrifugally washing the product obtained in the step five by water, removing supernatant, taking precipitate, and drying to obtain powder;
step seven, pyrolyzing the powder obtained in the step six under the protection of protective gas at 700-900 ℃ to obtain a sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material;
the mixed solution is a mixture of more than two of water, methanol, ethanol and acetonitrile;
in the first step, the iron precursor is any one of ferric tetrafluoroborate, ferrous sulfate, ferrous chloride and ferrous bromide, and the concentration is 0.0025-0.005 mol/L; the cobalt precursor is any one of cobalt nitrate, cobalt chloride and cobalt sulfate, and the concentration is 0.0025-0.005 mol/L;
in the second step, the organic ligand is dipyridyl disulfide or dipyridyl sulfide, and the concentration is 0.005-0.01 mol/L; the surface modifier is polyvinylpyrrolidone or polyethylene glycol, and the concentration is 0.075-0.2 mol/L.
2. The preparation method of the sulfur-nitrogen co-doped porous carbon-supported ternary transition metal composite material according to claim 1, characterized by comprising the following steps: and in the seventh step, the protective gas is nitrogen or argon.
3. The preparation method of the sulfur-nitrogen co-doped porous carbon-supported ternary transition metal composite material according to claim 1, characterized by comprising the following steps: in the seventh step, the heating rate of pyrolysis is 3-5 ℃/min, and the reaction time is 2-4 h.
4. The utility model provides a ternary transition metal composite that sulphur nitrogen codope porous carbon supported which characterized in that: obtained by the process according to any one of claims 1 to 3.
5. The sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material according to claim 4, characterized in that: the sulfur-nitrogen co-doped porous carbon supported ternary transition metal composite material is in a spindle shape and comprises the following elements in percentage by mass: n: 1-2 wt%, O: 3-5 wt%, S: 3-4 wt%, Fe: 3-5 wt%, Co: 4-5 wt%, Ni: 6-8 wt% and the balance of C.
6. The sulfur-nitrogen co-doped porous carbon support of claim 5The loaded ternary transition metal composite material is characterized in that: the Co, Ni, Fe and sulfur element form (Co, Ni, Fe)9S8And the trimetallic sulfide nanoparticles are embedded into the nitrogen-sulfur co-doped spindle porous carbon framework.
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