CN113003571A - Nitrogen-doped sodium alginate-based porous carbon material and preparation method and application thereof - Google Patents
Nitrogen-doped sodium alginate-based porous carbon material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen-doped sodium alginate-based porous carbon material, which takes sodium alginate as a carbon precursor, anhydrous potassium carbonate as an activating agent and melamine as a nitrogen dopant, and prepares the nitrogen-doped sodium alginate-based porous carbon material by one-step method for synchronous activation and high-temperature pyrolysis; the invention also discloses the nitrogen-doped sodium alginate-based porous carbon material prepared by the method and application of the nitrogen-doped sodium alginate-based porous carbon material in adsorption of bisphenol A in water. According to the invention, activation and high-temperature pyrolysis are carried out by a one-step method, so that an activating agent and a nitrogen doping agent simultaneously participate in the pore making process, the increase of the number of pore channels and the increase of the pore diameter in porous carbon are promoted, the specific surface area and the pore volume of the nitrogen-doped sodium alginate-based porous carbon material are improved, and the adsorption performance of the nitrogen-doped sodium alginate-based porous carbon material is further improved; the nitrogen-doped sodium alginate-based porous carbon material prepared by the invention has high bisphenol A adsorption capacity, high adsorption rate and strong stability.
Description
Technical Field
The invention belongs to the technical field of preparation of environment application type materials, and particularly relates to a nitrogen-doped sodium alginate-based porous carbon material and a preparation method and application thereof.
Background
Bisphenol A is a typical environmental endocrine disrupter, is widely used as a monomer in the manufacture of polycarbonate plastics or as an intermediate in the production of epoxy resins, and is widely used in the preparation of plastic containers, bottles, toys, medical devices, tableware in industrial products. The release rate of bisphenol A in a polycarbonate bottle is 0.20-0.79 ng.h at room temperature-1The release rate of bisphenol A in boiling water is up to 55 times of room temperature. It follows that the release of bisphenol a from plastic products into the environment has become a serious problem, regardless of the temperature. Thus, removal of bisphenol A in water is very important for environmental protection. At present, adsorption method is often used for removing pollutants in water, but according to literature reports, most of adsorbents have the problems of low adsorption capacity, high cost, difficult recovery and the like, so that the development of an efficient, low-cost and recyclable adsorbent for removing bisphenol A in wastewater is an urgent and important task.
Porous carbon materials are considered to be the most promising adsorbents for the removal of various contaminants due to their highly dense void structure, large specific surface area and relatively high adsorption capacity. In recent years, with the increasing complexity of wastewater compositions, porous carbon materials prepared with various carbon sources have been researched and developed, however, most of carbon precursors mostly form microporous carbon during carbonization and activation, greatly limiting the adsorption rate. Therefore, in order to improve the adsorption capacity, there is an urgent need to develop gradient porous carbon with rich pore structure from suitable carbon precursors.
Sodium alginate is a natural polysaccharide compound extracted from kelp or seaweed, and research is carried out to directly carbonize the sodium alginate to obtain oxygen-rich carbon, so that the oxygen-rich carbon can be used for preparing a super capacitor, shows good electrical storage performance and is mainly benefited from rich carbon skeleton and oxygen-containing functional groups. Based on the characteristics, the sodium alginate carbonized at high temperature can be applied to removing pollutants in water environment, on one hand, the pore structure in the carbon skeleton can adsorb the pollutants, and on the other hand, the oxygen-containing functional groups on the surface can carry out redox degradation on the pollutants. However, porous carbon prepared by directly carbonizing sodium alginate has a poorly developed pore structure and a relatively small specific surface area, and if the porous carbon is directly used for adsorbing pollutants, the adsorption rate and the adsorption quantity are not satisfactory enough. According to a plurality of researches, the porous carbon material prepared by a chemical activation method and a heteroatom doping modification mode not only can effectively improve the defects of direct carbonization in the aspects of pores and specific surface area, but also can increase hydrophilic functional groups on the surface of the porous carbon material by heteroatom doping, so that the wettability of the porous carbon material is improved, and the adsorption capacity of the porous carbon material to pollution is greatly improved. At present, relevant researches indicate that the obtained heteroatom-doped porous carbon material has a developed pore structure and stronger pollutant removal capacity by a preparation method for simultaneously improving the performance of the porous carbon material by using an activating agent and a heteroatom dopant.
