CN113148973A - Nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, and preparation and application methods thereof - Google Patents

Nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, and preparation and application methods thereof Download PDF

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CN113148973A
CN113148973A CN202110334211.9A CN202110334211A CN113148973A CN 113148973 A CN113148973 A CN 113148973A CN 202110334211 A CN202110334211 A CN 202110334211A CN 113148973 A CN113148973 A CN 113148973A
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nitrogen
electrode material
porous carbon
carbon electrode
doped porous
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CN113148973B (en
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王海鹰
贺颖捷
柴立元
吴弼朝
金林锋
杨志辉
侯兰晶
唐崇俭
刘恢
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/05Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4691Capacitive deionisation
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/03Particle morphology depicted by an image obtained by SEM
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/16Pore diameter
    • C01P2006/17Pore diameter distribution
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • C02F2001/46133Electrodes characterised by the material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • C02F2001/46152Electrodes characterised by the shape or form
    • C02F2001/46157Perforated or foraminous electrodes
    • C02F2001/46161Porous electrodes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates

Abstract

The invention provides a nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, which is characterized in that the nitrogen content of the nitrogen-doped porous carbon electrode material is 0.86-10.52 at.%, the carbon content is 74.2-93.39 at.%, and the oxygen content is 5.75-15.28 at.%; the particle size of the nitrogen-doped porous carbon electrode material is 0.5-3 mu m, and the specific surface area is 1189-3150 m2A pore volume of 0.55-2.30 cm3(ii) in terms of/g. The preparation process of the nitrogen-doped porous carbon electrode material comprises the following steps: carrying out polymerization reaction on m-phenylenediamine in aqueous solution containing persulfate, and separating, cleaning and drying a product after the polymerization reaction to obtain poly-m-phenylenediamine particles; subjecting the poly (m-phenylene)After mixing the amine particles with bicarbonate, in N2Activating at the temperature of 600-1000 ℃ in the atmosphere, and cleaning and drying after activation to finally obtain the nitrogen-doped porous carbon electrode material with excellent adsorption performance on hexavalent chromium in the water body.

Description

Nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, and preparation and application methods thereof
Technical Field
The invention relates to the field of water treatment, in particular to a nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, and a preparation method and an application method thereof.
Background
The chromium-containing wastewater is an important pollution source in the industrial processes of metallurgy and the like, the toxicity of hexavalent chromium is high, the human health and the ecological environment are seriously harmed, and the development of the high-efficiency treatment technology of the hexavalent chromium-containing wastewater is urgent. Capacitive Deionization (CDI), chemical precipitation, adsorption, ion exchange, membrane treatment, and the like are the main methods for removing hexavalent chromium. Among them, capacitive deionization has been widely noticed by researchers because of its advantages such as low cost, easy regeneration of electrodes, no secondary pollution, and simple operation.
Currently, the CDI process research at home and abroad mainly focuses on the development of carbon electrode materials, but because of the low specific capacitance of carbon materials, the carbon electrode has low electric adsorption capacity, and the development and application of CDI are greatly limited. In recent years, nitrogen (N) doping has received much attention from researchers as one of effective means for changing the electronic structure of carbon materials and improving their electrical, chemical, optical, and other properties; however, nitrogen-doped carbon is rarely applied to removing hexavalent chromium by CDI, and the action of nitrogen is not deeply studied, so that the development and application of nitrogen-doped porous carbon in the treatment of hexavalent chromium-containing wastewater are greatly limited, and the result of poor recovery efficiency of hexavalent chromium in the wastewater at present is caused.
In view of the above, it is necessary to provide a nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, and a preparation method and an application method thereof, so as to solve or at least alleviate the technical defect of poor recovery efficiency of hexavalent chromium in wastewater.
Disclosure of Invention
The invention mainly aims to provide a nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, and preparation and application methods thereof, and aims to solve the technical problem of poor recovery efficiency of hexavalent chromium in wastewater.
