CN112086298A - Modified activated carbon/ferroferric oxide composite material and preparation method and application thereof - Google Patents

Modified activated carbon/ferroferric oxide composite material and preparation method and application thereof Download PDF

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CN112086298A
CN112086298A CN202010979373.3A CN202010979373A CN112086298A CN 112086298 A CN112086298 A CN 112086298A CN 202010979373 A CN202010979373 A CN 202010979373A CN 112086298 A CN112086298 A CN 112086298A
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activated carbon
ferroferric oxide
composite material
iron
drying
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CN112086298B (en
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马宇辉
曹军瑞
谢宝龙
陈希
赵瑾
王勋亮
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Tianjin Institute of Seawater Desalination and Multipurpose Utilization MNR
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Tianjin Institute of Seawater Desalination and Multipurpose Utilization MNR
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    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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    • C02F2305/00—Use of specific compounds during water treatment
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Abstract

The invention provides a modified activated carbon/ferroferric oxide composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) carrying out first impregnation treatment on the activated carbon by using an organic acid solution, carrying out solid-liquid separation after the activated carbon is adsorbed and saturated, and obtaining solid which is the acid-impregnated activated carbon; (2) performing secondary impregnation treatment on the pickling activated carbon obtained in the step (1) by using an iron salt solution, and performing solid-liquid separation after the pickling activated carbon is adsorbed and saturated, wherein the obtained solid is the iron-loaded pickling activated carbon; (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) to obtain a modified activated carbon/ferroferric oxide composite material; wherein, the iron ions in the iron salt solution in the step (2) comprise Fe2+And/or Fe3+. The modified activated carbon/ferroferric oxide composite material can be used as an adsorption material, a superparamagnetic material, a Fenton-like catalyst or a supercapacitor electrode material.

Description

Modified activated carbon/ferroferric oxide composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite material preparation, particularly relates to a modified activated carbon composite material, and particularly relates to a modified activated carbon/ferroferric oxide composite material as well as a preparation method and application thereof.
Background
In recent years, the preparation and application of the activated carbon/ferroferric oxide composite material are receiving more and more attention. The ferroferric oxide particles are loaded on the surface of the active carbon, so that the particle agglomeration phenomenon can be effectively avoided.
The conventional preparation method of the active carbon/ferroferric oxide composite material based on the finished active carbon is a dipping-roasting method. The typical method comprises the steps of soaking activated carbon by using ferrous salt or ferric salt solution, then directly drying the solvent or carrying out solid-liquid separation by suction filtration, and then roasting the mixture of the ferrous salt or ferric salt and the activated carbon in an inert gas atmosphere (the roasting temperature is usually higher than 700 ℃), so that the activated carbon/ferroferric oxide composite material can be finally obtained.
The method has the disadvantages of harsh preparation conditions and high energy consumption. In addition, if the solution is completely dried, the surface of the activated carbon is easily covered by iron-containing compounds generated by ferrous salt or ferric salt hydrolysis, and pores can be blocked after roasting; ferrous ion (Fe) bonded with activated carbon if solid-liquid separation is performed by vacuum filtration2+) Or iron ion (Fe)3+) Mainly based on the chemical adsorption of surface functional groups to the surface of the activated carbon. Activated carbon is usually prepared by high temperature activation, and has fewer surface functional groups, so that Fe2+And Fe3+The amount of the iron oxide is less, so that the content of the ferroferric oxide in the final compound is lower.
Some documents adopt concentrated nitric acid to perform oxidation modification on commercial activated carbon under a heating condition, so that the content of oxygen-containing functional groups on the surface of the activated carbon is increased, and the adsorption capacity of the activated carbon on ferrous ions or ferric ions is further improved. However, concentrated nitric acid is used as an oxidizing agent with extremely strong corrosivity, the oxidation condition is not easy to control, if the oxidation degree is too high, a large number of carbon atoms in an activated carbon matrix are etched, and finally, the mechanical strength of the oxidized activated carbon is deteriorated, so that the use of the material is influenced; in addition, the concentrated nitric acid is easy to escape acid mist and nitrogen dioxide in the heating process, thereby causing environmental pollution.
CN 104190360A provides an oxidation-loaded iron modified activated carbon water treatment adsorbent and a preparation method thereof, the method comprises the steps of firstly adding nitric acid or phosphoric acid into activated carbon, and effectively increasing the number of acidic functional groups on the surface of the activated carbon by utilizing the strong oxidizing property of the nitric acid or phosphoric acid, so as to increase the adsorption sites of metal ions; then adding ferric chloride or ferric sulfate and the like to introduce metal (hydroxide), can increase the adsorption force on metal ions, and is combined with the properties of developed porosity, specific surface area and the like of the active carbon, thereby finally realizing the removal of various metal ions in water. However, the strong oxidizing acid used in the method is easy to corrode the pore structure of the activated carbon and weaken the mechanical strength of the activated carbon, thereby affecting the adsorption performance of the modified activated carbon and reducing the service life.