Such as: liang et al, "Preparation of nitrogen-doped porous carbon material by hydrothermal-activation of step method and its high-efficiency adsorption of Cr (VI)" published in Journal of Hazardous Materials by 2020; cui et al, "Zinc nitride as an Activation Agent for the Synthesis of Nitrogen-dot Porous Carbon and Its Application in CO2 addition," published by Energy & Fuels in 2020; li et al, "Efficient Nitrogen bonded porous carbon CO2 adsorbed minerals based on located in Journal of Environmental Sciences" published by Li et al 2021; liu et al published 2021 on Applied Surface Science, "Optimized synthesis of nitrogen-processed carbon with extreme high Surface area for administration and supercapacitor", and the like. From the above documents, we found that in the research of preparing the porous carbon material with high specific surface area, the pore structure of the porous carbon is improved by a chemical activating agent and a heteroatom dopant, but the method has the disadvantage that the preparation process is complicated by adopting a two-step method, namely a mode of activating before nitrogen doping or a mode of activating after nitrogen doping. Sodium alginate is used as a carbon source, a heteroatom-doped sodium alginate-based porous carbon material is prepared by one-step synchronous activation and doping, and the heteroatom-doped sodium alginate-based porous carbon material is applied to removal of pollutants in a water environment, which is not reported at present.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a nitrogen-doped sodium alginate-based porous carbon material, aiming at the defects of the prior art. According to the method, the carbon precursor sodium alginate, the activator anhydrous potassium carbonate and the nitrogen dopant melamine are subjected to activation high-temperature pyrolysis through a one-step method, so that the activator and the nitrogen dopant participate in the pore making process at the same time, the increase of the number of pore channels and the increase of the pore diameter in the porous carbon are promoted, the specific surface area and the pore volume of the nitrogen-doped sodium alginate-based porous carbon material (SAC/N) are greatly improved, and the adsorption performance of the nitrogen-doped sodium alginate-based porous carbon material is further improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the preparation method of the nitrogen-doped sodium alginate-based porous carbon material is characterized in that sodium alginate is used as a carbon precursor, anhydrous potassium carbonate is used as an activating agent, melamine is used as a nitrogen dopant, and the nitrogen-doped sodium alginate-based porous carbon material is prepared by one-step method synchronous activation and high-temperature pyrolysis.
In the research process of the invention, in the process of preparing the carbon material by adopting a two-step method, in the first step, the biomass precursor is subjected to primary carbonization at the temperature range of 300-600 ℃ to produce the biochar precursor, the thermal decomposition causes the release of volatile components in steam, tar and gas, and pores are formed in the obtained biochar precursor, and the low-temperature pyrolysis can generate some tar substances to deposit, fill or partially block the formed pores while obtaining higher carbon yield, so that the surface area of the biochar precursor is lower; and secondly, impregnating the biochar precursor by using a chemical active agent, activating the impregnated biochar precursor at the temperature of 700-1200 ℃, removing tar substances from pores through activation, and generating micropores in a carbon structure, so that the specific surface area of the carbon material is greatly improved. The carbon material prepared by adopting the two-step method can obtain more carbon yield, and the carbon material pores and preparation equipment are prevented from being blocked by tar substances, but the preparation process is longer and the process is relatively complex.
The method adopts a one-step method, and carries out activation pyrolysis on carbon precursor sodium alginate, activator anhydrous potassium carbonate and nitrogen dopant melamine, wherein in the activation pyrolysis process, the sodium alginate is pyrolyzed to form carbon, and simultaneously the activator anhydrous potassium carbonate reacts with the carbon at high temperature or is decomposed to generate metal K and metal K2O and release CO, CO2Forming pores as shown in the following reaction formulas (1), (2), (3) and (4), and embedding the metal K into the carbon skeleton, enlarging the original pore channels and promoting the formation of new pores; meanwhile, nitrogen atoms decomposed by melamine are doped in porous carbon formed by sodium alginate to participate in the process of activating and pore-making, a dopant melamine and an activator anhydrous potassium carbonate form a complex compound to generate KCNO at 500 ℃, and when the temperature is increased to 700 ℃, the carbon substrate reduces KCNO (KCNO + C → KCN + CO) to generate carbon thermal cycle, so that a new alkali substance (KCN) is generated and CO is released, the increase of the number of pore channels in the porous carbon and the increase of the pore diameter are further promoted, and the pore channels filled with the porous carbon material are prevented from being generated by a large amount of tar.
In conclusion, the method adopts a one-step method to synchronously activate and pyrolyze at high temperature, so that the activating agents anhydrous potassium carbonate and the nitrogen-doped melamine participate in the pore-making process at the same time, the increase of the number of pore channels and the increase of the pore diameter in the porous carbon are promoted, the specific surface area and the pore volume of the nitrogen-doped sodium alginate-based porous carbon material (SAC/N) are greatly improved, the adsorption performance of the nitrogen-doped sodium alginate-based porous carbon material is further improved, the process is simple, the flow is short, and the preparation efficiency is improved.
The preparation method of the nitrogen-doped sodium alginate-based porous carbon material is characterized by comprising the following steps of:
step one, placing sodium alginate, anhydrous potassium carbonate and melamine in a mortar and grinding uniformly to obtain mixed powder;
and step two, placing the mixed powder obtained in the step one in a porcelain boat, loading the porcelain boat into a tube furnace, heating the porcelain boat under the protection of nitrogen atmosphere to perform activation and high-temperature pyrolysis to obtain a black solid, then sequentially washing the black solid with dilute hydrochloric acid solution and deionized water until the black solid is neutral, and drying the black solid to obtain the nitrogen-doped sodium alginate-based porous carbon material.
