CN114784299A - Nitrogen-sulfur doped carbon material and preparation method and application thereof - Google Patents
Nitrogen-sulfur doped carbon material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nitrogen-sulfur doped carbon material and a preparation method and application thereof, wherein the preparation method comprises the following steps: and carrying out first solid-liquid separation on the first mixed metal organic framework compound solution and a cysteine solution to obtain a precursor material, and then calcining to obtain the nitrogen-sulfur doped carbon material. The preparation method of the nitrogen-sulfur doped carbon material has the advantages of environmental protection, low cost, simple and controllable synthesis process, high consistency and easy realization of batch production; the nitrogen-sulfur-doped carbon material has excellent ORR catalytic performance, the ORR catalytic performance of the nitrogen-sulfur-doped carbon material exceeds that of a commercial noble metal platinum carbon catalyst, and the nitrogen-sulfur-doped carbon material has high practical application potential.
Description
Technical Field
The invention belongs to the technical field of fuel cells, relates to a preparation method of a nitrogen-sulfur doped carbon material, and particularly relates to a nitrogen-sulfur doped carbon material and a preparation method and application thereof.
Background
In fuel cell stacks, the Oxygen Reduction Reaction (ORR) at the cathode primarily employs catalysts to overcome slow kinetics. The cathode catalyst is a main factor affecting the activation polarization of the fuel cell and is regarded as a key material of the fuel cell. At present, the catalyst which is most widely used commercially is still a supported catalyst Pt/C, but in working condition application, Pt-based materials have the disadvantages of high cost (accounting for about 20 percent of the cost of a fuel cell), easy dissolution, easy agglomeration and the like. The research on the high-activity non-noble metal catalyst to reduce the cost of the fuel cell has important significance.
The carbon material has the advantages of abundant resources in nature, low price, good conductivity, strong corrosion resistance and the like. However, the catalytic action of pure carbon on oxygen reduction is far from being required, and researchers have proven through a large number of experiments that transition metal (Fe, Co, etc.) and heteroatom (N, S, etc.) doped carbon materials exhibit excellent ORR electrocatalytic activity, and the high ORR activity of these carbon materials is attributed to the synergistic action of the transition metal and heteroatom with the carbon matrix to generate a large number of active sites. Therefore, the synthesized carbon-based catalyst is required to have the characteristics of high active site density, adjustable pore structure, high specific surface area, good stability, high atom doping amount, uniformly distributed active sites and the like. In order to impart the above properties to the non-metallic doped carbon material, the most effective method is to select the appropriate precursor doped with transition metal and heteroatom. The structure of metal organic framework Materials (MOFs) has the characteristics of adjustability, embellishment, easy functionalization and the like, and carbon-based catalytic materials constructed by using the MOFs as precursors have unique advantages in the aspects of heteroatom doping, particle confinement and pore channel design. In the current report of using metal organic framework materials as precursors, a plurality of organic solvents are applied in the preparation process, so that the preparation method is not environment-friendly, the preparation process is complex, the production cost is high, the preparation method is mainly in a laboratory stage, and the large-scale application is inconvenient.
CN109745950A discloses a method for preparing a micro-mesoporous carbon anode material by using an amino acid modified metal organic framework and application thereof. The method comprises the steps of synthesizing an amino acid modified metal organic framework material, pretreating the metal organic framework material, performing carbonization reaction and the like, and directly performing high-temperature carbonization treatment on the synthesized metal organic framework material after washing and drying treatment to obtain the nitrogen-doped porous carbon material with rich micro-mesoporous structure. However, the method for preparing the micro-mesoporous carbon cathode material by modifying the metal-organic framework with the amino acid has high cost and poor catalytic performance of the oxygen reduction reaction.
CN112591738A discloses a metal-doped graphene-like carbon material, a preparation method and an application thereof, and belongs to the field of materials. The method takes clay as a template and metal organic complex as a raw material, and prepares the metal-doped graphene-like carbon material through the processes of intercalation, dispersion, adsorption, coordination, drying, carbonization and template removal. However, the metal-doped graphene-like carbon material and the preparation method thereof cannot obtain a catalyst with strong catalytic performance of oxygen reduction reaction.
CN114204207A discloses a preparation method of a bifunctional lithium-air battery composite diaphragm, which comprises the following steps: preparing multi-metal co-catalysis MOFs by using various hydrated nitric acid transition metal salts and imidazole containing a nitrile group as raw materials; modifying the surface of the prepared MOFs under the synergistic catalysis of the multiple metals through the click reaction of a hydrophobic alkyl chain, so as to realize the super-hydrophobic functionalization of the MOFs; preparing the synthesized super-hydrophobized polymetallic concerted catalysis MOFs, a binder, a conductive agent and an organic solvent into slurry, and coating the slurry on a base membrane to obtain the difunctional lithium-air battery composite diaphragm. However, the preparation method of the composite diaphragm of the dual-function lithium-air battery has complex process and high preparation cost, and a large amount of organic solvent is adopted, so that the environment is polluted.
