CN112642457B - Hollow iron-based metal organic framework material, iron-doped carbon-nitrogen nano material and preparation method - Google Patents
Hollow iron-based metal organic framework material, iron-doped carbon-nitrogen nano material and preparation method Download PDFInfo
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- B01J27/24—Nitrogen compounds
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Abstract
The invention discloses a hollow iron-based metal organic framework material, an iron-doped carbon nitrogen nano material and a preparation method thereof, wherein the iron-based metal organic framework material has a hollow octahedral structure and a higher specific area, and the hollow octahedral structure can be reserved after the iron-based metal organic framework material is pyrolyzed, so that the conventional phenomenon that MOFs collapse after pyrolysis can not occur, and the pyrolyzed nano material, namely the iron-doped carbon nitrogen nano material still has a hollow structure and a higher specific surface area. In electrocatalytic application, the iron-doped carbon-nitrogen nano material shows half-wave potential E1/2The iron-doped carbon nitrogen nano material has the advantages of high current density, high cycling stability and the like, and the iron-doped carbon nitrogen nano material has high tolerance to methanol.
Description
Technical Field
The invention relates to a nano material, in particular to a hollow iron-based metal organic framework material, an iron-doped carbon-nitrogen nano material and a preparation method thereof.
Background
metal-Organic Framework Structures (MOFs) have attracted extensive research interest by the alternating construction of three-dimensionally tunable and highly porous structures of their metal ions and organic ligands. Based on these characteristics, the MOFs and their derived materials are widely used in the fields of gas adsorption, separation, catalysis, drug delivery, etc. Furthermore, by adjusting the size and morphology of the MOFs, catalytic performance can be enhanced and some unconventional functions can be obtained. For example, hollow MOFs and their derived materials exhibit better performance in drug delivery and selective catalysis. Compared with solid materials, the hollow structure nano material has the characteristics of low density, high surface area, material saving and the like, and can be widely applied to a plurality of important fields. Therefore, there is a need for rational design of MOFs synthesis processes that can control the structure and morphology of the final product.
In recent years, the synthesis of porous metal oxides, carbon/metal composites and monatomic materials using MOFs as precursors has been extensively studied. Although MOFs-derived materials show some advantages compared to conventional materials, the metal-doped nanomaterials obtained after pyrolysis of conventional MOFs exhibit half-wave potentials E in the field of electrocatalysis, in particular with respect to the application1/2Low current density and poor cycle stability.
Therefore, a half-wave potential E is developed1/2The metal-doped nano material with high current density and good cycling stability has great significance for the development of electrocatalysis.
Disclosure of Invention
The inventor of the invention finds out through research that: the doped nanomaterials obtained after thermal decomposition of conventional MOFs exhibit a half-wave potential E in the electrocatalytic field1/2Low current density, low cycling stability, and large relation with the change of the structure. Although efforts have been made to develop hollow MOFs, conventional hollow MOFs tend to have a problem of structural collapse and aggregation after thermal decomposition, so that the resulting doped nanomaterial after thermal decomposition hardly has a hollow structure in the precursor of the hollow MOFs, and thus reactants hardly reach the reaction sites, thereby making the electrocatalytic performance poor.
Based on the above findings, the present invention aims to provide a hollow iron-based metal organic framework material and an iron-doped carbon nitrogen nanomaterial, and a preparation method thereof, wherein the iron-based metal organic framework material has a hollow octahedral structure and a relatively high specific surface area, and moreover, after the iron-based metal organic framework material is pyrolyzed, the hollow octahedral structure can be retained without the conventional phenomenon that MOFs collapse after pyrolysis, so that the pyrolyzed nanomaterial, i.e., the iron-doped carbon nitrogen nanomaterial, still has a hollow structure and a relatively high specific surface area. In electrocatalytic application, the iron-doped carbon-nitrogen nano material shows half-wave potential E1/2Higher current density, good cycle stability, etcThe iron-doped carbon and nitrogen nano material has the advantages of high methanol tolerance.
In order to achieve the purpose, the first aspect of the invention provides an iron-based metal organic framework material, the particle size range of the iron-based metal organic framework material is 470-530nm, and the specific surface area of the iron-based metal organic framework material is 155-165m2(ii)/g; wherein the iron-based metal organic framework material has a hollow octahedral structure.