In order to achieve the purpose, the invention provides a nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, wherein the nitrogen content of the nitrogen-doped porous carbon electrode material is 0.86-10.52 at.%, the carbon content is 74.2-93.39 at.%, and the oxygen content is 5.75-15.28 at.%;
the particle size of the nitrogen-doped porous carbon electrode material is 0.5-3 mu m, and the specific surface area is 1189-3150 m2A pore volume of 0.55-2.30 cm3/g。
The invention also provides a preparation process of the nitrogen-doped porous carbon electrode material, which comprises the following steps:
s1, carrying out polymerization reaction on m-phenylenediamine in an aqueous solution containing persulfate, and then sequentially carrying out separation operation, first cleaning operation and first drying operation on a product obtained by the polymerization reaction to obtain poly (m-phenylenediamine) particles;
s2, mixing the particles of poly (m-phenylenediamine) with bicarbonate, and adding N2Activating at 600-1000 deg.C in atmosphere; and sequentially performing a second cleaning operation and a second drying operation on the activated product to obtain the nitrogen-doped porous carbon electrode material.
Further, in the S1, the step of subjecting m-phenylenediamine to polymerization reaction in an aqueous solution containing a persulfate includes: and adding the aqueous solution of the persulfate into the aqueous solution of the m-phenylenediamine, and stirring at the temperature of 0-40 ℃ for 0.5-48 h.
Further, in the step S1, the temperature of the stirring treatment is 25 ℃, and the time of the stirring treatment is 8 hours; in S2, the activation time is 2 h.
Further, in the S1, the molar ratio of the m-phenylenediamine to the persulfate is 1: 0.5 to 2;
in the S2, the mass ratio of the poly (m-phenylenediamine) particles to the potassium bicarbonate is 1: 3 to 5.
Further, the persulfate includes one of sodium persulfate and ammonium persulfate.
Further, the first washing operation includes: washing a product obtained by the polymerization reaction with an ammonia water solution and an aqueous solution in sequence;
the second cleaning operation comprises: and cleaning the product obtained after activation by using a hydrochloric acid solution and an aqueous solution in sequence.
The invention also provides a nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, which is prepared by adopting the preparation process of the nitrogen-doped porous carbon electrode material.
The invention also provides application of the nitrogen-doped porous carbon electrode material in adsorption of hexavalent chromium.
The invention also provides a method for adsorbing hexavalent chromium, which is characterized in that the nitrogen-doped porous carbon electrode material is used on an electrode of a capacitive deionization device;
carrying out hexavalent chromium adsorption treatment on a hexavalent chromium solution with the initial concentration of 50-300mg/L by using the capacitive deionization device; wherein the applied voltage of the capacitive deionization device is 0-1.2V.
Compared with the prior art, the invention has the following advantages:
the nitrogen-doped porous carbon electrode material has excellent electric adsorption performance on hexavalent chromium in a water body, can reach 140.4mg/g, is superior to most of the conventional electrode materials, and is suitable for purifying chromium pollutants in industrial wastewater and underground water; moreover, the nitrogen-doped porous carbon electrode material obtained by the preparation method has a large specific surface area, and in the preparation method, the N content can be regulated and controlled by changing the activation temperature, and the activation temperature can also be set to a specific value, so that the nitrogen-doped porous carbon electrode material with a better adsorption effect on hexavalent chromium in application can be obtained; in addition, the preparation method has simple process and easily controlled conditions, and is easy to realize industrialization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is an SEM image of nitrogen-doped porous carbon electrode materials prepared in examples 1-3;
FIG. 2 is a graph showing the pore size distribution of the nitrogen-doped porous carbon electrode material prepared in examples 1 to 3;
FIG. 3 is the EDS-mapping chart of NPC-800 in example 2;
FIG. 4 is a graph showing the electro-adsorption performance of NPC-600, NPC-800 and NPC-1000 on hexavalent chromium in example 4;
FIG. 5 is a graph showing the effect of NPC-800 in example 5 on the removal of hexavalent chromium at various voltages;
FIG. 6 is a graph showing the effect of NPC-800 on the removal of hexavalent chromium at different concentrations in example 6.
