CN112142033A - Method for preparing transition metal-nitrogen co-doped carbon material by using waste paper - Google Patents
Method for preparing transition metal-nitrogen co-doped carbon material by using waste paper Download PDFInfo
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- CN112142033A CN112142033A CN202011007539.1A CN202011007539A CN112142033A CN 112142033 A CN112142033 A CN 112142033A CN 202011007539 A CN202011007539 A CN 202011007539A CN 112142033 A CN112142033 A CN 112142033A
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- 238000001035 drying Methods 0.000 claims description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical group [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000010941 cobalt Chemical group 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
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- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
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- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
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- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical class OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 description 15
- 239000013049 sediment Substances 0.000 description 12
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical class ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 10
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 6
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- 239000000203 mixture Substances 0.000 description 3
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Abstract
The invention discloses a method for preparing a transition metal-nitrogen element co-doped carbon material by using waste paper. The waste paper sample and the transition metal phthalocyanine derivative are compounded, then the compound is placed in a tubular furnace for pyrolysis to obtain a transition metal-nitrogen element co-doped carbon material, and the transition metal phthalocyanine derivative solution left after compounding can be enriched and separated by quantitatively adding sodium chloride, so that the recovery of the transition metal phthalocyanine derivative is realized. The method has the advantages of simple operation, few steps, low requirement on experimental conditions and easy scale production. The processing is convenient, the cost is saved, the waste utilization is realized, and the elemental analysis result of the prepared composite material shows that a sample contains transition metal and nitrogen besides carbon element, so that the application range is wide.
Description
Technical Field
The invention belongs to the field of carbon materials, and particularly relates to a method for preparing a transition metal-nitrogen element co-doped carbon material by using waste paper.
Background
Solid wastes such as household garbage and industrial waste residue cause profound harm to the environment and human health. Waste paper, one of the main components of municipal and industrial solid waste, accounts for more than 35% of the total amount of lignocellulosic waste (agricultural, municipal and industrial waste). Each year, more than 4 million tons of waste paper are produced as a waste, recyclable resource, mainly used for the production of pulp in the paper industry. However, only about 50-65% of the used paper is actually recycled because the strength of the fibers in each cycle is gradually reduced, reducing the quality of the new paper, and thus, it can be recycled only 2.4 times on average when manufacturing new paper. At present, waste paper treatment is widely performed by methods such as landfill, composting and incineration, and secondary hazard is shown.
Researchers have conducted extensive research into the use and technology of waste paper conversion into valuable products in order to better recover and process the waste paper for environmental protection and resource saving. Among the important technologies to achieve this goal are pyrolysis. Pyrolysis belongs to thermal decomposition and is carried out under the condition of no air. Because the main component of the paper substance is cellulose, the pyrolysis technology utilizes the thermal instability of organic cellulose in the garbage, and the high-temperature pyrolysis method in a non-oxidation environment can directly convert carbon-containing waste into a carbon-based material with relatively high carbon content.
The carbon material has large specific surface area, strong adsorption decomposition, humidity regulation, purification, deodorization, far infrared ray and anion efficiency, is suitable for filling floors and walls in public and civil buildings, has the functions of absorbing and releasing water, can inhibit temperature rise and multiplication of mould and microorganism, and plays a unique role in preventing mould and regulating temperature. In addition, the carbon material plays a role in supporting a catalyst layer and stabilizing an electrode structure in a fuel cell electrode, and also has various functions of providing a gas channel, an electron channel, a water drainage channel, and the like for an electrode reaction. Therefore, the cheap and effective carbon material has considerable market application prospect.
