CN109037704B - Nitrogen-doped 3D porous carbon material and preparation method and application thereof - Google Patents
Nitrogen-doped 3D porous carbon material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of battery catalysts, and discloses a nitrogen-doped 3D porous carbon material and a preparation method and application thereof. The method comprises the following steps: (1) pretreating a biomass material in a cellulase solution to obtain a pretreated biomass material; the biomass material is eucalyptus and/or poplar; (2) carbonizing the pretreated biomass material to obtain a porous carbon material; (3) mixing porous carbon and a nitrogen-containing compound in water, drying and carbonizing to obtain a nitrogen-doped three-dimensional porous carbon material; the carbonization temperature is 800-1000 ℃. The nitrogen-doped three-dimensional porous carbon material has high specific surface area and a multi-level pore structure, and has good oxygen reduction and oxygen precipitation activities and high catalytic activity. The method is simple, and the used raw materials are biomass materials, are cheap and easily available and can be regenerated. The nitrogen-doped three-dimensional porous carbon material is applied to the field of catalysis.
Description
Technical Field
The invention belongs to the technical field of battery catalysts, relates to a nitrogen-doped 3D porous carbon material, and a preparation method and application thereof, and particularly relates to a nitrogen-doped 3D porous carbon material prepared by using eucalyptus wood pretreated by cellulase, and a method and application thereof. The carbon material acts as a catalyst to electrocatalysis a cathodic oxygen reduction reaction in a fuel cell.
Background
In recent years, environmental pollution and shortage of fossil fuels have severely restricted the development of the world economy and the stabilization of the ecological environment. The development of green energy will play a key role in solving these problems. The preparation of chemical devices from renewable compounds such as biomass as raw materials for capturing and storing these energy sources is a crucial step in the process. Carbon materials are considered to be the most important electrode materials for chemical devices such as supercapacitors and rechargeable batteries due to their advantages of large surface area, light weight, good electrical conductivity, high thermal/chemical stability, etc.
Compared with carbon materials with other structures, the 3D carbon nano material has an interconnected structure, so that the transport distance of ions in the carbon material can be shortened, and a continuous and rapid electron transmission way is provided. In addition, the structural interconnectivity ensures that the 3D carbon nanomaterial has higher electrical conductivity and better mechanical stability. Therefore, the design, manufacture and application of different forms of 3D carbon nanomaterials (such as carbon nanotube networks, graphene gels, graphene foams and 3D CNFs, etc.) are widely studied. However, most of these 3D carbon nanomaterials are prepared from small molecular compounds using a bottom-up method, which is complicated and time-consuming. Therefore, the development of a simple, convenient and easily-obtained carbon material with a 3D hierarchical porous structure and higher mechanical strength has important significance in energy conversion application.
Disclosure of Invention
Aiming at the problems of high price of raw materials, complex process, strong acid and strong base etching and the like in the traditional porous carbon preparation method, the invention aims to provide a nitrogen-doped 3D porous carbon material prepared by utilizing cellulase pretreatment and a method thereof. The method provided by the invention conforms to the concept of green and sustainable development, is simple and feasible, has low cost, and has an important application prospect in the field of catalysis. The nitrogen-doped 3D porous carbon material (three-dimensional porous carbon material) prepared by the invention has a hierarchical pore structure and higher strength, and has higher catalytic activity when being used in an electrocatalytic oxygen reduction reaction.
Another object of the present invention is to provide applications of the above nitrogen-doped 3D porous carbon material. The nitrogen-doped 3D porous carbon material is used as a catalyst, in particular a catalyst for a metal-air battery, a hydrogen-oxygen fuel cell, a methanol fuel cell and the like.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a nitrogen-doped 3D porous carbon material by cellulase pretreatment comprises the following steps:
(1) pretreating a biomass material in a cellulase solution to obtain a pretreated biomass material; the biomass material is eucalyptus and/or poplar;
(2) carbonizing the pretreated biomass material to obtain a porous carbon material;
(3) and (3) mixing the porous carbon and the nitrogen-containing compound in water, drying and carbonizing to obtain the nitrogen-doped three-dimensional porous carbon material.