The implementation, functional features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It should be noted that all the directional indicators (such as the upper and lower … …) in the embodiment of the present invention are only used to explain the relative position relationship, movement, etc. of the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
It will be appreciated by those skilled in the art that the Pore Diameter in the figures can be represented as aperture, q, without affecting the understanding of the present inventioneCan be expressed as a saturated Adsorption amount, an Applied voltage can be expressed as an Applied voltage, The removal rate of Cr can be expressed as a chromium removal rate, The initial concentration of Cr can be expressed as an initial concentration of chromium, and an Adsorption amount can be expressed as an Adsorption amount.
In order to improve the recovery efficiency of hexavalent chromium in wastewater, the invention provides a nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, which is used in a capacitive deionization device, so that the hexavalent chromium is efficiently adsorbed.
The nitrogen content of the nitrogen-doped porous carbon electrode material can be 0.86-10.52 at.%, the carbon content can be 74.2-93.39 at.%, and the oxygen content can be 5.75-15.28 at.%;
particle size of the nitrogen-doped porous carbon electrode materialCan be 0.5 to 3 mu m, and the specific surface area can be 1189 to 3150m2The pore volume can be 0.55-2.30 cm3(ii) in terms of/g. In the present invention, the size among the above particle sizes may be expressed as a particle diameter.
In addition, in order to further improve the recovery efficiency of hexavalent chromium in wastewater, the nitrogen content of the nitrogen-doped porous carbon electrode material can be 2.21 at.%, the carbon content can be 88.15 at.%, and the oxygen content can be 9.65 at.%;
when the particle size of the nitrogen-doped porous carbon electrode material is 0.5-3 mu m, the specific surface area can be 3150m2The pore volume can be 1.52 cm/g3/g。
In order to obtain the nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, the invention also provides a preparation process for preparing the nitrogen-doped porous carbon electrode material, which comprises the following steps:
s1, carrying out polymerization reaction on m-phenylenediamine in an aqueous solution containing persulfate, and then sequentially carrying out separation operation, first cleaning operation and first drying operation on a product obtained by the polymerization reaction to obtain the poly-m-phenylenediamine particles.
Wherein the separation operation may be performed by suction filtration after the polymerization reaction is completed, so as to obtain the poly-m-phenylenediamine particles. The first washing operation may include: washing a product obtained by the polymerization reaction with an ammonia water solution and an aqueous solution in sequence; the ammonia water may be a diluted solution having a dilution ratio of 50%.
S2, mixing the particles of poly (m-phenylenediamine) with bicarbonate, and adding N2Activating at 600-1000 deg.C in atmosphere; and sequentially performing a second cleaning operation and a second drying operation on the activated product to obtain the nitrogen-doped porous carbon electrode material.
Wherein the second washing operation may include: washing the product obtained after activation by using a hydrochloric acid solution and an aqueous solution in sequence; the concentration of the hydrochloric acid solution can be 0.1-1M generally, and the dosage can be 0.1-2L generally.
In the above embodiment, the nitrogen-doped porous carbon electrode material is synthesized by generating nitrogen-containing poly-m-phenylenediamine particles, utilizing the activation pore-forming effect of potassium bicarbonate and adopting the specific activation treatment process in step S2; the synthesis process is simple and quick, and the size, specific surface area, N content and pore volume of the product can be adjusted, so that when the product is applied to a capacitance deionization device, the optimal adsorption of hexavalent chromium can be achieved.
The nitrogen-doped porous carbon electrode material prepared by the method has high specific surface area (up to 3150 m)2The method has the characteristics of controllable N content (0.86-10.52 at.%), hierarchical porosity and the like, greatly improves the electric adsorption performance (140.4mg/g) on hexavalent chromium, and has a wide industrial prospect.
It is noted that, in the invention, the m-phenylenediamine and the persulfate are used as precursors, and the poly-m-phenylenediamine nanoparticles can be obtained based on the oxidation of the m-phenylenediamine by the persulfate through the ratio adjustment between the m-phenylenediamine and the persulfate; and then activating the poly-m-phenylenediamine by potassium bicarbonate at a specific high temperature, and then cleaning and drying to obtain the nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium.