CN 106268719A provides a preparation method of modified activated carbon loaded with ferroferric oxide particles, which comprises the steps of firstly preparing FeCl2、FeCl3Uniformly mixing the solid NaOH and the mixture, roasting and melting the mixture by microwave heating in a nitrogen atmosphere, and cooling the mixture after the melting is finished to obtain molten liquid; and sequentially adding sodium dodecyl benzene sulfonate and activated carbon prepared from the eupatorium adenophorum raw material into the molten liquid, uniformly mixing, carrying out loading under the ultrasonic-assisted condition, adding distilled water for cleaning after loading is finished, carrying out solid-liquid separation and drying to obtain the modified activated carbon loaded with the ferroferric oxide particles. However, the method cannot well avoid agglomeration of the ferroferric oxide particles in the drying process, and the loading under the ultrasonic-assisted condition is not suitable for large-scale production and application.
CN 105597682A provides a room-temperature formaldehyde-removing modified activated carbon and a preparation method thereof, wherein the modified activated carbon takes granular, columnar, spherical or honeycomb-shaped high-specific-surface-area coconut shell activated carbon as a carrier and CuCl2And FeCl3The mixed metal salt is used as a modified component and is prepared by adopting the processes of dipping, drying and calcining. The modified activated carbon has the characteristics of rapid capture, high-efficiency adsorption, long working period and the like on gaseous formaldehyde, and can meet the requirement of effectively removing formaldehyde for a long time in an indoor environment. However, the pores of the modified activated carbon are easily blocked by metal salts in the calcining process, and the surface metal adsorption amount of the modified activated carbon is not high due to the fact that the surface functional groups of the activated carbon are few, so that the formaldehyde adsorption performance is affected.
CN 109502583A provides a preparation method of modified activated carbon, which is characterized in that through a two-step modification method of organic acid and transition metal ions, carboxyl groups on the surface of the prepared activated carbon are increased, the bonding force between the transition metal ions and the surface of the activated carbon is enhanced, and the dispersibility of the metal ions is effectively improved; meanwhile, due to the reducibility of the carboxyl, the metal ions can be reduced into metal simple substances or low-valence metal ions, and the adsorption performance of the metal ions on low-concentration methylbenzene is obviously improved. The method has simple operation flow and low cost, and can be used for protective products such as activated carbon filter elements and the like. However, stable ferroferric oxide magnetic particles are not formed in the modified activated carbon prepared by the method, and the modified activated carbon can only be applied to the treatment of organic waste gas and cannot be applied to a liquid phase environment.
Therefore, how to provide a modified activated carbon/ferroferric oxide composite material and a preparation method and application thereof, wherein the preparation method is used for improving Fe on the surface of activated carbon2+And/or Fe3+The adsorption capacity is avoided, the damage of the activated carbon structure in the preparation process is avoided, the requirements of energy conservation and environmental protection are also required to be met, and the problem which needs to be solved urgently at present is solved.
Disclosure of Invention
The invention aims to provide a modified activated carbon/ferroferric oxide composite material as well as a preparation method and application thereof, wherein the preparation method improves Fe on the surface of the activated carbon2+And/or Fe3+The adsorption capacity, and simultaneously, the damage of the activated carbon structure in the preparation process is avoided, and the requirements of energy conservation and environmental protection are also met.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) carrying out first impregnation treatment on the activated carbon by using an organic acid solution, carrying out solid-liquid separation after the activated carbon is adsorbed and saturated, and obtaining solid which is the acid-impregnated activated carbon;
(2) performing secondary impregnation treatment on the pickling activated carbon obtained in the step (1) by using an iron salt solution, and performing solid-liquid separation after the pickling activated carbon is adsorbed and saturated, wherein the obtained solid is the iron-loaded pickling activated carbon;
(3) roasting the iron-loaded pickling activated carbon obtained in the step (2) to obtain a modified activated carbon/ferroferric oxide composite material;
wherein, the iron ions in the iron salt solution in the step (2) comprise Fe2+And/or Fe3+。
In the invention, the organic acid solution is used in the step (1) to modify the surface of the activated carbon, so that the damage of the conventional concentrated nitric acid modification to the structure of the activated carbon is avoided; meanwhile, the organic acid is selected for modification, so that the adsorption capacity of the active carbon to iron ions can be remarkably improved, and finally, the composite material contains more ferroferric oxide. In addition, the organic acid molecules on the surface of the acid-leaching activated carbon can realize selective complexing adsorption of iron ions, so that the iron ions are fixed on the adsorption active site of the activated carbon, the agglomeration of the iron ions in the subsequent drying and roasting processes is inhibited, and the blockage of active carbon pore channels is avoided, thereby being beneficial to maintaining the original pore structure of the activated carbon.
In the invention, the roasting in the step (3) can not only convert the iron ions in the iron-carrying pickling activated carbon into stable metal oxides, namely ferroferric oxide magnetic particles, but also enable organic acid molecules to escape through thermal cracking, reduce the residue of the organic acid molecules in the activated carbon and effectively avoid the release of the organic acid molecules in the practical application process; in addition, iron ions are firmly combined with the activated carbon through roasting, and the iron ions are not easy to fall off due to hydraulic impact under the application condition of a liquid phase environment.
Preferably, the first impregnation treatment of step (1) is an excess impregnation.
