CN111129521A - Preparation method of carbon-based oxygen reduction reaction electrocatalyst - Google Patents
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Abstract
The invention discloses a preparation method of a carbon-based oxygen reduction reaction electrocatalyst, which comprises the steps of firstly synthesizing silicon dioxide microspheres, coating the surfaces of the silicon dioxide microspheres with benzoxazine resin, etching the silicon dioxide by using a hydrogen fluoride solution, then impregnating and adsorbing an iron source and a nitrogen source on the silicon dioxide microspheres to synthesize a porous hollow nanosphere with the diameter of 170-230nm, wherein the diameter of an inner cavity of the hollow nanosphere is 95-115nm, the wall thickness of the hollow nanosphere is 30-40nm, and iron elements are uniformly dispersed and loaded on the hollow nanosphere‑1Has very high electrochemical oxygen reduction activity.
Description
Technical Field
The invention belongs to the technical field of electrochemical materials, and particularly relates to a preparation method of a carbon-based oxygen reduction reaction electrocatalyst.
Background
With the increasing global energy demand and the energy crisis and environmental pollution problems caused by the overuse of traditional fossil energy, a green renewable energy device is urgently needed. The fuel cell or the metal air battery is taken as an environment-friendly electrochemical energy conversion and storage device to bring opportunity for solving the global energy problem. The Oxygen Reduction Reaction (ORR) plays an important role as an important half reaction, but the oxygen reduction reaction has the problem of slow kinetics, and the high-efficiency electrocatalyst can greatly accelerate the kinetics of the reaction, thereby improving the reaction efficiency, but the noble metal platinum (Pt) is often needed, and as is well known, the platinum not only has a rare reserve but also is expensive, so that the development of a non-noble metal-based electrocatalyst for replacing the traditional platinum-based catalyst is urgently needed, and the Oxygen Reduction Reaction (ORR) has important significance not only in industrial application but also in cost saving.
Transition metal/nitrogen/carbon catalysts have been proven to be a non-noble metal-based electrocatalyst with excellent oxygen reduction properties, among which Fe/N/C catalysts have been widely noticed and studied in alkaline systems because they possess properties close to or even superior to those of platinum-based catalysts, however, it remains challenging to prepare Fe/N/C catalysts with both high electrocatalytic activity and excellent stability.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a carbon-based oxygen reduction electrocatalyst.
The technical scheme of the invention is as follows:
a preparation method of a carbon-based oxygen reduction electrocatalyst comprises the following steps:
(1) dispersing silicon dioxide in a mixed solution of ethanol and water, adding 3-aminophenol, formaldehyde, ethylenediamine and ethyl orthosilicate, reacting for 20-25h at 30-32 ℃, cooling to room temperature, centrifuging, washing and drying;
(2) dispersing the material obtained in the step (1) in deionized water, adding a hydrogen fluoride solution, and etching silicon dioxide at room temperature for 20-25 h;
(3) cleaning and drying the material obtained in the step (2), and dispersing the material in ethanol;
(4) respectively dissolving soluble ferric salt and a nitrogen source in ethanol, slowly dropping into the material obtained in the step (3), soaking and adsorbing for 3-8h, and centrifuging;
(5) vacuum drying the material obtained in the step (4), then carrying out heat preservation and calcination at 880-920 ℃ for 3-5h in a reaction atmosphere, and cooling to room temperature to obtain the carbon-based oxygen reduction reaction electrocatalyst; the reaction atmosphere consists of 8-12% ammonia and 88-92% argon.
In a preferred embodiment of the invention, the soluble iron salt comprises ferrous chloride.
In a preferred embodiment of the invention, the nitrogen source comprises urea.
Further preferably, the soluble ferric salt is ferrous chloride, and the nitrogen source is urea
In a preferred embodiment of the invention, the temperature of the vacuum drying is 75-85 ℃.
In a preferred embodiment of the invention, the reaction atmosphere consists of 10% ammonia and 90% argon.
In a preferred embodiment of the present invention, in said step (1), the ratio of silica, 3-aminophenol, formaldehyde, ethylenediamine and ethyl orthosilicate is 1 g: 0.64 g: 0.96 mL: 0.64 mL: 0.3 mL.