As a preferable production process of the particles of poly-m-phenylenediamine, in the step S1, the step of subjecting m-phenylenediamine to polymerization reaction in an aqueous solution containing persulfate includes: adding the aqueous solution of the persulfate into the aqueous solution of the m-phenylenediamine, and stirring at the temperature of 0-40 ℃ for 0.5-48 h; wherein, as a preferable mode, in the step S1, the temperature of the stirring treatment is 25 ℃, and the time of the stirring treatment is 8 hours; the molar ratio of the m-phenylenediamine to the persulfate is 1: 0.5 to 2.
With respect to the above embodiment, it is also necessary to know that the persulfate includes one of sodium persulfate and ammonium persulfate.
In addition, in the step S2, the mass ratio of the poly (m-phenylenediamine) particles to the potassium hydrogencarbonate is 1: 3-5; the activation time is 2h, and by determining the specific material proportion and the activation time length during activation, various characteristics and characteristics of the product can be better controlled under a specific activation process, so that a better effect is achieved.
As a further understanding of the present invention, the present invention also provides a nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, which is prepared by the preparation process of the nitrogen-doped porous carbon electrode material as described in any of the above embodiments.
In order to embody the application value of the nitrogen-doped porous carbon electrode material, the invention also provides the application of the nitrogen-doped porous carbon electrode material in the adsorption of hexavalent chromium.
In order to realize the application of the nitrogen-doped porous carbon electrode material to the adsorption of hexavalent chromium, the invention also provides a method for adsorbing hexavalent chromium, wherein the nitrogen-doped porous carbon electrode material in any embodiment is used on an electrode of a capacitive deionization device; carrying out hexavalent chromium adsorption treatment on the hexavalent chromium solution with the initial concentration of 50-300mg/L by the capacitance deionization device; wherein the applied voltage of the capacitive deionization device is 0-1.2V.
In addition to the above embodiments, the hexavalent chromium solution may be further defined, for example, the hexavalent chromium solution has an initial pH of 2 and a solution flow rate of 10 mL/min.
Specifically, as an alternative, the nitrogen-doped porous carbon material and polyvinylidene fluoride may be mixed, with carbon black in a ratio of 8: 1:1 mass ratio, adding N-methyl pyrrolidone, grinding into slurry, and coating on a titanium plate, thereby being used for a capacitive deionization device.
For further illustration of the present invention, the following are listed:
example 1
Nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium and preparation method thereof
1. Weighing 1g (namely 1mol) of m-phenylenediamine monomer, placing the monomer into a 250mL flat-bottomed flask, adding 100mL deionized water, and magnetically stirring to completely dissolve the m-phenylenediamine to obtain an m-phenylenediamine aqueous solution; 2.6191g (i.e., 1mol) of sodium persulfate was weighed into a beaker and dissolved in 20mL of deionized water to give an aqueous solution of sodium persulfate.
2. Dropwise adding the aqueous solution of sodium persulfate into a flat-bottomed flask filled with the aqueous solution of m-phenylenediamine, and continuously stirring for 8 hours at 25 ℃ to completely carry out the polymerization reaction; after the polymerization reaction is finished, separating a product obtained by the polymerization reaction through suction filtration, cleaning the product with 1:1 ammonia water and deionized water in sequence to remove impurities, and drying the product after cleaning to obtain black powder, namely the prepared poly (m-phenylenediamine) particles.
3. 1g of poly (m-phenylenediamine) particles were mixed with 4g of potassium bicarbonate and placed in a corundum boat, N2Activating for 2h at 600 ℃ in the atmosphere; and then washing the carbon material by using 0.5M hydrochloric acid solution and aqueous solution, and drying the carbon material at 60 ℃ to obtain black powder, namely the prepared nitrogen-doped porous carbon material for adsorbing hexavalent chromium, which is named as NPC-600.
Wherein the NPC-600 has a nitrogen content of 10.52 at.%, a carbon content of 74.2 at.%, and an oxygen content of 15.28 at.%; the NPC-600 has the particle size of 0.5-3 mu m and the specific surface area of 1189m2Per g, pore volume of 0.55cm3/g。
In addition, those skilled in the art may also refer to FIGS. 1 and 2 in understanding the structure of NPC-600. Wherein, an SEM image of the NPC-600 is shown in FIG. 1, from which the structure of the NPC-600 can be clearly and intuitively understood; the NPC-600 pore size distribution is shown in FIG. 2.
