CN114824327A - Iron-nitrogen double-doped carbon nanocomposite and preparation method thereof - Google Patents
Iron-nitrogen double-doped carbon nanocomposite and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an iron-nitrogen double-doped carbon nano composite material and a preparation method thereof, belonging to the technical field of nano composite material preparation. The method solves the technical problem that the structure collapse is easy to cause to influence the catalytic performance when the MOFs is adopted as a precursor to prepare the M/N/C-based ORR catalyst in the prior art. The preparation method comprises the following steps: (1) preparing a ferrous metal organic framework material Fe-ZIF-8; (2) Fe-ZIF-8, polyacrylonitrile and melamine are used for preparing the iron-nitrogen double-doped carbon nano composite material (Fe-CSFHs) by an electrostatic spinning method. Compared with the Pt/C catalyst sold in the market, the Fe-CSFHS composite material prepared by the preparation method disclosed by the invention has the advantages of excellent catalytic performance and durability, cheap and easily-obtained raw materials, simple process and easiness in industrial production.
Description
Technical Field
The invention belongs to the technical field of nano composite material preparation, and particularly relates to an iron-nitrogen double-doped carbon nano composite material and a preparation method thereof.
Background
In order to accelerate the wide application of sustainable energy technologies, researchers have focused on the development and utilization of energy conversion technologies such as fuel cells and metal-air batteries. However, the overall performance of the cathodes of fuel cells and metal-air batteries is seriously hindered due to slow kinetics, and the development of efficient, stable and low-cost electrocatalysts to reduce the overpotential of the oxidation-reduction reaction (ORR) is urgently needed.
Currently, commercial Pt/C is still the most effective catalyst for ORR. However, the development and wide application of the Pt/C catalyst are severely limited due to the problems of limited reserves of Pt on the earth, high price, poor toxicity resistance and the like. Therefore, researchers have developed inexpensive non-noble metal catalysts as alternatives, such as metal-free heteroatom-doped carbon materials, transition metal-doped carbon composites (M/N/C, M ═ Fe, Co, etc.), and carbon coordinated metals supported on nitrogen-deficient carbon nanomaterials (l.chen, x.xu, w.yang, j.jia, Chinese chem.lett.2020,31, 626-. Among them, the ORR catalyst based on M/N/C shows high catalytic activity and good stability, and is considered as a promising non-noble metal catalyst, and the common synthesis method is to combine metal source, nitrogen and carbon by means of pyrolysis, so that it is difficult to make the active sites uniformly distributed; or the metal is combined with Metal Organic Frameworks (MOFs) to prepare the composite material through pyrolysis, but the temperature is too high, so that the structure is easy to collapse, the surface area is reduced, the mass transmission is limited, and the activity is influenced.
Disclosure of Invention
The invention provides an iron-nitrogen double-doped carbon nano composite material and a preparation method thereof, aiming at solving the technical problem that the catalytic performance of an M/N/C-based ORR catalyst is influenced by structural collapse easily caused when MOFs are adopted as precursors in the prior art. The MOFs with intrinsic M-N sites has larger specific surface area and abundant pore structures, and is an effective precursor for preparing the ORR catalyst.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a preparation method of an iron-nitrogen double-doped carbon nano composite material, which comprises the following steps:
(1) preparation of Fe-ZIF-8 metal organic frame material containing iron
Mixing zinc nitrate hexahydrate, dimethyl imidazole, ferric acetylacetonate and an organic solvent, stirring, carrying out hydrothermal reaction, washing, centrifuging and drying to obtain Fe-ZIF-8;
(2) preparing the iron-nitrogen double-doped carbon nano composite material:
adding Fe-ZIF-8, Polyacrylonitrile (PAN) and melamine into an organic solvent, stirring, carrying out electrostatic spinning, drying and annealing treatment to obtain the iron-nitrogen double-doped carbon nano composite material (marked as Fe-CSFHs).
Preferably, in the step (1), the organic solvent is CH 3 OH, the volume is 45 mL; the mass ratio of zinc nitrate hexahydrate, dimethyl imidazole and ferric acetylacetonate is 1.190: 1.314: 0.141.
preferably, in the step (1), the hydrothermal reaction is carried out at 120 ℃ for 4 h.
Preferably, in the step (1), the drying temperature is 60-80 ℃ and the time is 12 h.
Preferably, in the step (2), the organic solvent is N, N-Dimethylformamide (DMF) and the volume is 6 mL; the mass ratio of Fe-ZIF-8 to PAN is 1.8: 1; the addition amount of melamine is 0.2-0.8 g.
Further preferably, in the step (2), the addition amount of melamine is 0.8 g.
Preferably, in the step (2), the electrostatic spinning voltage is 15kV, and the gel pushing speed is 0.6 mL/h.
Preferably, in the step (2), the annealing treatment is: the pyrolysis temperature is kept at 240 ℃ for 1-2h, then the temperature is raised to 800-.
