CN111354951A - Synthetic method and application of metal sulfide material based on encapsulated porphyrin - Google Patents
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- H—ELECTRICITY
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- H—ELECTRICITY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
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Abstract
The invention belongs to the field of preparation of metal organic materials, and particularly relates to a synthetic method and application of a metal sulfide material based on encapsulated porphyrin. The invention adopts a method of combining organic materials and inorganic materials, namely synthesizing porphyrin-coated metal organic framework PorM @ ZIF-67(M ═ H, Mn, Fe and Co) materials by adopting a method of shipbuilding in bottles, and researching the materials rich in carbon, nitrogen and metal sulfides (Co) formed after carbonization and vulcanizationxMy) The ORR catalytic activity of S/N-C (M ═ H, Mn, Fe, Co) materials shows high-efficiency catalytic activity in the ORR test, and the average value of the electron transfer number reaches 3.8, which indicates that the ORR reaction is mainly carried out in a 4-electron mode. And (Co)xMny) The S/N-C material only uses non-noble metals of cobalt and manganese, can replace noble metals of Pt/C catalyst, effectively solves the catalyst problem of new energy fuel cells, reduces the cost and improves the energy utilization efficiency.
Description
Technical Field
The invention belongs to the field of preparation of metal organic materials, in particular to combination of a porphyrin organic compound and a metal organic framework, and particularly relates to a synthetic method of a metal sulfide material based on encapsulated porphyrin and application of electrochemical oxygen catalysis.
Background
The social development and the improvement of human civilization enable the consciousness of people to be changed, and the environmental protection sustainable development is the necessary way for the next social development. Although the current power generation technology is increasingly perfect, a plurality of limiting factors exist: sustainable natural energy power generation such as wind power generation, hydroelectric power generation, solar power generation and the like is limited by a plurality of natural conditions and cannot be popularized and used all over the country; the main raw materials used in the traditional thermal power generation are non-renewable resources of coal, and the pollution degree of the thermal power generation to the environment is large; even though the technology of the nuclear power generation developed at present is continuously improved and broken through, the fear of the nuclear radiation of people also makes the nuclear power generation base difficult to be popularized and constructed comprehensively. As a hot spot of the current new energy research, the fuel cell has many advantages as follows in general: (1) the energy conversion rate is high, and chemical energy is directly converted into electric energy; (2) the fuel cell power station has the advantages of relatively small floor area, short construction period, flexible and convenient installation place; (3) most of the emissions of the fuel cell are moisture, and the concept of green sustainable development is met. Two chemical reactions mainly occur on the surface of an electrode of the fuel cell, wherein an Oxygen Reduction Reaction (ORR) mainly occurs on a cathode, and the key problem of low energy utilization rate of the fuel cell can be solved by researching an electrochemical oxygen catalyst with high-efficiency activity.
It is widely believed that the earth's rich variety of transition metals and their sulfide-based materials have very strong ORR catalytic activity in electrocatalytic applications. Whereas ZIF-67 derived catalysts, consisting of rich nitrogen-carbon doped structures and cobalt cations, have been shown to have good electrocatalytic activity towards ORR. Meanwhile, porphyrin organic compounds have wide application in electrocatalysis.
The rapid development of new energy fuel cells is limited due to the very expensive cost of industrial noble metal Pt/C catalysts. Aiming at the problem, an electrochemical catalyst which can replace noble metal Pt/C and is cheap and low in cost is synthesized, and is important for the development of new energy fuel cells. Therefore, the invention researches a brand-new non-noble metal material which is suitable for the ORR catalyst of the fuel cell.
Disclosure of Invention
The invention aims to provide a method for combining an organic material and an inorganic material, namely synthesizing a porphyrin-coated metal organic framework PorM @ ZIF-67(M ═ H, Mn, Fe and Co) material by adopting a method of shipbuilding in bottles, and researching the carbon-nitrogen-and metal-sulfide-rich (Co) material formed after carbonization and vulcanizationxMy) ORR catalytic activity of S/N-C (M ═ H, Mn, Fe, Co) materials.