Example 2
Nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium and preparation method thereof
1. Weighing 1g (namely 1mol) of m-phenylenediamine monomer, placing the monomer into a 250mL flat-bottomed flask, adding 100mL deionized water, and magnetically stirring to completely dissolve the m-phenylenediamine to obtain an m-phenylenediamine aqueous solution; 2.6191g (i.e., 1mol) of sodium persulfate was weighed into a beaker and dissolved in 20mL of deionized water to give an aqueous solution of sodium persulfate.
2. Dropwise adding the aqueous solution of sodium persulfate into a flat-bottomed flask filled with the aqueous solution of m-phenylenediamine, and continuously stirring for 8 hours at 25 ℃ to completely carry out the polymerization reaction; after the polymerization reaction is finished, separating a product obtained by the polymerization reaction through suction filtration, then sequentially cleaning the product with 1:1 ammonia water and deionized water to remove impurities, and drying the product after cleaning to obtain black powder, namely the prepared poly (m-phenylenediamine) particles;
3. 1g of poly (m-phenylenediamine) particles were mixed with 4g of potassium bicarbonate and placed in a corundum boat, N2Activating for 2h at 800 ℃ in the atmosphere; and then, washing the mixture by using a 0.5M hydrochloric acid solution and an aqueous solution, and drying the mixture at 60 ℃ to obtain black powder, namely the prepared nitrogen-doped porous carbon material for adsorbing hexavalent chromium, which is named as NPC-800.
Wherein the NPC-800 has a nitrogen content of 2.21 at.%, a carbon content of 88.15 at.%, and an oxygen content of 9.65 at.%; the NPC-800 has a particle size of 0.5-3 μm and a specific surface area of 3150m2G, pore volume of 1.52cm3/g。
In addition, those skilled in the art may also refer to FIG. 1, FIG. 2, and FIG. 3 in understanding the structure of the NPC-800. Wherein, an SEM image of the NPC-800 is shown in FIG. 1, from which the structure of the NPC-800 can be clearly and intuitively understood; the NPC-800 pore size distribution is shown in FIG. 2; the EDS-mapping chart (converted from color chart) of NPC-800 is shown in FIG. 3, where it is noted that in FIG. 3, a is SEM chart, b is C element distribution chart, C is O element distribution chart, and d is N element distribution chart.
Example 3
Nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium and preparation method thereof
1. Weighing 1g (namely 1mol) of m-phenylenediamine monomer, placing the monomer into a 250mL flat-bottomed flask, adding 100mL deionized water, and magnetically stirring to completely dissolve the m-phenylenediamine to obtain an m-phenylenediamine aqueous solution; 2.6191g (i.e., 1mol) of sodium persulfate was weighed into a beaker and dissolved in 20mL of deionized water to give an aqueous solution of sodium persulfate.
2. Dropwise adding the aqueous solution of sodium persulfate into a flat-bottomed flask filled with the aqueous solution of m-phenylenediamine, and continuously stirring for 8 hours at 25 ℃ to completely carry out the polymerization reaction; after the polymerization reaction is finished, separating a product obtained by the polymerization reaction through suction filtration, cleaning the product with 1:1 ammonia water and deionized water in sequence to remove impurities, and drying the product after cleaning to obtain black powder, namely the prepared poly (m-phenylenediamine) particles.
3. 1g of poly (m-phenylenediamine) particles were mixed with 4g of potassium bicarbonate and placed in a corundum boat, N2Activating for 2h at 1000 ℃ in the atmosphere; and then cleaning the mixture by using a 0.5M hydrochloric acid solution and an aqueous solution, and drying the mixture at 60 ℃ to obtain black powder, namely the prepared nitrogen-doped porous carbon material for adsorbing hexavalent chromium, which is named as NPC-1000.
