CN115672303A - Preparation method of carbon-based cathode catalytic material based on shaddock peel - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a preparation method of a carbon-based cathode catalytic material based on shaddock peel, which comprises the following steps of: (1) pretreating shaddock peel; (2) pre-carbonizing; (3) cleaning and grinding; (4) etching the biomass by using zinc chloride; (5) calcining; and (6) acid washing to obtain the catalyst. The obtained shaddock peel derived carbon-based catalyst can be used as a cheap, efficient and stable cathode catalyst, and has the advantages of easily obtained preparation materials, simple preparation process and green and environment-friendly preparation process.
Description
Technical Field
The invention relates to the technical field of new energy electrode materials, in particular to a preparation method of a carbon-based cathode catalytic material based on shaddock peel.
Background
At present, the research and development of new energy materials and devices are listed as an extremely important component of the national energy development strategy in China, and the research and development of new energy devices cannot leave the key component of electrode materials. The discharge process of common new energy devices such as the cathode of a fuel cell and a metal-air battery involves an Oxygen Reduction Reaction (ORR). The kinetic slowness of the oxygen reduction reaction, as a heterogeneous catalytic reaction, severely limits the performance of fuel cells and metal air cells. Therefore, great efforts have been made in academia and industry to develop cathodic electrocatalytic materials with superior performance.
Currently, the most advanced ORR catalysts Pt can reach over 10A mg Pt at 0.9V -1 Even in membrane electrode assemblies, ptCo can reach over 1.5APt at a potential of 0.9V -1 The mass activity of (1). However, the biggest challenges of platinum-based catalysts are high cost, scarce reserves, easy poisoning (such as methanol and CO) in working environment, and poor durability, thereby greatly limiting the large-scale practical application thereof. Therefore, people invest in great enthusiasm to develop cheap, efficient and stable non-platinum ORR catalysts.
In the search for inexpensive, efficient and stable catalysts, carbon-based catalysts have been found to be one of the most promising candidates. Although the conventional carbon-based electrode material has good catalytic performance, the disadvantages of high production cost, complex preparation process, serious environmental problems and the like seriously hinder the large-scale application of the conventional carbon-based electrode material. Therefore, the sustainable and green synthesized advanced carbon-based catalyst is developed from renewable and abundant resources, and has an important role in promoting the development of sustainable renewable energy devices.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon-based cathode catalytic material based on shaddock peel, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a carbon-based cathode catalytic material based on shaddock peel comprises the following steps of:
(1) Pretreating shaddock peel: washing pericarpium Citri Grandis with distilled water, soaking in nitric acid water solution, repeatedly washing with water to neutral, and standing overnight in vacuum drying oven to remove water;
(2) Pre-carbonization: weighing a proper amount of dried shaddock peel, putting the shaddock peel into a high-pressure reaction kettle, adding distilled water, putting the mixture into an oven to react for 12 hours to obtain black suspension, and performing centrifugal separation to obtain a black substance;
(3) Cleaning and grinding: repeatedly cleaning the black substance obtained after pre-carbonization with distilled water, centrifugally separating, drying in a vacuum drying oven overnight, taking out the dried black substance, putting into a mortar, grinding into black powder, and bagging for later use;
(4) And (3) zinc chloride etching of biomass: weighing a proper amount of zinc chloride, putting the zinc chloride into a beaker, adding distilled water to completely dissolve the zinc chloride, adding the black powder obtained in the step (3), continuously adding the distilled water, electromagnetically stirring for 24 hours at normal temperature, then increasing the temperature, heating to evaporate the water, and putting the obtained black substance into a vacuum drying oven to dry overnight to obtain black powder;
(5) And (3) calcining: placing a proper amount of black powder obtained in the step (4) in a tubular furnace, sealing, introducing nitrogen for protection, heating to 200 ℃ at a speed of 5 ℃/min, keeping the temperature for 30 minutes to remove water absorbed by deliquescence of zinc chloride in the sample, heating to 900 ℃ at the same speed, keeping the temperature for 3 hours, closing the tubular furnace after 3 hours, and naturally cooling to room temperature under the condition of introducing nitrogen to obtain black powder;
(6) Acid washing to obtain a catalyst: taking out the black powder obtained in the step (5), adding the black powder into a hydrochloric acid aqueous solution, electromagnetically stirring for 6 hours to remove impurities in the catalyst, filtering and washing the mixture to be neutral by using distilled water after centrifugal separation,
putting the mixture into a vacuum drying oven overnight to obtain the shaddock peel derived carbon-based catalyst.