Preferably, the time of the first impregnation treatment is 4 to 24 hours, for example, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the activated carbon can be any one commercial activated carbon, the maximum adsorption capacity of the activated carbon is calculated by using a static adsorption method before the organic acid solution is impregnated, and then the activated carbon is ensured to reach a state of saturated adsorption on the organic acid solution by using an excess impregnation method, namely, organic acid molecules occupy all active sites of the activated carbon which can be adsorbed.
Preferably, the solute of the organic acid solution in step (1) comprises any one or a combination of at least two of tartaric acid, oxalic acid, citric acid, malic acid, ascorbic acid or ethylenediaminetetraacetic acid, and typical but non-limiting combinations include a combination of tartaric acid and oxalic acid, a combination of oxalic acid and citric acid, a combination of citric acid and malic acid, a combination of malic acid and ascorbic acid, a combination of ascorbic acid and ethylenediaminetetraacetic acid, a combination of tartaric acid, oxalic acid and citric acid, a combination of oxalic acid, citric acid and malic acid, a combination of citric acid, malic acid and ascorbic acid, or a combination of malic acid, ascorbic acid and ethylenediaminetetraacetic acid.
Preferably, the solvent of the organic acid solution in the step (1) is deionized water.
Preferably, the solid-liquid separation mode in the step (1) comprises vacuum filtration and/or centrifugal dehydration.
Preferably, the solid-liquid separation in step (1) is followed by a drying treatment.
Preferably, the drying treatment is drying and/or airing, and more preferably drying.
Preferably, the temperature of the drying is 30 to 150 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the drying is used for removing moisture in the pickling activated carbon; the end point of the drying is that the quality of the acid leaching activated carbon is not changed any more.
Preferably, the second impregnation treatment of step (2) is an excess impregnation.
Preferably, the time of the second dipping treatment is 4 to 24 hours, for example, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, before the ferric salt solution is impregnated, the maximum adsorption capacity of the dried pickling activated carbon is calculated by using a static adsorption method, and then an excessive impregnation method is used for ensuring that the pickling activated carbon reaches a state of saturated adsorption on the ferric salt solution, namely that iron ions occupy all active sites of the pickling activated carbon which can be adsorbed.
Preferably, the solute of the iron salt solution of step (2) comprises FeSO4、FeCl2、Fe(NO3)2、Fe2(SO4)3、Fe(NO3)3Or FeCl3Any one or a combination of at least two of the above, typical but not limiting combinations include FeSO4With FeCl2Combinations of FeCl2With Fe (NO)3)2Combination of (1), Fe (NO)3)2With Fe2(SO4)3Combination of (1), Fe2(SO4)3With Fe (NO)3)3Combination of (1), Fe (NO)3)3With FeCl3Combination of (1), FeSO4、FeCl2With Fe (NO)3)2Combinations of FeCl2、Fe(NO3)2With Fe2(SO4)3Combination of (1), Fe (NO)3)2、Fe2(SO4)3With Fe (NO)3)3A combination of (1), or Fe2(SO4)3、Fe(NO3)3With FeCl3Combinations of (a) and (b).
Preferably, the solvent of the iron salt solution in the step (2) is deionized water.
Preferably, the solid-liquid separation mode in the step (2) comprises vacuum filtration and/or centrifugal dehydration.
Preferably, the solid-liquid separation in step (2) is followed by a drying treatment.
Preferably, the drying treatment is drying and/or airing, and more preferably drying.
Preferably, the temperature of the drying is 30 to 150 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the drying is used for removing moisture in the iron-carrying pickling activated carbon; the end point of the drying is that the quality of the iron-loaded pickling activated carbon is not changed any more.
Preferably, the calcination in step (3) is carried out under a protective atmosphere.
Preferably, the protective atmosphere comprises nitrogen and/or argon.
Preferably, the temperature of the calcination in step (3) is 300-.
Preferably, the calcination time in step (3) is 0.5-6h, such as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, organic acid molecules adsorbed on the surface of the iron-carrying pickling activated carbon can be decomposed within the temperature range of 300-350 ℃, and the decomposition products can participate in the conversion process of iron ions, so that the formation of ferroferric oxide particles in an activated carbon matrix can be promoted even at a mild roasting temperature. In the temperature range of 350-750 ℃, the carbon particles derived from organic acid molecules can serve as a reducing agent in the process of continuously increasing the temperature, and the intermediate product of the ferric oxide is promoted to be continuously converted into the ferroferric oxide. When the roasting temperature is lower than 250 ℃, iron ions cannot be fully converted into ferroferric oxide particles; when the roasting temperature is higher than 750 ℃, ferroferric oxide is continuously reduced by carbon in the activated carbon matrix, namely, a carbothermic reduction reaction occurs, so that the ferroferric oxide is converted into elementary iron.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) carrying out first excess impregnation treatment on the activated carbon for 4-24h by using an organic acid solution, carrying out vacuum filtration and/or centrifugal dehydration after the activated carbon is adsorbed and saturated, and drying at 30-150 ℃, wherein the obtained solid is the acid-impregnated activated carbon; the solute of the organic acid solution comprises one or the combination of at least two of tartaric acid, oxalic acid, citric acid, malic acid, ascorbic acid or ethylenediamine tetraacetic acid, and the solvent is deionized water;
(2) carrying out secondary excessive impregnation treatment on the pickling activated carbon obtained in the step (1) by using an iron salt solution for 4-24h, carrying out vacuum filtration and/or centrifugal dehydration after the pickling activated carbon is adsorbed and saturated, and drying at 30-150 ℃, wherein the obtained solid is iron-loaded pickling activated carbon; the solute of the iron salt solution comprises FeSO4、FeCl2、Fe(NO3)2、Fe2(SO4)3、Fe(NO3)3Or FeCl3Any one or a combination of at least two of the above, wherein the solvent is deionized water;
(3) and (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 0.5-6h at the temperature of 300-750 ℃ in the atmosphere with nitrogen and/or argon as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
In a second aspect, the invention provides a modified activated carbon/ferroferric oxide composite material prepared by the preparation method in the first aspect.