Wherein the NPC-1000 has a nitrogen content of 0.86 at.%, a carbon content of 93.39 at.%, and an oxygen content of 5.75 at.%; the NPC-1000 has the particle size of 0.5-3 mu m and the specific surface area of 2742m2Per g, pore volume of 2.30cm3/g。
In addition, those skilled in the art may also refer to FIGS. 1 and 2 in understanding the structure of NPC-1000. Wherein, an SEM image of the NPC-1000 is shown in FIG. 1, and the structure of the NPC-1000 can be clearly and intuitively understood; the NPC-1000 pore size distribution is shown in FIG. 2.
Example 4
Application of nitrogen-doped porous carbon electrode material in electric adsorption of hexavalent chromium in water body
NPC-600 prepared in example 1, NPC-800 prepared in example 2 and NPC-1000 prepared in example 3 are respectively applied to electrode materials in a capacitance deionization device at room temperature, wherein the masses of the NPC-600, the NPC-800 and the NPC-1000 are all 40 mg; the volume of the initial hexavalent chromium solution was 30mL and the initial hexavalent chromium concentration was 200 mg/L.
The voltage applied to the capacitive deionization apparatus was set to 1.2V, the adsorption time was set to 10 hours, the flow rate of the solution during adsorption was 10mL/min, and the concentration was measured by spectrophotometry after adsorption.
As shown in FIG. 4, the results of the above experiments indicate that the electro-adsorption capacities of NPC-600, NPC-800 and NPC-1000 reached 125.8mg/g, 140.4mg/g and 96.6mg/g, respectively.
Example 5
And (3) carrying out electric adsorption on hexavalent chromium in the water body by the nitrogen-doped porous carbon electrode material under different voltages.
The NPC-800 prepared in example 2 was applied to an electrode material in a capacitive deionization apparatus at room temperature, and the mass of the NPC-800 was 40 mg; the volume of the initial hexavalent chromium solution is 30mL, and the concentration of the hexavalent chromium is 200 mg/L.
The applied voltage of the capacitive deionization device is set to be 0-1.2V, the adsorption time is set to be 10h, the flow rate of the solution in the adsorption process is 10mL/min, and the concentration is measured by a spectrophotometry method after adsorption.
As shown in fig. 5, the results of the above experiments indicate that the removal rates of hexavalent chromium reach 60.2%, 65.3%, 78.1% and 91.8% at 0V, 0.4V, 0.8V and 1.2V, respectively.
Example 6
The N-doped porous carbon electrode material is applied to the electro-adsorption of hexavalent chromium in water bodies with different initial concentrations.
The NPC-800 prepared in example 2 was applied to an electrode material in a capacitive deionization apparatus at room temperature, and the mass of the NPC-800 was 40 mg; the volume of the initial hexavalent chromium solution is 30mL, and the concentration of the hexavalent chromium is 20-300 mg/L.
The voltage applied to the capacitive deionization apparatus was set to 1.2V, the adsorption time was set to 10 hours, the flow rate of the solution during adsorption was 10mL/min, and the concentration was measured by spectrophotometry after adsorption.
As shown in FIG. 6, the results of the above experiments revealed that the removal amounts of hexavalent chromium (i.e., the adsorption amounts corresponding to the drawing) were 15.3mg/g, 37.7mg/g, 70.8mg/g, 139.6mg/g and 186.5mg/g, respectively, at initial concentrations of 20mg/L, 50mg/L, 100mg/L, 200mg/L and 300 mg/L.
In the above technical solutions, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention include the claims of the present invention, which are directly or indirectly applied to other related technical fields by using the equivalent structural changes made in the content of the description and the drawings of the present invention.

Claims (10)

1. The nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium is characterized in that the nitrogen content of the nitrogen-doped porous carbon electrode material is 0.86-10.52 at.%, the carbon content is 74.2-93.39 at.%, and the oxygen content is 5.75-15.28 at.%;
the particle size of the nitrogen-doped porous carbon electrode material is 0.5-3 mu m, and the specific surface area is 1189-3150 m2A pore volume of 0.55-2.30 cm3/g。
2. A process for preparing a nitrogen-doped porous carbon electrode material as claimed in claim 1, comprising the steps of:
s1, carrying out polymerization reaction on m-phenylenediamine in an aqueous solution containing persulfate, and then sequentially carrying out separation operation, first cleaning operation and first drying operation on a product obtained by the polymerization reaction to obtain poly (m-phenylenediamine) particles;
s2, mixing the particles of poly (m-phenylenediamine) with bicarbonate, and adding N2Activating at 600-1000 deg.C in atmosphere; and sequentially performing a second cleaning operation and a second drying operation on the activated product to obtain the nitrogen-doped porous carbon electrode material.
