CN114275763A - Method for removing trace oxygen in porous carbon at low temperature - Google Patents
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Abstract
The invention discloses a method for removing trace oxygen in porous carbon at low temperature, and belongs to the technical field of modification of porous carbon. The method comprises the following steps: placing the porous carbon and a transition metal catalyst in a reactor, introducing a mixed gas of hydrogen and inert gas, heating, and cooling to room temperature after reaction to obtain the deoxidized porous carbon. According to the invention, hydrogen molecules are dissociated into high-activity hydrogen atoms at a lower temperature by the transition metal catalyst, so that oxygen-containing groups on the porous carbon are efficiently removed; the method has adjustability, and can accurately regulate the content of oxygen-containing groups of the porous carbon by selecting a proper transition metal catalyst, changing the reduction temperature and regulating the reduction time, thereby meeting various requirements of actual production.
Description
Technical Field
The invention relates to the technical field of modification of porous carbon, in particular to a method for removing trace oxygen in porous carbon at low temperature.
Background
Electric Double Layer Supercapacitors (EDLCs) are novel energy storage and conversion equipment, have the advantage of rapid charging and discharging, and are widely applied to the fields of power supplies, aerospace and the like. However, EDLCs have the disadvantage of low energy density, and there are two methods for increasing energy density: (1) the specific capacitance of the porous carbon electrode material is improved; (2) the voltage resistance of the porous carbon electrode material is improved. Compared with the two methods, the method has the advantages that the voltage resistance of the porous carbon electrode material is improved, and the energy density of the EDLCs can be improved by square times, so that the method has more advantages in practical application. However, the voltage resistance of the porous carbon electrode material is improvedThe key point of the property is to reduce the content of oxygen-containing functional groups in the porous carbon. This is because porous carbon has an abundant hierarchical pore structure, which inevitably brings about many defects (mainly oxygen-containing groups) to porous carbon. And the oxygen-containing group is under a high voltage window (>3.0V) can generate CO and CO by side reaction with electrolyte2Gas and a layer of solid electrolyte SEI film are generated to cover the surface of the porous carbon electrode, and the diffusion channel of electrolyte ions is damaged, so that the capacity of the EDLCs is rapidly attenuated, and the energy density is greatly reduced. Therefore, it is urgently needed to develop a new technology for removing the oxygen-containing functional groups on the surface of the porous carbon material.
The existing technology for removing oxygen-containing groups on the surface of porous carbon mainly comprises a chemical reduction method and a thermal reduction method. The chemical reduction method is to remove oxygen-containing functional groups such as hydroxyl, epoxy and the like on the surface of the porous carbon material by chemical reduction reagents such as hydrazine hydrate, sodium borohydride, tannic acid, ascorbic acid and the like; however, the chemical reduction method has high requirements for production equipment, and the use of chemical reagents is not environment-friendly. The thermal reduction method is to remove oxygen-containing groups on the surface of the porous carbon by high-temperature treatment in an inert atmosphere (nitrogen or argon) or a reducing atmosphere (hydrogen or ammonia); the specific principle is that thermodynamically unstable functional groups (such as carboxyl, hydroxyl, ester group, epoxy group and the like) on the surface of the porous carbon material are removed through the action of thermal bond scission; however, the thermal reduction method is restricted by the treatment temperature, the treatment temperature is generally 800-1000 ℃, the effect of removing oxygen-containing groups of the porous carbon is not obvious when the temperature is too low, and the specific surface area and the pore channel structure of the porous carbon are damaged when the treatment temperature is too high, so that the collapse of the pore channel structure is caused. Therefore, the two technologies are difficult to economically and efficiently remove the trace oxygen of the porous carbon, and obvious short plates exist.
Disclosure of Invention
In order to solve the problems, the invention provides a method for removing trace oxygen in porous carbon at low temperature. Dissociating hydrogen molecules into high-activity hydrogen atoms at a lower temperature through a transition metal catalyst, thereby efficiently removing oxygen-containing groups on the porous carbon; the method has adjustability, and can accurately regulate the content of oxygen-containing groups of the porous carbon by selecting a proper transition metal catalyst, changing the reduction temperature and regulating the reduction time, thereby meeting various requirements of actual production.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for removing trace oxygen in porous carbon at low temperature comprises the following steps:
placing the porous carbon and a transition metal catalyst in a reactor, introducing a mixed gas of hydrogen and inert gas, heating, and cooling to room temperature after reaction to obtain the deoxidized porous carbon.
