CN113410481A - Co atom-doped polyhedral MOFs material and preparation method and application thereof - Google Patents

Co atom-doped polyhedral MOFs material and preparation method and application thereof Download PDF

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CN113410481A
CN113410481A CN202110683288.7A CN202110683288A CN113410481A CN 113410481 A CN113410481 A CN 113410481A CN 202110683288 A CN202110683288 A CN 202110683288A CN 113410481 A CN113410481 A CN 113410481A
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高云芳
吴佳豪
武海华
徐新
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Zhejiang University of Technology ZJUT
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Abstract

The invention provides a Co atom doped polyhedral MOFs material and a preparation method and application thereof. Co atom doped polyhedral MOFsThe preparation method of the material comprises the following steps: adding dimethyl imidazole, zinc salt and cobalt salt into the methanol solution to carry out precursor synthesis reaction, and separating and drying a reaction product to obtain precursor powder; the dicyandiamide is roasted to prepare the g-C3N4Powder; mixing the precursor powder with g-C3N4Grinding and uniformly mixing the powder to obtain mixed powder, and calcining the mixed powder in an inert atmosphere; and (3) pickling the product obtained after the calcination treatment with sulfuric acid, carrying out solid-liquid separation, and drying to obtain the Co atom doped polyhedral MOFs material. The Co atom-doped polyhedral MOFs material prepared by the invention has higher nitrogen content and larger specific surface area, can be used for an electro-catalytic material of a zinc-air battery, and has more excellent electro-catalytic activity than a commercial 40% Pt/C catalyst.

Description

Co atom-doped polyhedral MOFs material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of zinc-air battery materials, and particularly relates to a Co atom doped polyhedral MOFs material as well as a preparation method and application thereof.
Background
Environmental pollution and energy shortage make the development of new energy more and more urgent, and in addition to the huge power consumption requirements of electric vehicles and power grids, the factors greatly promote the rapid development of energy storage equipment including zinc-air batteries, which has the characteristics of high energy density, low carbon, environmental protection and abundant earth reserves. The zinc-air battery has the characteristics of high theoretical power density, abundant earth Zn reserves, safe use and the like, and is expected to become a warped part in energy storage equipment in social development in the future. However, it appears that zinc-air batteries still face a number of problems: (1) the actual energy density of the zinc-air battery is low due to the slow kinetic reaction rate of the positive electrode of the zinc-air battery; (2) the zinc dendrite growth is caused by the uneven dissolution and deposition of zinc at the negative electrode of the zinc-air battery in the charging and discharging processes; (3) the electrolyte of the zinc-air battery can react with CO in the air2A reaction occurs to cause a reduction in the performance of the battery. These issues are all considered by the researchers in developing high oxygen reduction (ORR) catalytically active positive electrode catalyst materials. Whether these problems can be solved or not is crucial to improving the overall performance of the zinc-air battery.
Platinum-carbon (Pt/C) catalysts based on noble metal platinum are considered to be electrocatalysts having the highest oxygen reduction (ORR) activity, but their expensive price limits their mass production and commercial use. The organic metal frameworks (MOFs) are organic-inorganic hybrid materials with pores, which are connected by organic ligands and metal ions through coordination bonds, and have the advantages that: high specific surface area, good conductivity, good morphology and a large number of nitrogen ligands are increasingly gaining attention with the development of science and technology. In addition, nitrogen-doped carbon materials, such as aza-graphene, aza-carbon nanotubes, and the like, have good electrocatalytic oxygen reduction (ORR) activity under alkaline conditions.
