CN114864962A - Method for preparing polysaccharide-based porous carbon oxygen reduction catalyst by solvent-free molten salt - Google Patents

Method for preparing polysaccharide-based porous carbon oxygen reduction catalyst by solvent-free molten salt Download PDF

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CN114864962A
CN114864962A CN202210098966.8A CN202210098966A CN114864962A CN 114864962 A CN114864962 A CN 114864962A CN 202210098966 A CN202210098966 A CN 202210098966A CN 114864962 A CN114864962 A CN 114864962A
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polysaccharide
salt
porous carbon
oxygen reduction
based porous
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吴冬玲
韩晓枫
王涛
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Xinjiang University
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Xinjiang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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

Abstract

The invention discloses a method for preparing a polysaccharide-based porous carbon oxygen reduction catalyst in a solvent-free high-temperature molten salt environment, which comprises the following steps: uniformly grinding polysaccharide and mono-salt or bi-salt with the mass being more than or equal to 2 times of that of the polysaccharide to form a mixture, putting the mixture into a reaction kettle for pre-carbonization at a certain temperature, then carbonizing at a high temperature in an inert atmosphere, pickling, washing with water to be neutral, and drying to obtain the polysaccharide-based porous carbon material. The porous carbon material prepared by the invention has large specific surface area and hierarchical porous structure, and shows excellent oxygen reduction performance when used as an electrocatalytic oxygen reduction catalyst. The method has the advantages of simple preparation process, low cost and high carbon yield, and has important significance for the preparation of the polysaccharide-based porous carbon material and the application of the polysaccharide-based porous carbon material in oxygen reduction catalysis.

