CN113786799A - Preparation method of manganese dioxide/ferric oxide hydroxide loaded three-dimensional silicon dioxide adsorbent and application of adsorbent in adsorption of As (III) - Google Patents

Preparation method of manganese dioxide/ferric oxide hydroxide loaded three-dimensional silicon dioxide adsorbent and application of adsorbent in adsorption of As (III) Download PDF

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CN113786799A
CN113786799A CN202111089835.5A CN202111089835A CN113786799A CN 113786799 A CN113786799 A CN 113786799A CN 202111089835 A CN202111089835 A CN 202111089835A CN 113786799 A CN113786799 A CN 113786799A
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adsorbent
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崔俊硕
丛小珊
王丹丹
娄振宁
单炜军
于海彪
王月娇
冯小庚
熊英
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Liaoning University
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention discloses a preparation method of a manganese dioxide/ferric oxide hydroxide loaded three-dimensional silicon dioxide adsorbent and application of the adsorbent in adsorption of As (III). Three-dimensional mesoporous materials KIT-6 and FeCl3Mixing the solution and the HCl solution, stirring uniformly at room temperature, transferring to a reaction kettle for hydrothermal reaction, washing the obtained product to be neutral by using deionized water, and drying to obtain an intermediate product FeOOH/KIT-6; mixing MnSO4·H2Mixing O and FeOOH/KIT-6, adding KMnO after reflux reaction4The water solution is continuously refluxed and reacted, the obtained product is washed to be neutral by deionized water and dried to obtain the manganese dioxide/ferric oxide hydroxide loaded tris (oxide)A vitamin silica adsorbent. The adsorbent prepared by the invention is used for separating and removing heavy metal ions As (III), and the maximum saturated adsorption capacity is 39.77mg g‑1And an effective method is provided for detecting and controlling heavy metal pollution in an environmental water sample.

Description

Preparation method of manganese dioxide/ferric oxide hydroxide loaded three-dimensional silicon dioxide adsorbent and application of adsorbent in adsorption of As (III)
Technical Field
The invention belongs to the technical field of adsorbent material preparation, and particularly relates to a manganese dioxide/ferric oxide hydroxide loaded three-dimensional silicon dioxide adsorbent and a preparation method thereof.
Background
Industrial wastewater with excessive heavy metal content is discharged into the environment without proper treatment, which causes water pollution, damages aquatic ecosystem and threatens human health. Groundwater remains the major source of drinking water worldwide, and among the common heavy metal contaminants in water, arsenic is one of the most dangerous contaminants. This is mainly due to the fact that arsenic reacts with-SH on enzymes in the organism, thereby causing toxicity and harm to human body. And the research shows that the toxicity of trivalent arsenic in inorganic arsenic is 60 times of that of pentavalent arsenic. There is a need to design a new adsorbing material for reducing the arsenic content in water to make the concentration of arsenic reach the arsenic limit (0.01mg/L) of drinking water regulated by the world health organization.
At present, methods for treating heavy metal pollution mainly comprise a membrane separation method, a biological flocculation method, an ion exchange method, a chemical precipitation method and an adsorption method. Among the above methods, the adsorption method has the advantages of simple operation, economy, greenness, high efficiency, reproducibility and the like, and has become one of the most promising arsenic removal technologies. The adsorption technology is to adsorb and fix arsenic in water on the surface of an adsorbent through the actions of physics, chemical adsorption or ion exchange and the like, thereby achieving the purpose of removing arsenic from water. The technology is generally suitable for arsenic removal water treatment systems with large water body quantity and low pollutant concentration, and is particularly suitable for centralized water supply systems of small communities and villages. For adsorption processes, the main core is the choice of adsorbent.