In the invention, the structure of the PorM is as follows:
The preparation method of the metal sulfide material based on the encapsulated porphyrin comprises the following steps:
(1) synthesis of PorM @ ZIF-67
Weighing 2-methylimidazole, zinc nitrate hexahydrate and porphyrazine porom in proportion, placing the mixture into a pressure-resistant bottle, adding DMF (dimethyl formamide), performing ultrasonic treatment to completely dissolve and uniformly mix the mixture, placing the pressure-resistant bottle filled with reactants into a constant-temperature oven to perform hydrothermal reaction after the ultrasonic treatment is finished, centrifuging the mixture after the hydrothermal reaction is finished, washing, and performing vacuum drying to obtain the material PorM @ ZIF-67, wherein M is H, Mn, Fe or Co.
In the step (1), the molar ratio of zinc nitrate hexahydrate to 2-methylimidazole is 1:1 to 2, the molar ratio of the amino porphyrin to the 2-methylimidazole is 1:15 to 25, and the amount of DMF used is 4 to 6mL per 0.01mmol of amino porphyrin; the temperature of the hydrothermal reaction is controlled to be 120-150 ℃, and the reaction time is 36 h.
In the step (1), the ultrasonic time is 15 min; during centrifugation, the rotating speed of the centrifuge is 8000rbs, and the time is 6 min; washing with DMF for 3 times, and then washing with ethanol for 3 times; the temperature of vacuum drying is 70 ℃, and the drying time is 12 h.
Wherein PorH @ ZIF-67 is a brown solid (the porphyrin in the material should be metal cobalt porphyrin, but for distinguishing the material directly synthesized by PorCo, PorH @ ZIF-67 is used for representation), PorMn @ ZIF-67 is a dark green solid, PorFeCl @ ZIF-67 is a black green solid, and PorCo @ ZIF-67 is a mauve solid.
(2) Calcination and sulfidation of PorM @ ZIF-67
Placing the PorM @ ZIF-67 prepared in the step (1) into a tubular furnace, programming to the calcining temperature, naturally cooling to the room temperature after calcining, and continuously introducing protective gas in the whole calcining process;
dispersing the sample obtained after carbonization into a pressure-resistant glass bottle filled with ethanol, adding a vulcanized raw material thioacetamide TAA, then placing the pressure-resistant bottle in a constant-temperature drying oven for vulcanization reaction, naturally cooling to room temperature after reaction, centrifuging, washing, and drying in vacuum to obtain (Co)xMy) S/N-C, wherein M ═ H, Mn, Fe, Co.
M represents metal ions at the porphyrin center of PorM @ ZIF-67, and the carbonized and vulcanized materials of PorH @ ZIF-67, PorCo @ ZIF-67 and ZIF-67 only contain one metal of cobalt, so that the metal ions are respectively used as (Co)xHy)S/N-C、(CoxCoy) And S/N-C.
In the step (2), the calcining temperature is 780-820 ℃, and the calcining time is 2 h; the temperature programming rate is 2 ℃ min-1The protective gas is nitrogen or argon;
the mass ratio of the carbonized sample to thioacetamide is 1-10: 100, and the dosage of ethanol in each 0.1g of thioacetamide is 20-30 mL; the temperature of the vulcanization reaction is 150 ℃, and the reaction time is 6 hours; the washing is carried out 3 times by using ethanol, the temperature of vacuum drying is 70 ℃, and the drying time is 12 h.
The invention relates to the use of encapsulated porphyrin-based metal sulphides prepared according to the invention for electrochemical oxygen catalysis.
The invention has the beneficial effects that:
(1) the invention provides a cheap metal sulfide material aiming at the problem of high cost of industrial noble metal Pt/C catalyst of a new energy fuel cell. Based on amino on object porphyrin and C-H of 2-methylimidazole in the host ZIF-67, N-H bond can be formed, and interaction between the host and the object is enhanced, so that amino porphyrin is successfully wrapped in the cavity of the ZIF-67, a brand new wrapped porphyrin metal organic framework material is formed, and the synthesis conditions and experimental operation are relatively simple.
(2) The invention improves ORR catalytic activity by carbonization and vulcanization, wherein (Co)xMny) S/N-C shows high-efficiency catalytic activity in an ORR test, and the average value of the electron transfer number reaches 3.8, which indicates that the reaction is mainly carried out in a 4-electron mode in the ORR reaction. And (Co)xMny) The S/N-C material only uses non-noble metals of cobalt and manganese, can replace noble metals of Pt/C catalyst, effectively solves the catalyst problem of new energy fuel cells, reduces the cost and improves the energy utilization efficiency.