Description

Method for preparing polysaccharide-based porous carbon oxygen reduction catalyst by solvent-free molten salt
Technical Field
The invention relates to a method for preparing a polysaccharide-based porous carbon oxygen reduction catalyst by using solvent-free molten salt
Background
Due to the rapid consumption of fossil fuel resources and the increasingly prominent environmental problems, the vigorous development of green clean sustainable energy is one of the important approaches to solve the problems. The development of novel and efficient energy storage and conversion devices becomes an important research direction for sustainable energy development. Fuel cells are widely concerned for their advantages of high energy conversion efficiency, cleanliness and no pollution. However, the slow kinetics of the cathode reaction and the high potential of the fuel cell during energy conversion reduce the efficiency of the conversion device, and thus a catalyst with good performance is required to improve the catalytic activity of the cathode reaction. Currently, noble metal catalysts are the most commonly used cathode catalysts, but their high price and easy poisoning of active centers have led to the shift of attention to inexpensive carbon materials. Carbon materials are often used as non-metallic catalysts and catalyst support materials due to their good electrical conductivity, large specific surface area and hierarchical porous structure. How to select a proper carbonaceous precursor and a simple and controllable preparation method, and prepare an electrode material with excellent electrocatalytic performance on a large scale at low cost still remains the biggest challenge of developing a carbon-based catalyst at present. The biomass polysaccharide has the characteristics of low price, reproducibility, no toxicity and rich varieties, and is a high-quality carbonaceous precursor. It includes cellulose, agar, chitosan, starch, etc. The polysaccharide compound has high content of functional groups such as hydroxyl, carboxyl, amine and the like, and is easy to functionalize. However, the material obtained by directly carbonizing the material at high temperature is often single in pore channel and few in active site, and the material cannot be directly applied to the fields of fuel cells and the like. Therefore, it is necessary to develop a method for preparing carbon materials with controllable pore structure and surface properties. At present, the preparation method of the polysaccharide-based porous carbon material mainly comprises two methods of high-temperature carbonization and activation and hydrothermal pre-carbonization and high-temperature activation. These two methods usually require solvents to dissolve or disperse polysaccharide precursors, other activators, templates, etc., and drying treatment is required before high-temperature carbonization, which generally requires high drying technology, especially freeze drying or supercritical drying technology is often required for precursors that are easy to form gel structures to maintain the gel structures. The strict preparation conditions and high cost limit the large-scale preparation and wide application of the material.
Disclosure of Invention
The invention relates to a preparation method for preparing a polysaccharide-based porous carbon oxygen reduction catalyst by using solvent-free molten salt. The polysaccharide-based porous carbon material with excellent electro-catalytic oxygen reduction performance is obtained by two-step carbonization in a solvent-free high-temperature molten salt environment. The preparation method for preparing the polysaccharide-based porous carbon oxygen reduction catalyst by using the solvent-free molten salt has the advantages of simple preparation process, high efficiency and low cost.
The synthesis mainly comprises the following steps:
weighing a certain amount of polysaccharide, adding excessive single salt or double salt (transition metal hydrochloride, transition metal nitrate, transition metal phosphate, transition metal carbonate, organic salt and the like, wherein the mass ratio of the salt to the polysaccharide is more than or equal to 2-20), putting the mixture into an agate mortar, and fully grinding until the mixture is uniformly mixed. And (3) putting the mixture into a reaction kettle, heating for 2-12 hours at 100-180 ℃, and cooling to room temperature to obtain the carbon aerogel.
Putting the carbon aerogel into a porcelain boat, then putting the porcelain boat into a tube furnace, and preserving the heat for 0.5-5 hours (1-20 ℃ min) at 600-1000 ℃ under inert atmosphere -1 ). And cooling, taking out, washing with acid and water, and drying in an oven to obtain the polysaccharide-based porous carbon.
The invention has the following beneficial effects:
(1) the invention provides a porous carbon material obtained by two-step carbonization in a solvent-free high-temperature molten salt environment, which is simple to operate, low in cost and low in equipment requirement.
(2) The preparation process is simple, safe and efficient, the preparation process is few, the period is short, and the yield is high.
(3) The material has larger specific surface area (up to 2799.8 m) 2 g -1 ) The catalyst exhibits excellent performance as an oxygen reduction catalyst.
Drawings
The morphology of example 1 was analyzed by scanning electron microscopy using a SU8010 field emission microscope, as shown in FIG. 1.
The nitrogen adsorption/desorption isotherm assay of example 1 was carried out using an Autosorb-IQ instruments (Quantachrome) as shown in fig. 2.
Example 1 at 0.1mol L -1 The oxygen reduction catalytic performance of the polarization curve in potassium hydroxide is shown in figure 3.
The morphology analysis of example 2 was observed using a scanning electron microscope with field emission of SU8010 type as shown in FIG. 4.
Example 2 at 0.1mol L -1 The oxygen reduction catalytic performance of the polarization curve in potassium hydroxide is shown in figure 5.
0.1mol L of example 3 -1 The oxygen reduction catalytic performance of the polarization curve in potassium hydroxide is shown in figure 6.
The morphology analysis of example 4 was observed using a scanning electron microscope with field emission of SU8010 type as shown in FIG. 7.
Example 4 at 0.1mol L -1 The oxygen reduction catalytic performance of the polarization curve in potassium hydroxide is shown in figure 8.
The morphology analysis of example 5 was observed using a scanning electron microscope with field emission of SU8010 type as shown in FIG. 9.
The nitrogen adsorption/desorption isotherm assay of example 5 was carried out using an Autosorb-IQ instruments (Quantachrome) as shown in fig. 10.
Example 5 at 0.1mol L -1 The oxygen reduction catalytic performance of the polarization curve in potassium hydroxide is shown in figure 11.
The morphology analysis of example 6 was observed using a scanning electron microscope with field emission of SU8010 type as shown in FIG. 12.
Example 6 at 0.1mol L -1 The oxygen reduction catalytic performance of the polarization curve in potassium hydroxide is shown in figure 13.
Detailed Description
Example one
The most common starch in polysaccharide is used as precursor, and ferric chloride is molten salt. (changing the type of the single salt, the mass ratio of the polysaccharide to the salt is 1: 6)
0.5g of corn starch and 3g of ferric chloride are weighed and put into an agate mortar for full grinding. And (3) putting the mixture into a reaction kettle, heating at 160 ℃ for 8 hours, cooling to room temperature, and taking out the obtained black carbon aerogel.
Placing the carbon aerogel into a porcelain boat, placing the porcelain boat into a tube furnace, and keeping the temperature at 800 ℃ for 2 hours (5 ℃ min) under the nitrogen atmosphere -1 )。