The cathode catalyst of the fuel cell and the preparation method thereof disclosed at present have certain defects, and have the problems of complex preparation process, uncontrollable process, high production cost, environmental pollution and poor catalytic performance of the cathode catalyst in the oxygen reduction reaction. Therefore, a novel nitrogen-sulfur doped carbon material and a preparation method thereof are developed and designed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a nitrogen-sulfur doped carbon material and a preparation method and application thereof, and the preparation method of the nitrogen-sulfur doped carbon material has the advantages of environmental protection, low cost, simple and controllable synthesis process, high consistency and easiness in realizing batch production; the nitrogen-sulfur-doped carbon material has excellent ORR catalytic performance, the ORR catalytic performance of the nitrogen-sulfur-doped carbon material exceeds that of a commercial noble metal platinum carbon catalyst, and the nitrogen-sulfur-doped carbon material has high practical application potential.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a nitrogen-sulfur-doped carbon material, the method comprising:
and carrying out first solid-liquid separation on the first mixed metal organic framework compound solution and a cysteine solution to obtain a precursor material, and then calcining to obtain the nitrogen-sulfur doped carbon material.
According to the invention, the metal organic framework compound contains nitrogen element, the cysteine contains sulfur element, and the nitrogen element and the sulfur element are uniformly distributed in a carbon framework of the nitrogen-sulfur doped carbon material after the precursor material is carbonized at high temperature; due to the doping of nitrogen and sulfur, a large number of unconjugated carbon structures, namely carbon defects, exist in the nitrogen-sulfur doped carbon material, so that more active sites are generated, and the descriptor I of the defect degree and the graphitization degree of the carbon materialsD/IGThe numerical range of (A) is 1.05-1.89.
The nitrogen-sulfur doped carbon material is used as a catalyst for oxygen reduction reaction, and has a half-wave potential of not less than 0.83V and a current density of not less than 5.35mA/cm under an alkaline condition2。
The preparation method of the nitrogen-sulfur doped carbon material has the advantages of environmental protection, low cost, simple and controllable synthesis process, high consistency and easy realization of batch production; the nitrogen-sulfur-doped carbon material has excellent ORR catalytic performance, the ORR catalytic performance of the nitrogen-sulfur-doped carbon material exceeds that of a commercial noble metal platinum carbon catalyst, and the nitrogen-sulfur-doped carbon material has high practical application potential.
Preferably, the volume ratio of the metal-organic framework compound solution to the cysteine solution is (2-12): 1, and may be, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1 or 12:1, but is not limited to the data listed, and other values not listed in this range are also applicable.
Preferably, the mass ratio of the solute in the metal-organic framework compound solution to the solute in the cysteine solution is 4 (0.1-1), and may be, for example, 4:0.1, 4:0.2, 4:0.3, 4:0.4, 4:0.5, 4:0.6, 4:0.7, 4:0.8, 4:0.9 or 4:1, but is not limited to the data listed, and other values not listed within this range of values are equally applicable; when the mass ratio of the solute in the metal organic framework compound solution to the solute in the cysteine solution is lower, the half-wave potential becomes lower and the current density is reduced, because the doping amount of sulfur element is less, and the precursor can not generate enough active sites after carbonization; when the mass ratio of the solute in the metal-organic framework compound solution to the solute in the cysteine solution is higher, the half-wave potential becomes lower and the current density is reduced, because excessive doping of cysteine may cause collapse of the metal-organic framework, change the intrinsic morphology and cause a decrease in activity.
Preferably, the solvent of the cysteine solution comprises methanol and/or water.
The solvent required in the preparation process of the nitrogen-sulfur doped carbon material is only methanol or deionized water, so that the use of various organic solvents is avoided, and the preparation conditions are environment-friendly.
Preferably, the temperature of the first mixing is 15-35 ℃ and the time is 1-5 h.
The temperature of the first mixing is limited to 15 to 35 ℃ in the present invention, and may be, for example, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃ or 35 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
The first mixing time is limited to 1 to 5 hours, and may be, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours, but the present invention is not limited to the above-mentioned data, and other values not listed in the above-mentioned numerical range are also applicable.
Preferably, the method of first mixing comprises stirring and/or sonication.
Preferably, the first solid-liquid separation comprises centrifugation, washing and drying which are sequentially carried out.
Preferably, the calcination includes sequentially heating and holding.
Preferably, the temperature rise rate is 2-10 ℃/min, and the temperature rise end point temperature is 800-1000 ℃.