Drawings
FIG. 1 shows the synthesis route of PorM @ ZIF-67(M ═ H, Mn, Fe, Co).
Fig. 2 is an XRD pattern of ZIF-67, PorM @ ZIF-67(M ═ H, Mn, Fe, Co), and mock ZIF-67.
FIG. 3 is CoxS/N-C and (Co)xMy) XRD pattern of S/N-C (M ═ Mn, Fe, Co).
FIG. 4 shows CoxS/N-C and (Co)xMy) ORR test chart of S/N-C (M ═ H, Mn, Fe, Co).
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Comparative example
(1) Synthesis of ZIF-67
Cobalt nitrate hexahydrate (Zn (NO)3)2·6H2O, 2.0mmol, 582mg) and 2-methylimidazole (2-MeIm, 4.0mmol, 328mg) were dissolved in 25ml of methanol, respectively, the latter was added to the pink solution of the former under slow stirring at room temperature, and when the two solutions were completely mixed together, the stirring was stopped. And then standing the reaction mixture for 24 hours without stirring, precipitating to separate out a solid, finally centrifuging and collecting, washing with ethanol, and vacuum-drying at 50 ℃ for 12 hours to obtain the purple solid ZIF-67.
(2) Calcination of ZIF-67
And (2) heating the ZIF-67 prepared in the step (1) to 800 ℃ in a tubular furnace at the speed of 2 ℃ min < -1 >, calcining for 2 hours at constant temperature, naturally cooling to room temperature, and introducing argon for protection in the whole calcining process. The sample obtained after carbonization was redispersed in a pressure-resistant glass bottle containing 25mL of ethanol, and 0.1g of Thioacetamide (TAA) as a raw material for vulcanization was added. Placing the pressure-resistant bottle in a constant-temperature drying oven, reacting at 150 deg.C for 6h, naturally cooling to room temperature, separating solid material with centrifuge, washing with ethanol for 3 times, and drying at 70 deg.C for 12h in a vacuum oven to obtain black powder solid CoxS/N-C。
The synthetic route of PorM @ ZIF-67 is shown in figure 1:
example (1) Synthesis of PorM @ ZIF-67
Weighing 2-methylimidazole (2-MeIm, 0.33mmol, 27mg), zinc nitrate hexahydrate (Zn (NO3) 2.6H 2O, 0.28mmol, 83mg) and one amino porphyrin (PorM, 0.016mmol), placing the three compounds in a 48mL pressure-resistant bottle, adding 7.5mL of DMF, and then carrying out ultrasonic treatment for 15min to completely dissolve and uniformly mix the mixture. After the ultrasonic treatment is finished, the pressure-resistant bottle filled with the reactants is placed in a constant-temperature oven, and the reaction time is 36h at the temperature of 135 ℃. After the hydrothermal reaction is finished, the MOFs generated in the pressure-resistant bottle and the mother liquor are transferred into a 10mL centrifuge tube, the rotating speed of a centrifuge is set to 8000rbs for 6min, the mixture is washed by DMF (dimethyl formamide) until an absorption peak of ultraviolet visible spectrum in a test washing liquid does not contain porphyrin, then the mixture is washed by ethanol for 3 times, and then the mixture is dried in a vacuum drying oven at 70 ℃ for 12H, so that 4 powdery solid PorM @ ZIF-67(M ═ H, Mn, Fe or Co) materials are obtained.
Wherein PorH @ ZIF-67 is a brown solid (the porphyrin in the material should be metal cobalt porphyrin, but for distinguishing the material directly synthesized by PorCo, PorH @ ZIF-67 is used for representing), PorMn @ ZIF-67 is a dark green solid, PorFe @ ZIF-67 is a black green solid, and PorCo @ ZIF-67 is a mauve solid.