The invention has the beneficial effects that:
1. the preparation method comprises the steps of firstly synthesizing silicon dioxide microspheres, coating benzoxazine resin on the surfaces of the silicon dioxide microspheres, etching the silicon dioxide by using a hydrogen fluoride solution, and then impregnating and adsorbing an iron source and a nitrogen source on the silicon dioxide microspheres to synthesize the porous hollow nanospheres with the diameter of 170-230nm, wherein the diameter of an inner cavity of the hollow nanospheres is 95-115nm, the wall thickness of the hollow nanospheres is 30-40nm, and iron elements are uniformly dispersed and loaded on the hollow nanospheres-1Has very high electrochemical oxygen reduction activity.
2. The carbon-based oxygen reduction electrocatalyst prepared by the invention has excellent stability in alkaline electrolyte, the half-wave potential is only attenuated by 18mV after 5000 cycles at a scanning rate of 50mV in a potential interval of 0.6V-1V, 80000s is electrolyzed at a potential of 0.8V, the relative current is 70%, and the carbon-based oxygen reduction electrocatalyst is superior to the traditional platinum catalyst.
3. The good performance of the carbon-based oxygen reduction reaction electrocatalyst prepared by the invention comes from the porous nano shell, which provides a larger specific surface area, exposes more catalytic active sites, and the active sites distributed on the surface are more uniform, while the hollow porous structure is also beneficial to the mass transfer of oxygen, thereby having important significance in fuel cells and metal air cell devices limited by the oxygen reduction reaction kinetics, and greatly improving the energy conversion efficiency and stability.
Drawings
FIG. 1 shows the results of the electrocatalysts prepared in example 1 of the present invention and in comparative example 1 at 10mV s-1Recording Linear Sweep Voltammetry (LSV) in an oxygen saturated 0.1M KOH solution at a sweep rate to obtain a polarization curve;
FIG. 2 shows that the carbon-based oxygen reduction electrocatalyst prepared in example 1 of the present invention is used at 50mV s-1At a scan rate of 5000 cycles, a half-wave potential decay curve was scanned, wherein all electrode potential data were 80% iR compensated.
Fig. 3 is an XRD diffraction pattern of the electrocatalysts prepared in example 1 of the present invention and comparative example 1.
FIG. 4 is a Scanning Electron Microscope (SEM) test result of the carbon-based oxygen reduction electrocatalyst prepared in example 1 of the present invention.
FIG. 5 is a TEM test result of the carbon-based oxygen reduction electrocatalyst prepared in example 1 of the present invention.
FIG. 6 is an EDX test chart of the carbon-based oxygen reduction electrocatalyst prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Dispersing 1g of silicon dioxide into a mixed solution of ethanol and water (60mL of ethanol and 140mL of deionized water), adding 0.64g of 3-aminophenol, 0.96mL of formaldehyde, 0.64mL of ethylenediamine and 0.3mL of ethyl orthosilicate, reacting at 30 ℃ for 24 hours, cooling to room temperature, centrifugally washing, and drying;
(2) dispersing the material obtained in the step (1) in deionized water, adding a proper amount of hydrogen fluoride solution, and etching silicon dioxide at room temperature for 24 hours (keeping stirring in the etching process);
(3) after the material obtained in the step (2) is washed and dried, 0.5g of the material is taken and dispersed in 100mL of ethanol;
(4) respectively dissolving 0.05g of ferrous chloride tetrahydrate and 0.03g of urea in 2.5mL of ethanol, mixing to obtain 5mL of solution, slowly dripping the solution into the material obtained in the step (3), soaking and adsorbing for 4 hours, and centrifuging;
(5) and (3) drying the material obtained in the step (4) in vacuum at 80 ℃, then calcining the dried material at 900 ℃ in a tubular furnace for 4 hours in a reaction atmosphere (10% ammonia gas and 90% argon gas), cooling the calcined material to room temperature to obtain the carbon-based oxygen reduction reaction electrocatalyst, which is a porous hollow nanosphere with the diameter of 170-230nm, the diameter of an inner cavity of the hollow nanosphere is 95-115nm, the wall thickness of the hollow nanosphere is 30-40nm, and 2-3 wt% of iron element is uniformly dispersed and loaded on the hollow nanosphere.