At present, many researches on electro-catalytic materials of zinc-air batteries exist, for example, chinese patent CN202010841907.6 discloses a preparation method of a Cu-doped hollow hexagonal ZIF-8 material for a zinc-air battery, which comprises the following steps: synthesizing a ZIF-8 material by using dimethyl imidazole and zinc nitrate hexahydrate as raw materials; converting ZIF-8 to a hollow ZIF-8 material with tannic acid; and then putting the hollow ZIF-8 into a copper nitrate solution to prepare a CuHZ-8 precursor, calcining the precursor with dicyandiamide in a muffle furnace at 550 ℃ to obtain g-C3N4, uniformly mixing the CuHZ-8 and the g-C3N4, putting the mixture into a tubular furnace for calcining, and finally washing the mixture with sulfuric acid to obtain the Cu-loaded hollow hexagonal ZIF-8 material. Chinese patent CN201910398385.4 discloses a preparation method of an iron/copper aza graphene zinc air battery cathode catalyst, which comprises the following steps: (1) mixing iron oxyhydroxide, copper hydroxide, graphene oxide and graphite-phase carbon nitride (g-C3N4), and adding sodium alginate to obtain gel; (2) putting the gel into a quartz tube with one closed end, vacuumizing by using a centrifugal pump, putting the quartz tube into a muffle furnace with the temperature of 750 and 950 ℃ for calcining for 10-20min, and cooling at room temperature; (3) soaking the black solid obtained in the previous step in hydrochloric acid for 8-12h, keeping the temperature at 50-80 ℃, then washing the black solid with deionized water and ethanol to be neutral, drying the black solid, placing the dried black powder in a quartz tube with one closed end, vacuumizing the quartz tube, calcining the quartz tube at the temperature of 750-850 ℃ for 10-20min, and cooling the quartz tube to obtain the Fe/Cu aza-graphene.
Although various methods for preparing electrocatalytic materials for zinc-air batteries exist, few MOFs materials loaded with Co atoms are prepared, and the ORR activity of the MOFs is not high, so that the MOFs is difficult to apply to the zinc-air batteries. In addition, the MOFs material with high activity prepared by the prior art is relatively simple, and the MOFs material loaded with monatomic Co is not reported yet.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a Co atom doped polyhedral MOFs material, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a Co atom-doped polyhedral MOFs material comprises the following steps:
adding dimethyl imidazole, zinc salt and cobalt salt into the methanol solution to carry out precursor synthesis reaction, and separating and drying a reaction product to obtain precursor powder;
the dicyandiamide is roasted to prepare the g-C3N4Powder;
mixing said precursor powder with said g-C3N4Grinding and uniformly mixing the powder to obtain mixed powder, and calcining the mixed powder in an inert atmosphere;
and (3) pickling the product obtained after the calcination treatment with sulfuric acid, carrying out solid-liquid separation, and drying to obtain the Co atom doped polyhedral MOFs material.
Preferably, in the precursor synthesis reaction, the molar ratio of zinc to cobalt in the zinc salt and the cobalt salt is (0-4): 1.
Preferably, the reaction temperature of the precursor synthesis reaction is 20-30 ℃, and the reaction time is 22-25 h.
Preferably, the roasting temperature of the roasting treatment is 520-560 ℃, and the roasting time is 2-4 h.
Preferably, the temperature rise rate of the roasting treatment is 2-5 ℃/min.
Preferably, the calcining temperature of the calcining treatment is 850-950 ℃, and the calcining time is 2-4 h.
Preferably, the temperature rise rate of the calcination treatment is 2-5 ℃/min.
Preferably, the concentration of the sulfuric acid is 0.5-1 mol/L.
The invention also provides a Co atom doped multi-faceted MOFs material prepared by the preparation method of the Co atom doped multi-faceted MOFs materialThe content of nitrogen in the Co atom-doped polyhedral MOFs material is 2.86-8.34%, and the specific surface area is 192-911 m2/g。
The invention also provides an application of the Co atom-doped polyhedral MOFs material in a zinc-air battery catalytic material.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the Co atom-doped polyhedral MOFs material, in the precursor synthesis reaction, the cobalt salt is used as a Co-doped source, a large amount of Co can be loaded on the MOFs material to form Co-N-C, a Co simple substance cannot be formed, the Co single atom is favorably formed, the zinc salt can well isolate the Co atom to prevent the Co atom from agglomerating, the Co atom is enabled to form the Co single atom on the MOFs material, and the catalytic activity of the Co atom-doped polyhedral MOFs material is improved; dicyandiamide has the characteristics of low toxicity and abundant reserves, and is used for preparing g-C3N4Has the advantages of low cost, simple operation and low requirement on production equipment. The preparation method of the Co atom-doped polyhedral MOFs material is simple and easy to operate.