However, the common carbon-based material has a single structure, stable performance and lacks functionality, and cannot meet the application requirements of various fields, for example, the catalytic activation gain effect of the common carbon-based material is less and less obvious in the face of nowadays increasingly complex organic pollutants. Therefore, it has become an important research topic to modify and dope ordinary carbon materials reasonably, effectively regulate and control the physicochemical properties of the carbon materials, and further enhance the physicochemical properties of the carbon materials. For example, researchers have introduced nitrogen elements into carbon nanomaterials to construct nitrogen-doped carbon nanomaterials. The introduced nitrogen is doped by directly adding nitrogen atoms or nitrogen element-containing groups, and the doping can bring about the change of the structure of the carbon material and can certainly cause the occurrence of an electronic defect phenomenon. The appearance of the defect phenomenon can cause the change of the surface physical and chemical phenomenon of the nano material, so that the local regulation and control of the pore structure size and distribution and the improvement of the surface electron density distribution of the material can be carried out, and the changes finally show excellent electron transfer efficiency and play a role in accelerating the reaction process. The doping of the metal element into the carbon material can not only increase the electrical conductivity of the carbon, but also improve the oxygen reduction performance of the carbon material and endow the carbon material with magnetic characteristics.
The invention aims to provide a preparation method of a transition metal-nitrogen element co-doped carbon material, which has the advantages of convenient processing, wide application range, cost saving and waste utilization realization by properly modifying waste paper. The carbon material prepared by the invention has potential application value in the fields of electrode materials, separation, adsorption, sensing, catalysis, gas storage and the like due to the introduction of the transition metal and the nitrogen element at the same time, and is expected to greatly promote the rapid development of novel carbon nano materials in China. In addition, the carbon material also shows attractive application prospects in the fields of supercapacitors, lithium ion batteries, lithium sulfur batteries, fuel batteries and the like.
Disclosure of Invention
The invention aims to provide a method for preparing a transition metal-nitrogen element co-doped carbon material by utilizing waste paper.
The invention is realized by the following technical scheme:
the waste paper sample and the transition metal phthalocyanine derivative are compounded, then the compound is placed in a tubular furnace for pyrolysis to obtain a transition metal-nitrogen element co-doped carbon material, and the transition metal phthalocyanine derivative solution left after compounding can be enriched and separated by quantitatively adding sodium chloride, so that the recovery of the transition metal phthalocyanine derivative is realized.
The specific process for compounding the waste paper sample and the transition metal phthalocyanine derivative comprises the following steps: cutting waste paper into pieces not larger than 5 x 5mm2Adding a waste paper sample with a size into the transition metal phthalocyanine derivative solution, and stirring for 2-5h to realize that the transition metal phthalocyanine derivative molecules enter the internal structure of the waste paper fiber and reach adsorption balance; then, taking out a waste paper sample from the solution, and washing the waste paper sample for 3-5min by using 10-20ml of ethanol or acetone to remove the transition metal phthalocyanine derivative molecules accumulated on the surface of the waste paper; and finally, drying for 24 hours at 60 ℃ under vacuum, and finishing the compounding process.
In order to ensure carbonization and nano crystallization of the waste paper and the transition metal phthalocyanine derivative compound, the pyrolysis conditions are as follows: high-purity argon or nitrogen atmosphere, 500-700 ℃ pyrolysis for 4-6h, the heating rate is 3-10 ℃/min, and the cooling rate is 5-10 ℃/min.
The enrichment, separation and recovery processes of the transition metal phthalocyanine derivative solution are as follows: centrifuging the residual transition metal phthalocyanine derivative solution at 3000rpm of 2000-5 ℃ for 5-8min, removing bottom precipitate (small amount of waste paper fiber), taking the upper layer solution, adding 20-25g of sodium chloride into each 100ml of the solution under stirring to enable the solution to be nearly saturated, standing the obtained solution in a refrigerating chamber of a refrigerator for 4-6h, performing suction filtration to generate precipitate, washing the obtained precipitate with 5ml of distilled water at 2-5 ℃, centrifuging, repeating the washing and centrifuging operation for 3 times, wherein the centrifuging speed is 2000-3000rpm, the centrifuging time is 3-5min, obtaining the precipitate, and performing vacuum drying at 50 ℃ for 24h to obtain the transition metal phthalocyanine derivative.
The waste paper samples are toilet paper, box paper, printing paper, writing paper, napkin paper and filter paper.
The transition metal phthalocyanine derivative is a transition metal phthalocyanine molecule containing four amino groups, and the molecular structural formula is as follows:
wherein M is iron, cobalt or nickel ions.