The temperature rise rate is limited to 2-10 ℃/min, for example, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min, but the invention is not limited to the listed data, and other values not listed in the numerical range are also applicable.
The temperature of the end point of the temperature rise is 800 to 1000 ℃ as defined in the present invention, and may be, for example, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃ or 1000 ℃, but is not limited to the above-mentioned data, and other values not listed in the above-mentioned range of values are also applicable.
The temperature rise end point temperature is the heat preservation temperature, when the heat preservation temperature is lower or higher, the half-wave potential is lowered and the current density is reduced, because the graphitization degree of the catalyst is higher when the temperature is 800-1000 ℃, the electrochemical activity of the catalyst is more favorably improved.
Preferably, the incubation time is 2-4 hours, for example, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours or 4 hours, but not limited to the listed values, and other values not listed in the range of values are also applicable.
Preferably, the calcination is carried out in a protective atmosphere comprising nitrogen and/or an inert gas.
Preferably, the preparation method of the metal-organic framework compound solution comprises the following steps:
and carrying out second solid-liquid separation on the second mixed nitrogenous ligand solution and the transition metal salt solution to obtain a metal organic framework compound, and mixing the metal organic framework compound with methanol and/or water to obtain a metal organic framework compound solution.
Preferably, the solute of the solution of nitrogen-containing ligand comprises any one of or a combination of at least two of 2-methylimidazole, potassium ferricyanide, potassium ferrocyanide or potassium cobalt cyanide, typical but non-limiting combinations include a combination of 2-methylimidazole and potassium ferricyanide, a combination of potassium ferricyanide and potassium ferrocyanide, a combination of potassium ferrocyanide and potassium cobalt cyanide, a combination of 2-methylimidazole, potassium ferricyanide and potassium ferrocyanide, or a combination of 2-methylimidazole, potassium ferricyanide, potassium ferrocyanide and potassium cobalt cyanide.
In the preparation process of the metal organic framework compound solution, the nitrogen-containing ligand is used as a nitrogen source to enter the metal organic framework compound.
Preferably, the solvent of the nitrogen-containing ligand solution comprises methanol and/or water.
Preferably, the solute of the transition metal salt solution comprises any one of cobalt nitrate, iron nitrate, nickel nitrate, zinc nitrate or iron chloride or a combination of at least two thereof, and typical but non-limiting combinations include a combination of cobalt nitrate and iron nitrate, a combination of iron nitrate and nickel nitrate, a combination of nickel nitrate and zinc nitrate, a combination of zinc nitrate and iron chloride, a combination of cobalt nitrate, iron nitrate and nickel nitrate, or a combination of iron nitrate, nickel nitrate, zinc nitrate and iron chloride.
Preferably, the solvent of the transition metal salt solution comprises methanol and/or water.
Preferably, the volume ratio of the nitrogen-containing ligand solution to the transition metal salt solution is (0.8-1.2): 1, and may be, for example, 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1, 1.15:1, or 1.2:1, but is not limited to the recited values, and other values not recited within this range of values are equally applicable.
Preferably, the mass ratio of the solute in the nitrogen-containing ligand solution to the solute in the transition metal salt solution is (1-100): 1, and may be, for example, 1:1, 1.5:1, 2:1, 3:1, 5:1, 7:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 100:1, but is not limited to the data listed, and other values not listed within this numerical range are also applicable.
Preferably, the temperature of the second mixing is 15-35 ℃, and the time is 1-5 h.
The temperature of the second mixing is limited to 15 to 35 ℃ in the present invention, and may be, for example, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃ or 35 ℃, but is not limited to the above-mentioned data, and other values not listed in the above-mentioned numerical range are also applicable.
The second mixing time is limited to 1-5 h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, but the invention is not limited to the data listed, and other values not listed in the numerical range are also applicable.
Preferably, the method of second mixing comprises stirring and/or sonication.
Preferably, the second solid-liquid separation comprises centrifugation, washing and drying which are sequentially carried out.
Preferably, as a preferable technical solution of the preparation method of the first aspect, the preparation method comprises the steps of:
(1) mixing a nitrogen-containing ligand solution and a transition metal salt solution at 15-35 ℃ for 1-5 h by stirring and/or ultrasonic mixing, wherein the volume ratio of the nitrogen-containing ligand solution to the transition metal salt solution is (0.8-1.2): 1, and the mass ratio of a solute in the nitrogen-containing ligand solution to a solute in the transition metal salt solution is (1-100): 1; sequentially carrying out centrifugation, washing and drying to obtain a metal organic framework compound, and mixing the metal organic framework compound with methanol and/or water to obtain a metal organic framework compound solution;
(2) stirring and/or ultrasonically mixing the metal organic framework compound solution and the cysteine solution at the temperature of 15-35 ℃ for 1-5 h in a volume ratio of (2-12): 1, wherein the mass ratio of the solute in the metal organic framework compound solution to the solute in the cysteine solution is 4 (0.1-1); and sequentially carrying out centrifugation, washing and drying to obtain a precursor material, heating to 800-1000 ℃ at a heating rate of 2-10 ℃/min in a protective atmosphere, and carrying out heat preservation for 2-4 h to obtain the nitrogen-sulfur doped carbon material.