Preferably, the porous carbon comprises one or more of coal-based porous carbon, petroleum-based porous carbon, and biomass porous carbon.
Preferably, the transition metal catalyst includes one or more of a platinum-based catalyst, a palladium-based catalyst, and a nickel-based catalyst.
More preferably, the platinum-based catalyst is a Pt/C catalyst in which the Pt content is 0 to 20 wt% but not 0; the palladium-based catalyst is a Pd/C catalyst, wherein the Pd content is 0-20 wt% but not 0; the nickel-based catalyst is a Ni/C catalyst, wherein the Ni content is 0-20 wt% but not 0.
Preferably, the mass ratio of the porous carbon to the transition metal catalyst is 0.1-10.
Preferably, the porous carbon is placed at the position of an upper air inlet, the transition metal catalyst is placed at a lower air inlet, and the central distance between the porous carbon and the transition metal catalyst is 1 cm-10 cm.
Preferably, the inert gas is hydrogen-argon mixed gas; the hydrogen accounts for 5-10% of the volume percentage of the mixed gas; the introduction rate of the mixed gas is 20-100 mL/min in terms of the content of the mixed gas.
Preferably, the temperature rise is from 300 ℃ to 700 ℃ at a rate of 0.5 ℃/min to 10 ℃/min.
Preferably, the reaction time is 0.5-4 h.
Preferably, the cooling rate of the temperature to the room temperature is 0.5-10 ℃/min.
The invention has the following beneficial technical effects:
according to the invention, hydrogen molecules are dissociated into high-activity hydrogen atoms at a lower temperature by the transition metal catalyst, so that oxygen-containing groups on the porous carbon are efficiently removed; the method has adjustability, selects a proper transition metal catalyst, changes the reduction temperature, regulates and controls the reduction time, can accurately regulate and control the content of oxygen-containing groups of the porous carbon, and meets various requirements of actual production.
The method for removing the oxygen-containing groups in the porous carbon provided by the invention is composed of one step, has the advantages of simple operation, mild working condition, low energy consumption, good universality, high efficiency of removing the oxygen-containing groups and the like, enriches the method for removing the oxygen-containing groups in the porous carbon, and provides guiding significance for the production of voltage-resistant supercapacitors.
Drawings
FIG. 1 is a schematic diagram of the method for removing oxygen-containing groups from porous carbon by using a transition metal catalyst.
FIG. 2 is a graph showing the surface oxygen-containing group content and species of a 21-KSN type porous carbon feedstock used in an example of the present invention; wherein (a) is O1s high resolution spectrum, and (b) is C1s high resolution spectrum.
FIG. 3 is a graph showing the content and kind of oxygen-containing groups of the deoxidized porous carbon prepared in comparative example 2 of the present invention; wherein (a) is O1s high resolution spectrum, and (b) is C1s high resolution spectrum.
FIG. 4 shows the surface oxygen-containing group content and kind of the deoxidized porous carbon prepared in example 6 of the present invention; wherein (a) is O1s high resolution spectrum, and (b) is C1s high resolution spectrum.
FIG. 5 shows the surface oxygen-containing group content and kind of the deoxidized porous carbon prepared in example 14 of the present invention; wherein (a) is O1s high resolution spectrum, and (b) is C1s high resolution spectrum.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated value or intervening value in a stated range, and any other stated or intervening value in a stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The 21-KSN type porous carbon used in the present invention was korean PCT supercapacitor activated carbon.
The YP-50 type porous carbon used in the invention is Japanese Kuraray supercapacitor activated carbon.
Example 1
0.4g of 21-KSN type porous carbon and 0.1g of Pt/C (platinum content: 10 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 3.2 at% by XPS.
Example 2
0.1g of 21-KSN type porous carbon and 0.4g of Pt/C (platinum content: 10 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.4 at% by XPS.
Example 3
0.1g of 21-KSN type porous carbon and 0.1g of Pt/C (platinum content: 10 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 1 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.7 at% by XPS.