Example 2
(1) Dispersing 1g of silicon dioxide into a mixed solution of ethanol and water (60mL of ethanol and 140mL of deionized water), adding 0.64g of 3-aminophenol, 0.96mL of formaldehyde, 0.64mL of ethylenediamine and 0.3mL of ethyl orthosilicate, reacting at 30 ℃ for 24 hours, cooling to room temperature, centrifugally washing, and drying;
(2) dispersing the material obtained in the step (1) in deionized water, adding a proper amount of hydrogen fluoride solution, and etching silicon dioxide at room temperature for 24 hours (keeping stirring in the etching process);
(3) after the material obtained in the step (2) is washed and dried, 0.5g of the material is taken and dispersed in 50mL of ethanol;
(4) respectively dissolving 0.05g of ferrous chloride tetrahydrate and 0.03g of urea in 2.5mL of ethanol, mixing to obtain 5mL of solution, slowly dripping the solution into the material obtained in the step (3), soaking and adsorbing for 4 hours, and centrifuging;
(5) and (3) drying the material obtained in the step (4) in vacuum at 80 ℃, then calcining the dried material at 900 ℃ in a tubular furnace for 4 hours in a reaction atmosphere (10% ammonia gas and 90% argon gas), cooling the calcined material to room temperature to obtain the carbon-based oxygen reduction reaction electrocatalyst, which is a porous hollow nanosphere with the diameter of 170-230nm, the diameter of an inner cavity of the hollow nanosphere is 95-115nm, the wall thickness of the hollow nanosphere is 30-40nm, and 2-3 wt% of iron element is uniformly dispersed and loaded on the hollow nanosphere.
Example 3
(1) Dispersing 1g of silicon dioxide into a mixed solution of ethanol and water (60mL of ethanol and 140mL of deionized water), adding 0.64g of 3-aminophenol, 0.96mL of formaldehyde, 0.64mL of ethylenediamine and 0.3mL of ethyl orthosilicate, reacting at 30 ℃ for 24 hours, cooling to room temperature, centrifugally washing, and drying;
(2) dispersing the material obtained in the step (1) in deionized water, adding a proper amount of hydrogen fluoride solution, and etching silicon dioxide at room temperature for 24 hours (keeping stirring in the etching process);
(3) after the material obtained in the step (2) is washed and dried, 0.5g of the material is taken and dispersed in 200mL of ethanol;
(4) respectively dissolving 0.05g of ferrous chloride tetrahydrate and 0.03g of urea in 2.5mL of ethanol, mixing to obtain 5mL of solution, slowly dripping the solution into the material obtained in the step (3), soaking and adsorbing for 4 hours, and centrifuging;
(5) and (3) drying the material obtained in the step (4) in vacuum at 80 ℃, then calcining the dried material at 900 ℃ in a tubular furnace for 4 hours in a reaction atmosphere (10% ammonia gas and 90% argon gas), cooling the calcined material to room temperature to obtain the carbon-based oxygen reduction reaction electrocatalyst, which is a porous hollow nanosphere with the diameter of 170-230nm, the diameter of an inner cavity of the hollow nanosphere is 95-115nm, the wall thickness of the hollow nanosphere is 30-40nm, and 2-3 wt% of iron element is uniformly dispersed and loaded on the hollow nanosphere.
Example 4 electrochemical performance testing of non-noble metal-based oxygen reduction electrocatalyst prepared in examples 1-3
(1) Catalyst slurry was prepared by dispersing 6mg of the carbon-based oxygen reduction electrocatalyst prepared in examples 1 to 3 in a mixed solution containing 500. mu.L of deionized water, 470. mu.L of ethanol and 30. mu.L of 5% naphthol; then 10. mu.L of catalyst slurry was dropped onto a polished and clean rotating disk electrode and at room temperatureDrying overnight; electrochemical measurements were evaluated in a three-electrode setup with an Hg/HgO electrode as reference electrode and a graphite electrode as counter electrode, using a rotating disk electrode as working electrode; potential reference Reversible Hydrogen Electrode (RHE): eRHE＝EHg/HgO+0.098+0.059 XpH (0.1M KOH solution). And evaluating the half-wave potential according to the potential corresponding to the half-wave potential as half of the limiting current. At 10mV s-1Linear Sweep Voltammetry (LSV) was recorded in an oxygen saturated 0.1M KOH solution at the sweep rate to obtain a polarization curve, see fig. 1. Stability test at 50mV s at 0.6V-1V-1The scan rate of (2) cycles 5000 cycles, see fig. 2. All electrode potential data were 80% iR compensated.
(2) A quantity of the carbon-based oxygen reduction electrocatalyst prepared in example 1 was weighed for XRD, see FIG. 3.
(3) A certain amount of the carbon-based oxygen reduction electrocatalyst prepared in example 1 was weighed and observed under a scanning electron microscope, see FIG. 4.