(2) Calcination and sulfidation of PorM @ ZIF-67
Putting the PorM @ ZIF-67 prepared in the step (1) into a tubular furnace at the temperature of 2 ℃ for min-1The temperature is raised to 800 ℃, then the mixture is calcined for 2 hours at constant temperature, and is naturally cooled to the room temperature, and the whole calcining process is always protected by argon. The sample obtained after carbonization was further dispersed in a pressure-resistant glass bottle containing 25mL of ethanol, and 0.1g of Thioacetamide (TAA) as a raw material for vulcanization was added thereto. Placing the pressure bottle in a constant temperature drying oven, reacting at 150 deg.C for 6 hr, naturally cooling to room temperature, separating solid material with centrifuge, washing with ethanol for 3 times, and drying in a vacuum oven at 70 deg.C for 12 hr to obtain (Co)xMy) S/N-C (M ═ H, Mn, Fe, Co, M represents metal ion of porphyrin center of PorM @ ZIF-67, and the carbonized and vulcanized materials of PorH @ ZIF-67, PorCo @ ZIF-67 and ZIF-67 contain only one metal of cobalt, and thus are used as (Co @, Zn @, Fe, Co @, M ═ H @, Mn @, Fe, Co, M @, and M @xHy)S/N-C、(CoxCoy) S/N-C).
And (3) characterization:
at a scan rate of 6 deg. min-1Under the conditions of (1), diffraction peaks of XRD of several materials are measured, and crystal structures of the materials are researched. As shown in FIG. 2, the experimentally synthesized ZIF-67 was completely consistent with the simulated standard ZIF-67 and the diffraction peaks in the literature. The XRD spectrum of the PorM @ ZIF-67 material also has characteristic diffraction peaks which are the same as those of ZIF-67, such as 10.4 degrees, 12.7 degrees, 14.6 degrees, 16.3 degrees, 17.8 degrees and the like, and the material of the PorM @ ZIF-67 material also has a typical ZIF-67 zeolite structure. FIG. 3 is an XRD pattern of the carbonized and vulcanized ZIF-67 and PorM @ ZIF-67 materials, all having a distinct broad peak and centered at 22 deg. corresponding to the crystal planes of graphitized carbon material, showing that Co is presentxS/N-C and (Co)xMy) The S/N-C material has a highly graphitic carbon structure.
Study of the performance of the oxygen catalyst:
about 1mg of the catalyst was weighed, placed in a 1.5mL small centrifuge tube, and 250uL of a Nafion/EtOH (V: V ═ 2: 98) mixed solution was added thereto, and subjected to ultrasonic treatment for 25min to completely disperse the catalyst solid powder in the mixed solution. Sucking about 20uL of the solid suspension by a 100uL micro-sampling needle, dropwise adding the solid suspension on a glassy carbon disc electrode of a ring disc electrode, naturally volatilizing the last drop of liquid, then adding the next drop, and naturally airing for about 10min after the solution is completely dropwise added. The catalyst is then plated on the electrode and the electrochemical ORR test can be performed. The ORR performance test of all catalysts was carried out in 0.1MKOH electrolyte solution at 25 ℃.
Electrochemical performance testing of the metal sulfide material is shown in fig. 4. With (Co) of FIG. 4cxMny) S/N-C as an example, FIG. 4C1 is a CV diagram measured by cyclic voltammetry, in which a CV curve is first measured in a KOH solution containing saturated nitrogen (as indicated by a dotted line) and then measured in a KOH solution containing saturated oxygen (as indicated by a solid line) between-0.2V and-0.8V, and it can be seen that the CV diagram of the catalyst under oxygen has a reduction peak potential at-0.38V, indicating that (Co/N-C) (CoxMny) S/N-C has electrocatalytic activity. FIG. 4c2 is a plot of the limiting current curves LSV of the catalyst at different rpm in a KOH solution containing saturated oxygen, with the disk electrodes at 225, 400, 625, 900, 1225rpm, respectively. And finally, selecting 5 data on the potential of a certain point on the LSV curve according to a K-L equation, and obtaining the slope of a linear regression curve according to the relation between the rotating speed and the current so as to calculate the electron transfer number in the electrocatalysis reaction process. As shown in FIG. 4c3, 2 set-point potentials of-0.50V and-0.60V were selected, respectively, corresponding to calculated electron transfer numbers of 3.7 and 3.9.