Compared with unmodified activated carbon, the modified activated carbon/ferroferric oxide composite material has many advantages, which are mainly reflected in the following aspects:
(1) the modified active carbon/ferroferric oxide composite material can adsorb certain pollutants which cannot be adsorbed by the active carbon;
(2) based on superparamagnetism of ferroferric oxide, the modified activated carbon/ferroferric oxide composite material can be quickly separated from a liquid-phase medium through an external magnetic field;
(3) ferroferric oxide is used as a Fenton-like catalyst, the modified activated carbon/ferroferric oxide composite material can be used for catalytic oxidation decomposition of refractory organic matters, and an oxidizing agent can also be used for catalytic oxidation regeneration of the modified activated carbon/ferroferric oxide composite material saturated with organic matters;
(4) the ferroferric oxide can obviously improve the specific capacitance of the original activated carbon.
In a third aspect, the invention provides an application of the modified activated carbon/ferroferric oxide composite material as described in the second aspect in an adsorption material, a superparamagnetic material, a fenton-like catalyst or a supercapacitor electrode material.
According to the invention, when the modified activated carbon/ferroferric oxide composite material is adopted as the Fenton-like catalyst, the oxidizing agent is matched for degrading the organic pollutant methylene blue in water, and the degradation rate is up to 90-99%.
Preferably, the oxidant is hydrogen peroxide.
Preferably, the mass fraction of the hydrogen peroxide is 10-50%, and the dosage is 0.1-1mL/(g of catalyst).
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the organic acid solution is used for carrying out surface modification on the activated carbon, so that the damage of the conventionally selected concentrated nitric acid modification to the structure of the activated carbon is avoided, the adsorption quantity of the activated carbon to iron ions is increased, and finally, the composite material contains more ferroferric oxide;
(2) according to the invention, the organic acid molecules on the surface of the acid-leaching activated carbon realize selective complexing adsorption of iron ions, so that the iron ions are fixed at the adsorption active site of the activated carbon, and the agglomeration phenomenon of the iron ions in the subsequent drying and roasting processes is inhibited, thereby being beneficial to maintaining the original pore structure of the activated carbon;
(3) organic acid molecules adsorbed on the surface of the iron-carrying pickling activated carbon can be decomposed within the temperature range of 300-350 ℃, and decomposition products of the organic acid molecules can participate in the conversion process of iron ions, so that the formation of ferroferric oxide particles in an activated carbon matrix can be promoted even at a mild roasting temperature;
(4) according to the invention, iron ions and activated carbon can be firmly combined through the later roasting process, and the iron ions are not easy to fall off due to hydraulic impact under the application condition of a liquid phase environment;
(5) the preparation method of the invention avoids introducing impurities into the organic acid solution and the ferric salt solution, and only needs to change the concentrations of the impurities, so the impurities can be recycled by replenishing materials.
Drawings
FIG. 1 is XRD spectra of a modified activated carbon/ferroferric oxide composite material provided in example 1 and a modified activated carbon material and commercial activated carbon provided in comparative example 1;
FIG. 2 is an XRD spectrum of the modified activated carbon/ferroferric oxide composite material provided in example 2 and the modified activated carbon material provided in comparative example 2;
FIG. 3 is a nitrogen adsorption and desorption curve of the modified activated carbon/ferroferric oxide composite material provided in example 2;
FIG. 4 is a nitrogen adsorption and desorption curve of commercial activated carbon;
FIG. 5 is a graph showing the change in iron ion content before and after the modified activated carbon/ferroferric oxide composite material provided in example 3 and the modified activated carbon material provided in comparative example 3 are used in a liquid phase environment;
fig. 6 is XRD patterns of the modified activated carbon/ferroferric oxide composite material provided in example 4 and the modified activated carbon material provided in comparative example 4.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) preparing 50mL of 0.1g/mL citric acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotating speed of 180rpm by using the citric acid solution, carrying out first excess impregnation treatment for 14h, carrying out vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-impregnated activated carbon;
(2) 50mL of 0.1g/mL Fe (NO) was prepared with deionized water3)2Solution, reuse of said Fe (NO)3)2The solution is used for the pickling activated carbon obtained in the step (1) at room temperatureOscillating in an oscillator at the rotating speed of 180rpm, carrying out second excessive impregnation treatment for 14h, carrying out vacuum filtration after saturated absorption of the pickling activated carbon, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-loaded pickling activated carbon;
(3) and (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 3.25 hours at the temperature of 300 ℃ in the atmosphere taking nitrogen as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The XRD spectrum of the modified activated carbon/ferroferric oxide composite material obtained in the embodiment is shown in figure 1.