Preferably, the stirring speed during the process of compounding the waste paper sample and the transition metal phthalocyanine derivative is 300-500 rpm.
Preferably, the concentration of the transition metal phthalocyanine derivative solution is 3 to 5 mmol/L.
Preferably, 2g to 3g of waste paper samples can be processed per 100ml of the transition metal phthalocyanine derivative solution.
The method has the advantages of simple operation, few steps, low requirement on experimental conditions and easy scale production. The processing is convenient, the cost is saved, the waste utilization is realized, and the elemental analysis result of the prepared composite material shows that a sample contains transition metal and nitrogen besides carbon element, so that the application range is wide.
Drawings
FIG. 1 is a scanning electron microscope image of a transition metal-nitrogen co-doped carbon material sample prepared in example 1 of the present invention;
FIG. 2 is an EDS element distribution diagram of a transition metal-nitrogen element co-doped carbon material sample prepared in example 1 of the present invention;
fig. 3 is a transmission electron microscope image of a transition metal-nitrogen co-doped carbon material sample prepared in example 2 of the present invention.
Detailed Description
Example 1
Cutting 2g waste toilet paper into pieces with size not larger than 5 x 5mm2Soaking the sample in 100ml of iron phthalocyanine derivative solution (the concentration is 3mmol/L), stirring at the rotating speed of 300rpm for 5h, taking out the waste paper sample from the solution, taking 10ml of ethanol to wash the sample for 5min, and drying in vacuum at 60 ℃ for 24h to complete the compounding process. After the waste paper is compounded with the iron phthalocyanine derivative, the waste paper is placed in a tubular furnace, the temperature is raised to 500 ℃ at the speed of 3 ℃/min under the atmosphere of high-purity argon or nitrogen, the temperature is kept for 4 hours, and then the waste paper is cooled to room temperature at the speed of 5 ℃/min to obtain the iron-nitrogen element co-doped carbon material.
The process of enriching, separating and recovering the iron phthalocyanine derivative solution comprises the following steps: centrifuging the iron phthalocyanine derivative solution left after treatment at 2000rpm for 8min, removing bottom precipitate, collecting upper layer solution, adding 20g sodium chloride per 100ml solution under stirring to make the solution nearly saturated, standing the obtained solution in a refrigerator cold storage chamber for 6h, filtering, washing the obtained precipitate with 5ml distilled water at 2 deg.C, centrifuging, repeating the above washing and centrifuging operation for 3 times, wherein the centrifugal separation speed is 2000rpm, the centrifugal separation time is 3min to obtain precipitate, and vacuum drying at 50 deg.C for 24h to obtain iron phthalocyanine derivative.
As shown in fig. 1 and fig. 2, which are a scanning electron microscope image and an EDS element distribution diagram of the iron-nitrogen element co-doped carbon material sample prepared in this example, it can be clearly seen that the obtained sample contains iron and nitrogen elements in addition to carbon element. This shows that the invention successfully prepares the iron-nitrogen element co-doped carbon material.
Example 2
Cutting 2g waste toilet paper into pieces with size of about 4 x 5mm2Soaking the sample in 100ml of iron phthalocyanine derivative solution (the concentration is 3mmol/L), stirring at the rotating speed of 400rpm for 5h, taking out the waste paper sample from the solution, taking 15ml of acetone to wash the sample for 5min, and drying in vacuum at 60 ℃ for 24h to complete the compounding process. After the waste paper is compounded with the iron phthalocyanine derivative, the waste paper is placed in a tubular furnace, the temperature is raised to 700 ℃ at the speed of 10 ℃/min under the atmosphere of high-purity argon or nitrogen, the temperature is kept for 5 hours, and then the waste paper is cooled to room temperature at the speed of 5 ℃/min to obtain the iron-nitrogen element co-doped carbon material.
As shown in fig. 3, which is a transmission electron microscope image of the iron-nitrogen co-doped carbon material sample prepared in this example, zero-valent iron (Fe) can be clearly observed0) The nano microcrystal shows that the iron-nitrogen co-doped carbon material containing the zero-valent iron nanocrystal can be successfully prepared by the method.
