CN112310422B - Iron-nitrogen-doped hollow porous carbon material and preparation method thereof - Google Patents
Iron-nitrogen-doped hollow porous carbon material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an iron-nitrogen doped hollow porous carbon material and a preparation method thereof, and relates to a synthesis technology of a porous material. The preparation method comprises the following steps: (1) SiO22Synthesizing a ball; (2) polyelectrolyte-modified SiO2Preparing; (3) iron-doped ZIF-8 coated polyelectrolyte-modified SiO2Preparing a composite material; (4) and preparing the iron-nitrogen doped hollow porous carbon material. The iron-nitrogen doped hollow porous carbon material prepared by the preparation method has uniform size, good ORR catalytic activity and stability, and lower price compared with the traditional Pt/C catalyst.
Description
Technical Field
The invention relates to a synthesis technology of a porous material, in particular to an iron-nitrogen doped hollow porous carbon material and a preparation method thereof.
Background
The fuel cell is a representative of an energy conversion device, can directly convert chemical energy into electric energy, and becomes a core technology for solving the problems of energy crisis, environmental pollution and the like at present due to the characteristics of high energy conversion rate, small pollution, portability and the like. However, the cathode Oxygen Reduction Reaction (ORR) kinetics are slow, which limits the commercial application of fuel cells. The electrocatalyst with excellent performance can accelerate the electrochemical reaction kinetics of the fuel cell electrode-electrolyte interface, improve the performance of the fuel cell and prolong the service life of the fuel cell. Therefore, the research on the ORR electrocatalyst of the fuel cell has been an important matter for the research and invention of scientists.
In view of the increasing environmental pollution and the demand for clean energy devices such as fuel cells and metal-air batteries, the development of highly efficient and stable catalysts to reduce the overpotential of ORR is urgently required. To date, commercial Pt/C remains the most effective catalyst for ORR and is widely used in commercial fuel cells. However, the inevitable disadvantages of low reserves, high price, easy aggregation, etc. severely limit the large-scale commercial application of Pt/C based fuel cells. The most important task at present is to design inexpensive non-noble metal ORR catalysts with excellent activity and stability.
Porous carbon materials are promising carbon materials, and have attracted great interest due to their high electron transport ability, large specific surface area, and flexibility in shape and structure. The synthesis methods of porous carbon materials commonly used are classified into a template method and a non-template method. Among them, the template method is the most used method, and the template method is a commonly used method for efficiently preparing a porous carbon catalyst. The template method is classified into a hard template method and a soft template method according to the physicochemical properties of the selected template, for example, SiO2And metal oxides are typical of hard templates, while surfactants such as Pluronic P123 and Pluronic F127 may be used as typical soft templates. The large pore structure created by the removal of the template may maximize exposure of the reaction centers and facilitate mass transport during ORR.
Metal Organic Frameworks (MOFs) are crystalline materials formed by the coordination bonding of metal ions or metal clusters with rigid organic ligands and having an infinite network structure, consisting of two inorganic and organic moieties.