And cooling, taking out, removing impurities by using a hydrochloric acid solution, washing to be neutral by using water, and then putting into an oven for drying to obtain a final product.
From the SEM result (FIG. 1), the morphology of the material is in the shape of a nanosphere. The specific surface area can reach 2352.1m when the nitrogen adsorption and desorption curve is measured 2 g -1 The pore size distribution was analyzed by DFT and the material had a hierarchical multi-level pore structure (fig. 2). At 0.1mol L - 1 In KOH solution, the half-wave potential of the material can reach 0.86V and the limiting current density can reach 4.2mA cm -2 (FIG. 3).
Example two
The most common starch in polysaccharide is used as a precursor, and no salt is added. (pure starch without added salt)
Weighing 0.5g of corn starch, putting the corn starch into a reaction kettle, heating the corn starch at 160 ℃ for 8 hours, cooling the corn starch to room temperature, and taking out the obtained brown carbon aerogel.
Placing the carbon aerogel into a porcelain boat, placing the porcelain boat into a tube furnace, and keeping the temperature at 800 ℃ for 2 hours (5 ℃ min) under the nitrogen atmosphere -1 )。
And cooling, taking out, removing impurities by using a hydrochloric acid solution, washing to be neutral by using water, and then putting into an oven for drying to obtain a final product.
From the SEM result (FIG. 4), the morphology of the material was irregular and blocky. At 0.1mol L -1 The polarization curve measured in KOH solution at 1600rpm showed no oxygen reduction performance of the material (FIG. 5). The final carbon yield can reach 19.5%.
EXAMPLE III
The most common starch in polysaccharide is used as precursor, and ferric chloride is molten salt. (keeping the type of the simple salt, changing the mass ratio of the polysaccharide to the salt to 1: 2)
0.5g of corn starch and 1g of ferric chloride are weighed and put into an agate mortar for full grinding. And (3) putting the mixture into a reaction kettle, heating at 160 ℃ for 8 hours, cooling to room temperature, and taking out the obtained black carbon aerogel.
Placing the carbon aerogel into a porcelain boat, placing the porcelain boat into a tube furnace, and keeping the temperature at 800 ℃ for 2 hours (5 ℃ min) under the nitrogen atmosphere -1 )。
And cooling, taking out, removing impurities by using a hydrochloric acid solution, washing to be neutral by using water, and then putting into an oven for drying to obtain a final product.
At 0.1mol L -1 In KOH solution, the half-wave potential of the polarization curve display material can reach 0.71V and the limiting current density can reach 3.3mA cm at the rotating speed of 1600rpm -2 (FIG. 6).
Example four
The most common starch in polysaccharide is used as precursor, and zinc chloride is used as molten salt. (changing the type of the single salt, the mass ratio of the polysaccharide to the salt is 1: 6)
0.5g of corn starch and 3g of zinc chloride are weighed and put into an agate mortar for full grinding. Putting the mixture into a reaction kettle, heating at 160 ℃ for 8 hours, cooling to room temperature, and taking out the carbon aerogel-like black material.
Placing the carbon aerogel into a porcelain boat, placing the porcelain boat into a tube furnace, and keeping the temperature at 800 ℃ for 2 hours (5 ℃ min) under the nitrogen atmosphere -1 )。
And cooling, taking out, removing impurities by using a hydrochloric acid solution, washing to be neutral, and then putting into an oven for drying to obtain a final product.
From the SEM results (FIG. 7), the morphology of the material was broken blocks. At 0.1mol L -1 In KOH solution, the half-wave potential of the polarization curve display material can reach 0.80V and the limiting current density can reach 4.1mA cm at the rotating speed of 1600rpm -2 (FIG. 8).
EXAMPLE five
The most common starch in polysaccharide is used as precursor, and a mixture of ferric chloride and zinc chloride is used as molten salt. (the quality ratio of polysaccharide to salt is 1: 6 by changing the type of double salt)
0.5g of corn starch, 1g of zinc chloride and 2g of ferric chloride are weighed and put into an agate mortar for full grinding and uniform mixing. Putting the mixture into a reaction kettle, heating at 160 ℃ for 8 hours, cooling to room temperature, and taking out the carbon aerogel-like black material.
Placing the carbon aerogel into a porcelain boat, placing the porcelain boat into a tube furnace, and keeping the temperature at 800 ℃ for 2 hours (5 ℃ min) under the nitrogen atmosphere -1 )。
And cooling, taking out, removing impurities by using a hydrochloric acid solution, washing to be neutral by using water, and then putting into an oven for drying to obtain a final product. The final carbon yield can reach 34.1%.
From the SEM result (FIG. 9), the morphology of the material is rough nanosphere shape. The specific surface area can reach 2799.8m when the nitrogen adsorption and desorption curve is measured 2 g -1 The pore size distribution was analyzed by DFT and the material had a hierarchical multi-level pore structure (fig. 10). At 0.1mol L -1 In KOH solution, the half-wave potential of the material can reach 0.87V and the limiting current density can reach 5.2mA cm/cm when the polarization curve is measured at the rotating speed of 1600rpm -2 (FIG. 11).
EXAMPLE six
The most common starch in polysaccharide is used as precursor, and ferric chloride and ammonium chloride are used as molten salt. (the quality ratio of polysaccharide to salt is 1: 6 by changing the type of double salt)
0.5g of corn starch, 1g of ammonium chloride and 2g of ferric chloride are weighed and put into an agate mortar for fully grinding until the mixture is uniformly mixed. Putting the mixture into a reaction kettle, heating at 160 ℃ for 8 hours, cooling to room temperature, and taking out the carbon aerogel-like black material.
Placing the carbon aerogel into a porcelain boat, placing the porcelain boat into a tube furnace, and keeping the temperature at 800 ℃ for 2 hours (5 ℃ min) under the nitrogen atmosphere -1 )。
And cooling, taking out, removing impurities by using a hydrochloric acid solution, washing to be neutral by using water, and then putting into an oven for drying to obtain a final product.
From the SEM results (FIG. 12), the morphology of the material was fragmented. At 0.1mol L -1 In KOH solution, the half-wave potential of the material can reach 0.83V and the limiting current density can reach 4.6mA cm measured at the rotating speed of 1600rpm -2 (FIG. 13).
The above examples show that polysaccharide-based porous carbon oxygen reduction catalysts with different morphologies can be prepared by changing the type of molten salt and the quality of a molten salt system. Example 2 illustrates that the morphology and properties of the sample are not well modified by calcination when no salt is present, and example 3 illustrates that improvements in morphology and properties occur when the mass of salt in the molten salt system is 2 times greater than the mass of polysaccharide. When the mass ratio is less than 2, the molten salt system does not improve the polysaccharide sample and the performance well. Carbon materials of different salt types and different molten salt mass ratios can be obtained in examples 1, 4, 5 and 6. Has unique appearance and oxygen reduction performance and high carbon yield. The material obtained in the embodiment 5 has optimal oxygen reduction performance, the half-wave potential can reach 0.87V, and the limiting current density can reach 5.2mA cm -2 And is superior to most reported oxygen reduction performances.