The second aspect of the invention provides a preparation method of an iron-based metal organic framework material, which comprises the step of heating and reacting Fe-MOFs and hexamethylenetetramine in a mass ratio of 1:1.5-2.5 in an organic solvent.
The third aspect of the invention provides an iron-doped carbon-nitrogen nano material, the particle size range of the iron-doped carbon-nitrogen nano material is 220-280nm, and the specific surface area is 175-195m2(ii)/g; wherein the iron-doped carbon nitrogen nano material has a hollow octahedral structure.
The fourth aspect of the invention provides a preparation method of an iron-doped carbon-nitrogen nano material, which comprises the following steps: (1) heating Fe-MOFs and hexamethylenetetramine in a mass ratio of 1:1.5-2.5 in an organic solvent for reaction to obtain an iron-based metal organic framework material; (2) and pyrolyzing the iron-based metal organic framework material in a nitrogen atmosphere.
The fifth aspect of the invention provides an iron-doped carbon nitrogen nano material, and the iron-doped carbon nitrogen nano material is prepared by the preparation method of the fourth aspect of the invention.
The inventor of the invention discovers through research that the iron-doped carbon nitrogen nanomaterial obtained by heating and reacting Fe-MOFs and hexamethylenetetramine in a mass ratio of 1:1.5-2.5 in an organic solvent has a hollow octahedral structure and a large specific surface area, and the iron-doped carbon nitrogen nanomaterial obtained after pyrolysis of the iron-based metal organic framework material still has a hollow octahedral structure and a large specific surface area, namely, even after pyrolysis, the hollow octahedral structure and the large specific surface area are still remained in a product after pyrolysis, so that the defect that the conventional MOFs collapse after pyrolysis is overcome. In the electrocatalytic reactionIn use, the iron-doped carbon-nitrogen nano material prepared by the invention shows half-wave potential E1/2The iron-doped carbon nitrogen nano material has the advantages of high current density, high cycling stability and the like, and the iron-doped carbon nitrogen nano material has high tolerance to methanol. The reason for this is probably that the iron-doped carbon nitrogen nano material obtained by the invention not only has a hollow octahedral structure and a larger specific surface area, but also introduces hexamethylene tetramine in the preparation process, and the hexamethylene tetramine further provides an N source after pyrolysis, so that the obtained iron-doped carbon nitrogen nano material has more active sites, thereby improving the half-wave potential E1/2Current density and cycling stability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
in FIG. 1, (a) and (b) are both high angle annular dark field scanning transmission electron microscope (HAADF-STEM) images of hollow Fe-MOFs of example 1, (c) EDX element mapping images of hollow octahedral shape Fe-MOFs: fe. O, N and C are the distributions of the respective corresponding elements.
FIG. 2 is a high angle annular dark field scanning transmission electron microscope (HAADF-STEM) image of o-Fe/NC in example 1.
FIG. 3 is a high angle annular dark field scanning transmission electron microscope (HAADF-STEM) image of Fe/NC in comparative example 1.
FIG. 4 is a graph (a) showing an X-ray powder diffraction (XRD) pattern of o-Fe/NC in example 1, (b) showing a Raman spectrum (Raman spectrum) pattern of o-Fe/NC in example 1, and (c) showing an N pattern of o-Fe/NC in example 12Adsorption and desorption curves (BET diagram).
FIG. 5(a) shows the saturated CO of o-Fe/NC and commercial Pt/C at 0.1 mol/L KOH in example 12ORR polarization curve in solution. (b) J at 0.85 volts for o-Fe/NC and Pt/CkAnd E1/2. (c) With or without 1.0 mol/l CH3CV diagram of o-Fe/NC in 0.1 mol/l potassium hydroxide at OH. (d) Is the ORR polarization curve of 1600 rpm and 5 mV/s for the o-Fe/NC electrolytic catalyst after the initial phase and 5000 potential cycles.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The inventor of the invention discovers through research that: the doped nanomaterials obtained after thermal decomposition of conventional MOFs exhibit a half-wave potential E in the electrocatalytic field1/2Low current density, low cycling stability, and large relation with the change of the structure. Although efforts have been made to develop hollow MOFs, conventional hollow MOFs tend to have a problem of structural collapse and aggregation after thermal decomposition, so that the resulting doped nanomaterial after thermal decomposition hardly has a hollow structure in the precursor of the hollow MOFs, and thus reactants hardly reach the reaction sites, thereby making the electrocatalytic performance poor.
