CN113522334A - Method for synthesizing shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst - Google Patents
Method for synthesizing shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst Download PDFInfo
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- 244000276331 Citrus maxima Species 0.000 title claims abstract description 33
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 27
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- 238000000034 method Methods 0.000 title claims abstract description 17
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 238000012546 transfer Methods 0.000 abstract description 4
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
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Abstract
The invention discloses a method for synthesizing a shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst, which comprises the steps of pyrolyzing a mixture of shaddock peel, urea, ferric nitrate nonahydrate, basic zinc carbonate and zinc chloride in one step to obtain the shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst, wherein after nitrogen doping is carried out on a carbon material, the charge distribution and the spin density of carbon atoms around the carbon material are changed, and more reaction active sites are exposed on the surface of the carbon material. The template agent of the invention combines an iron-based template and a zinc-based template, micropores and mesopores are generated in the pyrolysis process, the micropores can enlarge the specific surface area of the corresponding carbon material, and the mesopores can provide a low-resistance channel for ion transfer.
Description
Technical Field
The invention belongs to the technical field of preparation of oxygen reduction catalysts, and particularly relates to a method for synthesizing a shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst.
Background
With the ever-increasing demand for energy and the adverse climate and environmental impact of fossil fuels, the development of clean and renewable energy sources has become of paramount importance. Electrochemical energy conversion and storage play a crucial role in the production of renewable energy sources. Fuel cells and metal air cells have great promise in different electrochemical devices. The Oxygen Reduction Reaction (ORR) is the cathode reaction of these devices, but due to its slow kinetics, it limits its power output, and becomes one of the bottlenecks in its practical application. Platinum catalysts have long been recognized as the most effective electrocatalysts for ORR. However, because platinum is expensive, scarce in resources, and lacks long-term stability and is vulnerable to surface poisoning by various chemicals such as methanol, it is important to find a suitable cathode material to replace platinum. In recent years, a biomass-derived metal-free porous carbon material as a catalyst has been proven to be an effective catalyst due to its various excellent properties such as high specific surface area, multi-stage porous structure, excellent electrical conductivity, and excellent chemical thermal stability.
Disclosure of Invention
The invention solves the technical problem of providing a method for synthesizing a shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst, which is simple and environment-friendly and can be prepared in a large scale. After the carbon material is doped with nitrogen, the charge distribution and the spin density of carbon atoms around the carbon material are changed, and more reactive active sites are exposed on the surface of the carbon material. The technical problems solved by the invention are as follows: firstly, the raw materials are derived from biological wastes, so that the problem of treatment of waste materials is well solved, and the environment-friendly requirement is met. The invention provides a novel combination form of the template agent, the iron-based template and the zinc-based template are combined, micropores and mesopores are generated in the pyrolysis process, the specific surface area of the corresponding carbon material can be enlarged, and a low-resistance channel can be provided for ion transfer. Therefore, the multi-stage porous carbon structure can remarkably improve the electrochemical catalytic performance.
The invention adopts the following technical scheme for solving the technical problems, and the method for synthesizing the shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst is characterized by comprising the following specific processes:
step S1: fully and uniformly mixing the shaddock peel powder obtained by completely drying and crushing with urea, ferric nitrate nonahydrate, basic zinc carbonate and zinc chloride to obtain a material A;
step S2: transferring the material A obtained in the step S1 to a corundum boat, placing the corundum boat in a tube furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under the protection of inert atmosphere, preserving heat for 60 min, heating to 800 ℃ at a heating rate of 8 ℃/min, preserving heat for 120 min, and naturally cooling to room temperature to obtain a material B;
step S3: and (4) transferring the material B obtained in the step (S2) to a container, adding an acid solution to soak for 24 h, washing with high-purity water until the filtrate is neutral, and then placing the filtrate in a forced air drying oven at 80 ℃ to dry for 12 h to obtain the shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst.