The Co atom-doped polyhedral MOFs material prepared by the invention is prepared by doping g-C in a cobalt-containing precursor3N4Thereby improving the content of pyridine nitrogen in the prepared MOFs material and further improving the ORR activity of the prepared MOFs material. The nitrogen content of the Co atom-doped polyhedral MOFs material prepared by the invention is higher and reaches 2.86-8.34%, and the specific surface area reaches 192-911 m2(ii)/g, can be used for an electrocatalytic material of a zinc-air battery, and has more excellent electrocatalytic activity than a commercial 40% Pt/C catalyst.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
It will be appreciated by those skilled in the art that the objects and advantages that can be achieved with the present invention are not limited to the specific details set forth above, and that these and other objects that can be achieved with the present invention will be more clearly understood from the detailed description that follows.
Drawings
FIG. 1 is a scanning electron microscope characterization result diagram of a Co atom-doped polyhedral MOFs material prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope characterization result diagram of the Co atom-doped polyhedral MOFs material prepared in example 1 of the present invention;
FIG. 3 is a nitrogen adsorption and desorption isotherm diagram of the Co atom-doped polyhedral MOFs material prepared in examples 1 to 4 of the present invention;
FIG. 4 is a pore size distribution diagram of Co atom-doped polyhedral MOFs materials prepared in embodiments 1 to 4 of the present invention;
FIG. 5 shows that the Co atom-doped polyhedral MOFs material prepared in example 1 of the present invention is respectively in saturated O2And a plot of cyclic voltammetry test results under Ar;
FIG. 6 is a graph of ORR performance test results of the Co atom-doped polyhedral MOFs materials prepared in examples 1 to 4 of the present invention compared with 40% Pt/C;
FIG. 7 is a graph showing the discharge curve test results of a zinc-air battery comparing Co atom-doped polyhedral MOFs materials prepared in examples 1 to 4 of the present invention with 40% Pt/C;
FIG. 8 is a graph of the power curve test results of a zinc-air battery comparing Co atom-doped polyhedral MOFs materials prepared in examples 1 to 4 of the present invention with 40% Pt/C.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
The embodiment of the invention provides a preparation method of a Co atom doped polyhedral MOFs material, which comprises the following steps:
(1) adding dimethyl imidazole, zinc salt and cobalt salt into the methanol solution to carry out precursor synthesis reaction, and separating and drying a reaction product to obtain precursor powder;
(2) the dicyandiamide is roasted to prepare the g-C3N4Powder;
(3) mixing the precursor powder with g-C3N4Grinding and uniformly mixing the powder to obtain mixed powder, and calcining the mixed powder in an inert atmosphere;
(4) and (3) pickling the product obtained after the calcination treatment with sulfuric acid, carrying out solid-liquid separation, and drying to obtain the Co atom doped polyhedral MOFs material.
In the precursor synthesis reaction in the step (1), the zinc salt and the cobalt salt can be common water-soluble salts, and the zinc salt can be zinc nitrate hexahydrate, zinc chloride, zinc sulfate and the like; the cobalt salt may be cobalt nitrate hexahydrate, cobalt chloride, cobalt sulfate, etc. Preferably, the molar ratio of zinc to cobalt in the zinc salt and the cobalt salt is (0-4): 1. In the specific embodiment of the present invention, zinc nitrate hexahydrate and cobalt nitrate hexahydrate are taken as examples for illustration, and the molar ratio of zinc nitrate hexahydrate and cobalt nitrate hexahydrate may be 0:1 or 1:1 or 2:1 or 4:1, and the like, wherein the molar ratio of zinc nitrate hexahydrate to cobalt nitrate hexahydrate is 2:1 is optimal, and the prepared Co atom-doped polyhedral MOFs material has the highest specific surface area and the best electrocatalytic activity performance. The precursor synthesis reaction can be carried out at room temperature, namely the reaction temperature is 20-30 ℃, and the reaction time is 22-25 h.