The traditional adsorbent mainly comprises a carbon-containing composite material, a plurality of active oxides, various inorganic synthetic adsorbing materials and the like, and has the defects of high cost, poor adsorption selectivity to heavy metals, relatively low adsorption capacity and the like. Mesoporous silica has wide application in adsorbents due to its high specific surface area and large porosity, but the adsorption performance of silica on metal ions is limited and its selectivity is poor. At present, researchers are dedicated to load or graft inorganic or organic functional groups with special adsorption functions on heavy metal ions on a porous carrier, increase the active sites of the inorganic or organic functional groups, and improve the adsorption capacity and selectivity of the inorganic or organic functional groups. So far, many organic functional groups having an adsorption effect on heavy metal ions are used to modify mesoporous silica, and these adsorbents are used to remove a series of toxic heavy metals such as cu (ii), pb (ii), hg (ii), as (iii), and cr (vi) in water. Therefore, the development of an adsorbing material which is economic and environment-friendly, is easy to separate and can efficiently remove As (III) and As (V) at the same time has important significance in providing an efficient, economical and practical technology for heavy metal water treatment.
Disclosure of Invention
The invention aims to provide a novel adsorbent for removing As (III) and a preparation method thereof.
The invention synthesizes pure three-dimensional silicon dioxide by taking tetraethoxysilane as a silicon source and triblock copolymer P123 as a template. And then loading an iron substance on carrier silicon dioxide with a large specific surface area by adopting an impregnation method, and then sequentially treating with manganese sulfate and potassium permanganate to prepare the manganese dioxide/ferric oxide hydroxide loaded three-dimensional silicon dioxide adsorbent.
The invention is realized by the following technical scheme: a preparation method of a manganese dioxide/ferric oxide hydroxide loaded three-dimensional silicon dioxide adsorbent comprises the following steps:
1) three-dimensional mesoporous materialKIT-6 and FeCl material3Mixing the solution and the HCl solution, stirring uniformly at room temperature, transferring to a reaction kettle for hydrothermal reaction, washing the obtained product to be neutral by using deionized water, and drying to obtain an intermediate product FeOOH/KIT-6;
2) mixing MnSO4·H2Mixing O and FeOOH/KIT-6, adding KMnO after reflux reaction4And (3) continuously carrying out reflux reaction on the aqueous solution, washing the obtained product to be neutral by using deionized water, and drying to obtain the manganese dioxide/ferric oxide hydroxide-loaded three-dimensional silicon dioxide adsorbent.
Further, in the preparation method, step 1), the preparation method of the three-dimensional mesoporous material KIT-6 includes the following steps: mixing 2-6 g of triblock copolymer P123, 100-140 g of deionized water and 20mL of concentrated hydrochloric acid, stirring at 35-45 ℃ for dissolution, adding 2-6 g of n-butyl alcohol, continuously stirring for 1-3 h, dropwise adding 6.6-10.6 g of ethyl orthosilicate, continuously stirring for 24-48 h, transferring the obtained mixture into a stainless steel reaction kettle, carrying out hydrothermal reaction at 80-120 ℃ for 24-48 h, naturally cooling the obtained product to room temperature, filtering, washing with water and ethanol to be neutral, drying, and roasting in a muffle furnace at 400-700 ℃ for 6-12 h to obtain the three-dimensional mesoporous material KIT-6.
Further, in the preparation method, the step 1) is specifically as follows: 3-7 g of three-dimensional mesoporous material KIT-6 is added to 20-50 mL of the three-dimensional mesoporous material KIT-6, wherein the concentration of the three-dimensional mesoporous material KIT-6 is 0.03-0.07 mol.L-1FeCl of3The solution and 1-10 mL of the solution with the concentration of 2-5 mol.L-1Mixing the HCl solutions, stirring for 1-3 h at room temperature, transferring to a reaction kettle, carrying out hydrothermal reaction for 6-12 h at 80-120 ℃, washing the obtained product to be neutral by deionized water, and drying to obtain an intermediate product FeOOH/KIT-6.
Further, in the preparation method, the step 2) is specifically as follows: mixing MnSO4·H2Mixing O and FeOOH/KIT-6, performing reflux reaction at the temperature of 60-100 ℃ for 10-20 min, and adding KMnO4And (3) continuously carrying out reflux reaction on the aqueous solution for 1-3 h, washing the obtained product to be neutral by using deionized water, and drying to obtain the manganese dioxide/ferric oxide hydroxide-loaded three-dimensional silicon dioxide adsorbent.