Further preferably, in step S1, the charging mass ratio of the shaddock peel powder, the urea, the ferric nitrate nonahydrate, the basic zinc carbonate and the zinc chloride is 1:1:0.5:0.6: 0.6.
Further preferably, the inert gas in step S2 is nitrogen.
Further preferably, the acidic solution in step S3 is a hydrochloric acid solution with a concentration of 2M.
Further preferably, the method for synthesizing the shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst is characterized by comprising the following specific steps of:
step S1: placing 1.0 g of fully dried shaddock peel powder, 1.0 g of urea, 0.5 g of ferric nitrate nonahydrate, 0.6 g of basic zinc carbonate and 0.6 g of zinc chloride in a mortar, and fully and uniformly mixing to obtain a material A4;
step S2: the material A4 obtained in the step S1 was placed in a tube furnace in N2Heating to 300 ℃ at the heating rate of 5 ℃/min in the atmosphere and preserving heat for 60 min, heating to 800 ℃ at the heating rate of 8 ℃/min and preserving heat for 120 min, and naturally cooling to room temperature to obtain a material B4;
step S3: transferring the material B4 obtained in the step S2 to a container, adding a hydrochloric acid solution with the concentration of 2M, soaking for 24 hours, washing the filtrate with high-purity water to be neutral, and then placing the filtrate in an air-blowing drying oven at 80 ℃ for drying for 12 hours to obtain the shaddock peel-derived porous nitrogen-doped carbon-based oxygen reduction catalyst, wherein the C content, the N content and the O content in the shaddock peel-derived porous nitrogen-doped carbon-based oxygen reduction catalyst are 81.19 wt%, 4.47 wt% and 14.34 wt%, and the prepared shaddock peel-derived porous nitrogen-doped carbon-based oxygen reduction catalyst has excellent oxygen reduction catalytic performance, stability and methanol interference resistance.
Compared with the prior art, the invention has the following beneficial effects:
1. the raw materials of the invention are derived from biological wastes, which not only solves the problem of processing waste materials, but also meets the requirement of environmental protection;
2. the invention provides a novel combination form of a template agent, an iron-based template and a zinc-based template are combined, micropores and mesopores are generated in the pyrolysis process, the micropores can enlarge the specific surface area of a corresponding carbon material, and the mesopores can provide a low-resistance channel for ion transfer. Therefore, the multi-stage porous carbon structure can remarkably improve the electrochemical catalytic performance.
Drawings
FIG. 1 is a transmission electron micrograph of a target product C4 prepared in example 1;
FIG. 2 is a diagram showing the pore size distribution of the objective product C4 prepared in example 1;
FIG. 3 is an X-ray diffraction pattern of the target products C1-C4 prepared in examples 1-4;
FIG. 4 is an X-ray photoelectron spectrum (full spectrum) of the target product C4 prepared in example 1;
FIG. 5 shows cyclic voltammograms of the target products C1-C4 prepared in examples 1-4.
FIG. 6 is a linear sweep voltammogram of the target products C1-C4 prepared in examples 1-4.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Step S1: placing 1.0 g of fully dried shaddock peel powder, 0.6 g of basic zinc carbonate and 0.6 g of zinc chloride in a mortar, and fully and uniformly mixing to obtain a material A1;
step S2: the material A1 obtained in the step S1 was placed in a tube furnace in N2Heating to 300 ℃ at the heating rate of 5 ℃/min in the atmosphere and preserving heat for 60 min, heating to 800 ℃ at the heating rate of 8 ℃/min and preserving heat for 120 min, and naturally cooling to room temperature to obtain a material B1;
step S3: and (4) transferring the material B1 obtained in the step S2 to a container, adding a hydrochloric acid solution with the concentration of 2M, soaking for 24 hours, washing the filtrate to be neutral by using high-purity water, and then placing the filtrate in an air-blast drying oven at 80 ℃ for drying for 12 hours to obtain a target product C1.