The invention firstly grinds and refines the carbon precursor sodium alginate, the activator anhydrous potassium carbonate and the nitrogen dopant melamine, so that the raw materials are fully contacted and uniformly mixed, thereby being beneficial to uniformly carrying out the subsequent activation high-temperature pyrolysis process, then heating under the protection of nitrogen atmosphere to activate and pyrolyze at high temperature, washing to remove redundant raw materials and impurities, drying to obtain the sodium alginate-doped porous carbon material, the process carries out activation high-temperature pyrolysis through direct temperature rise, nitrogen atoms are doped in the formed porous carbon in time when pore forming is activated, the specific surface area and the pore volume of the porous carbon material are improved, simultaneously avoids the phenomenon that the carbon precursor in the two-step method stays at low temperature for pyrolysis to generate a great amount of substances such as tar and the like to block the pores, meanwhile, due to the existence of the activating agent and the nitrogen doping agent, tar is effectively removed, the generation of a microporous structure is promoted, and the preparation efficiency of the porous carbon material is improved.
The preparation method of the nitrogen-doped sodium alginate-based porous carbon material is characterized in that in the first step, the mass ratio of sodium alginate to anhydrous potassium carbonate to melamine is 1: 0.5-4: 0.1 to 5; the process of heating up for activating high-temperature pyrolysis in the step two is as follows: heating from room temperature to 700-900 ℃ at the speed of 5 ℃/min and preserving heat for 1-3 h; and the drying temperature in the second step is 80-90 ℃. The optimized raw material mass ratio ensures that the activating agent and the nitrogen doping agent fully act on porous carbon formed by the sodium alginate, and further promotes the increase of the number of pore channels and the increase of the pore diameter in the porous carbon so as to improve the adsorption capacity of the porous carbon material and avoid the waste of raw materials; the preferred activation pyrolysis process promotes channel formation and pore size increase in the porous carbon material, improves the adsorption capacity of the porous carbon material, and simultaneously considers the carbon yield.
The preparation method of the nitrogen-doped sodium alginate-based porous carbon material is characterized in that in the first step, the mass ratio of sodium alginate to anhydrous potassium carbonate to melamine is 1: 1: 0.2; the process of heating up for activating high-temperature pyrolysis in the step two is as follows: heating from room temperature to 800 ℃ at the speed of 5 ℃/min and preserving heat for 2 h; the temperature of the drying in step two was 85 ℃. The optimal raw material mass ratio and the activation high-temperature pyrolysis process realize the balance of the adsorption capacity and the carbon yield of the porous carbon material, and the comprehensive adsorption performance of the obtained porous carbon reaches the best.
In addition, the invention also provides the nitrogen-doped sodium alginate-based porous carbon material prepared by the method.
The invention also provides application of the nitrogen-doped sodium alginate-based porous carbon material in adsorption of bisphenol A in water.
The nitrogen-doped sodium alginate-based porous carbon material prepared by the method has higher specific surface area and pore volume, and further has stronger absorptionWhen the adsorption capacity is applied to adsorbing bisphenol A (BPA) in water, the adsorption behavior of the adsorption capacity to BPA is more consistent with Langmiur isothermal model and pseudo-second order kinetics, and the saturated adsorption capacity reaches 1180.02mg g under 308K-1And the adsorption balance can be achieved only in 30min, and the carbon material still keeps stable, efficient and rapid adsorption on BPA under the interference of different metal ions and natural organic matters, so that the nitrogen-doped sodium alginate-based porous carbon material has high adsorption capacity, high adsorption rate and strong stability on bisphenol A in water, and has great advantages.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the carbon precursor sodium alginate, the activator anhydrous potassium carbonate and the nitrogen dopant melamine are subjected to activation high-temperature pyrolysis by adopting a one-step method, so that the activator anhydrous potassium carbonate and the nitrogen dopant melamine participate in the pore making process at the same time, the increase of the number of pore channels and the increase of the pore diameter in the porous carbon are promoted, the specific surface area and the pore volume of the nitrogen-doped sodium alginate-based porous carbon material (SAC/N) are greatly improved, and the adsorption performance of the nitrogen-doped sodium alginate-based porous carbon material is further improved.
2. The method adopts a one-step method to simultaneously realize nitrogen doping and activated pore-forming, has simple process and short flow, improves the preparation efficiency, has low requirement on equipment and is easy to realize.
3. The nitrogen-doped sodium alginate-based porous carbon material has strong adsorption capacity, is applied to removal of bisphenol A in water, has high adsorption capacity, high adsorption rate and strong stability, and shows great advantages.
4. The nitrogen-doped sodium alginate-based porous carbon material has an obvious sheet-shaped carbon nano structure, the structure shortens the transmission distance of BPA molecules between pores, increases the contact probability between the carbon material and BPA, and effectively improves the adsorption rate of BPA.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1a is a diagram of a process for preparing a nitrogen-doped sodium alginate-based porous carbon material in examples 1 to 3 of the present invention.