In a second aspect, the present invention provides a nitrogen-sulfur-doped carbon material obtained by the preparation method of the first aspect.
The nitrogen-sulfur doped carbon material disclosed by the invention is uniform in size distribution, maintains the original appearance of a precursor material, effectively solves the problem of agglomeration of transition metal atoms, and is beneficial to further improvement of catalytic activity through effective compounding with heteroatoms.
Preferably, the mass fraction of transition metal in the nitrogen-sulfur doped carbon material is 2.22 to 8.50 wt%, based on the mass of the nitrogen-sulfur doped carbon material, and may be, for example, 2.22 wt%, 2.3 wt%, 2.5 wt%, 2.7 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, or 8.5 wt%, but is not limited to the recited data, and other non-recited values within this range of values are equally applicable.
In a third aspect, the present invention provides the use of a nitrogen-sulfur-doped carbon material as described in the second aspect as a cathode catalyst for a fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the nitrogen-sulfur doped carbon material has the advantages of low cost, simple and controllable synthesis process, high consistency and easiness in realization of batch production, the solvent required in the preparation process of the nitrogen-sulfur doped carbon material is only methanol or deionized water, the use of various organic solvents is avoided, and the preparation conditions are environment-friendly;
(2) the nitrogen-sulfur doped carbon material disclosed by the invention is uniform in size distribution, maintains the original appearance of a precursor material, effectively solves the problem of agglomeration of transition metal atoms, and is beneficial to further improvement of catalytic activity through effective compounding with heteroatoms;
(3) according to the invention, the metal organic framework compound contains nitrogen element, cysteine contains sulfur element, and the nitrogen element and the sulfur element are uniformly distributed in a carbon skeleton of the nitrogen-sulfur doped carbon material after the precursor material is carbonized at high temperature; due to the doping of nitrogen and sulfur, a large number of unconjugated carbon structures, namely carbon defects, exist in the nitrogen-sulfur doped carbon material, and further more active sites are generated, and the descriptors I of the defect degree and the graphitization degree of the carbon materials areD/IGThe numerical range of (A) is 1.05-1.89;
(4) the nitrogen-sulfur doped carbon material is used as a catalyst for oxygen reduction reaction, and has a half-wave potential of not less than 0.83V and a current density of not less than 5.35mA/cm under an alkaline condition2The ORR catalytic performance of the nitrogen-sulfur doped carbon material exceeds that of a commercial noble metal platinum-carbon catalyst, and the nitrogen-sulfur doped carbon material has high practical application potential.
Drawings
FIG. 1 is a scanning electron micrograph of the precursor material of example 1.
FIG. 2 is a transmission electron micrograph of a nitrogen-sulfur-doped carbon material in example 1.
FIG. 3 is a C element distribution diagram of a carbon material doped with nitrogen and sulfur in example 1.
FIG. 4 is a distribution diagram of the S element of the carbon material doped with nitrogen and sulfur in example 1.
FIG. 5 is a distribution diagram of N element in the carbon material doped with nitrogen and sulfur in example 1.
FIG. 6 is a Raman spectrum of the carbon material doped with nitrogen and sulfur in example 1.
FIG. 7 is an X-ray diffraction pattern of the precursor materials of examples 1, 6 and 7 and Co-ZIF of comparative example 1.
FIG. 8 is a graph comparing the linear sweep voltammograms of the nitrogen sulfur doped carbon material of example 1 with the commercial 20% Pt/C electrode of comparative example 2.
FIG. 9 is a graph comparing the linear sweep voltammograms of the nitrogen sulfur doped carbon material of example 2 with the commercial 20% Pt/C electrode of comparative example 2.
FIG. 10 is a graph comparing the linear sweep voltammograms of the nitrogen sulfur doped carbon material of example 3 with the commercial 20% Pt/C electrode of comparative example 2.