Example 2
Step S1: placing 1.0 g of fully dried shaddock peel powder, 0.5 g of ferric nitrate nonahydrate, 0.6 g of basic zinc carbonate and 0.6 g of zinc chloride in a mortar, and fully and uniformly mixing to obtain a material A2;
step S2: the material A2 obtained in the step S1 was placed in a tube furnace in N2Heating to 300 ℃ at the heating rate of 5 ℃/min in the atmosphere and preserving heat for 60 min, heating to 800 ℃ at the heating rate of 8 ℃/min and preserving heat for 120 min, and naturally cooling to room temperature to obtain a material B2;
step S3: and (4) transferring the material B2 obtained in the step S2 to a container, adding a hydrochloric acid solution with the concentration of 2M, soaking for 24 hours, washing the filtrate to be neutral by using high-purity water, and then placing the filtrate in an air-blast drying oven at 80 ℃ for drying for 12 hours to obtain a target product C2.
Example 3
Step S1: placing 1.0 g of fully dried shaddock peel powder, 1.0 g of urea, 0.6 g of basic zinc carbonate and 0.6 g of zinc chloride in a mortar, and fully and uniformly mixing to obtain a material A3;
step S2: the material A3 obtained in the step S1 was placed in a tube furnace in N2Heating to 300 ℃ at the heating rate of 5 ℃/min in the atmosphere and preserving heat for 60 min, heating to 800 ℃ at the heating rate of 8 ℃/min and preserving heat for 120 min, and naturally cooling to room temperature to obtain a material B3;
step S3: and (4) transferring the material B3 obtained in the step S2 to a container, adding a hydrochloric acid solution with the concentration of 2M, soaking for 24 hours, washing the filtrate to be neutral by using high-purity water, and then placing the filtrate in an air-blast drying oven at 80 ℃ for drying for 12 hours to obtain a target product C3.
Example 4
Step S1: placing 1.0 g of fully dried shaddock peel powder, 1.0 g of urea, 0.5 g of ferric nitrate nonahydrate, 0.6 g of basic zinc carbonate and 0.6 g of zinc chloride in a mortar, and fully and uniformly mixing to obtain a material A4;
step S2: the material A4 obtained in the step S1 was placed in a tube furnace in N2Heating to 300 ℃ at the heating rate of 5 ℃/min in the atmosphere and preserving heat for 60 min, heating to 800 ℃ at the heating rate of 8 ℃/min and preserving heat for 120 min, and naturally cooling to room temperature to obtain a material B4;
step S3: and (4) transferring the material B4 obtained in the step S2 to a container, adding a hydrochloric acid solution with the concentration of 2M, soaking for 24 hours, washing the filtrate to be neutral by using high-purity water, and then placing the filtrate in an air-blast drying oven at 80 ℃ for drying for 12 hours to obtain a target product C4.
Example 5
Weighing a certain amount of powdery three-template synthesized shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst samples C1, C2, C3 and C4 by using an electronic balance, uniformly mixing the samples with a certain amount of 5 wt% Nafion and high-purity water, and performing ultrasonic treatment for several minutes to obtain a uniform ink-shaped dispersion liquid. Using a liquid-transferring gun to transfer a proper amount of the prepared ink-like solution to clean glassAnd (4) naturally airing the glassy carbon electrode at room temperature, and finishing the preparation of the working electrode. All electrochemical tests used a three-electrode system. In the Linear Sweep Voltammetry (LSV) test, the working electrode was a 5 mm diameter glassy carbon electrode with a platinum ring coated with a volume of active material (the above prepared ink-like solution) at a concentration, and the reference and counter electrodes were Hg/HgO and Pt (1 cm) respectively2) The electrolyte is O2/N2Saturated 0.1 mol. L1KOH solution of (5) with a scanning speed of 10 mV · s in the test1The rotation speed is 1600 rpm, and the scanning range is-0.8V-0.4V. In the Cyclic Voltammetry (CV) test, the working electrode was a glassy carbon electrode having a diameter of 3 mm coated with a certain volume and a certain concentration of an active material (the above prepared ink-like solution), and the reference electrode, the counter electrode, the electrolyte, and the test conditions were the same as those of the above LSV.