As a further scheme of the invention: the shaddock peel is washed by distilled water and then is soaked in a nitric acid water solution for 30 minutes, and the ratio of the nitric acid water solution is nitric acid: distilled water =1:6.
as a further scheme of the invention: the temperature of the vacuum drying oven in the steps (1), (3) and (4) is 80 ℃.
As a further scheme of the invention: the temperature of the vacuum drying oven in the step (6) is 60 ℃.
As a further scheme of the invention: the oven temperature in the step (2) is 190 ℃.
As a further scheme of the invention: the proportion of the hydrochloric acid aqueous solution in the step (6) is hydrochloric acid: distilled water =1:6.
compared with the prior art, the invention has the beneficial effects that: the obtained shaddock peel derived carbon-based catalyst can be used as a cheap, efficient and stable cathode catalyst, and has the advantages of easily obtained preparation materials, simple preparation process and green and environment-friendly preparation process.
Drawings
Fig. 1 is an XRD of a shaddock peel-derived carbon-based catalyst.
Fig. 2 is an SEM of a shaddock peel-derived carbon-based catalyst.
Fig. 3 is a nitrogen adsorption-desorption isotherm and pore size distribution curve of a shaddock peel-derived carbon-based catalyst.
Fig. 4 is a CV curve of a shaddock peel-derived carbon-based catalyst in KOH solution saturated with nitrogen or oxygen.
Fig. 5 is a graph comparing the LSVs of shaddock peel derived carbon based catalysts and commercial Pt/C catalysts prepared under different conditions for oxygen reduction reaction.
FIG. 6 is a LSV graph of shaddock peel derived carbon based catalyst prepared at 900 ℃ at different rotation speeds.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
A preparation method of a carbon-based cathode catalytic material based on shaddock peel comprises the following steps of preparing raw materials of shaddock peel:
step 1: pretreating shaddock peel, washing the shaddock peel with distilled water, soaking in a nitric acid aqueous solution (nitric acid: distilled water = 1;
step 2: pre-carbonizing, weighing 2g of dried shaddock peel, putting into a high-pressure reaction kettle with the capacity of 100ml, adding 80ml of distilled water, putting into a 190 ℃ oven for reaction for 12 hours to obtain black suspension, and performing centrifugal separation;
and 3, step 3: cleaning and grinding, repeatedly cleaning the obtained black substance after pre-carbonization with distilled water, placing the black substance in a vacuum drying oven for drying overnight at 80 ℃ after centrifugal separation, taking out the dried black substance, placing the black substance in a mortar, grinding the black substance into black powder and bagging the black powder for later use;
and 4, step 4: the method comprises the following steps of (1) etching biomass by zinc chloride, weighing a proper amount of zinc chloride, putting the zinc chloride into a 100ml beaker, adding 20ml of distilled water to dissolve the zinc chloride completely, adding 0.5g of pre-carbonized black powder into the zinc chloride, continuously adding 20ml of distilled water, electromagnetically stirring the mixture for 24 hours at normal temperature, adjusting the temperature to 80 ℃, heating the mixture to dry the mixture to dryness, and putting the obtained black substance into a vacuum drying oven to dry the mixture overnight at 80 ℃ to obtain black powder;
and 5: calcining, namely placing a proper amount of black powder in a tubular furnace, sealing, introducing nitrogen for protection, heating to 200 ℃ at a speed of 5 ℃/min, keeping the temperature for 30 minutes to remove moisture absorbed by deliquescence of zinc chloride in the sample, heating to 900 ℃ at the same speed, keeping the temperature for 3 hours, closing the tubular furnace after 3 hours, and naturally cooling to room temperature under the condition of introducing nitrogen to obtain black powder;
step 6: acid-washing to obtain a catalyst, taking out black powder, adding the black powder into an aqueous hydrochloric acid solution (hydrochloric acid: distilled water = 1).