Example 4
0.1g of 21-KSN type porous carbon and 0.1g of Pt/C (platinum content: 10 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 10 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 3.7 at% by XPS.
Example 5
0.1g of 21-KSN type porous carbon and 0.1g of Pt/C (platinum content: 10 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 500 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 3.1 at% by XPS.
Example 6
0.1g of 21-KSN type porous carbon and 0.1g of Pt/C (platinum content: 10 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.7 at% by XPS.
Example 7
0.1g of 21-KSN type porous carbon and 0.1g of Pt/C (platinum content: 10 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating the mixture to 700 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%), keeping the temperature for 1h, and cooling the mixture to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.6 at% by XPS.
Example 8
0.1g of 21-KSN type porous carbon and 0.1g of Pt/C (platinum content: 10 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 2h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.2 at% by XPS.
Example 9
0.1g of 21-KSN type porous carbon and 0.1g of Pt/C (platinum content: 10 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min at the heating rate of 5 ℃/min, keeping the temperature for 4h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 1.8 at% by XPS.
Example 10
0.1g of 21-KSN type porous carbon and 0.1g of Pt/C (platinum content: 5 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.9 at% by XPS.
Example 11
0.1g of 21-KSN type porous carbon and 0.1g of Pt/C (platinum content: 5 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 2h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.5 at% by XPS.
Example 12
0.1g of 21-KSN type porous carbon and 0.1g of Pt/C (platinum content: 5 wt%) as a platinum carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min at the heating rate of 5 ℃/min, keeping the temperature for 4h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.2 at% by XPS.
Example 13
0.1g of 21-KSN type porous carbon and 0.1g of Ni/C catalyst (nickel content 5 wt%) are respectively put into adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was measured by XPS to be 4.0 at%.
Example 14
0.1g of 21-KSN type porous carbon and 0.1g of Ni/C catalyst (nickel content 5 wt%) are respectively put into adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 655 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%), keeping the temperature for 1h, and then cooling to room temperature at 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 3.4 at% by XPS.
Example 15
0.1g of 21-KSN type porous carbon and 0.1g of Ni/C catalyst (nickel content 5 wt%) are respectively put into adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating the mixture to 700 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%), keeping the temperature for 1h, and cooling the mixture to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 3.1 at% by XPS.
Example 16
0.1g of 21-KSN type porous carbon and 0.1g of Ni/C catalyst (nickel content 5 wt%) are respectively put into adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 655 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%), keeping the temperature for 2h, and cooling to room temperature at 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 3.0 at% by XPS.
Example 17
0.1g of 21-KSN type porous carbon and 0.1g of Ni/C catalyst (nickel content 5 wt%) are respectively put into adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 655 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%), keeping the temperature for 4h, and cooling to room temperature at 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.8 at% by XPS.
Example 18
0.1g of 21-KSN type porous carbon and 0.1g of Pd/C (palladium content 5 wt%) as a palladium carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 500 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 3.5 at% by XPS.
Example 19
0.1g of 21-KSN type porous carbon and 0.1g of Pd/C (palladium content 5 wt%) as a palladium carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 3.1 at% by XPS.
Example 20
0.1g of 21-KSN type porous carbon and 0.1g of Pd/C (palladium content 5 wt%) as a palladium carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating the mixture to 700 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%), keeping the temperature for 1h, and cooling the mixture to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.8 at% by XPS.
Example 21
0.1g of 21-KSN type porous carbon and 0.1g of Pd/C (palladium content 5 wt%) as a palladium carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 2h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.6 at% by XPS.
Example 22
0.1g of 21-KSN type porous carbon and 0.1g of Pd/C (palladium content 5 wt%) as a palladium carbon catalyst are respectively placed in adjacent positions in a nickel boat, and the distance between the center positions of the two is 2 cm. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min at the heating rate of 5 ℃/min, keeping the temperature for 4h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.3 at% by XPS.
Example 23
0.1gYP-50 type porous carbon and 0.1g Pt/C (platinum content 10 wt%) platinum carbon catalyst were placed in adjacent positions in a nickel boat, respectively, with a distance of 2cm between the centers. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 2.8 at% by XPS.