Based on the above findings, the present invention aims to provide an iron-based metal organic framework material and an iron-doped carbon nitrogen nanomaterial, and a preparation method thereof, wherein the iron-based metal organic framework material has a hollow octahedral structure and a relatively high specific surface area, and moreover, after the iron-based metal organic framework material is pyrolyzed, the hollow octahedral structure can be retained without the conventional phenomenon that MOFs collapses after pyrolysis, so that the pyrolyzed nanomaterial, i.e., the iron-doped carbon nitrogen nanomaterial, still has a hollow structure and a relatively high specific surface areaAnd (4) accumulating. In electrocatalytic application, the iron-doped carbon-nitrogen nano material shows half-wave potential E1/2The iron-doped carbon nitrogen nano material has the advantages of high current density, high cycling stability and the like, and the iron-doped carbon nitrogen nano material has high tolerance to methanol.
The first aspect of the invention provides a hollow Fe-based metal organic framework material, the particle size range of the Fe-based metal organic framework material is 470-530nm, and the specific surface area is 155-165m2(ii)/g; wherein the iron-based metal organic framework material has a hollow structure. Even after the iron-based metal organic framework material is pyrolyzed, the hollow structure of the obtained iron-doped carbon nitrogen nano material can be reserved, and the phenomenon that the conventional MOFs collapse after pyrolysis can not occur. Preferably, the iron-based metal organic framework material has a hollow octahedral structure.
According to the invention, the pore diameter of the iron-based metal organic framework material is preferably 2.8-3.8 nm. In this preferred embodiment, the half-wave potential E of the resulting iron-doped carbon nitrogen nanomaterial can be further increased1/2Current density and cycling stability.
The second aspect of the invention provides a preparation method of an iron-based metal organic framework material, which comprises the step of heating and reacting Fe-MOFs and hexamethylenetetramine in a mass ratio of 1:1.5-2.5 in an organic solvent.
Even after the iron-based metal organic framework material is pyrolyzed, the hollow octahedral structure of the obtained iron-doped carbon nitrogen nanometer material can be reserved, and the phenomenon that the conventional MOFs collapse after pyrolysis can not occur. Moreover, in the preparation process, hexamethylenetetramine is introduced, and after pyrolysis, hexamethylenetetramine further provides an N source, so that the obtained iron-doped carbon-nitrogen nano material has more active sites, and the half-wave potential E is improved1/2Current density and cycling stability.
According to the invention, the mass ratio of Fe-MOFs to hexamethylenetetramine is preferably 1: 1.8-2.2; in this preferred embodiment, the half-wave potential E of the resulting iron-doped carbon nitrogen nanomaterial can be further increased1/2Current density ofAnd cycle stability.
According to the present invention, the conditions of the heating reaction can be adjusted within a wide range, and preferably, the conditions of the heating reaction include: the temperature is 150-190 ℃.
According to the present invention, the conditions of the heating reaction can be adjusted within a wide range, and preferably, the conditions of the heating reaction include: the time is 15-25 h.
According to the invention, Fe-MOFs can be obtained by conventional preparation methods, in order to further increase the half-wave potential E of the obtained iron-doped carbon nitrogen nano-material1/2Current density and cycling stability. Preferably, the Fe-MOFs are obtained by: dispersing ferric trichloride and terephthalic acid in a mass ratio of 1-2:1 in a mixed solvent of dimethylformamide and ethanol, reacting at 130-170 ℃ for 2-4h, and cleaning and drying to obtain the product.
According to the invention, the volume ratio of the dimethyl formamide to the ethanol is preferably 3-5: 1; in this preferred embodiment, the half-wave potential E of the resulting iron-doped carbon nitrogen nanomaterial can be further increased1/2Current density and cycling stability.
According to the invention, in order to further improve the half-wave potential E of the obtained iron-doped carbon-nitrogen nano material1/2Current density and circulation stability, and preferably, the mass concentration of ferric trichloride in the mixed solvent is 6-14 g/L.
The third aspect of the invention provides an iron-doped carbon-nitrogen nano material, the particle size range of the iron-doped carbon-nitrogen nano material is 220-280nm, and the specific surface area is 175-195m2(ii)/g; wherein the iron-doped carbon nitrogen nano material has a hollow structure. Thus, the iron-doped carbon nitrogen nano material can provide more reaction sites in electrocatalysis, so that the electrocatalysis activity is improved. Preferably, the iron-doped carbon nitrogen nanomaterial has a hollow octahedral structure.