FIG. 11 is a graph comparing the linear sweep voltammograms of the nitrogen sulfur doped carbon material of example 4 with the commercial 20% Pt/C electrode of comparative example 2.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a nitrogen-sulfur doped carbon material, which comprises the following steps:
(1) stirring and mixing a 2-methylimidazole methanol solution and a cobalt nitrate methanol solution at a volume ratio of 1:1 at 25 ℃ for 4 hours, wherein the mass ratio of solute in the 2-methylimidazole methanol solution to solute in the cobalt nitrate methanol solution is 50: 1; sequentially centrifuging, washing and drying to obtain a metal organic framework compound (Co-ZIFs), and mixing the Co-ZIFs with methanol to obtain a Co-ZIFs methanol solution;
(2) mixing the Co-ZIFs methanol solution obtained in the step (1) and the cysteine aqueous solution at 25 ℃ for 3h in a stirring volume ratio of 5:1, wherein the mass ratio of the solute in the Co-ZIFs methanol solution to the solute in the cysteine aqueous solution is 4: 0.5; and sequentially carrying out centrifugation, washing and drying to obtain a precursor material, heating to 950 ℃ at a heating rate of 6 ℃/min in nitrogen, and keeping the temperature for 2.5 hours to obtain the nitrogen-sulfur doped carbon material, wherein the mass fraction of transition metals in the nitrogen-sulfur doped carbon material is 5.4 wt% based on the mass of the nitrogen-sulfur doped carbon material.
Scanning the precursor material by using a scanning electron microscope to obtain a scanning electron microscope image of the precursor material as shown in figure 1;
scanning the nitrogen-sulfur-doped carbon material by a transmission electron microscope to obtain a scanning electron microscope image of the nitrogen-sulfur-doped carbon material as shown in fig. 2, a C element distribution diagram as shown in fig. 3, an S element distribution diagram as shown in fig. 4, and an N element distribution diagram as shown in fig. 5;
the raman spectrometer is used to obtain the full spectrum of the nitrogen-sulfur doped carbon material as shown in fig. 6.
Example 2
The embodiment provides a preparation method of a nitrogen-sulfur doped carbon material, which comprises the following steps:
(1) ultrasonically mixing a 2-methylimidazole methanol solution and an iron nitrate methanol solution at the temperature of 20 ℃ for 3 hours, wherein the volume ratio of the solute in the 2-methylimidazole methanol solution to the solute in the iron nitrate methanol solution is 30: 1; sequentially carrying out centrifugation, washing and drying to obtain a metal organic framework compound (Fe-ZIFs), and mixing the Fe-ZIFs with methanol to obtain a Fe-ZIFs methanol solution;
(2) mixing the Fe-ZIFs methanol solution and the cysteine aqueous solution obtained in the step (1) at 30 ℃ for 2h by ultrasonic mixing in a volume ratio of 7:1, wherein the mass ratio of the solute in the Fe-ZIFs methanol solution to the solute in the cysteine aqueous solution is 4: 0.3; and sequentially centrifuging, washing and drying to obtain a precursor material, heating to 900 ℃ at a heating rate of 8 ℃/min in nitrogen, and keeping the temperature for 3 hours to obtain the nitrogen-sulfur doped carbon material, wherein the mass fraction of transition metals in the nitrogen-sulfur doped carbon material is 3.8 wt% based on the mass of the nitrogen-sulfur doped carbon material.
Example 3
The embodiment provides a preparation method of a nitrogen-sulfur doped carbon material, which comprises the following steps:
(1) mixing a potassium ferrocyanide aqueous solution and a nickel nitrate aqueous solution at 30 ℃ for 2h by ultrasonic for 0.8:1, wherein the mass ratio of a solute in the potassium ferrocyanide aqueous solution to a solute in the nickel nitrate aqueous solution is 80: 1; sequentially centrifuging, washing and drying to obtain a metal organic framework compound (FeNi-PBA), and mixing the FeNi-PBA with water to obtain a FeNi-PBA aqueous solution;
(2) stirring and mixing the FeNi-PBA aqueous solution and the cysteine methanol solution obtained in the step (1) at the temperature of 20 ℃ for 4h, wherein the volume ratio of the solute in the FeNi-PBA aqueous solution to the solute in the cysteine methanol solution is 4: 0.8; and sequentially centrifuging, washing and drying to obtain a precursor material, heating to 850 ℃ at a heating rate of 4 ℃/min in argon, and keeping the temperature for 3.5 hours to obtain the nitrogen-sulfur doped carbon material, wherein the mass fraction of transition metals in the nitrogen-sulfur doped carbon material is 6.50 wt% based on the mass of the nitrogen-sulfur doped carbon material.