FIG. 1b is a mechanism diagram of bisphenol A adsorption by the nitrogen-doped sodium alginate-based porous carbon material of the present invention.
FIG. 2 is a scanning electron microscope image of the nitrogen-doped sodium alginate-based porous carbon material prepared in example 3 of the present invention.
FIG. 3 shows N of the nitrogen-doped sodium alginate-based porous carbon material prepared in example 3 of the present invention2Adsorption-desorption isotherm diagram.
FIG. 4 is a scanning electron microscope image of the sodium alginate-based porous carbon material prepared in comparative example 1 of the present invention.
FIG. 5 is N of the sodium alginate-based porous carbon material prepared in comparative example 1 of the present invention2Adsorption-desorption isotherm diagram.
FIG. 6 is a graph showing the effect of the action time on the adsorption performance of the nitrogen-doped sodium alginate-based porous carbon material prepared in example 3 of the present invention.
FIG. 7 is a graph showing the influence of the action time on the adsorption performance of the sodium alginate-based porous carbon material prepared in comparative example 1 of the present invention.
FIG. 8 is a graph showing the effect of humic acid concentration on adsorption performance of the nitrogen-doped sodium alginate-based porous carbon material prepared in example 3 of the present invention.
FIG. 9 is a graph showing the influence of ion concentration on adsorption performance of the nitrogen-doped sodium alginate-based porous carbon material prepared in example 3 of the present invention.
FIG. 10 is a graph showing the regeneration performance of the nitrogen-doped sodium alginate-based porous carbon material prepared in example 3 of the present invention.
Detailed Description
As shown in fig. 1a, the preparation process of the nitrogen-doped sodium alginate-based porous carbon material in the embodiments 1 to 3 of the present invention is as follows: activating and pyrolyzing sodium alginate, anhydrous potassium carbonate and melamine at high temperature, and then washing with dilute hydrochloric acid solution and deionized water in sequence to prepare the nitrogen-doped sodium alginate-based porous carbon material.
As shown in fig. 1b, the mechanism of the nitrogen-doped sodium alginate-based porous carbon material of the present invention for adsorbing bisphenol a is: the nitrogen-doped sodium alginate-based porous carbon material has high specific surface area and large pore volume, and the adsorption of the nitrogen-doped sodium alginate-based porous carbon material to bisphenol A is mainly based on pore filling.
The preparation method of the nitrogen-doped sodium alginate-based porous carbon material of the present invention is described in detail by examples 1 to 3 and comparative example 1.
Example 1
The preparation method of the embodiment takes sodium alginate as a carbon precursor, anhydrous potassium carbonate as an activating agent and melamine as a nitrogen dopant, and prepares the nitrogen-doped sodium alginate-based porous carbon material by one-step synchronous activation and high-temperature pyrolysis, and the preparation method comprises the following steps:
step one, placing 1g of sodium alginate, 0.5g of anhydrous potassium carbonate and 0.1g of melamine in a mortar and grinding uniformly to obtain mixed powder;
and step two, placing the mixed powder obtained in the step one in a porcelain boat, loading the porcelain boat into a tube furnace, heating the porcelain boat to 700 ℃ at the speed of 5 ℃/min under the protection of nitrogen atmosphere, keeping the temperature for 1h for activation and high-temperature pyrolysis to obtain a black solid, then sequentially washing the black solid by using a dilute hydrochloric acid solution and deionized water until the black solid is neutral, and then placing the black solid in a drying oven to dry the black solid to constant weight at the temperature of 80 ℃ to obtain the nitrogen-doped sodium alginate-based porous carbon material.
Example 2
The preparation method of the embodiment takes sodium alginate as a carbon precursor, anhydrous potassium carbonate as an activating agent and melamine as a nitrogen dopant, and prepares the nitrogen-doped sodium alginate-based porous carbon material by one-step synchronous activation and high-temperature pyrolysis, and the preparation method comprises the following steps:
step one, placing 1g of sodium alginate, 4g of anhydrous potassium carbonate and 5g of melamine in a mortar and grinding uniformly to obtain mixed powder;
and step two, placing the mixed powder obtained in the step one in a porcelain boat, loading the porcelain boat into a tube furnace, heating the porcelain boat to 900 ℃ at the speed of 5 ℃/min under the protection of nitrogen atmosphere, keeping the temperature for 3 hours, carrying out activation and high-temperature pyrolysis to obtain a black solid, then sequentially washing the black solid by using a dilute hydrochloric acid solution and deionized water until the black solid is neutral, and then placing the black solid in a drying oven to dry the black solid to a constant weight at the temperature of 90 ℃ to obtain the nitrogen-doped sodium alginate-based porous carbon material.