Metal Organic Frameworks (MOFs) with intrinsic M-N sites have large specific surface area and abundant pore structure, and are effective precursors for preparing ORR catalysts. However, poor electrical conductivity is a fatal disadvantage, which severely restricts the application of MOFs in the field of electrocatalysis.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an ORR (oxygen radical reduction) efficient and stable iron-nitrogen doped hollow porous carbon material and a preparation method thereof. Compared with the traditional Pt/C catalyst, the catalyst is also lower in price.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of an iron-nitrogen doped hollow porous carbon material comprises the following steps:
(1) synthesis of silica spheres: mixing ethyl orthosilicate, ethanol, ammonia water and deionized water, stirring, centrifuging, washing and drying to obtain silicon dioxide spheres;
(2) polyelectrolyte-modified SiO2(PP-SiO2) The preparation of (1): adding the silica spheres into a poly (diallyldimethylammonium chloride) (PDDA) solution, stirring, centrifuging, and washing to obtain PDDA modified SiO2(P-SiO2) (ii) a Then adding P-SiO2Adding into sodium polystyrene sulfonate (PSS) solution, stirring, centrifuging to obtain polyelectrolyte-modified SiO2(PP-SiO2)；
The mass fraction of the poly (diallyldimethylammonium chloride) in the poly (diallyldimethylammonium chloride) solution is 0.8-1.2%, and the ratio of the mass of the silicon dioxide spheres to the volume of the poly (diallyldimethylammonium chloride) solution is 3 (70-90) g/mL; the mass fraction of the sodium polystyrene sulfonate in the sodium polystyrene sulfonate solution is 0.8-1.2%;
(3) iron-doped ZIF-8 coated PP-SiO2Composite material (PP-SiO)2@ ZIF-8-Fe): dissolving 2-methylimidazole in an organic solvent to obtain a 2-methylimidazole solution; then six willZinc nitrate, PP-SiO2Dissolving ferric nitrate nonahydrate in an organic solvent to obtain a mixed solution A; dripping the 2-methylimidazole solution into the mixed solution A, stirring, aging, centrifuging, collecting solids, and finally washing and drying to obtain the PP-SiO2@ZIF-8-Fe；
(4) Preparation of iron-nitrogen doped hollow porous carbon materials (Fe/N-HPCs): and (4) calcining the composite material obtained in the step (3) under nitrogen at the temperature of 800-1000 ℃ for 1.5-2.5h, cooling to 25-30 ℃ after calcination, carrying out acid washing to remove the silicon dioxide template, washing and drying to obtain the iron-nitrogen doped hollow porous carbon material.
Preferably, in the step (1), the volume ratio of the tetraethoxysilane, the ethanol, the ammonia water and the deionized water is as follows: ethyl orthosilicate: ethanol: ammonia water: deionized water ═ (0.5-0.7): (13-17): (0.5-0.9): (3-7).
In the step (1), the volume ratio of the ethyl orthosilicate, the ethanol, the ammonia water and the deionized water is as follows: ethyl orthosilicate: ethanol: ammonia water: deionized water 0.6: 15: 0.7: 5.
preferably, in the step (2), when the mass fraction of the poly (diallyldimethylammonium chloride) in the poly (diallyldimethylammonium chloride) solution is 1%, the ratio of the mass of the silica spheres to the volume of the poly (diallyldimethylammonium chloride) solution is: 3:80 g/mL; in the sodium polystyrene sulfonate solution, when the mass fraction of the sodium polystyrene sulfonate is 1%, the SiO is2The ratio of the mass of (2) to the volume of the sodium polystyrene sulfonate is 3:80 g/mL.
Preferably, in the step (3), zinc nitrate hexahydrate and polyelectrolyte-modified SiO2The mass ratio of ferric nitrate nonahydrate to 2-methylimidazole is as follows: zinc nitrate hexahydrate: polyelectrolyte-modified SiO2: ferric nitrate nonahydrate: 2-methylimidazole ═ (105-: (180-220): (5-30): (140-260); the stirring time is 10-14h, and the aging time is 10-14 h.
Preferably, in the step (3), zinc nitrate hexahydrate and polyelectrolyte-modified SiO2The mass ratio of ferric nitrate nonahydrate to 2-methylimidazole is as follows: zinc nitrate hexahydrate:polyelectrolyte-modified SiO2: ferric nitrate nonahydrate: 2-methylimidazole ═ 150: 200: 5: 200 of a carrier; the time required for stirring is 12h, and the time required for aging is 12 h.
Preferably, in the step (4), the acid cleaning is performed by hydrofluoric acid, and the mass fraction of HF in the hydrofluoric acid is 4-6%.
Meanwhile, the invention discloses the iron-nitrogen doped hollow porous carbon material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that: the invention discloses a preparation method of an iron-nitrogen doped hollow porous carbon material, the carbon material prepared by the method has uniform size, and the introduction of iron atoms and nitrogen atoms into the porous carbon material not only increases the density of active sites of a catalyst, but also enhances the conductivity and stability of the catalyst, thereby obviously improving the catalytic performance and durability of the catalyst.