The concentration of the cellulase in the cellulase solution in the step (1) is 10-400U/mL;
the mass-volume ratio of the biomass material to the cellulase solution in the step (1) is (1-5) g: 50 mL;
the pretreatment conditions in the step (1) are as follows: the temperature of pretreatment is 30-50 ℃, the speed of a shaking table is 50-150 rpm, and the heat preservation time is 2-48 h;
in the step (2), the carbonization temperature is 500-800 ℃, and the carbonization time is 0.5-2 h;
the temperature rise rate of carbonization temperature rise is 1-10 ℃/min;
in the step (3), the nitrogen-containing compound is more than one of ammonium chloride, ammonium phosphate, urea, thiourea and ammonium dihydrogen phosphate;
the mass ratio of the porous carbon to the nitrogen-containing compound is 1 g: (1-50) g;
the drying temperature is 60-105 ℃;
in the step (3), the carbonization temperature is 800-1000 ℃, the carbonization time is 0.5-4 h, and the temperature rise rate of carbonization temperature rise is 1-10 ℃/min.
The carbonization in the steps (2) and (3) is carried out in a protective gas atmosphere.
The nitrogen-doped 3D porous carbon material is prepared by the method.
The nitrogen-doped 3D porous carbon material is applied to the field of catalysts, in particular to the application of the nitrogen-doped 3D porous carbon material in electrocatalysis of metal-air batteries, hydrogen-oxygen fuel cells and/or methanol fuel cells, and the nitrogen-doped 3D porous carbon material is used as a catalytic material for electrocatalysis of oxygen reduction reaction. The metal-air battery is preferably a zinc-air battery.
When the nitrogen-doped 3D porous carbon is used as a zinc-air battery oxygen electrode catalytic material, 6M potassium hydroxide and 0.2M zinc acetate solution are prepared to be used as electrolyte solution, and electrochemical performance test is carried out.
The nitrogen-doped 3D porous carbon is applied to a super capacitor.
According to the invention, the 3D carbon nanomaterial with a hierarchical pore structure and high strength is obtained by adopting cellulase to pretreat the biological materials of eucalyptus and poplar and combining a carbonization method, and the 3D carbon nanomaterial has high catalytic activity when being used in an electrocatalytic oxygen reduction reaction. Renewable resources are fully used in the whole material preparation process, and the principle of green chemistry is reflected.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the raw materials used in the invention are biomass materials, are cheap and easily available, are renewable, fully utilize renewable biomass resources, and are a green way for preparing the 3D porous carbon material; the method is simple and easy to realize;
(2) the 3D porous carbon material can also be used as a substrate to be applied to various catalysis fields;
(3) the nitrogen-doped three-dimensional porous carbon material has high specific surface area and a multi-level pore structure, and has good oxygen reduction and oxygen precipitation activities and high catalytic activity.
Drawings
Fig. 1 is an SEM image of cellulose pretreated eucalyptus-based nitrogen-doped porous carbon (nitrogen-doped 3D porous carbon material) prepared in example 1; wherein a and B are SEM images of enzyme treated eucalyptus wood, C and D are enzyme treated eucalyptus wood carbon (i.e., porous carbon material), E and F are nitrogen doped 3D porous carbon material (i.e., 3D eucalyptus porous carbon), magnification: a: 10 mu m; b: 200 nm; c: 5 μm; d: 200 nm; e: 5 μm; f: 200 nm;
FIG. 2 is a nitrogen adsorption and desorption curve of the nitrogen-doped 3D porous carbon material prepared in examples 1-3 and the nitrogen-doped porous carbon prepared in example 4; wherein example 1: nitrogen doped porous carbon-900, example 2: nitrogen doped porous carbon-800, example 3: nitrogen doped porous carbon-1000, example 4: nitrogen-doped carbon-900;
FIG. 3 is an XRD (diagram b) and a Raman spectrum (diagram a) of the nitrogen-doped 3D porous carbon material prepared in examples 1-3;
FIG. 4 is an XPS analysis spectrum (panel a) and a nitrogen content histogram (panel b) of nitrogen-doped 3D porous carbon materials prepared in examples 1-3 and nitrogen-doped porous carbon prepared in example 4;
FIG. 5 is a graph showing oxygen reduction and oxygen evolution activities of the nitrogen-doped 3D porous carbon material prepared in examples 1 to 3 and the nitrogen-doped porous carbon prepared in example 4; wherein A: cyclic voltammetry curves; b: an oxygen reduction polarization curve; c: a kinetic current comparison curve; d: time-current curve (oxygen reduction); e: an oxygen evolution polarization curve; f: time-current curve (oxygen evolution); example 1: nitrogen doped porous carbon-900, example 2: nitrogen doped porous carbon-800, example 3: nitrogen doped porous carbon-1000, example 4: nitrogen-doped carbon-900;
FIG. 6 is a graph showing the performance test curves of the zinc-air battery when the nitrogen-doped 3D porous carbon material prepared in example 1 is used as a catalytic material of the zinc-air battery electrode; a: polarization and energy density curves for zinc-air cells; b: a charge-discharge polarization curve; c: constant current charge and discharge curve; d: constant current charge-discharge cycle curve.