Further preferably, in the step (2), the annealing treatment is: n is a radical of 2 Keeping at 240 deg.C for 2h under atmosphere, heating to 900 deg.C, calcining for 3h at a heating rate of 3 deg.C/min -1 。
The invention also provides the iron-nitrogen double-doped carbon nano composite material prepared by the preparation method.
The invention has the beneficial effects that:
according to the preparation method of the iron-nitrogen double-doped carbon nano composite material, the Fe-MOFs is stringed by using an electrostatic spinning technology, so that the Fe-MOFs can be prevented from collapsing when being heated; meanwhile, the introduction of the nano-fiber is beneficial to forming a three-dimensional structure, increasing the active area of the structure and providing more active sites, and the content of N can be increased by adding melamine so as to improve the active sites of Fe-N; and the addition of the melamine can make the diameter of the fiber smaller, and obviously improve the performance of the catalyst, such as the activity and durability of the catalyst. Compared with the Pt/C catalyst sold in the market, the Fe-CSFHS material of the invention has higher ORR activity, and the raw materials are cheap and easy to obtain, the process is simple, and the industrial production is easy to realize.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a transmission electron micrograph of Fe-ZIF-8 prepared in example 1;
FIG. 2 is a transmission electron micrograph of 0.8g-Fe-CSFHS-900 catalyst prepared in example 1;
FIG. 3 is a graph comparing the ORR performance of the catalysts prepared in examples 1-5 with that of Pt/C;
FIG. 4 is a graph comparing the ORR performance of the catalysts prepared in example 1 and comparative examples 1-2, and Pt/C catalysts;
FIG. 5 is a graph comparing the durability of the catalyst prepared in example 1 with that of the Pt/C catalyst.
Detailed Description
Example 1
The preparation method of the iron-nitrogen double-doped carbon nano composite material comprises the following steps:
(1) and (3) synthesizing Fe-ZIF-8:
1.314g of dimethylimidazole were dissolved in 15mL of CH 3 In OH, 1.190g Zn (NO) was added 3 ) 2 ·6H 2 O and 0.141g of iron acetylacetonate dissolved in 30mL of CH 3 And (3) performing ultrasonic treatment on OH for 5min respectively, mixing the OH and the water uniformly, placing a magnetic rotator, stirring for 1h, transferring to a hydrothermal reaction kettle, placing in an oven, and keeping for 4h at 120 ℃. And after cooling to room temperature, washing with methanol for multiple times, centrifuging, drying for 12 hours in a vacuum drying oven at 60 ℃, and grinding the light yellow powder by using a mortar to obtain light yellow Fe-ZIF-8.
(2) Preparation of 0.8 g-Fe-CSFHS-900:
1.340g of Fe-ZIF-8 was dissolved in 3mL of DMF by sonication for 60min, 0.8g of melamine was added, and 0.7776g of PAN was dissolved in 3mL of DMF by sonication for 30 min. And mixing and stirring the two for 32h, transferring the obtained electrospinning precursor solution into a needle cylinder provided with a 7' needle head for electrospinning, setting the voltage to be 15kV, fixing the distance between a collecting plate and the needle head to be 13cm, and setting the flow rate to be 0.6mL/h, thus preparing the Fe-ZIF-8@ PAN fiber. The prepared Fe-ZIF-8@ PAN fiber is firstly dried in an oven at 120 ℃ for 2 hours and then placed in a tube furnace N 2 Treating at 240 deg.C for 2h in atmosphere, heating to 900 deg.C, calcining for 3h at a heating rate of 3 deg.C/min -1 . The resulting target catalyst was named 0.8g-Fe-CSFHS-900 (where 0.8g represents the melamine addition, 900 is the final calcination temperature).
The transmission electron microscope image of FIG. 1 shows that the prepared Fe-ZIF-8 material is a uniformly dispersed metal organic framework material, and the transmission electron microscope image of FIG. 2 shows that after calcination at 900 ℃, the obtained 0.8g-Fe-CSFHS-900 is a beaded nanocomposite material which is relatively uniformly distributed and has no obvious agglomerated parts.
Example 2
The embodiment of the preparation method of the iron-nitrogen double-doped carbon nanocomposite material is different from the embodiment 1 only in that the addition amount of melamine is 0.4g, and the obtained target catalyst is named as 0.4 g-Fe-CSFHS-900.
Example 3
The embodiment of the preparation method of the iron-nitrogen double-doped carbon nanocomposite material is different from the embodiment 1 only in that the addition amount of melamine is 0.6g, and the obtained target catalyst is named as 0.6 g-Fe-CSFHS-900.
Example 4
An example of the preparation method of the iron-nitrogen double-doped carbon nanocomposite material of the invention is different from the example 1 only in that the pyrolysis calcination temperature is 1000 ℃, and the obtained target catalyst is named as 0.8 g-Fe-CSFHS-1000.
Example 5
An example of the preparation method of the iron-nitrogen double-doped carbon nanocomposite material of the invention is different from the example 1 only in that the pyrolysis calcination temperature is 800 ℃, and the obtained target catalyst is named as 0.8 g-Fe-CSFHS-800.