Example 3
The preparation method of the embodiment takes sodium alginate as a carbon precursor, anhydrous potassium carbonate as an activating agent and melamine as a nitrogen dopant, and prepares the nitrogen-doped sodium alginate-based porous carbon material by one-step synchronous activation and high-temperature pyrolysis, and the preparation method comprises the following steps:
step one, placing 1g of sodium alginate, 1g of anhydrous potassium carbonate and 0.2g of melamine in a mortar and grinding uniformly to obtain mixed powder;
and step two, placing the mixed powder obtained in the step one in a porcelain boat, loading the porcelain boat into a tube furnace, heating the porcelain boat to 800 ℃ at the speed of 5 ℃/min under the protection of nitrogen atmosphere, keeping the temperature for 2 hours, carrying out activation high-temperature pyrolysis to obtain a black solid, then sequentially washing the black solid by using a dilute hydrochloric acid solution and deionized water until the black solid is neutral, and then placing the black solid in a drying oven to dry the black solid to constant weight at 85 ℃ to obtain the nitrogen-doped sodium alginate-based porous carbon material.
Fig. 2 is a scanning electron microscope image of the nitrogen-doped sodium alginate-based porous carbon material prepared in this example, and as can be seen from fig. 2, the pores in the nitrogen-doped sodium alginate-based porous carbon material are very dense, the pore structure is quite abundant, and the surface presents an obvious and thin carbon nanosheet structure.
FIG. 3 shows N in the nitrogen-doped sodium alginate-based porous carbon material prepared in this example2An adsorption-desorption isotherm diagram, and as can be seen from FIG. 3, the N of the nitrogen-doped sodium alginate-based porous carbon material2The adsorption-desorption isotherm diagram is an obvious combined adsorption behavior of I-type and IV-type curves, and an H4-type hysteresis loop also exists, which indicates that a large number of micropores and a small number of mesopore structures exist in the nitrogen-doped sodium alginate-based porous carbon material; at the same time, in a relatively low-voltage region (P/P)00-0.1), the gas adsorption capacity of the nitrogen-doped sodium alginate-based porous carbon material is increased linearly and reaches a higher adsorption platform, which shows that the nitrogen-doped sodium alginate-based porous carbon material has a large amount of adsorption of a microporous structure and has a relative pressureHigher region (P/P)00.02-0.99), the gas adsorption capacity of the nitrogen-doped sodium alginate-based porous carbon material is still increased, but the acceleration is slow, and an obvious hysteresis loop appears, wherein the hysteresis loop is usually generated by a stacked layered structure, which indicates that the nitrogen-doped sodium alginate-based porous carbon material has a layered porous structure, and a large number of micropores and a small number of mesopores exist.
Comparative example 1
The preparation method of the comparative example takes sodium alginate as a carbon precursor and anhydrous potassium carbonate as an activating agent, and the sodium alginate-based porous carbon material is prepared by one-step synchronous activation and high-temperature pyrolysis, and the preparation method comprises the following steps:
step one, placing 1g of sodium alginate and 1g of anhydrous potassium carbonate in a mortar and grinding uniformly to obtain mixed powder;
and step two, placing the mixed powder obtained in the step one in a porcelain boat, loading the porcelain boat into a tube furnace, heating the porcelain boat to 800 ℃ at the speed of 5 ℃/min under the protection of nitrogen atmosphere, keeping the temperature for 2 hours, carrying out activation and high-temperature pyrolysis to obtain a black solid, then sequentially washing the black solid by using a dilute hydrochloric acid solution and deionized water until the black solid is neutral, and then placing the black solid in a drying oven to dry the black solid to a constant weight at 85 ℃ to obtain the sodium alginate-based porous carbon material.
Fig. 4 is a scanning electron microscope image of the sodium alginate-based porous carbon material prepared in the comparative example, and as can be seen from fig. 4, the sodium alginate-based porous carbon material has a relatively uniform nanosheet structure.
FIG. 5 is N of sodium alginate-based porous carbon material prepared in this comparative example2Adsorption-desorption isotherm diagram, and as can be seen from FIG. 5, the sodium alginate-based porous carbon material is in a relatively low pressure region (P/P)00-0.1), belonging to typical microporous material characteristics, from relative pressure P/P0A small hysteresis phenomenon starts to appear when the value is 0.4, indicating that a type IV isotherm exists in the isotherm, which indicates that the sodium alginate-based porous carbon material has a small amount of mesoporous structure.
Comparing fig. 2 and fig. 4, it can be seen that compared with the sodium alginate-based porous carbon material without nitrogen doping, the nitrogen-doped sodium alginate-based porous carbon material has more obvious interconnected sheet-like structures, and greatly shortens the time for transporting the adsorbed substance such as bisphenol a molecules in the nitrogen-doped sodium alginate-based porous carbon material, thereby effectively improving the adsorption rate.
Comparing fig. 2 and fig. 4, it can be seen that, compared with the sodium alginate-based porous carbon material without nitrogen doping, the nitrogen-doped sodium alginate-based porous carbon material has more mesopore and micropore structures, and the nitrogen adsorption capacity is also improved by nearly one time, which indicates that the specific surface area and pore structure of the nitrogen-doped sodium alginate-based porous carbon material are larger, and illustrates that, in the one-step preparation process of the invention, nitrogen atoms in the dopant melamine can form a complex with the activator anhydrous potassium carbonate, and generate KCNO at 500 ℃, and when the temperature is increased to 700 ℃, the carbon substrate reduces KCNO (KCNO + C → KCN + CO) to generate carbon thermal cycle, so as to generate a new alkali substance (KCN), release CO, and promote the formation of the mesopore structure of the nitrogen-doped porous carbon material.