The process of enriching, separating and recovering the iron phthalocyanine derivative solution comprises the following steps: centrifuging 100ml of iron phthalocyanine derivative solution left in the compounding process at 3000rpm for 5min, removing bottom precipitate to obtain supernatant, adding 25g of sodium chloride under stirring, standing the obtained solution in a refrigerator for 4h to obtain precipitate, performing suction filtration, washing the obtained precipitate with 5ml of distilled water at 5 ℃, centrifuging, repeating the washing and centrifuging operations for 3 times, wherein the centrifugal separation speed is 3000rpm, the centrifugal separation time is 3min to obtain precipitate, and vacuum drying at 50 ℃ for 24h to obtain the iron phthalocyanine derivative.
Example 3
Cutting 3g of waste paper into 3 x 5mm2The sample is soaked in 120ml of cobalt phthalocyanine derivative solution (the concentration is 4mmol/L), the mixture is stirred for 2.5h at the rotating speed of 500rpm, the waste paper sample is taken out of the solution, then 20ml of ethanol is taken to wash the sample for 5min, the sample is dried in vacuum for 24h at the temperature of 60 ℃, and the compounding process is finished. And (3) compounding the sample with the cobalt phthalocyanine derivative, placing the mixture in a tubular furnace, heating to 600 ℃ at the speed of 5 ℃/min under the atmosphere of high-purity argon or nitrogen, preserving heat for 4h, and cooling to room temperature at the speed of 10 ℃/min to obtain the cobalt-nitrogen element co-doped carbon material.
The enrichment, separation and recovery process of the cobalt phthalocyanine derivative solution comprises the following steps: centrifuging 100ml of the cobalt phthalocyanine derivative solution left after treatment at the speed of 2500rpm for 6min, removing bottom sediment, taking the upper layer solution, adding 23g of sodium chloride under stirring to enable the solution to be nearly saturated, standing the obtained solution in a refrigerator for 5h to generate sediment, performing suction filtration, washing the obtained sediment with 5ml of distilled water at the temperature of 4 ℃, centrifuging, repeating the washing and centrifuging operations for 3 times, wherein the centrifugal speed is 2500rpm, the centrifugal time is 4min to obtain sediment, and performing vacuum drying at the temperature of 50 ℃ for 24h to obtain the cobalt phthalocyanine derivative.
Example 4
Cutting 2.5g waste paper of printing paper into 3 x 5mm2The sample is soaked in 120ml of cobalt phthalocyanine derivative solution (the concentration is 4mmol/L), the mixture is stirred for 3 hours at the rotating speed of 500rpm, the waste paper sample is taken out of the solution, then 10ml of acetone is taken to wash the sample for 3 minutes, the sample is dried in vacuum at 60 ℃ for 24 hours, and the compounding process is finished. And (3) compounding the sample with the cobalt phthalocyanine derivative, placing the compound in a tubular furnace, heating to 500 ℃ at the speed of 5 ℃/min under the atmosphere of high-purity argon or nitrogen, preserving heat for 4h, and cooling to room temperature at the speed of 10 ℃/min to obtain the cobalt-nitrogen element co-doped carbon material.
The enrichment, separation and recovery process of the cobalt phthalocyanine derivative solution comprises the following steps: centrifuging 100ml of the cobalt phthalocyanine derivative solution left after treatment at the speed of 2500rpm for 7min, removing bottom sediment, taking the upper layer solution, adding 23g of sodium chloride under stirring to enable the solution to be nearly saturated, standing the obtained solution in a refrigerator for 5h to generate sediment, performing suction filtration, washing the obtained sediment with 5ml of distilled water at the temperature of 3 ℃, centrifuging, repeating the washing and centrifuging operations for 3 times, wherein the centrifugal speed is 2000rpm, the centrifugal time is 5min to obtain sediment, and performing vacuum drying at the temperature of 50 ℃ for 24h to obtain the cobalt phthalocyanine derivative.