Example two
A preparation method of a carbon-based cathode catalytic material based on shaddock peel comprises the following steps of:
step 1: pretreating shaddock peel, washing the shaddock peel with distilled water, soaking in a nitric acid aqueous solution (nitric acid: distilled water = 1;
step 2: pre-carbonizing, weighing 2g of dried shaddock peel, putting into a high-pressure reaction kettle with the capacity of 100ml, adding 80ml of distilled water, putting into a 190 ℃ oven for reaction for 12 hours to obtain black suspension, and performing centrifugal separation;
and step 3: cleaning and grinding, namely repeatedly cleaning the obtained black substance after pre-carbonization by using distilled water, centrifugally separating, putting the black substance into a vacuum drying oven, drying the black substance overnight at 80 ℃, taking out the dried black substance, putting the dried black substance into a mortar, grinding the black substance into black powder, and bagging the black powder for later use;
and 4, step 4: the method comprises the following steps of (1) etching biomass by zinc chloride, weighing a proper amount of zinc chloride, putting the zinc chloride into a 100ml beaker, adding 20ml of distilled water for complete dissolution, adding 0.5g of pre-carbonized black powder into the zinc chloride, continuously adding 20ml of distilled water, electromagnetically stirring the mixture for 24 hours at normal temperature, adjusting the temperature to 80 ℃, heating the mixture to dry the water by distillation, and putting the obtained black substance into a vacuum drying oven to dry the black substance overnight at 80 ℃ to obtain black powder;
and 5: calcining, namely placing a proper amount of black powder in a tubular furnace, sealing, introducing nitrogen for protection, heating to 200 ℃ at a speed of 5 ℃/min, keeping the temperature for 30 minutes to remove moisture absorbed by deliquescence of zinc chloride in the sample, heating to 800 ℃ at the same speed, keeping the temperature for 3 hours, closing the tubular furnace after 3 hours, and naturally cooling to room temperature under the condition of introducing nitrogen to obtain black powder;
and 6: acid-washing to obtain a catalyst, taking out black powder, adding the black powder into a hydrochloric acid aqueous solution (hydrochloric acid: distilled water = 1).
EXAMPLE III
A preparation method of a carbon-based cathode catalytic material based on shaddock peel comprises the following steps of:
step 1: pretreating shaddock peel, washing the shaddock peel with distilled water, soaking in a nitric acid aqueous solution (nitric acid: distilled water = 1;
step 2: pre-carbonizing, weighing 2g of dried shaddock peel, putting into a high-pressure reaction kettle with the capacity of 100ml, adding 80ml of distilled water, putting into an oven at 190 ℃ for reacting for 12 hours to obtain black suspension, and performing centrifugal separation;
and step 3: cleaning and grinding, namely repeatedly cleaning the obtained black substance after pre-carbonization by using distilled water, centrifugally separating, putting the black substance into a vacuum drying oven, drying the black substance overnight at 80 ℃, taking out the dried black substance, putting the dried black substance into a mortar, grinding the black substance into black powder, and bagging the black powder for later use;
and 4, step 4: the method comprises the following steps of (1) etching biomass by zinc chloride, weighing a proper amount of zinc chloride, putting the zinc chloride into a 100ml beaker, adding 20ml of distilled water for complete dissolution, adding 0.5g of pre-carbonized black powder into the zinc chloride, continuously adding 20ml of distilled water, electromagnetically stirring the mixture for 24 hours at normal temperature, adjusting the temperature to 80 ℃, heating the mixture to dry the water by distillation, and putting the obtained black substance into a vacuum drying oven to dry the black substance overnight at 80 ℃ to obtain black powder;
and 5: calcining, namely placing a proper amount of black powder in a tubular furnace, sealing, introducing nitrogen for protection, heating to 200 ℃ at the speed of 5 ℃/min, keeping the temperature for 30 minutes to remove water absorbed by deliquescence of zinc chloride in a sample, heating to 1000 ℃ at the same speed, keeping the temperature for 3 hours, closing the tubular furnace after 3 hours, and naturally cooling to room temperature under the condition of introducing nitrogen to obtain black powder;
step 6: acid-washing to obtain a catalyst, taking out black powder, adding the black powder into a hydrochloric acid aqueous solution (hydrochloric acid: distilled water = 1).