3. The process for preparing a nitrogen-doped porous carbon electrode material according to claim 2, wherein in the step of S1, the step of subjecting m-phenylenediamine to polymerization reaction in an aqueous solution containing persulfate comprises: and adding the aqueous solution of the persulfate into the aqueous solution of the m-phenylenediamine, and stirring at the temperature of 0-40 ℃ for 0.5-48 h.
4. The preparation process of the nitrogen-doped porous carbon electrode material according to claim 3, wherein in the step S1, the stirring treatment temperature is 25 ℃, and the stirring treatment time is 8 h; in S2, the activation time is 2 h.
5. The process for preparing a nitrogen-doped porous carbon electrode material according to claim 4, wherein in the S1, the molar ratio of the m-phenylenediamine to the persulfate is 1: 0.5 to 2;
in the S2, the mass ratio of the poly (m-phenylenediamine) particles to the potassium bicarbonate is 1: 3 to 5.
6. The preparation process of the nitrogen-doped porous carbon electrode material according to claim 5, wherein the persulfate comprises one of sodium persulfate and ammonium persulfate.
7. The process for preparing a nitrogen-doped porous carbon electrode material according to any one of claims 2 to 6, wherein the first cleaning operation comprises: washing a product obtained by the polymerization reaction with an ammonia water solution and an aqueous solution in sequence;
the second cleaning operation comprises: and cleaning the product obtained after activation by using a hydrochloric acid solution and an aqueous solution in sequence.
8. A nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, which is prepared by the preparation process of the nitrogen-doped porous carbon electrode material according to any one of claims 2 to 7.
9. Use of the nitrogen-doped porous carbon electrode material of claim 1 or 8 for adsorbing hexavalent chromium.
10. A method for adsorbing hexavalent chromium, wherein the nitrogen-doped porous carbon electrode material according to claim 1 or 8 is used on an electrode of a capacitive deionization apparatus;
carrying out hexavalent chromium adsorption treatment on a hexavalent chromium solution with the initial concentration of 50-300mg/L by using the capacitive deionization device; wherein the applied voltage of the capacitive deionization device is 0-1.2V.
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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0474936A1 (en) * 1990-09-14 1992-03-18 The State Of Israel, Atomic Energy Commission, Nuclear Research Center Negev Electrochemical process for purifying chromium-containing wastes
CN103922305A (en) * 2014-03-26 2014-07-16 同济大学 Preparation method of high nitrogen content-doped porous carbon with high specific surface area
CN106629655A (en) * 2017-01-05 2017-05-10 中国科学院新疆理化技术研究所 Application and preparation method of biomass-based nitrogen-doped porous carbon
CN106745556A (en) * 2017-01-17 2017-05-31 常州大学 A kind of Electro Sorb removes chromium in water removal(Sexavalence)The method of ion
CN107282082A (en) * 2017-06-15 2017-10-24 南京大学 Loaded noble metal catalyst with clad structure and preparation method thereof and in Cr(Ⅵ)Application in liquid phase catalytic reduction
CN107572497A (en) * 2017-09-26 2018-01-12 南京理工大学 The preparation method of N doping grade hole carbon material
CN108190855A (en) * 2018-01-23 2018-06-22 上海大学 Three-dimensional porous carbon of doping for the removing of water intermediate ion and preparation method thereof
CN108584951A (en) * 2018-06-27 2018-09-28 中国地质大学(武汉) The preparation method of nitrogen-phosphor codoping carbon electrode material with graded porous structure
CN109133276A (en) * 2018-10-08 2019-01-04 天津科技大学 A kind of functionalization mesoporous carbon electrode material and preparation method thereof
CN109767927A (en) * 2019-01-17 2019-05-17 中南大学 A kind of preparation method of the supercapacitor biomass porous carbon of high-performance N doping