(4) A quantity of the carbon-based oxygen reduction reaction electrocatalyst prepared in example 1 was weighed for transmission electron microscopy, see FIG. 5.
(5) A certain amount of the carbon-based oxygen reduction electrocatalyst prepared in step 1 was weighed to test EDX, see fig. 6.
Comparative example 1
(1) Dispersing 1g of silicon dioxide into a mixed solution of ethanol and water (60mL of ethanol and 140mL of deionized water), adding 0.64g of 3-aminophenol, 0.96mL of formaldehyde, 0.64mL of ethylenediamine and 0.3mL of ethyl orthosilicate, reacting at 30 ℃ for 24 hours, cooling to room temperature, centrifugally washing, and drying;
(2) dispersing the material obtained in the step (1) in deionized water, adding a proper amount of hydrogen fluoride solution, and etching silicon dioxide at room temperature for 24 hours (keeping stirring in the etching process);
(3) after the material obtained in the step (2) is washed and dried, 0.5g of the material is taken and dispersed in 100mL of ethanol;
(4) respectively dissolving 0.05g of ferrous chloride tetrahydrate and 0.03g of urea in 2.5mL of ethanol, mixing to obtain 5mL of solution, slowly dripping the solution into the material obtained in the step (3), soaking and adsorbing for 4 hours, and centrifuging;
(5) and (4) drying the material obtained in the step (4) at 80 ℃ in vacuum, then calcining the material at 900 ℃ in a tube furnace for 4 hours in an argon atmosphere, and cooling the material to room temperature to obtain the final product.
(6) Preparing a catalyst slurry by dispersing 6mg of the final product obtained in step (5) in a mixed solution containing 500. mu.L of deionized water, 470. mu.L of ethanol and 30. mu.L of 5% naphthol; then 10 μ L of catalyst slurry was dropped onto a polished and clean rotating disk electrode and dried overnight at room temperature; at 10mV s-1Linear Sweep Voltammetry (LSV) was recorded in an oxygen-saturated 0.1m koh solution at a sweep rate to obtain a polarization curve, and as a result, referring to fig. 1, it can be seen that the half-wave potential of the catalyst prepared in comparative example 1 was 0.887V. All electrode potential data were compensated for 80% of the voltage drop.
(7) A certain amount of the final product prepared in step (1) was weighed for XRD, see FIG. 3.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (7)
1. A preparation method of a carbon-based oxygen reduction electrocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) dispersing silicon dioxide in a mixed solution of ethanol and water, adding 3-aminophenol, formaldehyde, ethylenediamine and ethyl orthosilicate, reacting for 20-25h at 30-32 ℃, cooling to room temperature, centrifuging, washing and drying;
(2) dispersing the material obtained in the step (1) in deionized water, adding a hydrogen fluoride solution, and etching silicon dioxide at room temperature for 20-25 h;
(3) cleaning and drying the material obtained in the step (2), and dispersing the material in ethanol;
(4) respectively dissolving soluble ferric salt and a nitrogen source in ethanol, slowly dropping into the material obtained in the step (3), soaking and adsorbing for 3-8h, and centrifuging;
(5) vacuum drying the material obtained in the step (4), then carrying out heat preservation and calcination at 880-920 ℃ for 3-5h in a reaction atmosphere, and cooling to room temperature to obtain the carbon-based oxygen reduction reaction electrocatalyst; the reaction atmosphere consists of 8-12% ammonia and 88-92% argon.
2. The method of claim 1, wherein: the soluble iron salt comprises ferrous chloride.
3. The method of claim 1, wherein: the nitrogen source comprises urea.
4. The production method according to any one of claims 1 to 3, characterized in that: the soluble ferric salt is ferrous chloride, and the nitrogen source is urea.
5. The method of claim 1, wherein: the temperature of the vacuum drying is 75-85 ℃.
6. The method of claim 1, wherein: the reaction atmosphere consisted of 10% ammonia and 90% argon.
7. The method of claim 1, wherein: in the step (1), the proportion of the silicon dioxide, the 3-aminophenol, the formaldehyde, the ethylenediamine and the ethyl orthosilicate is 1g to 0.64g to 0.96mL to 0.64mL to 0.3 mL.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114361480A (en) * | 2021-12-31 | 2022-04-15 | 江苏大学 | Method for preparing zinc-air battery electrode material by xerogel method |
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