Example 5
Cutting 3g of waste writing paper into paper with size of about 4 x 5mm2Soaking the sample in 150ml of nickel phthalocyanine derivative solution (the concentration is 4mmol/L), stirring at the rotating speed of 400rpm for 3h, taking out the waste paper sample from the solution, then taking 20ml of ethanol to wash the sample for 4min, and drying in vacuum at 60 ℃ for 24h, thus completing the compounding process. And compounding the waste paper with a nickel phthalocyanine derivative, placing the waste paper in a tubular furnace, heating to 500 ℃ at the speed of 6 ℃/min under the atmosphere of high-purity argon or nitrogen, preserving the heat for 5h, and cooling to room temperature at the speed of 10 ℃/min to obtain the nickel-nitrogen element co-doped carbon material.
The enrichment, separation and recovery processes of the nickel phthalocyanine derivative solution are as follows: and (2) taking 150ml of the nickel phthalocyanine derivative solution left after treatment, carrying out centrifugal separation at the speed of 3000rpm for 6min, removing bottom sediment, taking the upper layer solution, adding 32g of sodium chloride under the stirring condition to enable the solution to be close to saturation, standing the obtained solution in a refrigerator for 4h to allow sediment to be generated, carrying out suction filtration, washing the obtained sediment with 5ml of distilled water at the temperature of 5 ℃, carrying out centrifugal separation, repeating the washing and centrifugal separation for 3 times, wherein the centrifugal rotation speed is 2000rpm, the centrifugal time is 5min to obtain sediment, and carrying out vacuum drying at the temperature of 50 ℃ for 24h to obtain the nickel phthalocyanine derivative.
Example 6
Cutting 2.5g waste napkin paper into pieces with size of about 4 x 5mm2Soaking the sample in 120ml of nickel phthalocyanine derivative solution (with the concentration of 5mmol/L), stirring at 300rpm for 4h, taking out the waste paper sample from the solution, taking 20ml of acetone to wash the sample for 5min, vacuum drying at 60 ℃ for 24h, and compoundingAnd (4) finishing. And compounding the waste paper with a nickel phthalocyanine derivative, placing the waste paper in a tubular furnace, heating to 600 ℃ at the speed of 5 ℃/min under the atmosphere of high-purity argon or nitrogen, preserving the heat for 4h, and cooling to room temperature at the speed of 10 ℃/min to obtain the nickel-nitrogen element co-doped carbon material.
The enrichment, separation and recovery processes of the nickel phthalocyanine derivative solution are as follows: centrifuging 100ml of the nickel phthalocyanine derivative solution left after treatment at 2000rpm for 8min, removing bottom precipitate, taking the upper layer solution, adding 20g of sodium chloride under stirring to enable the solution to be nearly saturated, standing the obtained solution in a refrigerator for 4h to generate precipitate, performing suction filtration, washing the obtained precipitate with 5ml of distilled water at 5 ℃, centrifuging, repeating the washing and centrifuging operation for 3 times, wherein the centrifugal speed is 2000rpm, the centrifugal time is 3min to obtain the precipitate, and performing vacuum drying at 50 ℃ for 24h to obtain the nickel phthalocyanine derivative.
Example 7
Cutting 2g of qualitative filter paper waste paper for laboratory use to a size of about 4 x 5mm2Soaking the sample in 100ml of nickel phthalocyanine derivative solution (the concentration is 3mmol/L), stirring at 500rpm for 4h, taking out the waste paper sample from the solution, taking 15ml of ethanol to wash the sample for 4min, and drying in vacuum at 60 ℃ for 24h to complete the compounding process. And compounding the waste paper with a nickel phthalocyanine derivative, placing the waste paper in a tubular furnace, heating to 500 ℃ at the speed of 5 ℃/min under the atmosphere of high-purity argon or nitrogen, preserving the heat for 6h, and cooling to room temperature at the speed of 10 ℃/min to obtain the nickel-nitrogen element co-doped carbon material.