US20190225513A1 (en) * 2018-01-24 2019-07-25 Ut-Battelle, Llc Carbon electrodes based capacitive deionization for the desalination of water
US20200071200A1 (en) * 2018-08-06 2020-03-05 William Marsh Rice University Electrodes for selective removal of multivalent ions through capacitive deionization
CN110937668A (en) * 2019-12-03 2020-03-31 中南大学 Nitrogen-phosphorus atom co-doped CDI active material and preparation and application thereof
CN111790350A (en) * 2020-05-26 2020-10-20 福州大学 Preparation method of nitrogen-doped carbon material and application of nitrogen-doped carbon material in removal of sulfur-containing gas
CN112028188A (en) * 2020-08-24 2020-12-04 盐城工学院 Preparation method of biomass carbon-based electrode for asymmetric capacitive desalination device
CN112062128A (en) * 2020-09-10 2020-12-11 中国矿业大学 Preparation method and application of nitrogen-doped porous carbon material based on crop straws

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0474936A1 (en) * 1990-09-14 1992-03-18 The State Of Israel, Atomic Energy Commission, Nuclear Research Center Negev Electrochemical process for purifying chromium-containing wastes
CN103922305A (en) * 2014-03-26 2014-07-16 同济大学 Preparation method of high nitrogen content-doped porous carbon with high specific surface area
CN106629655A (en) * 2017-01-05 2017-05-10 中国科学院新疆理化技术研究所 Application and preparation method of biomass-based nitrogen-doped porous carbon
CN106745556A (en) * 2017-01-17 2017-05-31 常州大学 A kind of Electro Sorb removes chromium in water removal(Sexavalence)The method of ion
CN107282082A (en) * 2017-06-15 2017-10-24 南京大学 Loaded noble metal catalyst with clad structure and preparation method thereof and in Cr(Ⅵ)Application in liquid phase catalytic reduction
CN107572497A (en) * 2017-09-26 2018-01-12 南京理工大学 The preparation method of N doping grade hole carbon material
CN108190855A (en) * 2018-01-23 2018-06-22 上海大学 Three-dimensional porous carbon of doping for the removing of water intermediate ion and preparation method thereof
US20190225513A1 (en) * 2018-01-24 2019-07-25 Ut-Battelle, Llc Carbon electrodes based capacitive deionization for the desalination of water
CN108584951A (en) * 2018-06-27 2018-09-28 中国地质大学(武汉) The preparation method of nitrogen-phosphor codoping carbon electrode material with graded porous structure
US20200071200A1 (en) * 2018-08-06 2020-03-05 William Marsh Rice University Electrodes for selective removal of multivalent ions through capacitive deionization
CN109133276A (en) * 2018-10-08 2019-01-04 天津科技大学 A kind of functionalization mesoporous carbon electrode material and preparation method thereof
CN109767927A (en) * 2019-01-17 2019-05-17 中南大学 A kind of preparation method of the supercapacitor biomass porous carbon of high-performance N doping
CN110937668A (en) * 2019-12-03 2020-03-31 中南大学 Nitrogen-phosphorus atom co-doped CDI active material and preparation and application thereof
CN111790350A (en) * 2020-05-26 2020-10-20 福州大学 Preparation method of nitrogen-doped carbon material and application of nitrogen-doped carbon material in removal of sulfur-containing gas
CN112028188A (en) * 2020-08-24 2020-12-04 盐城工学院 Preparation method of biomass carbon-based electrode for asymmetric capacitive desalination device
CN112062128A (en) * 2020-09-10 2020-12-11 中国矿业大学 Preparation method and application of nitrogen-doped porous carbon material based on crop straws

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
X. F. ZHANG,等: "Three-dimensional honeycomb-like porous carbon derived from corncob for the removal of heavy metals from water by capacitive deionization", 《RSC ADVANCES》 *
YONG LIU,等: "Nitrogen-doped porous carbon spheres for highly efficient capacitive deionization", 《ELECTROCHIMICA ACTA》 *
马库斯.安东尼提,等: "《石墨烯及碳材料的化学合成与应用》", 31 January 2020 *

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