According to the invention, preferably, the pore diameter of the iron-doped carbon nitrogen nano material is 2.5-4 nm; in this preferred embodiment, the iron-doped carbon nitrogen nanomaterial has more active sites, thereby further increasing the half-wave potentialE1/2Current density and cycling stability.
According to the invention, the iron-doped carbon-nitrogen nanomaterial is preferably detected by Raman spectroscopy at 1593.2cm-1And 1346.4cm-1Respectively show sp2Graphitic carbon G bands and sp3Representative peak of defective carbon D band.
According to the invention, it is further preferred that I of the D-band and G-bandD/IGThe ratio was 1.05.
The fourth aspect of the invention provides a preparation method of an iron-doped carbon-nitrogen nano material, which comprises the following steps: (1) heating Fe-MOFs and hexamethylenetetramine in a mass ratio of 1:1.5-2.5 in an organic solvent for reaction to obtain an iron-based metal organic framework material; (2) and pyrolyzing the iron-based metal organic framework material in a nitrogen atmosphere.
The inventor of the invention discovers through research that the iron-doped carbon nitrogen nanomaterial obtained by heating and reacting Fe-MOFs and hexamethylenetetramine in a mass ratio of 1:1.5-2.5 in an organic solvent has a hollow octahedral structure and a large specific surface area, and the iron-doped carbon nitrogen nanomaterial obtained after pyrolysis of the iron-based metal organic framework material still has a hollow octahedral structure and a large specific surface area, namely, even after pyrolysis, the hollow octahedral structure and the large specific surface area are still remained in a product after pyrolysis, so that the defect that the conventional MOFs collapse after pyrolysis is overcome. In the electrocatalysis application, the iron-doped carbon nitrogen nano material obtained by the invention shows half-wave potential E1/2The iron-doped carbon nitrogen nano material has the advantages of high current density, high cycling stability and the like, and the iron-doped carbon nitrogen nano material has high tolerance to methanol. The reason for this is probably that the iron-doped carbon nitrogen nano material obtained by the invention not only has a hollow octahedral structure and a larger specific surface area, but also introduces hexamethylene tetramine in the preparation process, and the hexamethylene tetramine further provides an N source after pyrolysis, so that the obtained iron-doped carbon nitrogen nano material has more active sites, thereby improving the half-wave potential E1/2Current density and cycling stability.
According to the invention, wherein the pyrolysis conditions comprise: the pyrolysis temperature is 800-1000 ℃; and/or the time is 2-4 h.
According to the present invention, preferably, the pyrolyzed product is subjected to a step of acid washing and drying. The purpose of the acid wash is to remove the reactive elemental iron.
According to the invention, the heating reaction conditions in the step (1) comprise: the temperature is 150-190 ℃; and/or the time is 15-25 h.
According to the invention, the mass ratio of Fe-MOFs to hexamethylenetetramine is preferably 1: 1.8-2.2; in this preferred embodiment, the half-wave potential E of the resulting iron-doped carbon nitrogen nanomaterial can be further increased1/2Current density and cycling stability.
According to the invention, in order to further improve the half-wave potential E of the obtained iron-doped carbon nitrogen nano material1/2Current density and cycle stability, preferably, the Fe-MOFs in step (1) is obtained by: dispersing ferric trichloride and terephthalic acid in a mass ratio of 1-2:1 in a mixed solvent of dimethylformamide and ethanol, reacting at 130-170 ℃ for 2-4h, and cleaning and drying to obtain the product.
According to the invention, in order to further improve the half-wave potential E of the obtained iron-doped carbon-nitrogen nano material1/2Current density and cycling stability, preferably the volume ratio of dimethylformamide to ethanol is 3-5: 1.
According to the invention, in order to further improve the half-wave potential E of the obtained iron-doped carbon-nitrogen nano material1/2Current density and circulation stability, and preferably, the mass concentration of ferric trichloride in the mixed solvent is 6-14 g/L.
In the fifth aspect of the invention, an iron-doped carbon nitrogen nano material is provided, and the iron-doped carbon nitrogen nano material is prepared by the preparation method in the fourth aspect of the invention.