Claims (6)

1. The method for preparing the polysaccharide-based porous carbon oxygen reduction catalyst in the environment of solvent-free high-temperature molten salt comprises the following steps
(1) Weighing 0.5-5 g of polysaccharide and single salt or double salt (the mass of the polysaccharide is more than or equal to 2) in an agate mortar, grinding for 0.5h, and putting the mixture in a reaction kettle, heating at 100-180 ℃ for 2-12 h to form the carbon aerogel.
(2) Keeping the temperature of the aerogel at 600-1000 ℃ for 0.5-5 h under inert atmosphere (the heating rate is 1-20 ℃ for min) -1 )。
(3) And cooling to room temperature, taking out, removing impurities by using a hydrochloric acid solution, washing to be neutral, and then putting into an oven for drying to obtain the polysaccharide-based porous carbon material with large specific surface area, wherein the carbon yield is high.
2. The method according to claim 1, wherein the polysaccharide in step (1) is one of the following, animal and plant polysaccharides: chitosan, chitin, glucose, arabinose, agar, starch, cellulose, dextran, fructose, galactose, arabinose, xylose, rhamnose, fucose, mannose, cyclodextrin and the like.
3. The method according to claim 1, wherein the salt in step (1) is one of the following salts or a mixed salt of two or more of the following salts: transition metal hydrochlorides, transition metal nitrates, transition metal phosphates, transition metal carbonates, and organic salts (e.g., transition metal salts of iron, cobalt, nickel, manganese, copper, zinc, etc.).
4. The method according to claim 1, wherein in the step (1), the mass of the single salt or the mixed salt is 2-20 times that of the polysaccharide.
5. The method according to claim 1, wherein the pre-carbonization temperature in step (1) is 100-180 ℃ and the pre-carbonization time is 2-12 h.
6. The method according to claim 1, wherein the inert gas in step (2) is selected from the group consisting of nitrogen, argon and helium. Carbonizing at 600-1000 ℃ in the atmosphere of inert gas, and keeping the temperature for 0.5-5 hours; in the process, the temperature rise rate is controlled to be 1-20 ℃ min -1 。
CN202210098966.8A 2022-01-25 2022-01-25 Method for preparing polysaccharide-based porous carbon oxygen reduction catalyst by solvent-free molten salt Pending CN114864962A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104495788A (en) * 2014-12-12 2015-04-08 南京工业大学 Preparation method of porous carbon
CN104528720A (en) * 2014-12-19 2015-04-22 浙江大学 Preparation method and product of multistage porous carbon material
CN109516457A (en) * 2018-12-05 2019-03-26 华南师范大学 A kind of chitosan-based porous carbon ball and preparation method thereof
CN110668441A (en) * 2019-10-17 2020-01-10 北京化工大学 Crop tuber-based porous carbon material and preparation method and application thereof
CN112520738A (en) * 2020-12-04 2021-03-19 上海海事大学 Efficient low-cost preparation method of super activated carbon

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104495788A (en) * 2014-12-12 2015-04-08 南京工业大学 Preparation method of porous carbon
CN104528720A (en) * 2014-12-19 2015-04-22 浙江大学 Preparation method and product of multistage porous carbon material
CN109516457A (en) * 2018-12-05 2019-03-26 华南师范大学 A kind of chitosan-based porous carbon ball and preparation method thereof
CN110668441A (en) * 2019-10-17 2020-01-10 北京化工大学 Crop tuber-based porous carbon material and preparation method and application thereof
CN112520738A (en) * 2020-12-04 2021-03-19 上海海事大学 Efficient low-cost preparation method of super activated carbon

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Application publication date: 20220805