Example 24
0.1gYP-50 type porous carbon and 0.1g Pt/C (platinum content 5 wt%) platinum carbon catalyst were placed in adjacent positions in a nickel boat, respectively, with a distance of 2cm between the centers. Then the nickel boat is put into a tube furnace, the catalyst is positioned at the upper tuyere position, and the porous carbon is positioned at the lower tuyere position. Heating to 600 ℃ at the heating rate of 5 ℃/min in hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%) with the flow rate of 50mL/min, keeping the temperature for 1h, and cooling to room temperature at the temperature of 5 ℃/min to obtain the deoxidized porous carbon. The surface oxygen content of the porous carbon was determined to be 3.0 at% by XPS.
Comparative example 1
Compared with the embodiment 6, the deoxidation process does not introduce a catalyst, only 0.1g of 21-KSN type porous carbon is put into a tube furnace, and the porous carbon is heated to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere of hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%, and the flow rate of the mixed gas is 50mL/min), kept at the constant temperature for 1h, and then cooled to the room temperature at 5 ℃/min, so that the deoxidation porous carbon is obtained. The surface oxygen content of the porous carbon was measured by XPS to be 4.0 at%.
Comparative example 2
Compared with the example 14, the deoxidation process does not introduce a catalyst, only 0.1g of 21-KSN type porous carbon is put into a tube furnace, and the porous carbon is heated to 655 ℃ at the heating rate of 5 ℃/min under the atmosphere of hydrogen-argon mixed gas (the hydrogen content is 7.0 vol%, and the flow rate of the mixed gas is 50mL/min), kept at the constant temperature for 1h, and then cooled to the room temperature at 5 ℃/min, so that the deoxidation porous carbon is obtained. The surface oxygen content of the porous carbon was determined to be 3.8 at% by XPS.
Some process parameters of examples 1 to 24 and comparative examples 1 to 2 of the present invention and the surface oxygen content of the finally prepared deoxidized porous carbon are shown in table 1.
TABLE 1
The content and the type of the surface oxygen-containing group of the 21-KSN type porous carbon raw material used in the embodiment of the invention are shown in figure 2; wherein (a) is O1s high resolution spectrum, and (b) is C1s high resolution spectrum.
The oxygen-containing group content and the kind of the deoxidized porous carbon prepared by the comparative example 2 of the invention are shown in figure 3; wherein (a) is O1s high resolution spectrum, and (b) is C1s high resolution spectrum.
The content and the type of the oxygen-containing groups on the surface of the deoxidized porous carbon prepared in the embodiment 6 of the invention are shown in figure 4; wherein (a) is O1s high resolution spectrum, and (b) is C1s high resolution spectrum.
The content and the type of the oxygen-containing groups on the surface of the deoxidized porous carbon prepared in the embodiment 14 of the invention are shown in figure 5; wherein (a) is O1s high resolution spectrum, and (b) is C1s high resolution spectrum.
Comparing fig. 2 and 3, it can be seen that the contents of C-O, C ═ O and COOH oxygen-containing groups on the surface of the 21-KSN type porous carbon were reduced by the conventional thermal reduction method (hydrogen atmosphere). This is because deoxidation and hydrogenation occur during thermal reduction, and COOH, which is poor in thermal stability, is pyrolyzed into CO2A gas. And the more stable C ═ O and hydrogen molecules are subjected to hydrogenation reaction and converted into CO gas for removal or hydrogenation to be converted into C-OH. The C-O group is removed from the surface of the porous carbon in the form of CO by the high-temperature reduction of hydrogen. Under the action of the traditional thermal reduction method (hydrogen atmosphere), the content of C-O is obviously reduced from 2.19at percent of the raw material 21-KSN to 0.74at percent.
Comparing fig. 3 and 5, it can be seen that the low-temperature deoxidation effect using Ni/C as a catalyst (example 14) is better than that of the conventional thermal reduction method (hydrogen atmosphere). In particular, the C-O content is significantly reduced (1.82 at%). This is because the deoxidation process using Ni/C as a catalyst includes a strong hydrogenation reaction involving a high-activity hydrogen atom in addition to the deoxidation reaction and the hydrogenation reaction, and therefore, a better deoxidation effect is exhibited.