The sixth aspect of the invention provides a method for preparing an iron-based metal organic framework material, wherein the iron-based metal organic framework material is prepared by the preparation method of the second aspect of the invention.
Even after the iron-based metal organic framework material is pyrolyzed, the hollow octahedral structure of the obtained iron-doped carbon nitrogen nanometer material can be reserved, and the phenomenon that the conventional MOFs collapse after pyrolysis can not occur. Moreover, in the preparation process, hexamethylenetetramine is introduced, and after pyrolysis, hexamethylenetetramine further provides an N source, so that the obtained iron-doped carbon-nitrogen nano material has more active sites, and the half-wave potential E is improved1/2Current density and cycling stability.
The present invention will be described in detail below by way of examples. Pt/C was purchased from Aladdin; the detection method of the specific surface area is N2The absorption and desorption method comprises the steps that a testing instrument is a physical adsorption instrument of ASAP 2460Version 3.01, and a detection method of pore size distribution is a BJH pore size distribution calculation model.
Example 1
(1) Dissolving ferric trichloride and terephthalic acid in a mass ratio of 3:2 in a mixed solvent of dimethylformamide and ethanol (in a volume ratio of 4:1), wherein the mass concentration of the ferric trichloride is 10 g/L, stirring at room temperature (25 ℃) for 60 minutes, and transferring the mixture into a reaction kettle. And (3) reacting for 3 hours in an oven at 150 ℃, cooling to room temperature (25 ℃), adding a proper amount of ethanol, and centrifuging and washing for multiple times to obtain Fe-MOFs.
(2) 100 mg of Fe-MOFs and 200 mg of Hexamethylenetetramine (HMT) were dissolved in 30 ml of ethanol, stirred for 30 minutes, transferred to a reaction kettle, placed in an oven, and reacted at 170 ℃ for 20 hours. And cooling to room temperature, adding a proper amount of ethanol, centrifuging and washing for many times to obtain the iron-based metal organic framework material (hollow Fe-MOFs for short).
In fig. 1, (a) and (b) are high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) images of the iron-based metal organic framework material, and (c) is an EDX element mapping image of the iron-based metal organic framework material. It can be seen from the graphs (a) and (b) that the iron-based metal organic framework material has a hollow octahedral structure. It can be seen from the graph (C) that the elements of Fe, O, N and C are uniformly distributed throughout the hollow iron-based metal organic framework material. N of hollow Fe-MOFs2The result of the adsorption and desorption curve shows that the hollow part is formedThe specific surface area of the Fe-MOFs is 158.85 square meters per gram, and the pore size distribution of the hollow Fe-MOFs shows that the pore size of the hollow Fe-MOFs is intensively distributed at 3.58 nm.
(3) And (3) pyrolyzing the iron-based metal organic framework material obtained in the step (2) at 900 ℃ in a nitrogen atmosphere for 3 hours, cooling to room temperature (25 ℃), pickling the sample with 1 mol/L hydrochloric acid, and stirring for 10 hours to remove unstable iron, thereby finally obtaining the iron-doped carbon nitrogen nano material (o-Fe/NC for short).
FIG. 2 is a high angle annular dark field scanning transmission electron microscope (HAADF-STEM) image of o-Fe/NC, from which it can be seen that Fe/NC presents a hollow octahedral structure.
Fig. 3 is a high angle annular dark field scanning transmission electron microscope (HAADF-STEM) image of the product of comparative example 1, and from fig. 3 it can be seen that the product of comparative example 1 exhibits not a hollow octahedral structure but a collapsed structure, which further demonstrates that the hollow structure can exist stably because it is protected by the ligand HMT.
FIG. 4 shows (a) an x-ray powder diffraction (XRD) pattern of o-Fe/NC and (b) a Raman spectrum (Raman spectrum) pattern of o-Fe/NC, from which two distinct peaks at 1593.2cm each are observed-1And 1346.4cm-1At, respectively correspond to sp2Graphitic carbon (G band) and sp3Representative peaks of defective carbons (D band), I in the D and G bandsD/IGThe ratio was 1.05. This indicates a high degree of defects in o-Fe/NC. (c) N being o-Fe/NC2The adsorption and desorption curves (BET diagram) show that the specific surface area of o-Fe/NC is 187.57 square meters per gram, and (d) is the pore size distribution diagram of o-Fe/NC, and the pore size concentration distribution of o-Fe/NC is 3.63 nanometers.