Dicyandiamide is used in step (2) as a preparation g-C3N4The dicyandiamide as the raw material of powder is a white crystalline powder with the characteristics of low toxicity, rich reserves, wide application and the like, and the dicyandiamide is used for preparing the g-C3N4Has the advantages of simple operation, low requirement on production equipment and the like. Controlling the roasting temperature of roasting treatment to be 520-560 ℃, and the roasting time to be 2-4 h, thereby obtaining g-C3N4And (3) powder. The temperature rise rate of the roasting treatment can be controlled to be 2-5 ℃/min. In the embodiment of the present invention, the temperature increase rate of the calcination treatment can be controlled to be 2 ℃/min.
The calcination treatment in the step (3) is generally carried out in inert atmosphere such as nitrogen or argon, the calcination temperature is 850-950 ℃, and the calcination time is 2-4 h. Compared with other preparation methods of MOFs materials, the calcination treatment process has lower energy consumption and low cost; and the material can be prevented from being oxidized under the inert atmosphere. The temperature rise rate of the calcination treatment can be controlled to be 2-5 ℃/min. In the embodiment of the present invention, the temperature increase rate of the calcination treatment can be controlled to 2 ℃/min. Mixing the precursor powder and g-C in the powder in the step (3)3N4The mass ratio of the powders may be 1: (1-8), preferably, precursor powder and g-C3N4The mass ratio of the powder is 1: 2.
the concentration of sulfuric acid used for acid washing in the step (4) is 0.5-1 mol/L, the acid washing time is 8-12h, and Co particles and other impurities on the surface of the prepared material can be removed through acid washing, so that the catalytic activity of the material is improved.
The embodiment of the invention also provides a Co atom-doped polyhedral MOFs material prepared by the preparation method of the Co atom-doped polyhedral MOFs material, wherein the nitrogen content of the Co atom-doped polyhedral MOFs material is 2.86-8.34%, and the specific surface area of the Co atom-doped polyhedral MOFs material is 192-911 m2/g。
The embodiment of the invention also provides application of the Co atom-doped polyhedral MOFs material in a zinc-air battery catalytic material.
In the preparation method of the Co atom doped polyhedral MOFs material, the invention is used in the synthesis reaction of a precursorThe cobalt salt is used as a doped Co source, a large amount of Co can be loaded on the MOFs material to form Co-N-C, a Co simple substance cannot be formed, Co single atoms can be formed favorably, and the zinc salt can well isolate the Co atoms to prevent the Co atoms from agglomerating, so that the Co atoms form the Co single atoms on the MOFs material, and the catalytic activity of the Co atoms is improved; dicyandiamide has the characteristics of low toxicity and abundant reserves, and is used for preparing g-C3N4Has the advantages of low cost, simple operation and low requirement on production equipment. The preparation method of the Co atom-doped polyhedral MOFs material is simple and easy to operate.
The Co atom-doped polyhedral MOFs material prepared by the invention is prepared by doping g-C in a cobalt-containing precursor3N4Thereby improving the content of pyridine nitrogen in the prepared MOFs material and further improving the ORR activity of the prepared MOFs material. The nitrogen content of the Co atom-doped polyhedral MOFs material prepared by the invention is higher and reaches 2.86-8.34%, and the specific surface area reaches 192-911 m2(ii)/g, can be used for an electrocatalytic material of a zinc-air battery, and has more excellent electrocatalytic activity than a commercial 40% Pt/C catalyst.
The following is a further description with reference to specific examples.
Example 1
The embodiment 1 of the invention provides a Co atom doped polyhedral MOFs material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) at room temperature of 25 ℃, zinc nitrate hexahydrate and cobalt nitrate hexahydrate are mixed according to a molar ratio of 2:1, putting the mixture into a methanol solution in proportion, stirring and reacting for 24 hours, and centrifuging and drying a product after reaction to obtain precursor powder;
(2) calcining 5.5 g dicyandiamide in a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, and calcining for 2h at the temperature to obtain g-C3N4Powder;
(3) mixing the precursor powder of the step (1) and the g-C of the step (2)3N4Uniformly mixing the powder in a mortar according to the mass ratio of 1:2, grinding for 20min, and then putting the mixture into a tubular furnace for calcining for 3 h at 900 ℃ (heating to 900 ℃ at the speed of 2 ℃/min) in the atmosphere of nitrogen to obtain ZIF-Zn: Co-2: 1;
(4) and (3) washing ZIF-Zn: Co-2:1 with 0.5 mol/L sulfuric acid for 10 hours, and then filtering and drying to obtain the Co atom doped polyhedral MOFs material.