Detailed Description
The invention will be further described with reference to specific examples and figures, but the scope of the invention as claimed is not limited thereto.
Example 1
A method for preparing a nitrogen-doped 3D porous carbon material by cellulase pretreatment comprises the following steps:
(1) dispersing 1g of eucalyptus wood in 50mL of 10U/mL cellulase solution (neutral condition, cellulase is purchased from Shanghai leaf Biotech Co., Ltd.), shaking at constant temperature of 40 ℃ and 90rpm for 24h, filtering, washing with deionized water, and drying at 60 ℃ to obtain cellulase-pretreated eucalyptus wood (namely enzyme-treated eucalyptus wood);
(2) calcining the eucalyptus wood pretreated by the cellulase at the constant temperature of 700 ℃ for 1h in a nitrogen atmosphere (the heating rate is 5 ℃/min) to obtain a porous carbon material (namely the eucalyptus wood carbon treated by the cellulase);
(3) mixing a porous carbon material and ammonium chloride in water according to a mass ratio of 1:20 (the mass volume ratio of the ammonium chloride to the water is 20 g: 60mL), evaporating to dryness at 60 ℃, grinding, and calcining for 2h at 900 ℃ in a nitrogen atmosphere to obtain a cellulase-pretreated eucalyptus-based nitrogen-doped porous carbon (namely, a nitrogen-doped 3D porous carbon material, a nitrogen-doped porous carbon-900); the nitrogen-doped porous carbon has a hierarchical pore structure.
Example 2
A method for preparing a nitrogen-doped 3D porous carbon material by cellulase pretreatment comprises the following steps:
(1) dispersing 1g of eucalyptus in 50mL of 10U/mL cellulase solution (cellulase dissolved in water), shaking at a constant temperature of 40 ℃ and 90rpm for 24h, filtering, washing and drying to obtain cellulase pretreated eucalyptus;
(2) calcining the eucalyptus wood pretreated by the cellulase at the constant temperature of 700 ℃ for 1h in a nitrogen atmosphere (the heating rate is 5 ℃/min) to obtain a porous carbon material (namely the eucalyptus wood carbon treated by the cellulase);
(3) mixing a porous carbon material and ammonium chloride in water according to a mass ratio of 1:20 (the mass volume ratio of the ammonium chloride to the water is 20 g: 60mL), evaporating to dryness at 60 ℃, grinding, and calcining for 2h at 800 ℃ in a nitrogen atmosphere to obtain the eucalyptol-based nitrogen-doped porous carbon (namely, the nitrogen-doped 3D porous carbon material, the nitrogen-doped porous carbon-800) pretreated by the cellulase; the nitrogen-doped porous carbon has a hierarchical pore structure.
Example 3
A method for preparing a nitrogen-doped 3D porous carbon material by cellulase pretreatment comprises the following steps:
(1) dispersing 1g of eucalyptus in 50mL of 10U/mL cellulase solution, shaking at 40 ℃, 90rpm for 24h at constant temperature, filtering, washing with deionized water, and drying at 60 ℃ to obtain cellulase-pretreated eucalyptus (namely enzyme-treated eucalyptus);
(2) calcining the obtained eucalyptus wood at the constant temperature of 700 ℃ in a nitrogen atmosphere for 1h (the heating rate is 5 ℃/min) after the eucalyptus wood is pretreated by cellulase to obtain a porous carbon material (namely, the eucalyptus wood carbon is treated by the enzyme);
(3) mixing a porous carbon material and ammonium chloride in water according to a mass ratio of 1:20 (the mass volume ratio of the ammonium chloride to the water is 20 g: 60mL), evaporating to dryness at 60 ℃, grinding, and calcining for 2h at 1000 ℃ in a nitrogen atmosphere to obtain the eucalyptol-based nitrogen-doped porous carbon (namely, the nitrogen-doped 3D porous carbon material, the nitrogen-doped porous carbon-1000) pretreated by the cellulase; the nitrogen-doped porous carbon has a hierarchical pore structure.