As shown in FIG. 5, for cyclic voltammograms of all of the products of examples C1, C2, C3, C4, the corresponding oxygen reduction potentials (relative to standard hydrogen electrode) were 0.837V, 0.843V, 0.824V and 0.873V, respectively. As shown in FIG. 6, for the linear sweep voltammograms of all the products of examples C1, C2, C3, C4, the corresponding initial potentials (relative to the standard hydrogen electrode) were 0.907V, 0.912V, 0.886V and 0.919V, respectively.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (5)
1. A method for synthesizing a shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst is characterized by comprising the following specific steps:
step S1: fully and uniformly mixing the shaddock peel powder obtained by completely drying and crushing with urea, ferric nitrate nonahydrate, basic zinc carbonate and zinc chloride to obtain a material A;
step S2: transferring the material A obtained in the step S1 to a corundum boat, placing the corundum boat in a tube furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under the protection of inert atmosphere, preserving heat for 60 min, heating to 800 ℃ at a heating rate of 8 ℃/min, preserving heat for 120 min, and naturally cooling to room temperature to obtain a material B;
step S3: and (4) transferring the material B obtained in the step (S2) to a container, adding an acid solution to soak for 24 h, washing with high-purity water until the filtrate is neutral, and then placing the filtrate in a forced air drying oven at 80 ℃ to dry for 12 h to obtain the shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst.
2. The method of synthesizing a shaddock peel-derived porous nitrogen-doped carbon-based oxygen reduction catalyst as recited in claim 1, wherein: in the step S1, the feeding mass ratio of the shaddock peel powder, the urea, the ferric nitrate nonahydrate, the basic zinc carbonate and the zinc chloride is 1:1:0.5:0.6: 0.6.
3. The method of synthesizing a shaddock peel-derived porous nitrogen-doped carbon-based oxygen reduction catalyst as recited in claim 1, wherein: the inert gas in step S2 is nitrogen.
4. The method of synthesizing a shaddock peel-derived porous nitrogen-doped carbon-based oxygen reduction catalyst as recited in claim 1, wherein: the acidic solution in step S3 is a hydrochloric acid solution with a concentration of 2M.
5. The method for synthesizing the shaddock peel-derived porous nitrogen-doped carbon-based oxygen reduction catalyst as claimed in claim 1, wherein the method comprises the following specific steps:
step S1: placing 1.0 g of fully dried shaddock peel powder, 1.0 g of urea, 0.5 g of ferric nitrate nonahydrate, 0.6 g of basic zinc carbonate and 0.6 g of zinc chloride in a mortar, and fully and uniformly mixing to obtain a material A4;
step S2: the material A4 obtained in the step S1 was placed in a tube furnace in N2Heating to 300 deg.C at a rate of 5 deg.C/min in the atmosphere, maintaining the temperature for 60 min, and heating againHeating to 800 ℃ at the heating rate of 8 ℃/min, preserving the heat for 120 min, and then naturally cooling to room temperature to obtain a material B4;
step S3: transferring the material B4 obtained in the step S2 to a container, adding a hydrochloric acid solution with the concentration of 2M, soaking for 24 hours, washing the filtrate with high-purity water to be neutral, and then placing the filtrate in an air-blowing drying oven at 80 ℃ for drying for 12 hours to obtain the shaddock peel-derived porous nitrogen-doped carbon-based oxygen reduction catalyst, wherein the C content, the N content and the O content in the shaddock peel-derived porous nitrogen-doped carbon-based oxygen reduction catalyst are 81.19 wt%, 4.47 wt% and 14.34 wt%, and the prepared shaddock peel-derived porous nitrogen-doped carbon-based oxygen reduction catalyst has excellent oxygen reduction catalytic performance, stability and methanol interference resistance.
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