Example 2
The embodiment 2 of the invention provides a Co atom-doped polyhedral MOFs material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) at room temperature of 28 ℃, zinc nitrate hexahydrate and cobalt nitrate hexahydrate are mixed according to a molar ratio of 4:1, putting the mixture into a methanol solution, stirring and reacting for 22 hours, and centrifuging and drying a product after reaction to obtain precursor powder;
(2) calcining 5.5 g dicyandiamide in a muffle furnace, heating to 520 ℃ at the speed of 2 ℃/min, and calcining for 3 h at the temperature to obtain g-C3N4Powder;
(3) mixing the precursor powder of the step (1) and the g-C of the step (2)3N4Uniformly mixing the powder in a mortar according to the mass ratio of 1:2, grinding for 20min, and then putting the mixture into a tubular furnace for calcination treatment for 4 h at 850 ℃ (heating to 850 ℃ at 2 ℃/min) in a nitrogen atmosphere to obtain ZIF-Zn: Co-4: 1;
(4) and (3) washing ZIF-Zn: Co-4:1 with 0.5 mol/L sulfuric acid for 10 hours, and then filtering and drying to obtain the Co atom doped polyhedral MOFs material.
Example 3
The embodiment 3 of the invention provides a Co atom-doped polyhedral MOFs material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) at room temperature of 23 ℃, zinc nitrate hexahydrate and cobalt nitrate hexahydrate are mixed according to a molar ratio of 1:1, putting the mixture into a methanol solution in proportion, stirring and reacting for 25 hours, centrifuging and drying a product after reaction to obtain precursor powder;
(2) calcining 5.5 g dicyandiamide in a muffle furnace, heating to 560 ℃ at 2 ℃/min, and calcining for 2h at the temperature to obtain g-C3N4Powder;
(3) mixing the precursor powder of the step (1) and the g-C of the step (2)3N4Uniformly mixing the powder in a mortar according to the mass ratio of 1:2, grinding for 20min, putting the mixture into a tubular furnace, calcining for 2h at 950 ℃ (heating to 950 ℃ at 2 ℃/min), and introducing a calcining gasObtaining ZIF-Zn: Co-1:1 under nitrogen atmosphere;
(4) and (3) washing ZIF-Zn: Co-1:1 with 1 mol/L sulfuric acid for 8 hours, and then filtering and drying to obtain the Co atom doped polyhedral MOFs material.
Example 4
The embodiment 4 of the invention provides a Co atom-doped polyhedral MOFs material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) at room temperature of 26 ℃, zinc nitrate hexahydrate and cobalt nitrate hexahydrate are mixed according to a molar ratio of 0:1, putting the mixture into a methanol solution, stirring and reacting for 24 hours, centrifuging and drying a product after reaction to obtain precursor powder;
(2) calcining 5.5 g dicyandiamide in a muffle furnace, heating to 540 ℃ at the speed of 2 ℃/min, and roasting at the temperature for 4 h to obtain g-C3N4Powder;
(3) mixing the precursor powder of the step (1) and the g-C of the step (2)3N4Uniformly mixing the powder in a mortar according to the mass ratio of 1:2, grinding for 20min, and then putting the mixture into a tubular furnace for calcining for 3 h at 900 ℃ (heating to 900 ℃ at the speed of 2 ℃/min, wherein the calcining atmosphere is nitrogen, so as to obtain ZIF-Zn: Co-0: 1;
(4) and (3) washing ZIF-Zn: Co-0:1 with 1 mol/L sulfuric acid for 12h, filtering and drying to obtain the Co atom doped polyhedral MOFs material.
The morphology of the Co atom-doped polyhedral MOFs material prepared in example 1 was characterized by using a Hitachi S4700 scanning electron microscope of Hitachi corporation, japan, and the microscopic morphology of the Co single atom-doped MOFs material was studied, and the results are shown in fig. 1. As can be clearly seen from FIG. 1, the prepared Co monatomic doped MOFs material is of a polyhedral structure and well inherits the morphology of ZIF-67.