TABLE 1 reduction potential (Epa) and number of electron transfers (n) of the compound during ORR catalyzed reaction
And the reduction peak potentials and the electron transfer numbers of all the materials tested were counted, as shown in Table 1, to obtain a metal sulfide material (Co)xMy) S/N-C all show higher catalytic activity, especially bimetallic sulfide material (Co)xMny) The electron transfer number of S/N-C reached an average value of 3.8, indicating that (Co)xMny) The S/N-C material is mainly carried out in a 4e mode in the ORR catalytic reaction, and the products generated by the reaction are basically pollution-free water. And (Co)xMny) The S/N-C material has the highest activity and shows a synergistic effect among metals. Albeit (Co)xFey) S/N-C is also a bimetallic sulfide, however (Co)xMny) MnS formed in the S/N-C has stronger electric conductivity, and is beneficial to the implementation of electrocatalysis.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. The method for synthesizing the metal sulfide material based on the encapsulated porphyrin is characterized by comprising the following steps of:
(1) synthesis of PorM @ ZIF-67
Weighing 2-methylimidazole, zinc nitrate hexahydrate and porphyrazine porom in proportion, placing the mixture into a pressure-resistant bottle, adding DMF (dimethyl formamide), performing ultrasonic treatment to completely dissolve and uniformly mix the mixture, placing the pressure-resistant bottle filled with reactants into a constant-temperature oven to perform hydrothermal reaction after the ultrasonic treatment is finished, centrifuging the mixture after the hydrothermal reaction is finished, washing, and performing vacuum drying to obtain a porom @ ZIF-67 material, wherein M is H, Mn, Fe or Co;
(2) calcination and sulfidation of PorM @ ZIF-67
Placing the PorM @ ZIF-67 prepared in the step (1) into a tubular furnace, programming to the calcining temperature, naturally cooling to the room temperature after calcining, and continuously introducing protective gas in the whole calcining process;
dispersing the sample obtained after carbonization into a pressure-resistant glass bottle filled with ethanol, adding a vulcanized raw material thioacetamide TAA, then placing the pressure-resistant bottle in a constant-temperature drying oven for vulcanization reaction, naturally cooling to room temperature after reaction, centrifuging the mixture, washing, and drying in vacuum to obtain (Co)xMy) S/N-C, wherein M ═ H, Mn, Fe, Co.
2. The method for synthesizing encapsulated porphyrin-based metal sulfide material as recited in claim 1, wherein said encapsulated porphyrin-based metal sulfide material is encapsulated in a solventThe structural formula of the amino porphyrin PorM is as follows:
wherein M is H, Mn, Fe or Co.
3. The method for synthesizing encapsulated porphyrin-based metal sulfide material as recited in claim 1, wherein in step (1), said zinc nitrate hexahydrate and 2-methylimidazole are present in a molar ratio of 1:1 to 2, the molar ratio of the amino porphyrin to the 2-methylimidazole is 1:15 to 25, and the amount of DMF is 4 to 6mL per 0.01mmol of amino porphyrin.
4. The method for synthesizing the metal sulfide material based on encapsulated porphyrin as claimed in claim 1, wherein in step (1), the temperature of the hydrothermal reaction is controlled to be 120-150 ℃ and the reaction time is 36 h.
5. The method for synthesizing encapsulated porphyrin-based metal sulfide material as recited in claim 1, wherein in step (1), the ultrasound time is 15 min; during centrifugation, the rotating speed of the centrifuge is 8000rbs, and the time is 6 min; washing with DMF for 3 times, and then washing with ethanol for 3 times; the temperature of vacuum drying is 70 ℃, and the drying time is 12 h.
6. The method for synthesizing encapsulated porphyrin-based metal sulfide material as recited in claim 1, wherein in step (2), said calcining temperature is 780-820 ℃ and calcining time is 2 h; the temperature programming rate is 2 ℃ min-1The protective gas is nitrogen or argon.
7. The method for synthesizing encapsulated porphyrin-based metal sulfide material according to claim 1, wherein in the step (2), the mass ratio of the carbonized sample to thioacetamide is 1-10: 100, and the amount of ethanol used per 0.1g of thioacetamide is 20-30 mL.
8. The method for synthesizing encapsulated porphyrin-based metal sulfide material as recited in claim 1, wherein in step (2), the temperature of the sulfidation reaction is 150 ℃ and the reaction time is 6 h; the washing is carried out 3 times by using ethanol, the temperature of vacuum drying is 70 ℃, and the drying time is 12 h.
9. A metal sulfide material based on encapsulated porphyrin, characterized in that it is prepared by the method of claims 1-6.
10. Use of the encapsulated porphyrin-based metal sulfide material of claim 9 for electrochemical oxygen catalysis.
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Application publication date: 20200630 |