Example 4
A method of preparing nitrogen-doped porous carbon comprising the steps of:
calcining 1g of eucalyptus wood at the constant temperature of 700 ℃ for 1h in a nitrogen atmosphere (the heating rate is 5 ℃/min) to obtain a porous carbon material; mixing a porous carbon material and ammonium chloride in water according to the mass ratio of 1:20, evaporating to dryness at 60 ℃, grinding, and calcining for 2h at 900 ℃ in a nitrogen atmosphere to obtain nitrogen-doped porous carbon (nitrogen-doped carbon-900).
Structural characterization and performance testing:
fig. 1 is an SEM image of cellulose pretreated eucalyptus-based nitrogen-doped porous carbon (nitrogen-doped 3D porous carbon material) prepared in example 1; wherein a and B are SEM images of enzyme treated eucalyptus wood, C and D are enzyme treated eucalyptus wood carbon (i.e., porous carbon material), E and F are nitrogen doped 3D porous carbon material (i.e., 3D eucalyptus porous carbon), magnification: a: 10 mu m; b: 200 nm; c: 5 μm; d: 200 nm; e: 5 μm; f: 200 nm.
In the figure, A and B are the enzyme-treated eucalyptus wood material obtained in example 1, and the cellulase pretreatment can cause the surface of the eucalyptus wood to form a large number of holes, because the cellulase hydrolyzes the cellulose in the eucalyptus wood to lead the surface of the eucalyptus wood to be rough, and the structure of the eucalyptus wood becomes loose, thus being beneficial to the generation of subsequent carbonized holes. And the graphs C and D show that the eucalyptus carbon is treated by enzyme, and the more violent interconnected pore channel structures appear on the surface of the carbonized eucalyptus, because the surface of the eucalyptus becomes rough and the structure becomes loose at the same time of the pretreatment by the cellulase, and the pore channel generation is accelerated by the further carbonization. And the graphs E and F show that after the nitrogen-doped 3D porous carbon material is further mixed and carbonized with a nitrogen-containing compound, the pore structure becomes more uniform, and the 3D structure of the eucalyptus wood is kept.
FIG. 2 is a nitrogen adsorption and desorption curve of the nitrogen-doped 3D porous carbon material prepared in examples 1-3 and the nitrogen-doped porous carbon prepared in example 4; wherein example 1: nitrogen doped porous carbon-900, example 2: nitrogen doped porous carbon-800, example 3: nitrogen doped porous carbon-1000, example 4: nitrogen doped carbon-900. As can be seen from the nitrogen adsorption and desorption experiment of fig. 2, the cellulase-pretreated eucalyptus wood has the highest adsorption amount at 900 ℃ carbonization, thereby illustrating that it has the largest specific surface area. A larger specific surface area may provide more catalytically active sites. In addition, eucalyptus wood without cellulase treatment (example 4) had the smallest amount of nitrogen adsorption after carbonization, indicating that cellulase treatment can increase the specific surface area of the final carbon material.
FIG. 3 is an XRD (diagram b) and a Raman spectrum (diagram a) of the nitrogen-doped 3D porous carbon material prepared in examples 1-3; example 1: nitrogen doped porous carbon-900, example 2: nitrogen doped porous carbon-800, example 3: nitrogen doped porous carbon-1000. As can be seen from the analysis of the structure in FIG. 3, the obtained carbon material has similar ID/IGValues and similar crystal structures.
Fig. 4 is an XPS analysis spectrum (fig. a) of the nitrogen-doped 3D porous carbon material prepared in example 1 and a nitrogen content histogram (fig. b) of the nitrogen-doped 3D porous carbon materials prepared in examples 1 to 3 and the nitrogen-doped porous carbon prepared in example 4. As can be seen from fig. 4, the surface nitrogen element analysis of the porous carbon material revealed that example 1 had the highest nitrogen element content of 3.7%, and the N spectrum of the porous carbon material obtained in example 1 was peaked to correspond to pyridine nitrogen, pyrrole nitrogen, and graphite nitrogen at 397.9,400.0 eV and 401.3eV, respectively.