Example 2
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) preparing 50mL of 0.1g/mL oxalic acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotating speed of 180rpm by using the oxalic acid solution, performing first excess impregnation treatment for 9 hours, performing centrifugal dehydration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 60 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is pickling activated carbon;
(2) 50mL of 0.1g/mL FeCl was prepared with deionized water2Solution, reuse of said FeCl2Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 9 hours, carrying out centrifugal dehydration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 60 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-loaded pickling activated carbon;
(3) and (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 5 hours at 750 ℃ in an atmosphere taking argon as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The XRD spectrum of the modified activated carbon/ferroferric oxide composite material obtained in the embodiment is shown in figure 2, and the nitrogen adsorption and desorption curve is shown in figure 3.
As can be seen from FIG. 3, the specific surface area of the product of example 2The volume and total pore volume were 1085m, respectively2G and 0.539cm3(ii)/g; as can be seen from FIG. 4, the specific surface area and the total pore volume of the commercial activated carbon were 1197m2G and 0.585cm3(ii) in terms of/g. The results show that the introduction of the ferroferric oxide particles can cause slight blockage of the original pores of the activated carbon, and the specific surface area and the total pore volume of the activated carbon are still kept above 90 percent of the original level.
Example 3
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) preparing 50mL of 0.1g/mL malic acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotation speed of 180rpm by using the malic acid solution, performing first excess impregnation treatment for 19 hours, performing centrifugal dehydration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 120 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-soaked activated carbon;
(2) 50mL of 0.1g/mL Fe was prepared with deionized water2(SO4)3Solution, reuse of said Fe2(SO4)3Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, performing secondary excess dipping treatment for 19 hours, performing centrifugal dehydration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 120 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-loaded pickling activated carbon;
(3) and (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 2 hours at 700 ℃ in an atmosphere taking argon as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The crystal phase structure and the pore structure of the modified activated carbon/ferroferric oxide composite material obtained in this embodiment are similar to those of the modified activated carbon/ferroferric oxide composite material obtained in example 2, and therefore, the description thereof is omitted.
0.5g of the modified activated carbon/ferroferric oxide composite material obtained in the embodiment is placed in a 50mL conical flask, 20mL deionized water is added, and the conical flask is placed in a shaking table to oscillate at the rotating speed of 180rpm after being sealed. Sampling and detecting the concentration of iron ions in the deionized water after 0h, 8h, 16h and 24h after the beginning of oscillation respectively.
The content of iron ions of the modified activated carbon/ferroferric oxide composite material obtained in the embodiment is shown in fig. 5 before and after the modified activated carbon/ferroferric oxide composite material is used in a liquid phase environment.
Example 4
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) preparing 50mL of 0.1g/mL tartaric acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotation speed of 180rpm by using the tartaric acid solution, performing first excess impregnation treatment for 4 hours, performing vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 30 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is pickling activated carbon;
(2) 50mL of 0.1g/mL FeSO was prepared with deionized water4Solution, reuse of the FeSO4Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 4 hours, carrying out vacuum filtration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at the temperature of 30 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-loaded pickling activated carbon;
(3) and (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 6 hours at 550 ℃ in an atmosphere taking nitrogen as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The XRD spectrum of the modified activated carbon/ferroferric oxide composite material obtained in the embodiment is shown in figure 6.
Example 5
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) preparing 50mL of 0.1g/mL ascorbic acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotating speed of 180rpm by using the ascorbic acid solution, carrying out first excessive impregnation treatment for 24 hours, carrying out vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, drying at 150 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-impregnated activated carbon;
(2) 50mL of 0.1g/mL Fe (NO) was prepared with deionized water3)3Solution, reuse of said Fe (NO)3)3Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 24 hours, carrying out vacuum filtration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 150 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is iron-loaded pickling activated carbon;
(3) and (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) at 400 ℃ in an atmosphere taking nitrogen as protective gas for 0.5h to obtain the modified activated carbon/ferroferric oxide composite material.
The crystal phase structure and the pore structure of the modified activated carbon/ferroferric oxide composite material obtained in this embodiment are similar to those of the modified activated carbon/ferroferric oxide composite material obtained in example 2, and therefore, the description thereof is omitted.
Example 6
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) preparing 50mL of 0.1g/mL ethylene diamine tetraacetic acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotating speed of 180rpm by using the ethylene diamine tetraacetic acid solution, performing first excessive impregnation treatment for 14h, performing centrifugal dehydration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-impregnated activated carbon;
(2) 50mL of 0.1g/mL FeCl was prepared with deionized water3Solution, reuse of said FeCl3Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 14 hours, and centrifuging after the pickling activated carbon is adsorbed and saturatedDehydrating, washing the obtained solid until the washing liquid is colorless and transparent, drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-carrying pickling activated carbon;
(3) and (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 3.25 hours at 550 ℃ in an atmosphere taking argon as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The crystal phase structure and the pore structure of the modified activated carbon/ferroferric oxide composite material obtained in this embodiment are similar to those of the modified activated carbon/ferroferric oxide composite material obtained in example 2, and therefore, the description thereof is omitted.