Comparative example 1
Iron-doped carbon nitrogen nanomaterials were prepared as in example 1 except that HTM was not added in preparation step (2) of example 1.
The obtained high-angle annular dark-field scanning transmission electron microscope image of the nano material is shown in the attached figure 3. The nanomaterial exhibited a collapsed morphology of the framework, and several metal aggregates were clearly observed. Compared with example 1, it is shown that the HTM ligand regulation strategy not only serves to stabilize the precursor structure, but also avoids metal aggregation during Fe-MOFs carbonization.
Example 2
A preparation method of an octahedral hollow iron-based metal organic framework material comprises the following steps:
(1) dissolving ferric trichloride and terephthalic acid in a mass ratio of 1:2 in a mixed solvent of dimethylformamide and ethanol in a volume ratio of 3:1, wherein the mass concentration of the ferric trichloride is 8 g/L, stirring at room temperature for 60 minutes, and transferring to a reaction kettle. And (3) reacting for 2 hours in an oven at 170 ℃, cooling to room temperature, adding a proper amount of ethanol, and centrifugally washing for multiple times to obtain Fe-MOFs.
(2) Dissolving Fe-MOFs and Hexamethylenetetramine (HMT) in 30 ml of ethanol according to the mass ratio of 1:1.8, stirring for 30 minutes, transferring the mixture into a reaction kettle, putting the reaction kettle into an oven, and reacting for 15 hours at 190 ℃. And cooling to room temperature, adding a proper amount of ethanol, and centrifuging and washing for multiple times to obtain the iron-based metal organic framework material.
(3) Pyrolyzing the iron-based metal organic framework material at 800 ℃ in a nitrogen atmosphere for 4 hours, cooling to room temperature, pickling a sample with 1 mol/L hydrochloric acid, and stirring for 10 hours to remove unstable iron, thereby finally obtaining the o-Fe/NC material.
The morphology of the sample obtained was essentially the same as in example 1.
Example 3
(1) Dissolving ferric trichloride and terephthalic acid in a mass ratio of 2:2 in a mixed solvent of dimethylformamide and ethanol in a volume ratio of 5:1, wherein the mass concentration of the ferric trichloride is 12 g/L, stirring at room temperature for 60 minutes, and transferring to a reaction kettle. And (3) reacting for 4 hours in an oven at 130 ℃, cooling to room temperature, adding a proper amount of ethanol, and centrifugally washing for multiple times to obtain Fe-MOFs.
(2) Dissolving Fe-MOFs and Hexamethylenetetramine (HMT) in 30 ml of ethanol in a mass ratio of 1:2.2, stirring for 30 minutes, transferring the mixture into a reaction kettle, putting the reaction kettle into an oven, and reacting for 25 hours at 150 ℃. And cooling to room temperature, adding a proper amount of ethanol, and centrifugally washing for multiple times to obtain the iron-based metal organic framework material.
(3) Pyrolyzing the iron-based metal organic framework material at 1000 ℃ in a nitrogen atmosphere for 2 hours, cooling to room temperature, pickling a sample with 1 mol/L hydrochloric acid, and stirring for 10 hours to remove unstable iron, thereby finally obtaining the o-Fe/NC material.
The morphology of the sample obtained was essentially the same as in example 1.
Example 4
Prepared according to the method of example 1, except that in step (2) the Fe-MOFs and Hexamethylenetetramine (HMT) are in a mass ratio of 1: 1.5.
Example 5
Prepared according to the method of example 1, except that in step (2) the Fe-MOFs and Hexamethylenetetramine (HMT) are in a mass ratio of 1: 2.5.
Detection example 1
The electrocatalytic ORR process is as follows:
the ORR performance of the catalysts (doped nanomaterials from examples and comparative examples) was determined in 0.1 mol/l potassium hydroxide electrolyte using a three electrode system in the CHI760E electrochemical workstation. 10 mg of the catalyst was dispersed in 2 ml of a mixture of ethanol (0.990 ml), water (0.990 ml) and Nafion solution (20. mu.l), and sonicated for 30 minutes to prepare a catalyst ink. Then 20 microliters of the catalyst suspension was dropped onto a fresh Gas Chromatography (GC) electrode. The substrate of the working electrode used a 5 mm diameter Rotating Disk Electrode (RDE). Graphite rods and silver/silver chloride electrodes were selected as counter and reference electrodes, respectively. Cyclic Voltammetry (CV) tests were performed in 0.1 mol/l potassium hydroxide solution saturated with oxygen, with a scan rate of 50 mv/sec. Linear Sweep Voltammetry (LSV) tests were performed by RDE testing (1600 rpm).