The morphology characterization of the Co atom-doped polyhedral MOFs material prepared in example 1 was performed by using a Tecnai G2F 30S-Twin type transmission electron microscope of Philips-FEI, the Netherlands, and the microscopic morphology of the Co single atom-doped MOFs material was studied, and the results are shown in FIGS. 2 (a) and 2 (b). From fig. 2 (a), it can be clearly seen that the prepared Co monatomic doped MOFs material is a polyhedral structure. From fig. 2 (b), it can be seen that Co exists in the form of a single atom.
The Co atom-doped polyhedral MOFs materials prepared in examples 1 to 4 were subjected to analysis of apparent density, specific surface area and pore volume by using an ASAP2020 full-automatic physical-chemical adsorption apparatus manufactured by Micromeritics. Specific surface area measurement N was adsorbed at 77K through the pores of the material by gas adsorption2Obtaining an adsorption isotherm (shown in FIG. 3), and calculating the adsorption N of the material2The surface area was calculated by fitting the measured values to a Brunauer-Emmet-teller (bet) model, and the results are shown in table 1. As shown in Table 1, the specific surface area of the Co atom-doped polyhedral MOFs material prepared in the embodiments 1 to 4 of the invention is 192 to 911 m2(ii) in terms of/g. The specific surface area of the Co atom-doped polyhedral MOFs material prepared in example 1 reaches 911 m2And/g, belongs to a material with larger specific surface area in the positive electrode material of the zinc-air battery.
Figure 189628DEST_PATH_IMAGE001
The pore size distribution of the Co atom-doped polyhedral MOFs material was obtained by measuring the nitrogen desorption isotherm (shown in FIG. 3). The pore size distribution analysis of the Co atom-doped polyhedral MOFs materials prepared in examples 1 to 4 was performed by using an ASAP2020 full-automatic physical-chemical adsorption apparatus produced by Micromeritics. The test temperature is 77K, and the adsorption medium is N2. The pore size distribution was calculated by the non-local density functional theory (NLDFT) method. Fig. 3 is a nitrogen adsorption and desorption isotherm diagram of a Co atom-doped polyhedral MOFs material, and it can be seen from the diagram that the nitrogen adsorption and desorption isotherm of the Co atom-doped polyhedral MOFs material is of a typical type iv, which indicates that a sample has mesoporous channels, and the mesopores can improve a large number of active sites for a carbon material, thereby improving the activity. FIG. 4 is a pore size distribution diagram of a Co atom-doped polyhedral MOFs material, and it can be seen from the diagram that the pore size of the carbon material is mainly micropore and assisted by mesopore and macropore, the micropore can provide an active site, and the mesopore and the macropore provide channels, so that the ORR activity of the catalyst is effectively improved。
The Co atom-doped polyhedral MOFs material 6 mg prepared in example 1 was used as a zinc-air battery catalyst, and was uniformly dispersed in a mixed solution of 2mL of ethanol and 50uL of nafion (5% by weight), followed by ultrasonic treatment in an ultrasonic machine for 2 hours, so that the catalyst was completely dispersed in the mixed solution. And (3) uniformly coating 25uL of catalyst slurry on a glassy carbon electrode by using a liquid transfer gun, naturally airing at room temperature, and using for CV test and LSV test. The electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the Hg/HgO electrode is used as a reference electrode, a 0.1M KOH solution is used as an electrolyte, and a cyclic voltammetry test is carried out by using a three-electrode test, wherein the test result is shown in figure 5. The ORR activity test is shown in FIG. 6, from which we can see that the half-wave potential of the material is even 20mV higher than that of the commercial 40% Pt/C, and the limiting current is 1.5 mA/cm higher than that of the commercial 40% Pt/C2This material shows a stronger ORR activity than the commercial 40% Pt/C catalyst.
The results of comparing the Co atom-doped polyhedral MOFs materials prepared in the embodiments 1 to 4 of the invention with the half-wave potential of commercial 40% Pt/C are shown in Table 2.