Example 7
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) preparing 15mL of 0.05g/mL citric acid solution and 15mL of 0.05g/mL oxalic acid solution by using deionized water, and mixing the two organic acid solutions to obtain a mixed organic acid solution; oscillating 15g of commercial activated carbon in an oscillator at the rotating speed of 180rpm at room temperature by using the mixed organic acid solution, carrying out first excessive impregnation treatment for 14h, carrying out vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the acid-impregnated activated carbon;
(2) 50mL of 0.1g/mL Fe (NO) was prepared with deionized water3)2Solution, reuse of said Fe (NO)3)2Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 14 hours, carrying out vacuum filtration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is iron-loaded pickling activated carbon;
(3) and (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 3.25 hours at the temperature of 300 ℃ in the atmosphere taking nitrogen as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The crystal phase structure and the pore structure of the modified activated carbon/ferroferric oxide composite material obtained in this embodiment are similar to those of the modified activated carbon/ferroferric oxide composite material obtained in example 2, and therefore, the description thereof is omitted.
Example 8
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) preparing 60mL of 0.1g/mL citric acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotating speed of 180rpm by using the citric acid solution, carrying out first excess impregnation treatment for 14h, carrying out vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-impregnated activated carbon;
(2) 25mL of 0.05g/mL Fe (NO) was prepared with deionized water3)2Solution and 25mL of 0.05g/mL Fe (NO)3)3Mixing the two ferric salt solutions to obtain a mixed ferric salt solution; oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the mixed iron salt solution, carrying out second excessive dipping treatment for 14 hours, carrying out vacuum filtration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, drying at 90 ℃ until the activated carbon is completely dehydrated, and obtaining the solid which is the iron-carrying pickling activated carbon;
(3) and (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 3.25 hours at the temperature of 300 ℃ in the atmosphere taking nitrogen as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The crystal phase structure and the pore structure of the modified activated carbon/ferroferric oxide composite material obtained in this embodiment are similar to those of the modified activated carbon/ferroferric oxide composite material obtained in example 2, and therefore, the description thereof is omitted.
Comparative example 1
The present comparative example provides a method of preparing a modified activated carbon material, the method comprising the steps of:
(1) 50mL of 0.1g/mL Fe (NO) was prepared with deionized water3)2Solution, reuse of said Fe (NO)3)2Oscillating commercial activated carbon in an oscillator at the rotating speed of 180rpm at room temperature by using the solution, carrying out excessive impregnation treatment for 14h, carrying out vacuum filtration after the impregnated activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is iron-loaded activated carbon;
(2) and (2) roasting the iron-loaded activated carbon obtained in the step (1) at 300 ℃ in an atmosphere with nitrogen as a protective gas for 3.25 hours to obtain the modified activated carbon material.
The XRD pattern of the modified activated carbon material obtained in the comparative example is shown in figure 1.
As can be seen from FIG. 1, the XRD pattern of the commercial activated carbon has two wider diffraction peaks at 23 degrees and 46 degrees, which indicates the existence of amorphous carbon in the commercial activated carbon; the XRD pattern of the product of example 1, in addition to having diffraction peaks for amorphous carbon, also has sharp diffraction peaks at 30 °, 35 °, 56 °, 62 °, indicating the presence of a crystalline phase of ferriferrous oxide in the product of example 1; the XRD pattern of the product of comparative example 1 was similar to that of commercial activated carbon, indicating that the product of comparative example 1 did not contain the ferriferrous oxide crystalline phase. From this, it was found that the surface modification of activated carbon with an organic acid solution in advance enabled successful preparation of a modified activated carbon/ferroferric oxide composite material even at a calcination temperature of 300 ℃.
Comparative example 2
The present comparative example provides a method of preparing a modified activated carbon material, the method comprising the steps of:
(1) 50mL of 0.1g/mL FeCl was prepared with deionized water2Solution, reuse of said FeCl2Oscillating commercial activated carbon in an oscillator at the rotating speed of 180rpm at room temperature by using the solution, carrying out excessive impregnation treatment for 9 hours, carrying out centrifugal dehydration after the impregnated activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 60 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is iron-loaded activated carbon;
(2) and (2) roasting the iron-loaded activated carbon obtained in the step (1) at 750 ℃ in an atmosphere taking argon as a protective gas for 5 hours to obtain the modified activated carbon material.
The XRD pattern of the modified activated carbon material obtained in the comparative example is shown in figure 2.
As can be seen from fig. 2, the XRD pattern of the product of example 2 shows diffraction peaks with distinct intensities at 30 °, 35 °, 53 °, 56 °, 62 °, whereas the XRD pattern of the product of comparative example 2 shows diffraction peaks only at 30 ° and 35 °, which are weaker in intensity. The method comprises the following steps of (1) in example 2, performing surface modification on activated carbon in advance by using organic acid, and successfully preparing a modified activated carbon/ferroferric oxide composite material loaded with a large amount of ferroferric oxide crystals under the condition that the roasting temperature is 850 ℃; in comparative example 2, the surface of the activated carbon is not modified in advance by using the organic acid, so that only a small amount of ferroferric oxide crystals are formed even if the roasting temperature reaches 750 ℃, and the qualified modified activated carbon/ferroferric oxide composite material cannot be successfully prepared. Therefore, the organic acid is used for carrying out surface modification on the active carbon in advance, and the content of the ferroferric oxide crystal in the final composite material can be greatly improved.