To further determine their durability, we performed durability tests in which the cells were continuously cycled between 0.6 and 1.0 volts (vs. rhe) in 0.1 moles/liter koh solution saturated with oxygen.
To further determine their durability, we performed durability tests in which the cells were continuously cycled between potentials of 0.6 to 1.0 volts (relative to a standard hydrogen electrode) in 0.1 mol/l potassium hydroxide solution saturated with oxygen. In addition, the inventive method is characterized in thatAnd (3) measuring the tolerance of the catalyst to methanol by adopting cyclic voltammetry: the catalyst was added to a 0.1 mol/l potassium hydroxide solution saturated with oxygen, and a 0.1 mol/l methanol solution was added or not added to the mixed solution, and the test was conducted in this control case. FIG. 5(a) shows the results of example 1 in O-Fe/NC and commercial Pt/C in O2ORR polarization curve in 0.1 mol/L KOH was saturated. The half-wave potentials and kinetic current densities of o-Fe/NC and commercial Pt/C were obtained from FIG. 5(a), and are summarized in FIG. 5 (b). Half-wave potential (E) of the o-Fe/NC1/2) At 0.883 volts, and a kinetic current density (J) at 0.85 volts (relative to a standard hydrogen electrode)k) E of 29.22 milliamperes per square centimeter versus commercial Pt/C1/2Values (0.851V vs. standard hydrogen electrode) and JkThe electrocatalytic performance of the o-Fe/NC was all superior (5.438 mA/cm), (Pt/C available from Aladdin, having the same ORR performance test procedure as in test example 1).
In addition, as shown in FIG. 5(c), when the stability of the catalyst was tested by adding methanol to the electrolyte, it was observed that the current density of o-Fe/NC decreased by less than 0.05 mA/cm, the current density remained over 98% of the original value, and the o-Fe/NC had good methanol tolerance. The current density of the other examples was maintained at 97% or more of the original value.
FIG. 5(d) is an ORR polarization curve of o-Fe/NC at 1600 rpm sweep speed and 5 mV/s before and after 5000 cycles. The current density of o-Fe/NC remained good during the continuous potential cycles, half-wave potential (E) after 5000 cycles1/2) Is less than 0.001 volts, indicating that o-Fe/NC has good durability. Other examples half-wave potential after 5000 cycles (E)1/2) Is less than 0.003 volts.
The specific surface area and electrocatalytic performance of the products of examples 2 to 5 were examined in the same manner as in example 1, and it was found that the specific surface area and electrocatalytic performance (half-wave potential and current density) of the o-Fe/NC materials of examples 2 to 3 were close to those of example 1, the o-Fe/NC materials of examples 4 and 5 were lower than those of examples 1 to 3, and the half-wave potential and current density were also lower than those of examples 1 to 3, but the o-Fe/NC materials of examples 4 and 5 were superior to commercial Pt/C in both half-wave potential and current density.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. A preparation method of a hollow iron-based metal organic framework material is characterized by comprising the steps of heating Fe-MOFs and hexamethylenetetramine in an organic solvent according to the mass ratio of 1:1.5-2.5 for reaction;
wherein the Fe-MOFs are obtained by the following steps: dispersing ferric trichloride and terephthalic acid in a mass ratio of 1-2:1 in a mixed solvent of dimethylformamide and ethanol, reacting at 130-170 ℃ for 2-4h, and cleaning and drying to obtain the product.
2. The production method according to claim 1, wherein the mass ratio of Fe-MOFs to hexamethylenetetramine is 1: 1.8-2.2.
3. The production method according to claim 2, wherein the conditions for heating the reaction include: the temperature is 150-190 ℃; and/or the time is 15-25 h.
4. The production method according to claim 1, wherein the volume ratio of dimethylformamide to ethanol is 3-5: 1.
5. The production method according to claim 1, wherein the mass concentration of ferric trichloride in the mixed solvent is 6 to 14 g/L.