Fig. 1 is XRD results of the shaddock peel-derived carbon-based catalyst, and the results show that the sample obtained in step 5 is graphene regardless of whether pyrolysis is performed at 800 ℃,900 ℃ or 1000 ℃.
FIG. 2 is an SEM photograph of a shaddock peel-derived carbon-based catalyst, and the result shows that the sample is formed by bonding spherical carbon particles together, the particle size of the particles is 10-15 nm, the particles are bonded tightly, pores with different sizes are formed, and a large number of large pores are formed, so that the structural characteristics are favorable for exposing active sites and conveying electrolyte.
Fig. 3 is a nitrogen adsorption-desorption isotherm and pore size distribution curve of a shaddock peel-derived carbon-based catalyst. The results show that the carbon materials obtained by pyrolysis at different temperatures have large specific surface areas and typical mesoporous structures, and the specific surface area is 1241m at 800 DEG C 2 G, specific surface area at 900 ℃ is 1631m 2 Per g, specific surface area at 1000 ℃ of 1474m 2 (ii)/g; the pore size distribution of the three is shown in FIG. 3b, and the average pore size is 3.63nm, 4.05nm and 4.45nm, respectively. The results show that the shaddock peel derived carbon has large specific surface area and contains a large number of mesopores, which has very important promotion effect on the mass transfer process in the catalysis process.
An electrode is prepared from shaddock peel derived carbon obtained by pyrolysis at 900 ℃, an Ag/AgCl electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, 0.1MKOH is used as electrolyte, and an oxygen reduction reaction electrocatalysis test is carried out by applying a cyclic voltammetry under the condition of introducing oxygen or nitrogen, and the result is shown in figure 4. The result shows that the shaddock peel derived carbon generates an obvious oxygen reduction peak at 0.91V (vs. RHE), the peak current is also large, and good oxygen reduction reaction electrocatalytic performance is shown.
FIG. 5 is a graph of linear volts under the same conditions as in FIG. 4And (3) obtaining linear voltammetry scanning curves of different materials by an ampere scanning method. As can be seen from the figure, znCl is not added with an activator 2 The initial reduction potentials of the carbon material of (1), the carbon material having a pyrolysis temperature of 800 ℃, the carbon material having a pyrolysis temperature of 900 ℃, the carbon material having a pyrolysis temperature of 1000 ℃, and commercial Pt/C were 0.90V, 0.94V, 0.98V, 0.95V, and 0.98V, respectively. Several shaddock peel derived carbons all have very high initial reduction potentials, while the carbon material with the pyrolysis temperature of 900 ℃ has the same initial reduction potential as commercial Pt/C, and the limiting diffusion current is far larger than that of other carbon materials, but is almost the same as the commercial Pt/C, so that the shaddock peel derived carbon shows excellent oxygen reduction electrocatalytic performance.