Example 4
The embodiment provides a preparation method of a nitrogen-sulfur doped carbon material, which comprises the following steps:
(1) mixing a potassium cobalt cyanide aqueous solution and a nickel nitrate aqueous solution at 15 ℃ for 5 hours under stirring, wherein the volume ratio of the solute in the potassium cobalt cyanide aqueous solution to the solute in the nickel nitrate aqueous solution is 1: 1; sequentially centrifuging, washing and drying to obtain a metal organic framework compound (CoNi-PBA), and mixing the CoNi-PBA with water to obtain a CoNi-PBA aqueous solution;
(2) mixing the CoNi-PBA aqueous solution and the cysteine aqueous solution obtained in the step (1) at 35 ℃ for 1h by ultrasonic mixing in a volume ratio of 2:1, wherein the mass ratio of the solute in the CoNi-PBA aqueous solution to the solute in the cysteine aqueous solution is 4: 0.1; and sequentially centrifuging, washing and drying to obtain a precursor material, heating to 800 ℃ at a heating rate of 10 ℃/min in helium, and keeping the temperature for 4 hours to obtain the nitrogen-sulfur doped carbon material, wherein the mass fraction of transition metals in the nitrogen-sulfur doped carbon material is 2.22 wt% based on the mass of the nitrogen-sulfur doped carbon material.
Example 5
The embodiment provides a preparation method of a nitrogen-sulfur doped carbon material, which comprises the following steps:
(1) mixing a 2-methylimidazole methanol solution and a ferric chloride methanol solution at 35 ℃ for 1h in a stirring volume ratio of 1.2:1, wherein the mass ratio of a solute in the 2-methylimidazole methanol solution to a solute in the ferric chloride methanol solution is 100: 1; sequentially carrying out centrifugation, washing and drying to obtain a metal organic framework compound (Fe-ZIFs), and mixing the Fe-ZIFs with methanol to obtain a Fe-ZIFs methanol solution;
(2) stirring and mixing the Fe-ZIFs methanol solution and the cysteine methanol solution obtained in the step (1) at the temperature of 15 ℃ for 5 hours at the volume ratio of 12:1, wherein the mass ratio of solute in the Fe-ZIFs methanol solution to solute in the cysteine methanol solution is 4: 1; and sequentially carrying out centrifugation, washing and drying to obtain a precursor material, heating to 1000 ℃ at a heating rate of 2 ℃/min in nitrogen, and keeping the temperature for 2h to obtain the nitrogen-sulfur doped carbon material, wherein the mass fraction of the transition metal in the nitrogen-sulfur doped carbon material is 8.50 wt% based on the mass of the nitrogen-sulfur doped carbon material.
Example 6
This example provides a method for preparing a nitrogen-sulfur doped carbon material, which is the same as example 1 except that the mass ratio of the solute in the Co-ZIFs methanol solution to the solute in the cysteine aqueous solution is 4: 0.05.
Example 7
This example provides a method for preparing a nitrogen-sulfur doped carbon material, which is the same as example 1 except that the mass ratio of the solute in the Co-ZIFs methanol solution to the solute in the cysteine aqueous solution is 4: 1.5.
Example 8
The embodiment provides a preparation method of a nitrogen-sulfur doped carbon material, which is the same as the embodiment 1 except that the precursor material is heated to 700 ℃ at a heating rate of 6 ℃/min in nitrogen and is kept warm for 2.5 hours.
Example 9
The embodiment provides a preparation method of a nitrogen-sulfur doped carbon material, which is the same as the embodiment 1 except that a precursor material is heated to 1100 ℃ at a heating rate of 6 ℃/min in nitrogen and is kept for 2.5 hours.
Comparative example 1
This comparative example provides Co-ZIFs, which is the same as that in example 1.
Comparative example 2
This comparative example provides a commercial 20% Pt/C electrode.
The X-ray diffraction patterns obtained by carrying out X-ray diffraction on the precursor materials in the examples 1, 6 and 7 and the Co-ZIF in the comparative example 1 are shown in FIG. 7;
performing electrochemical test on the nitrogen-sulfur doped carbon material in the examples 1-9, Co-ZIFs in the comparative example 1 and a commercial 20% Pt/C electrode in the comparative example 2 to obtain a linear sweep voltammetry curve, wherein the electrochemical test method comprises the following steps: and (3) taking 0.1MKOH solution as electrolyte, introducing oxygen for 30min before testing to perform dissolved gas replacement, always keeping the oxygen in the electrolyte saturated in the testing process, wherein the testing potential interval is 0.2-1.1V (vs. RHE), the sweep rate is 10mV/s, and the rotating speed of the rotating disc electrode is 1600 rpm.
A comparison of the linear sweep voltammograms tested for the nitrogen and sulfur doped carbon material of example 1 versus the commercial 20% Pt/C electrode of comparative example 2 is shown in FIG. 8;
a comparison of the linear sweep voltammograms tested for the nitrogen and sulfur doped carbon material of example 2 versus the commercial 20% Pt/C electrode of comparative example 2 is shown in FIG. 9;
a comparison of the linear sweep voltammograms tested for the nitrogen and sulfur doped carbon material of example 3 versus the commercial 20% Pt/C electrode of comparative example 2 is shown in FIG. 10;
a comparison of the linear sweep voltammograms of the nitrogen sulfur-doped carbon material of example 4 versus the commercial 20% Pt/C electrode of comparative example 2 is shown in FIG. 11;
the half-wave potential and current density obtained by the test are shown in table 1.