6. A preparation method of an iron-doped carbon-nitrogen nano material is characterized by comprising the following steps:
(1) heating Fe-MOFs and hexamethylenetetramine in a mass ratio of 1:1.5-2.5 in an organic solvent for reaction to obtain an iron-based metal organic framework material;
(2) a step of pyrolyzing the iron-based metal organic framework material in a nitrogen atmosphere;
wherein the Fe-MOFs in the step (1) is obtained by the following steps: ferric trichloride and terephthalic acid with the mass ratio of 1-2:1 are dispersed in a mixed solvent of dimethylformamide and ethanol, react for 2-4h at the temperature of 130-170 ℃, and are obtained after cleaning and drying.
7. The production method according to claim 6, wherein the pyrolysis conditions include: the pyrolysis temperature is 800-1000 ℃; and/or the time is 2-4 h.
8. The method according to claim 7, wherein the product after pyrolysis is subjected to a step of acid washing and drying.
9. The production method according to claim 6 or 7, wherein the mass ratio of Fe-MOFs to hexamethylenetetramine is 1: 1.8-2.2.
10. The production method according to claim 9, wherein the conditions for the heating reaction in step (1) include: the temperature is 150 ℃ and 190 ℃; and/or the time is 15-25 h.
11. The production method according to claim 6, wherein the volume ratio of dimethylformamide to ethanol is 3-5: 1.
12. The production method according to claim 6, wherein the mass concentration of ferric trichloride in the mixed solvent is 6 to 14 g/L.
13. An iron-doped carbon nitrogen nanomaterial, characterized in that the iron-doped carbon nitrogen nanomaterial is prepared by the preparation method of claim 6 or 7 or 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092341A (en) * | 2018-08-08 | 2018-12-28 | 东华大学 | The nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated and preparation |
| CN110416548A (en) * | 2019-08-15 | 2019-11-05 | 合肥工业大学 | A kind of preparation method and applications of the two-dimensional structure of N doping porous carbon |
| KR20200099356A (en) * | 2019-02-14 | 2020-08-24 | 한국화학연구원 | Method for preparing hetero-metal ion-exchanged MOF and composition based on MOF for hetero-metal cation-exchange produced by post-synthetic modification used therein |
| CN111744521A (en) * | 2020-06-29 | 2020-10-09 | 华南理工大学 | Method for preparing cobaltosic oxide with different morphologies in recoverable mode by taking metal organic framework as precursor ligand and application of method |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101787190B1 (en) * | 2015-07-02 | 2017-10-18 | 한국과학기술원 | Gas sensor and member using porous metal oxide semiconductor composite nanofibers including nanoparticle catalyst functionalized by nano-catalyst included within metal-organic framework, and manufacturing method thereof |
| GB201515869D0 (en) * | 2015-09-08 | 2015-10-21 | Johnson Matthey Fuel Cells Ltd | Oxygen reduction reactor catalyst |
| CN107434815B (en) * | 2016-05-27 | 2020-01-10 | 北京化工大学 | Method for preparing multi-shell hollow structure metal organic framework material |
| CN107359338B (en) * | 2017-07-17 | 2020-02-21 | 吉林大学 | Cobalt oxide/carbon composite hollow nano-structure material with dodecahedron structure and application thereof in lithium battery cathode |
| CN109174147A (en) * | 2018-08-08 | 2019-01-11 | 东华大学 | The nitrogen-doped carbon nanocomposite of hollow Fe2O3 doping cobalt oxide nickel coated and preparation |
| CN109449451A (en) * | 2018-11-28 | 2019-03-08 | 上海电力学院 | One kind is by derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs and preparation method thereof |
| CN110776651B (en) * | 2019-11-13 | 2022-02-01 | 苏州大学 | Hollow nano material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092341A (en) * | 2018-08-08 | 2018-12-28 | 东华大学 | The nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated and preparation |
| KR20200099356A (en) * | 2019-02-14 | 2020-08-24 | 한국화학연구원 | Method for preparing hetero-metal ion-exchanged MOF and composition based on MOF for hetero-metal cation-exchange produced by post-synthetic modification used therein |
| CN110416548A (en) * | 2019-08-15 | 2019-11-05 | 合肥工业大学 | A kind of preparation method and applications of the two-dimensional structure of N doping porous carbon |
| CN111744521A (en) * | 2020-06-29 | 2020-10-09 | 华南理工大学 | Method for preparing cobaltosic oxide with different morphologies in recoverable mode by taking metal organic framework as precursor ligand and application of method |
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