Fig. 6 is a linear voltammogram scan curve of a carbon material having a pyrolysis temperature of 900 deg.c obtained by a linear voltammogram scan under the same conditions as in fig. 5 at different electrode rotation speeds. It can be seen from the figure that the initial reduction potential of the sample is constant at different rotation speeds, but the limiting diffusion current increases with the rotation speed.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. A preparation method of a carbon-based cathode catalytic material based on shaddock peel is characterized by comprising the following steps: the raw material comprises shaddock peel, and the preparation process mainly comprises the following steps:
(1) Pretreating shaddock peel: washing pericarpium Citri Grandis with distilled water, soaking in nitric acid water solution, repeatedly washing with water to neutral, and standing overnight in vacuum drying oven to remove water;
(2) Pre-carbonization: weighing a proper amount of dried shaddock peel, putting the shaddock peel into a high-pressure reaction kettle, adding distilled water, then putting the mixture into an oven to react for 12 hours to obtain black suspension, and performing centrifugal separation to obtain a black substance;
(3) Cleaning and grinding: repeatedly cleaning the black substance obtained after pre-carbonization with distilled water, centrifugally separating, drying in a vacuum drying oven overnight, taking out the dried black substance, putting into a mortar, grinding into black powder, and bagging for later use;
(4) And (3) zinc chloride etching of biomass: weighing a proper amount of zinc chloride, putting the zinc chloride into a beaker, adding distilled water to completely dissolve the zinc chloride, adding the black powder obtained in the step (3), continuously adding the distilled water, electromagnetically stirring for 24 hours at normal temperature, then increasing the temperature, heating to evaporate the water, and putting the obtained black substance into a vacuum drying oven to dry overnight to obtain black powder;
(5) And (3) calcining: placing a proper amount of black powder obtained in the step (4) in a tubular furnace, sealing, introducing nitrogen for protection, heating to 200 ℃ at a speed of 5 ℃/min, keeping the temperature for 30 minutes to remove moisture absorbed by deliquescence of zinc chloride in the sample, heating to 900 ℃ at the same speed, keeping the temperature for 3 hours, closing the tubular furnace after 3 hours, and naturally cooling to room temperature under the condition of introducing nitrogen to obtain black powder;
(6) Acid washing to obtain a catalyst: and (3) taking the black powder obtained in the step (5) out, adding the black powder into a hydrochloric acid aqueous solution, electromagnetically stirring for 6 hours to remove impurities in the catalyst, filtering and washing the mixture to be neutral by using distilled water after centrifugal separation, and putting the mixture into a vacuum drying oven overnight to obtain the shaddock peel derived carbon-based catalyst.
2. The preparation method of the shaddock peel-based carbon-based cathode catalytic material as claimed in claim 1, wherein the preparation method comprises the following steps: the shaddock peel is washed by distilled water and then is soaked in a nitric acid water solution for 30 minutes, and the ratio of the nitric acid water solution is nitric acid: distilled water =1:6.
3. the preparation method of the shaddock peel-based carbon-based cathode catalytic material as claimed in claim 1, wherein the preparation method comprises the following steps: the temperature of the vacuum drying oven in the steps (1), (3) and (4) is 80 ℃.
4. The preparation method of the carbon-based cathode catalytic material based on the shaddock peel as claimed in claim 1, wherein the preparation method comprises the following steps: the temperature of the vacuum drying oven in the step (6) is 60 ℃.
5. The preparation method of the carbon-based cathode catalytic material based on the shaddock peel as claimed in claim 1, wherein the preparation method comprises the following steps: the temperature of the oven in the step (2) is 190 ℃.
6. The preparation method of the carbon-based cathode catalytic material based on the shaddock peel as claimed in claim 1, wherein the preparation method comprises the following steps: the proportion of the hydrochloric acid aqueous solution in the step (6) is hydrochloric acid: distilled water =1:6.
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| CN113184848A (en) * | 2021-04-22 | 2021-07-30 | 合肥工业大学 | Method for preparing biomass porous carbon for supercapacitor based on shaddock peel |
| CN113839058A (en) * | 2021-09-23 | 2021-12-24 | 重庆文理学院 | Carbon-based oxygen reduction reaction catalyst and preparation method thereof |
| WO2022036878A1 (en) * | 2020-08-20 | 2022-02-24 | 浙江大学 | High-nitrogen biochar composite material, preparation method therefor, and application thereof |
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| CN106711468A (en) * | 2016-11-17 | 2017-05-24 | 中国林业科学研究院林产化学工业研究所 | Carbon material with catalytic performance on ORR (Oxygen Reduction Reaction) as well as preparation method and application of carbon material |
| CN109603873A (en) * | 2018-11-08 | 2019-04-12 | 东莞理工学院 | It is a kind of using discarded pomelo peel as Fe-N-C catalyst of carbon source and its preparation method and application |
| WO2022036878A1 (en) * | 2020-08-20 | 2022-02-24 | 浙江大学 | High-nitrogen biochar composite material, preparation method therefor, and application thereof |
| CN113184848A (en) * | 2021-04-22 | 2021-07-30 | 合肥工业大学 | Method for preparing biomass porous carbon for supercapacitor based on shaddock peel |
| CN113839058A (en) * | 2021-09-23 | 2021-12-24 | 重庆文理学院 | Carbon-based oxygen reduction reaction catalyst and preparation method thereof |
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