The use of the nitrogen-doped sodium alginate-based porous carbon material of the present invention for adsorbing bisphenol a in water is described in detail in example 4.
Example 4
The application of the embodiment comprises the following steps: the nitrogen-doped sodium alginate-based porous carbon material prepared in example 3 was added to an aqueous solution containing bisphenol a, and the mixture was subjected to shaking adsorption, and then the adsorption complex was removed by filtration to obtain an adsorbed aqueous solution.
XRD analysis is carried out on the nitrogen-doped sodium alginate-based porous carbon material adopted in the embodiment 4, the short and flat ordered graphitized structure exists in the nitrogen-doped sodium alginate-based porous carbon material to serve as a pi-electron acceptor, an aromatic ring structure in BPA molecules can serve as a pi-electron donor, and the nitrogen-doped sodium alginate-based porous carbon material in the adsorption compound is combined with BPA through pi-pi EDA interaction and hydrogen bond interaction; furthermore, XPS analysis shows that a certain amount of pyridine-N and pyrrole-N exist in the nitrogen-doped sodium alginate-based porous carbon material and are used as a base and a hydrogen acceptor to help to realize the adsorption performance on BPA.
The performance of the nitrogen-doped sodium alginate-based porous carbon material for adsorbing bisphenol A is researched, and the specific research process comprises the following steps:
preparing a bisphenol A solution: weighing a bisphenol A sample, dissolving the bisphenol A sample with methanol, adding deionized water to a constant volume, and preparing a bisphenol A solution with the concentration of 250mg/L (the mass content of the methanol is not more than 0.2%).
(1) Influence of action time on adsorption performance of nitrogen-doped sodium alginate-based porous carbon material
Respectively measuring 11 groups of 10mL of 250mg/L bisphenol A solution, respectively placing the 250mg/L bisphenol A solution in 11 centrifugal tubes, respectively adding 2mg of the nitrogen-doped sodium alginate-based porous carbon material prepared in the embodiment 3 into each centrifugal tube, then placing the centrifugal tubes in a constant-temperature water bath oscillator with the temperature of 303K and the oscillation speed of 150r/min for oscillation, respectively controlling the oscillation time of the 11 centrifugal tubes to be 1min, 5min, 15min, 30min, 60min, 90min, 120min, 180min, 360min, 480min and 600min, respectively sampling and filtering the samples by a 0.22 mu m filter head to obtain filtrate, measuring the concentration of bisphenol A (BPA) in the filtrate at 280nm by using a high performance liquid chromatograph, and further calculating the adsorption capacity Qt(mg/g), the time t of the shaking was plotted on the abscissa and the adsorption capacity Qt (mg/g) was plotted on the ordinate, and the results are shown in FIG. 6.
Fig. 6 is a graph showing the influence of the action time on the adsorption performance of the nitrogen-doped sodium alginate-based porous carbon material prepared in example 3 of the present invention, and it can be seen from fig. 6 that the adsorption rate of the nitrogen-doped sodium alginate-based porous carbon material to bisphenol a in a bisphenol a solution is very fast in the first 20min, and the adsorption reaches a balance after 30min, which indicates that the surface of the nitrogen-doped sodium alginate-based porous carbon material has a large number of abundant active sites, and when bisphenol a molecules contact with the nitrogen-doped sodium alginate-based porous carbon material, the active sites are quickly occupied, and the bisphenol a molecules are diffused through the interconnected sheet-shaped nanostructure layer in the nitrogen-doped sodium alginate-based porous carbon material, so that the transport distance of the bisphenol a molecules is shortened, the transport speed is increased, the adsorption process is quickly balanced, and the equilibrium adsorption capacity reaches over 1000 mg/g.
(2) Influence of action time on adsorption performance of sodium alginate-based porous carbon material
Respectively measuring 11 groups10mL of 250mg/L bisphenol A solution is respectively placed in 11 centrifugal tubes, 2mg of the sodium alginate-based porous carbon material prepared in the comparative example 1 is respectively added into each centrifugal tube, then the centrifugal tubes are all placed in a constant-temperature water bath oscillator with the temperature of 303K and the oscillation speed of 150r/min for oscillation, the oscillation time of the 11 centrifugal tubes is respectively controlled to be 1min, 5min, 15min, 30min, 60min, 90min, 120min, 180min, 360min, 480min and 600min, then the samples are respectively sampled and filtered through a 0.22 mu m filter head to obtain filtrate, the concentration of bisphenol A (BPA) in the filtrate is measured at 280nm by adopting a high performance liquid chromatograph, and the adsorption capacity Q, BPA, is further calculatedt(mg/g), the time t of the shaking was plotted on the abscissa and the adsorption capacity Qt (mg/g) was plotted on the ordinate, and the results are shown in FIG. 7.