The enrichment, separation and recovery processes of the nickel phthalocyanine derivative solution are as follows: centrifuging 100ml of the nickel phthalocyanine derivative solution left after treatment at 3000rpm for 5min, removing bottom precipitate, taking the upper layer solution, adding 20g of sodium chloride under stirring to enable the solution to be nearly saturated, standing the obtained solution in a refrigerator for 6h to generate precipitate, performing suction filtration, washing the obtained precipitate with 5ml of distilled water at the temperature of 3 ℃, centrifuging, repeating the washing and centrifuging operation for 3 times, wherein the centrifugal speed is 3000rpm, the centrifugal time is 3min to obtain the precipitate, and performing vacuum drying at 50 ℃ for 24h to obtain the nickel phthalocyanine derivative.
Claims (9)
1. A method for preparing a transition metal-nitrogen element co-doped carbon material by using waste paper is characterized by comprising the following steps: the waste paper sample and the transition metal phthalocyanine derivative are compounded, then the compound is placed in a tubular furnace for pyrolysis to obtain a transition metal-nitrogen element co-doped carbon material, and the transition metal phthalocyanine solution left after compounding can be enriched and separated by quantitatively adding sodium chloride, so that the recovery of the transition metal phthalocyanine derivative is realized.
2. The method for preparing the transition metal-nitrogen co-doped carbon material by using the waste paper as claimed in claim 1, wherein: the waste paper sample and the transition metal phthalocyanine derivative are compounded as follows:
cutting waste paper into pieces not larger than 5 x 5mm2Adding a waste paper sample with a size into the transition metal phthalocyanine derivative solution, and stirring for 2-5h to realize that the transition metal phthalocyanine derivative molecules enter the internal structure of the waste paper fiber and reach adsorption balance; then, taking out a waste paper sample from the solution, and washing the waste paper sample for 3-5min by using 10-20ml of ethanol or acetone to remove the transition metal phthalocyanine derivative molecules accumulated on the surface of the waste paper; and finally, drying for 24 hours at 60 ℃ under vacuum, and finishing the compounding process.
3. The method for preparing the transition metal-nitrogen co-doped carbon material by using the waste paper as claimed in claim 1, wherein: the pyrolysis conditions for pyrolysis in the tube furnace are as follows: high-purity argon or nitrogen atmosphere, 500-700 ℃ pyrolysis for 4-6h, the heating rate is 3-10 ℃/min, and the cooling rate is 5-10 ℃/min.
4. The method for preparing the transition metal-nitrogen co-doped carbon material by using the waste paper as claimed in claim 1, wherein: the enrichment, separation and recovery processes of the transition metal phthalocyanine derivative solution are as follows: centrifuging the treated transition metal phthalocyanine derivative solution at 3000rpm of 2000-5 for 5-8min, removing bottom precipitate, collecting the upper layer solution, adding 20-25g sodium chloride into each 100ml solution under stirring to make the solution nearly saturated, standing the obtained solution in a refrigerator for 4-6h to generate precipitate, suction filtering, washing the obtained precipitate with 5ml distilled water at 2-5 deg.C, centrifuging at 3000rpm of 2000-5 min for 3 times, and vacuum drying at 50 deg.C for 24h to obtain the transition metal phthalocyanine derivative.
5. The method for preparing the transition metal-nitrogen element co-doped carbon material using the waste paper as set forth in claim 1 or 2, wherein: the waste paper samples are toilet paper, box paper, printing paper, writing paper, napkin paper and filter paper.
6. The method for preparing the transition metal-nitrogen element co-doped carbon material by using the waste paper as claimed in claim 1, 2 or 4, wherein: the transition metal phthalocyanine derivative is a transition metal phthalocyanine molecule containing four amino groups, and the molecular structural formula is as follows:
wherein M is iron, cobalt or nickel ions.
7. The method for preparing the transition metal-nitrogen co-doped carbon material by using the waste paper as claimed in claim 2, wherein: in the process of compounding the waste paper sample and the transition metal phthalocyanine derivative, the stirring speed is 300-500 rpm.
8. The method for preparing the transition metal-nitrogen element co-doped carbon material using the waste paper as set forth in claim 2 or 4, wherein: the concentration of the phthalocyanine derivative solution is 3-5 mmol/L.
9. The method for preparing the transition metal-nitrogen co-doped carbon material by using the waste paper as claimed in claim 2, wherein: 2g to 3g of waste paper samples can be treated per 100ml of said metal phthalocyanine solution.
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