Figure 172628DEST_PATH_IMAGE002
As can be seen from tables 1 and 2, when Zn: Co =2:1, the specific surface area of the active material is the largest and the ORR activity thereof is the best, because: the mesoporous volume fraction, area fraction and specific surface area of the prepared material are increased along with the increase of Zn doping amount, the electrochemical performance is also increased, and when Zn: Co =4:1 is reached, the content of Co in unit volume is too small due to the fact that Co is separated too far, and the ORR activity is reduced. The aperture size and the nitrogen content of the prepared MOFs material can be controlled by regulating the Zn-Co ratio, so that the Co atom-doped polyhedral MOFs material with the required aperture and specific surface area is obtained.
Co atom doping prepared in embodiments 1-4 of the inventionThe discharge curve test result of the zinc-air battery comparing the heteropolyhedron MOFs material with 40% Pt/C is shown in FIG. 7, and the power curve test result of the zinc-air battery is shown in FIG. 8. As seen from FIGS. 7 and 8, when the Co atom-doped polyhedral MOFs material prepared in example 1 is used as a zinc-air battery electrode catalytic material, the power density reaches 260 mW/cm2. The current density at 1V reaches 183 mA/cm2The invention shows more excellent electrocatalysis performance than commercial 40% Pt/C, and provides good prospect for applying non-noble metal to zinc-air batteries.
The protective scope of the present invention is not limited to the above-described embodiments, and it is apparent that various modifications and variations can be made to the present invention by those skilled in the art without departing from the scope and spirit of the present invention. It is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims (10)

1. A preparation method of a Co atom-doped polyhedral MOFs material is characterized by comprising the following steps:
adding dimethyl imidazole, zinc salt and cobalt salt into the methanol solution to carry out precursor synthesis reaction, and separating and drying a reaction product to obtain precursor powder;
the dicyandiamide is roasted to prepare the g-C3N4Powder;
mixing said precursor powder with said g-C3N4Grinding and uniformly mixing the powder to obtain mixed powder, and calcining the mixed powder in an inert atmosphere;
and (3) pickling the product obtained after the calcination treatment with sulfuric acid, carrying out solid-liquid separation, and drying to obtain the Co atom doped polyhedral MOFs material.
2. The method for preparing the Co atom-doped polyhedral MOFs material according to claim 1, wherein in the precursor synthesis reaction, the molar ratio of zinc to cobalt in the zinc salt and the cobalt salt is (0-4): 1.
3. The preparation method of the Co atom-doped polyhedral MOFs material according to claim 1, wherein the reaction temperature of the precursor synthesis reaction is 20-30 ℃ and the reaction time is 22-25 h.
4. The preparation method of the Co atom-doped polyhedral MOFs material according to claim 1, wherein the calcination temperature of the calcination treatment is 520-560 ℃, and the calcination time is 2-4 h.
5. The method for preparing the Co atom-doped polyhedral MOFs material according to claim 4, wherein the temperature rise rate of the roasting treatment is 2-5 ℃/min.
6. The method for preparing the Co atom-doped polyhedral MOFs material according to claim 1, wherein the calcination temperature of the calcination treatment is 850-950 ℃, and the calcination time is 2-4 h.
7. The method for preparing the Co atom-doped polyhedral MOFs material according to claim 6, wherein the temperature rise rate of the calcination treatment is 2-5 ℃/min.
8. The method for preparing the Co atom-doped polyhedral MOFs material according to claim 1, wherein the concentration of the sulfuric acid is 0.5-1 mol/L.
9. The Co atom-doped polyhedral MOFs material prepared by the preparation method of the Co atom-doped polyhedral MOFs material of any one of claims 1 to 8, wherein the nitrogen content of the Co atom-doped polyhedral MOFs material is 2.86-8.34%, and the specific surface area of the Co atom-doped polyhedral MOFs material is 192-911 m2/g。
10. Use of the Co atom-doped polyhedral MOFs material of claim 9 in zinc-air battery catalytic materials.
CN202110683288.7A 2021-06-21 2021-06-21 Co atom-doped polyhedral MOFs material and preparation method and application thereof Pending CN113410481A (en)

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