FIG. 7 is a graph showing the influence of the action time on the adsorption performance of the sodium alginate-based porous carbon material prepared in comparative example 1 of the present invention, and it can be seen from FIG. 7 that the adsorption rate of the sodium alginate-based porous carbon material on bisphenol A in a bisphenol A solution is relatively high in 30min at the initial stage, the adsorption reaches an equilibrium at about 360min, and the equilibrium adsorption capacity is about 565 mg/g.
Comparing fig. 6 and fig. 7, it can be seen that the equilibrium adsorption capacity and adsorption rate of the nitrogen-doped sodium alginate-based porous carbon material for bisphenol a are far greater than those of the sodium alginate-based porous carbon material, which indicates that the nitrogen-doped sodium alginate-based porous carbon material has a larger specific surface area and pore volume, so that bisphenol a is rapidly contacted and adsorbed and transferred to the pore channel of the nitrogen-doped sodium alginate-based porous carbon material, the equilibrium adsorption capacity is improved, and meanwhile, the dense layered nanostructure in the nitrogen-doped sodium alginate-based porous carbon material greatly shortens the transfer and transportation rate of bisphenol a, thereby improving the adsorption rate.
(3) Influence of humic acid concentration on adsorption performance of nitrogen-doped sodium alginate-based porous carbon material
To better simulate the actual wastewater components, 5 groups of humic acid-bisphenol A aqueous solutions were prepared, and the concentrations of bisphenol A in the 5 groups of humic acid-bisphenol A aqueous solutions were all 250mg/L, the concentrations of humic acid were 0mg/L, 10mg/L, 25mg/L, 50mg/L and 100mg/L, 10mL of the 5 groups of humic acid-bisphenol A aqueous solutions were taken, and 2.0mg of the nitrogen-doped seaweed prepared in example 3 was addedThe sodium-based porous carbon material is placed in a constant-temperature water bath oscillator with the temperature of 303K and the oscillation speed of 150r/min for oscillation for 12 hours, then the samples are respectively sampled and filtered by a 0.22 mu m filter head to obtain filtrate, the concentration of bisphenol A (BPA) in the filtrate is measured by adopting a high performance liquid chromatograph under the condition of 280nm, and further the equilibrium adsorption capacity Q is calculatede(mg/g) equilibrium adsorption capacity Q with humic acid concentration (mg/L) as abscissae(mg/g) is plotted as a bar graph on the ordinate, and the result is shown in FIG. 8.
Fig. 8 is a graph showing the influence of humic acid concentration on the adsorption performance of the nitrogen-doped sodium alginate-based porous carbon material prepared in example 3 of the present invention, and it can be seen from fig. 8 that, as the humic acid concentration in the humic acid-bisphenol a aqueous solution increases, the equilibrium adsorption capacity of the nitrogen-doped sodium alginate-based porous carbon material to bisphenol a shows a weak tendency to decrease, which indicates that van der waals force is formed between the nitrogen-doped sodium alginate-based porous carbon material and humic acid molecules, and pi-pi EDA effect is generated to effectively block the pores of the nitrogen-doped sodium alginate-based porous carbon material; in addition, the surface of the nitrogen-doped sodium alginate-based porous carbon material tends to form hydrophobic interactions with humic acid molecules and effectively compete with bisphenol a, resulting in a decrease in adsorption capacity, but the decrease effect is insignificant.
(4) Influence of ion concentration on adsorption performance of nitrogen-doped sodium alginate-based porous carbon material
The existence of ionic strength causes electrostatic shielding effect, influences the action strength between the adsorbent and the adsorbate, thereby influencing the adsorption performance, and in order to research the influence of the ionic strength on the adsorption effect, Na which is four common cations in water is used+、K+、Ca2+And Mg2+Respectively using NaCl, KCl and CaCl2And MgCl2The four groups of cation-bisphenol A mixed solutions are prepared by adding the four groups of cation-bisphenol A mixed solutions into bisphenol A, the concentration of the bisphenol A in the four groups of cation-bisphenol A mixed solutions is 250mg/L, and the cation Na+、K+、Ca2+And Mg2+Respectively has a concentration of 100mmol/L, and is provided with bisphenol A solution without cation and with a concentration of 250mg/L as blank control solution, and 10mL of 4 groups of cation-bisphenol A aqueous solution and blank pair are respectively takenAccording to the solution, respectively adding 2.0mg of the nitrogen-doped sodium alginate-based porous carbon material prepared in the embodiment 3, placing the materials in a constant-temperature water bath oscillator with the temperature of 303K and the oscillation speed of 150r/min for oscillation for 12h, respectively sampling, filtering by a filter head of 0.22 mu m to obtain filtrate, measuring the concentration of bisphenol A (BPA) in the filtrate by using a high performance liquid chromatograph under 280nm, and further calculating the equilibrium adsorption capacity Qe(mg/g) equilibrium adsorption Capacity Q with different cation species as abscissae(mg/g) is plotted as a bar graph on the ordinate, and the result is shown in FIG. 9.