Comparing fig. 4 and fig. 5, it can be seen that the deoxidation effect under the action of the Pt/C catalyst is more obvious compared with that of the Ni/C catalyst. The C-O, C-O and COOH group contents were reduced to 0.47 at%, 1.53 at% and 0.70 at%, respectively. The better catalytic system helps to dissociate more high-activity hydrogen atoms, thereby showing better deoxidation effect.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A method for removing trace oxygen in porous carbon at low temperature is characterized by comprising the following steps:
placing the porous carbon and a transition metal catalyst in a reactor, introducing a mixed gas of hydrogen and inert gas, heating, and cooling to room temperature after reaction to obtain the deoxidized porous carbon.
2. The method for removing trace oxygen in porous carbon at low temperature according to claim 1, wherein the porous carbon comprises one or more of coal-based porous carbon, petroleum-based porous carbon and biomass porous carbon.
3. The method for removing trace oxygen from porous carbon at low temperature according to claim 1, wherein the transition metal catalyst comprises one or more of a platinum-based catalyst, a palladium-based catalyst and a nickel-based catalyst.
4. The method for removing trace oxygen in porous carbon at low temperature according to claim 3, wherein the platinum-based catalyst is a Pt/C catalyst, wherein the Pt content is 0-20 wt% but not 0; the palladium-based catalyst is a Pd/C catalyst, wherein the Pd content is 0-20 wt% but not 0; the nickel-based catalyst is a Ni/C catalyst, wherein the Ni content is 0-20 wt% but not 0.
5. The method for removing the trace oxygen in the porous carbon at the low temperature according to claim 1, wherein the mass ratio of the porous carbon to the transition metal catalyst is 0.1-10.
6. The method for removing the trace oxygen in the porous carbon at the low temperature according to claim 1, wherein the porous carbon is placed at an upper air inlet, the transition metal catalyst is placed at a lower air inlet, and the central distance between the porous carbon and the lower air inlet is 1 cm-10 cm.
7. The method for removing trace oxygen in porous carbon at low temperature according to claim 1, wherein the inert gas is hydrogen-argon mixed gas; the hydrogen accounts for 5-10% of the volume percentage of the mixed gas; the introduction rate of the mixed gas is 20-100 mL/min in terms of the content of the mixed gas.
8. The method for removing trace oxygen in porous carbon at low temperature according to claim 1, wherein the temperature is raised to 300-700 ℃ at a rate of 0.5-10 ℃/min.
9. The method for removing the trace oxygen in the porous carbon at the low temperature according to claim 1, wherein the reaction time is 0.5-4 h.
10. The method for removing trace oxygen in porous carbon at low temperature according to claim 1, wherein the cooling rate to room temperature is 0.5-10 ℃/min.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140177136A1 (en) * | 2012-12-14 | 2014-06-26 | Samsung Electro-Mechanics Co., Ltd. | Activated carbon, method for preparing the same, and electrochemical capacitor including the same |
CN110482548A (en) * | 2019-09-04 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A method of removing super capacitor active carbon oxygen-containing functional group |
US20210060534A1 (en) * | 2017-12-29 | 2021-03-04 | Hanwha Solutions Corporation | Carbon-based noble metal-transition metal catalyst enabling high selective conversion and production method therefor |
-
2021
- 2021-12-27 CN CN202111616148.4A patent/CN114275763A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140177136A1 (en) * | 2012-12-14 | 2014-06-26 | Samsung Electro-Mechanics Co., Ltd. | Activated carbon, method for preparing the same, and electrochemical capacitor including the same |
US20210060534A1 (en) * | 2017-12-29 | 2021-03-04 | Hanwha Solutions Corporation | Carbon-based noble metal-transition metal catalyst enabling high selective conversion and production method therefor |
CN110482548A (en) * | 2019-09-04 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A method of removing super capacitor active carbon oxygen-containing functional group |
Non-Patent Citations (1)
Title |
---|
ZHUANGZHUANG ZHENG ET AL: "Hydrogen Spillover Facilitating Reduction of Surface Oxygen Species on Porous Carbon", CHEMISTRYSELECT, vol. 6, no. 9, pages 1 - 2 * |
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