Drawings
FIG. 1 is SiO prepared in example 12Transmission electron microscopy of the ball;
FIG. 2 is the Fe-doped ZIF-8 coated polyelectrolyte-modified SiO prepared in example 12Transmission electron micrographs of the composite;
FIG. 3 is a transmission electron microscope image of an iron-nitrogen doped hollow porous carbon material prepared in example 1;
FIG. 4 is a graph of ORR polarization curves for examples 1-6 and comparative examples 1-2;
FIG. 5 is a graph of i-t curves for example 1 and Pt/C.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
In an embodiment of the iron-nitrogen-doped hollow porous carbon material of the present invention, a preparation method of the iron-nitrogen-doped hollow porous carbon material includes the following steps:
(1)SiO2synthesis of the ball: mixing 0.6mL of ethyl orthosilicate, 15mL of ethanol and 0.7mL of ethanol in mass percentMixing 25-28% ammonia water and 5mL deionized water, stirring for 10h, centrifuging at 8000rpm for 3min, washing with ethanol for 3 times, drying in vacuum drying oven for 12h to obtain the SiO2A ball;
(2)PP-SiO2the preparation of (1): 3g of SiO2Adding the ball into 80mL of PDDA solution with the mass fraction of 1%, stirring for 1h, centrifuging, and washing to obtain P-SiO2(ii) a Then the prepared P-SiO2Adding 80mL of PSS solution with the mass fraction of 1% of PSS, stirring for 1h, centrifuging and washing to obtain the PP-SiO2；
(3)PP-SiO2Preparation of @ ZIF-8-Fe: dissolving 200mg of 2-methylimidazole in 10mL of methanol to obtain a 2-methylimidazole solution; then 150mg of zinc nitrate hexahydrate and 200mg of PP-SiO2And 5mg of ferric nitrate nonahydrate are dissolved in 20mL of methanol to obtain a mixed solution A; dropwise adding the 2-methylimidazole solution into the mixed solution A, stirring for 12h, aging, standing for 12h, centrifuging at the rotating speed of 6000rpm, collecting solids, washing for 3 times by using methanol, and drying at 60 ℃ for 12h to obtain the PP-SiO2@ZIF-8-Fe；
(4) Preparation of Fe/N-HPCs: subjecting the PP-SiO of step (3) to2And @ ZIF-8-Fe is calcined under nitrogen, the calcining temperature is 900 ℃, the calcining time is 2 hours, the calcination is cooled to room temperature after the calcination is finished, then hydrofluoric acid with the HF mass fraction of 5% is used for soaking for 24 hours, a silicon dioxide template is removed, the washing is carried out for 3 times by using deionized water, and the drying is carried out in a vacuum drying oven for 12 hours, so that the Fe/N-HPCs are obtained.
Example 2
In an embodiment of the iron-nitrogen-doped hollow porous carbon material of the present invention, the preparation method of the iron-nitrogen-doped hollow porous carbon material is the same as that in embodiment 1 except that the content of ferric nitrate nonahydrate is 10 mg.
Example 3
In an embodiment of the iron-nitrogen-doped hollow porous carbon material according to the present invention, in the preparation method of the iron-nitrogen-doped hollow porous carbon material according to the embodiment, the content of iron nitrate nonahydrate is 20mg, the usage amount of the PDDA solution is 90mL, the mass fraction of PDDA in the PDDA solution is 0.8%, the usage amount of the PSS solution is 90mL, the mass fraction of PSS in the PSS solution is 0.8%, and the remaining preparation steps are the same as those in embodiment 1.