FIG. 9 is a graph showing the influence of ion concentration on the adsorption performance of the nitrogen-doped sodium alginate-based porous carbon material prepared in example 3 of the present invention, and it can be seen from FIG. 9 that four common cations, namely Na, are present in water+、K+、Ca2+And Mg2+The nitrogen-doped sodium alginate-based porous carbon material has little influence on the adsorption performance, which shows that the electrostatic effect between the metal cations and the nitrogen-doped sodium alginate-based porous carbon material has no obvious influence on the adsorption of the bisphenol A, and the nitrogen-doped sodium alginate-based porous carbon material is suitable for treating bisphenol A wastewater in a high-salt environment.
(5) Research on regeneration performance of nitrogen-doped sodium alginate-based porous carbon material
After the nitrogen-doped sodium alginate-based porous carbon material prepared in the embodiment 3 of the invention achieves adsorption balance on bisphenol A, the nitrogen-doped sodium alginate-based porous carbon material is placed into 50mL of methanol to be continuously stirred for 12h for bisphenol A desorption, then ultrapure water is used for washing until the pH value is neutral and drying is carried out, a regeneration experiment is completed, the nitrogen-doped sodium alginate-based porous carbon material after desorption is obtained, 2.0mg of the nitrogen-doped sodium alginate-based porous carbon material after desorption is thrown into a bisphenol A solution with the concentration of 250mg/L, then the nitrogen-doped sodium alginate-based porous carbon material is placed into a constant-temperature water bath oscillator with the temperature of 303K and the oscillation speed of 150r/min for oscillation for 12h for reabsorption, then a sample is filtered through a 0.22 mu m filter head, filtrate is obtained, the concentration of bisphenol A (BPA) in the filtrate is measured at 280nm by adopting at(mg/g); repeating the above regeneration experiment, re-adsorption process and detection steps for 4 times, plotting the cycle times as abscissa and adsorption capacity Qt (mg/g) as ordinate,the results are shown in FIG. 10.
Fig. 10 is a graph of the regeneration performance of the nitrogen-doped sodium alginate-based porous carbon material prepared in example 3 of the present invention, and it can be seen from fig. 10 that after 4 regeneration experiments, the adsorption capacity of the nitrogen-doped sodium alginate-based porous carbon material is reduced from 894.31mg/g to 610.45mg/g, the reduction ratio is 31.74%, and still higher adsorption capacity is shown, which indicates that the doped sodium alginate-based porous carbon material prepared by the method of the present invention has excellent reusability, and has a great application prospect as a phenol pollutant adsorbent for large-scale sewage treatment.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (6)
1. The preparation method of the nitrogen-doped sodium alginate-based porous carbon material is characterized in that sodium alginate is used as a carbon precursor, anhydrous potassium carbonate is used as an activating agent, melamine is used as a nitrogen dopant, and the nitrogen-doped sodium alginate-based porous carbon material is prepared by one-step method synchronous activation and high-temperature pyrolysis.
2. The method for preparing the nitrogen-doped sodium alginate-based porous carbon material according to claim 1, which is characterized by comprising the following steps of:
step one, placing sodium alginate, anhydrous potassium carbonate and melamine in a mortar and grinding uniformly to obtain mixed powder;
and step two, placing the mixed powder obtained in the step one in a porcelain boat, loading the porcelain boat into a tube furnace, heating the porcelain boat under the protection of nitrogen atmosphere to perform activation and high-temperature pyrolysis to obtain a black solid, then sequentially washing the black solid with dilute hydrochloric acid solution and deionized water until the black solid is neutral, and drying the black solid to obtain the nitrogen-doped sodium alginate-based porous carbon material.
3. The method for preparing the nitrogen-doped sodium alginate-based porous carbon material according to claim 2, wherein the mass ratio of the sodium alginate to the anhydrous potassium carbonate to the melamine in the step one is 1: 0.5-4: 0.1 to 5; the process of heating up for activating high-temperature pyrolysis in the step two is as follows: heating from room temperature to 700-900 ℃ at the speed of 5 ℃/min and preserving heat for 1-3 h; and the drying temperature in the second step is 80-90 ℃.
4. The method for preparing the nitrogen-doped sodium alginate-based porous carbon material according to claim 2, wherein the mass ratio of the sodium alginate to the anhydrous potassium carbonate to the melamine in the step one is 1: 1: 0.2; the process of heating up for activating high-temperature pyrolysis in the step two is as follows: heating from room temperature to 800 ℃ at the speed of 5 ℃/min and preserving heat for 2 h; the temperature of the drying in step two was 85 ℃.
5. A nitrogen-doped sodium alginate-based porous carbon material prepared by the method of any one of claims 1 to 4.
6. The use of the nitrogen-doped sodium alginate-based porous carbon material of claim 5 for adsorbing bisphenol A in water.
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