TABLE 1
From Table 1 and FIGS. 1 to 11, it can be seen that:
(1) as can be seen from fig. 1, the morphology of the precursor material is kept rhombic dodecahedron, and as can be seen from fig. 7, the diffraction peaks of the Co-ZIF in the precursor materials of examples 1, 6 and 7 are consistent with those of the Co-ZIF in the comparative example 1, which indicates that the addition of cysteine does not destroy the crystal structure of the Co-ZIF; as can be seen from FIGS. 2 to 5, nitrogen and sulfur are uniformly distributed in the framework of the carbon material, and the original morphology of the precursor is not changed; as can be seen from FIG. 6, 1330cm-1And 1580cm-1Two typical characteristic peaks of D band and G band, ID/IGThe value of (A) reaches 1.89;
(2) obtained as in examples 1 to 5When the nitrogen-sulfur doped carbon material is used as a catalyst for oxygen reduction reaction, the half-wave potential is not lower than 0.83V, and the current density is not lower than 5.35mA/cm2；
(3) As can be seen from the comparison between example 1 and examples 6 and 7, the mass ratio of the solute in the metal-organic framework compound solution to the solute in the cysteine solution affects the catalytic performance of the nitrogen-sulfur doped carbon material; when the mass ratio of the solute in the metal-organic framework compound solution to the solute in the cysteine solution is low, the half-wave potential becomes low and the current density is reduced, because the doping amount of sulfur element is less, and the precursor cannot generate enough active sites after carbonization; when the mass ratio of the solute in the metal-organic framework compound solution to the solute in the cysteine solution is higher, the half-wave potential becomes lower and the current density is reduced, because excessive doping of cysteine may cause collapse of the metal-organic framework, change the inherent morphology and reduce the activity;
(4) as can be seen from the comparison between the example 1 and the examples 8 and 9, the heat preservation temperature of the invention can influence the catalytic performance of the nitrogen-sulfur doped carbon material; when the heat preservation temperature is lower or higher, the half-wave potential is lowered and the current density is reduced, because the graphitization degree of the catalyst is higher when the temperature is 800-1000 ℃, the electrochemical activity of the catalyst is more favorably improved;
(5) as can be seen from the comparison of example 1 with comparative example 1, the incorporation of cysteine according to the present invention helps to improve the catalytic performance of the metal-organic framework compound; the metal organic framework compound contains nitrogen element, cysteine contains sulfur element, and the nitrogen element and the sulfur element are uniformly distributed in a carbon skeleton of a nitrogen-sulfur doped carbon material after a precursor material is carbonized at high temperature; due to the doping of nitrogen and sulfur, a large number of unconjugated carbon structures, namely carbon defects, exist in the nitrogen-sulfur doped carbon material, and further more active sites are generated, and the descriptors I of the defect degree and the graphitization degree of the carbon materials areD/IGThe numerical range of (A) is 1.05-1.89;
(6) as can be seen from the comparison between example 1 and comparative example 2, the catalytic performance of the nitrogen-sulfur doped carbon material exceeds that of a commercial 20% Pt/C electrode catalyst, and the nitrogen-sulfur doped carbon material has high practical application potential.
In conclusion, the preparation method of the nitrogen-sulfur doped carbon material has the advantages of low cost, simple and controllable synthesis process, high consistency and easiness in realization of batch production, the solvent required in the preparation process of the nitrogen-sulfur doped carbon material is only methanol or deionized water, the use of various organic solvents is avoided, and the preparation conditions are environment-friendly;
the nitrogen-sulfur doped carbon material disclosed by the invention is uniform in size distribution, maintains the original appearance of a precursor material, effectively solves the problem of agglomeration of transition metal atoms, and is beneficial to further improvement of catalytic activity through effective compounding with heteroatoms;
according to the invention, the metal organic framework compound contains nitrogen element, cysteine contains sulfur element, and the nitrogen element and the sulfur element are uniformly distributed in a carbon skeleton of the nitrogen-sulfur doped carbon material after the precursor material is carbonized at high temperature; due to the doping of nitrogen and sulfur, a large number of unconjugated carbon structures, namely carbon defects, exist in the nitrogen-sulfur doped carbon material, and further more active sites are generated, and the descriptors I of the defect degree and the graphitization degree of the carbon materials areD/IGThe numerical range of (A) is 1.05-1.89;
the nitrogen-sulfur doped carbon material is used as a catalyst for oxygen reduction reaction, and has a half-wave potential of not less than 0.83V and a current density of not less than 5.35mA/cm under an alkaline condition2The ORR catalytic performance of the nitrogen-sulfur doped carbon material exceeds that of a commercial noble metal platinum carbon catalyst, and the nitrogen-sulfur doped carbon material has high practical application potential.