FIG. 5 is a graph showing oxygen reduction and oxygen evolution activities of the nitrogen-doped 3D porous carbon material prepared in examples 1 to 3 and the nitrogen-doped porous carbon prepared in example 4; wherein A: cyclic voltammetry curves; b: an oxygen reduction polarization curve; c: a kinetic current comparison curve; d: time-current curve (oxygen reduction); e: an oxygen evolution polarization curve; f: time-current curve (oxygen evolution). As can be seen from the oxygen reduction cyclic voltammogram (a) of fig. 5, the nitrogen-doped porous carbon obtained at 900 ℃ has an oxygen reduction peak comparable to that of platinum carbon. Polarization curve analysis of the obtained carbon material shows that (B) the nitrogen-doped porous carbon obtained at 900 ℃ has the same initial potential and half-wave potential as platinum carbon, but the kinetic current (C) is larger than that of commercial platinum carbon, so that the nitrogen-doped porous carbon obtained at 900 ℃ has better oxygen reduction activity. The stability of the platinum-carbon composite material is tested and found to be superior to that of the commercial platinum-carbon composite material (D). As can be seen from the oxygen precipitation activity test of the carbon materials obtained in examples 1 to 4, the nitrogen-doped porous carbon obtained at 900 ℃ has good oxygen precipitation activity (E) and stability (F).
FIG. 6 is a graph showing the performance test curves of the zinc-air battery when the nitrogen-doped 3D porous carbon material prepared in example 1 is used as a catalytic material of the zinc-air battery electrode; a: polarization and energy density curves for zinc-air cells; b: a charge-discharge polarization curve; c: constant current charge and discharge curve; d: constant current charge-discharge cycle curve. As can be seen from FIG. 6, the open circuit voltage of the zinc-air battery assembled was 1.49V, and the maximum energy density was 49.9mW cm at a voltage of 0.7V-2，10mA cm-2Has 801mA h g when discharging-1The capacity of (c). The cyclic stability of the polymer is tested at a current density of 10mA cm-2The charging and discharging cycle is carried out, and the charging and discharging efficiency is still better after 235 times (40h) of cycle.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. The application of the nitrogen-doped 3D porous carbon material in the field of catalysts is characterized in that: the application of the nitrogen-doped 3D porous carbon material in electrocatalysis of a metal-air battery, a hydrogen-oxygen fuel cell and/or a methanol fuel cell;
the preparation method of the nitrogen-doped 3D porous carbon material comprises the following steps:
(1) pretreating a biomass material in a cellulase solution to obtain a pretreated biomass material; the biomass material is eucalyptus and/or poplar;
(2) carbonizing the pretreated biomass material to obtain a porous carbon material; the carbonization temperature in the step (2) is 500-800 ℃;
(3) mixing porous carbon and a nitrogen-containing compound in water, drying and carbonizing to obtain a nitrogen-doped three-dimensional porous carbon material; the carbonization temperature in the step (3) is 900 ℃; in the step (3), the nitrogen-containing compound is more than one of ammonium chloride, ammonium phosphate, urea, thiourea and ammonium dihydrogen phosphate;
the pretreatment conditions in the step (1) are as follows: the temperature of pretreatment is 30-50 ℃, the speed of a shaking table is 50-150 rpm, and the heat preservation time is 2-48 h;
the carbonization time in the step (2) is 0.5-2 h; in the step (3), the mass ratio of the porous carbon to the nitrogen-containing compound is 1 g: (1-50) g; and (4) carbonizing for 0.5-4 h in the step (3).
2. Use according to claim 1, characterized in that: the concentration of the cellulase in the cellulase solution in the step (1) is 10-400U/mL;
the mass-volume ratio of the biomass material to the cellulase solution in the step (1) is (1-5) g: 50 mL.
3. Use according to claim 1, characterized in that: the carbonization in the steps (2) and (3) is carried out in a protective gas atmosphere.
4. Use according to claim 1, characterized in that: the metal air battery is a zinc air battery.
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