Comparative example 1
This comparative example provides a method of preparing a catalyst. According to the preparation method of the catalyst in the comparative example, Fe-ZIF-8 is not added, PAN is dissolved in DMF to prepare an electrospinning precursor solution with the mass fraction of 9%, the obtained electrospinning precursor solution is transferred into a needle cylinder provided with a 7' needle head to be electrospun, the voltage is set to be 15kV, the distance between a collecting plate and the needle head is fixed to be 13cm, the flow rate is 0.6mL/h, and the PAN fiber is prepared. Drying the prepared PAN fiber in an oven at 120 ℃ for 2h, and then placing the PAN fiber in a tube furnace for N 2 Treating at 240 deg.C for 2h in atmosphere, heating to 900 deg.C, calcining for 3h at a heating rate of 3 deg.C/min -1 . The catalyst obtained was named NC.
Comparative example 2
This comparative example provides a method of preparing a catalyst. The preparation method of the catalyst of the comparative example does not add melamine spinning, other steps are synthesized by the same steps as 0.8g of-Fe-CSFHs-900, and the obtained target catalyst is named as Fe-CSFHs.
Example of effects: electrochemical testing
The catalysts prepared in examples 1-5, the catalysts prepared in comparative examples 1-2 and the commercial Pt/C catalyst were electrochemically tested on an electrochemical workstation, respectively. As shown in FIG. 3, the ORR activity of the catalyst of example 1 in 0.10M KOH solution saturated with oxygen was more excellent than those of the catalysts of examples 2 to 5, and the initial potential (E) of the catalyst of example 1 was onset ) And half-wave potential (E) 1/2 ) 0.97 and 0.87V, respectively, were measured, more positive than the potential of commercial Pt/C catalysts (0.96 and 0.81V). This is a good indication that the example 1 catalyst has a favorable kinetic process comparable to commercial Pt/C catalysts.
As shown in FIG. 4, the activity of the catalyst of example 1 (E) onset ＝0.97V，E 1/2 0.87V) is much greater than the catalyst of comparative example 1 (E) onset ＝0.72V，E 1/2 0.68V), comparative example2 catalyst (E) onset ＝0.87V，E 1/2 0.81V), with a more positive half-wave potential and a smaller limiting current, indicating that the catalyst of example 1 has a more excellent ORR activity.
As shown in the chronoamperometric curve of fig. 5, the current density of the catalyst of example i can be maintained at 97.6% after the test of 20000s, while the current density of the Pt/C catalyst is maintained at only 85.9%, so the catalyst of example 1 exhibits good stability.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the iron-nitrogen double-doped carbon nano composite material is characterized by comprising the following steps of:
(1) preparation of Fe-ZIF-8 metal organic frame material containing iron
Mixing zinc nitrate hexahydrate, dimethyl imidazole, ferric acetylacetonate and an organic solvent, stirring, carrying out hydrothermal reaction, washing, centrifuging and drying to obtain Fe-ZIF-8;
(2) synthesis of iron-nitrogen double-doped carbon nano composite material
Adding Fe-ZIF-8, polyacrylonitrile and melamine into an organic solvent, stirring, carrying out electrostatic spinning, drying and annealing treatment to obtain the iron-nitrogen double-doped carbon nano composite material.
2. The method according to claim 1, wherein the organic solvent used in the step (1) is CH 3 OH, the volume is 45 mL; the mass ratio of zinc nitrate hexahydrate, dimethyl imidazole and ferric acetylacetonate is 1.190: 1.314: 0.141.
3. the method according to claim 1, wherein the hydrothermal reaction is carried out at 120 ℃ for 4 hours in the step (1).
4. The method according to claim 1, wherein the drying temperature in step (1) is 60-80 ℃ and the time is 12 hours.
5. The preparation method according to claim 1, wherein in the step (2), the organic solvent is N, N-dimethylformamide and the volume is 6 mL; the mass ratio of Fe-ZIF-8 to polyacrylonitrile is 1.8: 1; the addition amount of melamine is 0.2-0.8 g.
6. The production method according to claim 5, wherein in the step (2), the melamine is added in an amount of 0.8 g.
7. The preparation method according to claim 1, wherein in the step (2), the electrospinning voltage is 15kV, and the gel-pushing speed is 0.6 mL/h.
8. The method of claim 1, wherein the annealing process is: the pyrolysis temperature is kept at 240 ℃ for 1-2h, then the temperature is raised to 800-.
9. The manufacturing method according to claim 8, wherein in the step (2), the annealing treatment is: n is a radical of 2 Keeping at 240 deg.C for 2h under atmosphere, heating to 900 deg.C, calcining for 3h at a heating rate of 3 deg.C/min -1 。
10. An iron-nitrogen double-doped carbon nanocomposite material prepared by the preparation method of any one of claims 1 to 9.
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| CN116364960A (en) * | 2023-03-24 | 2023-06-30 | 常州大学 | ZIF-8/lignin-based iron-nitrogen-sulfur co-doped porous carbon material and preparation method and application thereof |
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