The above description is only for the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. A preparation method of a nitrogen-sulfur doped carbon material is characterized by comprising the following steps:
and carrying out first solid-liquid separation on the first mixed metal organic framework compound solution and a cysteine solution to obtain a precursor material, and then calcining to obtain the nitrogen-sulfur doped carbon material.
2. The preparation method according to claim 1, wherein the volume ratio of the metal-organic framework compound solution to the cysteine solution is (2-12): 1;
preferably, the mass ratio of the solute in the metal organic framework compound solution to the solute in the cysteine solution is 4 (0.1-1);
preferably, the solvent of the cysteine solution comprises methanol and/or water.
3. The method according to claim 1 or 2, wherein the temperature of the first mixing is 15 to 35 ℃ and the time is 1 to 5 hours;
preferably, the method of first mixing comprises stirring and/or sonication;
preferably, the first solid-liquid separation comprises centrifugation, washing and drying which are sequentially carried out.
4. The production method according to any one of claims 1 to 3, wherein the calcination includes sequentially performing temperature rise and temperature preservation;
preferably, the heating rate is 2-10 ℃/min, and the temperature of the heating end point is 800-1000 ℃;
preferably, the heat preservation time is 2-4 h;
preferably, the calcination is carried out in a protective atmosphere comprising nitrogen and/or an inert gas.
5. The method according to any one of claims 1 to 4, wherein the method for preparing the metal-organic framework compound solution comprises the steps of:
and (3) carrying out second solid-liquid separation on the second mixed nitrogenous ligand solution and the transition metal salt solution to obtain a metal organic framework compound, and mixing the metal organic framework compound with methanol and/or water to obtain a metal organic framework compound solution.
6. The method according to claim 5, wherein the solute of the nitrogen-containing ligand solution comprises any one of 2-methylimidazole, potassium ferricyanide, potassium ferrocyanide or potassium cobaltcyanide or a combination of at least two of them;
preferably, the solvent of the nitrogen-containing ligand solution comprises methanol and/or water;
preferably, the solute of the transition metal salt solution comprises any one of cobalt nitrate, iron nitrate, nickel nitrate, zinc nitrate or ferric chloride or a combination of at least two of the above;
preferably, the solvent of the transition metal salt solution comprises methanol and/or water;
preferably, the volume ratio of the nitrogen-containing ligand solution to the transition metal salt solution is (0.8-1.2): 1;
preferably, the mass ratio of the solute in the nitrogen-containing ligand solution to the solute in the transition metal salt solution is (1-100): 1;
preferably, the temperature of the second mixing is 15-35 ℃ and the time is 1-5 h;
preferably, the method of second mixing comprises stirring and/or sonication;
preferably, the second solid-liquid separation comprises centrifugation, washing and drying which are carried out in sequence.
7. The method according to any one of claims 1 to 6, wherein the method comprises the steps of:
(1) stirring and/or ultrasonically mixing a nitrogen-containing ligand solution and a transition metal salt solution at 15-35 ℃ for 1-5 h in a volume ratio of (0.8-1.2): 1, wherein the mass ratio of solute in the nitrogen-containing ligand solution to solute in the transition metal salt solution is (1-100): 1; sequentially carrying out centrifugation, washing and drying to obtain a metal organic framework compound, and mixing the metal organic framework compound with methanol and/or water to obtain a metal organic framework compound solution;
(2) stirring and/or ultrasonically mixing the metal organic framework compound solution and the cysteine solution at the temperature of 15-35 ℃ for 1-5 h in a volume ratio of (2-12): 1, wherein the mass ratio of the solute in the metal organic framework compound solution to the solute in the cysteine solution is 4 (0.1-1); and sequentially centrifuging, washing and drying to obtain a precursor material, heating to 800-1000 ℃ at a heating rate of 2-10 ℃/min in a protective atmosphere, and keeping the temperature for 2-4 h to obtain the nitrogen-sulfur doped carbon material.
8. A nitrogen-sulfur-doped carbon material obtained by the production method according to any one of claims 1 to 7.
9. The nitrogen-sulfur-doped carbon material according to claim 8, wherein the mass fraction of the transition metal in the nitrogen-sulfur-doped carbon material is 2.22 to 8.50 wt% based on the mass of the nitrogen-sulfur-doped carbon material.
10. Use of the nitrogen-sulfur-doped carbon material according to claim 8 or 9 as a cathode catalyst for a fuel cell.
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