Example 4
In an embodiment of the iron-nitrogen-doped hollow porous carbon material according to the present invention, in the preparation method of the iron-nitrogen-doped hollow porous carbon material according to the embodiment, the content of iron nitrate nonahydrate is 30mg, the usage amount of the PDDA solution is 70mL, the mass fraction of PDDA in the PDDA solution is 1.2%, the usage amount of the PSS solution is 70mL, the mass fraction of PSS in the PSS solution is 1.2%, and the remaining preparation steps are the same as those in embodiment 1.
Example 5
In an embodiment of the iron-nitrogen-doped hollow porous carbon material of the present invention, the preparation method of the iron-nitrogen-doped hollow porous carbon material described in this embodiment is the same as that in embodiment 1 except that, in step (3), the mass of zinc nitrate hexahydrate is 105mg, and the mass of 2-methylimidazole is 140 mg.
Example 6
In an embodiment of the iron-nitrogen-doped hollow porous carbon material of the present invention, a preparation method of the iron-nitrogen-doped hollow porous carbon material described in this embodiment is the same as that of embodiment 1 except that the mass of zinc nitrate hexahydrate in step (3) is 195mg and the mass of 2-methylimidazole is 260 mg.
Comparative example 1
An iron-nitrogen doped hollow porous carbon material was prepared according to the method of this comparative example using the same procedures as in example 1 except that iron nitrate nonahydrate was replaced with ferrous sulfate heptahydrate.
Comparative example 2
An iron-nitrogen doped hollow porous carbon material was prepared according to the same method as in example 1, except that iron nitrate nonahydrate was replaced with iron acetylacetonate.
1) Topography characterization
FIG. 1 shows SiO prepared in example 1 of the present invention2Transmission electron micrograph of ball1, SiO2The balls are very regular in shape and relatively uniform in size. FIG. 2 is the Fe-doped ZIF-8 coated polyelectrolyte-modified SiO prepared in example 12The transmission electron microscope picture of the composite material can be seen from figure 2, the edge of the particle is in a burr shape, which shows that organic matter is coated on SiO2The surface of the ball. FIG. 3 is a transmission electron micrograph of an iron-nitrogen doped hollow porous carbon material prepared in example 1, from which it can be seen that SiO is etched away with hydrofluoric acid2Hollow Fe-CN spheres with a shell of about 10nm were obtained.
2) Performance characterization
FIG. 4 is a graph showing the polarization curves of the catalysts prepared in examples 1 to 6 and comparative examples 1 to 2, and it can be seen from the graphs that the ORR activity (E) of example 1 is measured in a 0.10M KOH solution saturated with oxygenonset＝0.96V,E 1/20.86V) greater than commercial Pt/C (E)onset＝0.96V,E 1/20.81V) with better peak potential and peak current density. In addition, other examples also have more positive half-wave potential than the comparative example, indicating that the catalyst prepared by the preparation method disclosed in the present invention has more excellent ORR activity.
To further evaluate the stability of the material, we performed chronoamperometric curve measurements on the catalyst of example 1 and on a commercial Pt/C (fig. 5). As shown in FIG. 5, after 20000s measurement, the current of the target catalyst reached 95.8%, while the current of the commercial Pt/C reached 78.3%, and the stability of the target catalyst was much higher than that of the commercial Pt/C as shown by comparison.