Comparative example 3
The present comparative example provides a method of preparing a modified activated carbon material, the method comprising the steps of:
(1) preparing 50mL of 0.1g/mL malic acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotation speed of 180rpm by using the malic acid solution, performing first excess impregnation treatment for 19 hours, performing centrifugal dehydration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 120 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-soaked activated carbon;
(2) 50mL of 0.1g/mL Fe was prepared with deionized water2(SO4)3Solution, reuse of said Fe2(SO4)3Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, performing secondary excess dipping treatment for 19 hours, performing centrifugal dehydration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 120 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-loaded pickling activated carbon.
The change of the iron ion content of the modified activated carbon material obtained in the comparative example before and after the use in a liquid phase environment is shown in FIG. 5.
As can be seen from FIG. 5, the sample prepared in example 3 did not release iron ions at all times during the shaking process; in the sample prepared by the comparative example, the phenomenon of continuous and obvious release of iron ions exists in the liquid phase oscillation process. In addition, after shaking for 24h, the immersion liquid of example 3 was still colorless, while the color of the immersion liquid of the sample prepared in this comparative example changed from the initial colorless to yellow. The results show that the roasting process can firmly combine iron ions with the activated carbon, and the iron ions are not easy to fall off due to hydraulic impact under the application condition of a liquid phase environment.
Comparative example 4
The present comparative example provides a method of preparing a modified activated carbon material, the method comprising the steps of:
(1) preparing 50mL of 0.1g/mL nitric acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotating speed of 180rpm by using the nitric acid solution, performing first excess impregnation treatment for 4 hours, performing vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 30 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-soaked activated carbon;
(2) 50mL of 0.1g/mL FeSO was prepared with deionized water4Solution, reuse of the FeSO4Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 4 hours, carrying out vacuum filtration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at the temperature of 30 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-loaded pickling activated carbon;
(3) and (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) at 550 ℃ in an atmosphere taking nitrogen as protective gas for 6 hours to obtain the modified activated carbon material.
The XRD pattern of the modified activated carbon material obtained in the comparative example is shown in figure 6.
As can be seen from fig. 6, in both the XRD patterns of the sample obtained in the present comparative example and the sample obtained in example 4, a diffraction peak of ferroferric oxide appears, but the intensity of the diffraction peak of ferroferric oxide is weak, which indicates that the ferroferric oxide contained therein has a small crystal phase, which indicates that the content of ferroferric oxide crystals in the modified activated carbon material cannot be increased by performing surface modification on the activated carbon with an inorganic acid at room temperature.
Application example 1
In the application example, the modified activated carbon/ferroferric oxide composite material provided in embodiment 1 is used as a fenton-like catalyst, and is used in combination with hydrogen peroxide to degrade methylene blue, which is an organic pollutant in water, and the specific operation is as follows:
preparing a methylene blue solution with the concentration of 500mg/L, putting 60mL of the methylene blue solution into a 250mL conical flask, adding 0.1g of the modified activated carbon/ferroferric oxide composite material prepared in the embodiment 1, then adding 50 mu L of hydrogen peroxide solution with the mass fraction of 30%, sealing, putting into a shaking table, oscillating at 180rpm for 4h, measuring the content of methylene blue in the solution by a spectrophotometry method, and further calculating the removal rate. In a comparison experiment, only the modified activated carbon/ferroferric oxide composite material and hydrogen peroxide are respectively added, the other conditions are kept unchanged, and the removal rate of a single element on methylene blue is inspected.
The results of the relevant experiments are shown in table 1.
TABLE 1
Materials and reagents Removal pathway Removal Rate (%)
Modified active carbon/ferroferric oxide composite material and hydrogen peroxide Catalytic oxidative decomposition 95.3％
Modified active carbon/ferroferric oxide compositeComposite material Adsorption 63.6％
Hydrogen peroxide solution Oxidation by oxygen 5.2％
The results in table 1 show that the removal rate of methylene blue in the solution by the single modified activated carbon/ferroferric oxide composite material and hydrogen peroxide is relatively limited, and when the single modified activated carbon/ferroferric oxide composite material and the hydrogen peroxide are used in combination, the removal rate is obviously increased, which shows that a synergistic effect exists between the two materials, namely, the modified activated carbon/ferroferric oxide composite material is used as a fenton-like catalyst to catalyze the decomposition of hydrogen peroxide in hydrogen peroxide to generate hydroxyl radicals with strong oxidizability, and the purpose of advanced oxidation is achieved.
Therefore, the organic acid solution is used for carrying out surface modification on the activated carbon, so that the damage of the conventionally selected concentrated nitric acid modification to the structure of the activated carbon is avoided, the adsorption quantity of the activated carbon to iron ions is increased, and finally, the composite material contains more ferroferric oxide; according to the invention, the organic acid molecules on the surface of the acid-leaching activated carbon realize selective complexing adsorption of iron ions, so that the iron ions are fixed at the adsorption active site of the activated carbon, and the agglomeration phenomenon of the iron ions in the subsequent drying and roasting processes is inhibited, thereby being beneficial to maintaining the original pore structure of the activated carbon; organic acid molecules adsorbed on the surface of the iron-carrying pickling activated carbon can be decomposed within the temperature range of 300-350 ℃, and decomposition products of the organic acid molecules can participate in the conversion process of iron ions, so that the formation of ferroferric oxide particles in an activated carbon matrix can be promoted even at a mild roasting temperature; according to the invention, iron ions and activated carbon can be firmly combined through the later roasting process, and the iron ions are not easy to fall off due to hydraulic impact under the application condition of a liquid phase environment; the preparation method of the invention avoids introducing impurities into the organic acid solution and the ferric salt solution, and only needs to change the concentrations of the impurities, so the impurities can be recycled by replenishing materials.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A preparation method of a modified activated carbon/ferroferric oxide composite material is characterized by comprising the following steps:
(1) carrying out first impregnation treatment on the activated carbon by using an organic acid solution, carrying out solid-liquid separation after the activated carbon is adsorbed and saturated, and obtaining solid which is the acid-impregnated activated carbon;
(2) performing secondary impregnation treatment on the pickling activated carbon obtained in the step (1) by using an iron salt solution, and performing solid-liquid separation after the pickling activated carbon is adsorbed and saturated, wherein the obtained solid is the iron-loaded pickling activated carbon;
(3) roasting the iron-loaded pickling activated carbon obtained in the step (2) to obtain a modified activated carbon/ferroferric oxide composite material;
wherein, the iron ions in the iron salt solution in the step (2) comprise Fe2+And/or Fe3+。
2. The production method according to claim 1, wherein the first impregnation treatment of step (1) is excess impregnation;
preferably, the time of the first impregnation treatment is 4 to 24 hours.
3. The method according to claim 1 or 2, wherein the solute of the organic acid solution of step (1) comprises any one or a combination of at least two of tartaric acid, oxalic acid, citric acid, malic acid, ascorbic acid or ethylenediaminetetraacetic acid;
preferably, the solvent of the organic acid solution in the step (1) is deionized water.
4. The production method according to any one of claims 1 to 3, wherein the solid-liquid separation in step (1) comprises vacuum filtration and/or centrifugal dehydration;
preferably, the solid-liquid separation in the step (1) is followed by a drying treatment;
preferably, the drying treatment is drying and/or airing, and further preferably drying;
preferably, the temperature of the drying is 30-150 ℃.
5. The production method according to any one of claims 1 to 4, wherein the second impregnation treatment of step (2) is excess impregnation;
preferably, the time of the second impregnation treatment is 4-24 h;
preferably, the solute of the iron salt solution of step (2) comprises FeSO4、FeCl2、Fe(NO3)2、Fe2(SO4)3、Fe(NO3)3Or FeCl3Any one or a combination of at least two of;
preferably, the solvent of the iron salt solution in the step (2) is deionized water.
6. The production method according to any one of claims 1 to 5, wherein the solid-liquid separation in step (2) comprises vacuum filtration and/or centrifugal dehydration;
preferably, the solid-liquid separation in the step (2) is followed by a drying treatment;
preferably, the drying treatment is drying and/or airing, and further preferably drying;
preferably, the temperature of the drying is 30-150 ℃.
7. The production method according to any one of claims 1 to 6, wherein the firing in step (3) is performed under a protective atmosphere;
preferably, the protective gas used in the protective atmosphere comprises nitrogen and/or argon;
preferably, the roasting temperature in the step (3) is 300-750 ℃;
preferably, the roasting time of the step (3) is 0.5-6 h.
8. The method of any one of claims 1 to 7, comprising the steps of:
(1) carrying out first excess impregnation treatment on the activated carbon for 4-24h by using an organic acid solution, carrying out vacuum filtration and/or centrifugal dehydration after the activated carbon is adsorbed and saturated, and drying at 30-150 ℃, wherein the obtained solid is the acid-impregnated activated carbon; the solute of the organic acid solution comprises one or the combination of at least two of tartaric acid, oxalic acid, citric acid, malic acid, ascorbic acid or ethylenediamine tetraacetic acid, and the solvent is deionized water;
(2) carrying out secondary excessive impregnation treatment on the pickling activated carbon obtained in the step (1) by using an iron salt solution for 4-24h, carrying out vacuum filtration and/or centrifugal dehydration after the pickling activated carbon is adsorbed and saturated, and drying at 30-150 ℃, wherein the obtained solid is iron-loaded pickling activated carbon; the solute of the iron salt solution comprises FeSO4、FeCl2、Fe(NO3)2、Fe2(SO4)3、Fe(NO3)3Or FeCl3Any one or a combination of at least two of the above, wherein the solvent is deionized water;
(3) and (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 0.5-6h at the temperature of 300-750 ℃ in the atmosphere with nitrogen and/or argon as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
9. The modified activated carbon/ferroferric oxide composite material prepared by the preparation method according to any one of claims 1 to 8.
10. The use of the modified activated carbon/ferroferric oxide composite material according to claim 9 in an adsorbent material, a superparamagnetic material, a fenton-like catalyst or a supercapacitor electrode material.
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