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 has been 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 (7)
1. A preparation method of an iron-nitrogen doped hollow porous carbon material is characterized by comprising the following steps:
(1)SiO2synthesis of the ball: mixing ethyl orthosilicate, ethanol, ammonia water and deionized water, stirring, centrifuging, washing and drying to obtain SiO2A ball;
(2) polyelectrolyte-modified SiO2The preparation of (1): mixing SiO2Adding the balls into a poly (diallyldimethylammonium chloride) solution, stirring, centrifuging, and washing to obtain the SiO modified by poly (diallyldimethylammonium chloride)2(ii) a SiO modified by polydiallyl dimethyl ammonium chloride2Adding into sodium polystyrene sulfonate solution, stirring, centrifuging to obtain polyelectrolyte-modified SiO2；
Wherein in the poly diallyl dimethyl ammonium chloride solution, the mass fraction of poly diallyl dimethyl ammonium chloride is 0.8-1.2%; the SiO2The ratio of the mass of the ball to the volume of the poly (diallyldimethylammonium chloride) solution is 3 (70-90) g/mL; in the sodium polystyrene sulfonate solution, the mass fraction of the sodium polystyrene sulfonate is 0.8-1.2%;
(3) iron-doped ZIF-8 coated polyelectrolyte-modified SiO2Preparing a composite material: dissolving 2-methylimidazole in an organic solvent to obtain a 2-methylimidazole solution; then, zinc nitrate hexahydrate and polyelectrolyte modified SiO2Dissolving ferric nitrate nonahydrate in an organic solvent to obtain a mixed solution A; dropwise adding the 2-methylimidazole solution into the mixed solution A, stirring, aging, centrifuging, collecting solids, washing and drying to obtain the iron-doped ZIF-8 coated polyelectrolyte modified SiO2A composite material; the mass ratio of the zinc nitrate hexahydrate, the SiO2 modified by polyelectrolyte, the ferric nitrate nonahydrate and the 2-methylimidazole is as follows: zinc nitrate hexahydrate: polyelectrolyte-modified SiO 2: ferric nitrate nonahydrate: 2-methylimidazole ═ (150-: 200: (5-30): (200- > 260); the stirring time is 10-14h, and the aging time is 10-14 h.
(4) Preparing an iron-nitrogen doped hollow porous carbon material: calcining the composite material obtained in the step (3) under nitrogen at the temperature of 800-1000 ℃ for 1.5-2.5h, cooling to the temperature of 25-30 ℃ after calcination, and pickling to remove SiO2The template is washed and dried to obtain the productThe iron-nitrogen doped hollow porous carbon material.
2. The method for preparing an iron-nitrogen doped hollow porous carbon material according to claim 1, wherein in the step (1), the volume ratio of the tetraethoxysilane to the ethanol to the ammonia water to the deionized water is as follows: ethyl orthosilicate: ethanol: ammonia water: deionized water ═ (0.5-0.7): (13-17): (0.5-0.9): (3-7).
3. The method for preparing an iron-nitrogen doped hollow porous carbon material according to claim 2, wherein in the step (1), the volume ratio of the tetraethoxysilane to the ethanol to the ammonia water to the deionized water is as follows: ethyl orthosilicate: ethanol: ammonia water: deionized water 0.6: 15: 0.7: 5.
4. the method for preparing an iron-nitrogen doped hollow porous carbon material according to claim 1, wherein in the step (2), when the mass fraction of poly (diallyldimethylammonium chloride) in the poly (diallyldimethylammonium chloride) solution is 1%, the ratio of the mass of the silica spheres to the volume of the poly (diallyldimethylammonium chloride) solution is: 3:80 g/mL; in the sodium polystyrene sulfonate solution, when the mass fraction of the sodium polystyrene sulfonate is 1%, the SiO is2The ratio of the mass of (2) to the volume of the sodium polystyrene sulfonate is 3:80 g/mL.
5. The method for preparing an iron-nitrogen doped hollow porous carbon material according to claim 1, wherein in the step (3), zinc nitrate hexahydrate and polyelectrolyte-modified SiO2The mass ratio of ferric nitrate nonahydrate to 2-methylimidazole is as follows: zinc nitrate hexahydrate: polyelectrolyte-modified SiO2: ferric nitrate nonahydrate: 2-methylimidazole ═ 150: 200: 5: 200 of a carrier; the time required for stirring is 12h, and the time required for aging is 12 h.
6. The method according to claim 1, wherein the step (4) comprises pickling with hydrofluoric acid, wherein the hydrofluoric acid contains 4 to 6% by mass of HF.
7. An iron-nitrogen doped hollow porous carbon material, which is prepared by the method for preparing an iron-nitrogen doped hollow porous carbon material according to any one of claims 1 to 6.
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