Further, the above-mentioned preparation methodIn step 2), MnSO4·H2In the molar ratio of O to FeOOH/KIT-6, Fe and Mn are 1: 8-8: 1.
The invention provides application of a manganese dioxide/ferric oxide hydroxide loaded three-dimensional silica adsorbent As an adsorbent in adsorption of As (III).
Further, the method is as follows: after the solution containing As (III) is adjusted to pH 1-4, a three-dimensional silica adsorbent loaded with manganese dioxide/ferric oxide hydroxide is added, and the mixture is vibrated and adsorbed in a shaking box for 24 hours.
Further, the pH of the solution containing As (III) is adjusted to 1.
Further comprises an elution step of adding an eluant into the three-dimensional silicon dioxide adsorbent loaded with manganese dioxide/ferric oxide hydroxide after adsorbing As (III).
Furthermore, the eluent is a NaOH solution with the mass percentage concentration of 0.30-1.0%.
The invention has the beneficial effects that:
1. the three-dimensional silicon dioxide adsorbent loaded with manganese dioxide/ferric oxide hydroxide prepared by the invention has high separation and enrichment efficiency, and can efficiently separate and adsorb arsenic from an arsenic-containing solution. The method is rapid, simple, convenient and novel, and the synthesized adsorbent has large adsorption capacity on arsenic element, good selectivity on arsenic and practical applicability.
2. The three-dimensional silicon dioxide adsorbent loaded with manganese dioxide/ferric oxide hydroxide, prepared by the invention, improves the adsorption performance of the silicon-based material, widens the application range of the silicon-based material, and expands the application of the silicon-based material in the field of water micro-pollution control.
3. The manganese dioxide/ferric oxide hydroxide loaded three-dimensional silica adsorbent prepared by the invention has large adsorption capacity to arsenic in solution in the pH range of 1-4, and the maximum adsorption capacity to arsenic is 39.77mg g at the pH of 1-1。
4. In the invention, As (III) in the aqueous solution is oxidized into As (V), and absorbent MnO is2the/FeOOH/KIT-6 reacts with As (V) by electrostatic attraction, and on the other hand, M-OH and MnO on the adsorbent2With As (III) by chelation atTogether. In addition, five times of cycle elution experiments prove that the adsorbent prepared by the invention has better reusability and practicability. The modified adsorbent prepared by the method is novel and simple, the used experimental medicine has little pollution to the environment, and the use of a silane coupling agent and an organic amine reagent is avoided.
5. The invention designs and synthesizes the functional silica-based material adsorbent, prepares the functional silica-based material KIT-6 by an inorganic modification method, improves the adsorption performance of the silica-based material, widens the application range of the silica-based material, expands the application of the silica-based material in the field of water micro-pollution control, provides theoretical support for the application of the silica-based material in the field of typical pollutants, and provides scientific basis and new thinking for water pollution control and water purification.
In conclusion, the manganese dioxide/ferric oxide hydroxide loaded three-dimensional silica adsorbent prepared by the invention can effectively adsorb arsenic ions, and the adsorbent is quick, simple and convenient to prepare, high in adsorption rate, good in selectivity and practical.
Drawings
FIG. 1 shows a three-dimensional silica adsorbent MnO supporting manganese dioxide/ferric oxide hydroxide2Schematic synthesis of/FeOOH/KIT-6.
FIG. 2 shows KIT-6(A), FeOOH/KIT-6(B) and MnO2Transmission electron microscope of/FeOOH/KIT-6 (C).
FIG. 3 shows an adsorbent MnO2X-ray diffraction pattern of/FeOOH/KIT-6.
FIG. 4a shows an adsorbent MnO prepared by different Mn to Fe ratios2Analysis chart of arsenic adsorption performance of/FeOOH/KIT-6 under different acidity.
Fig. 4b is a graph of the arsenic adsorption performance of different adsorbents at different acidity.
FIG. 5 shows an adsorbent MnO2Analysis chart of arsenic adsorption performance of/FeOOH/KIT-6 under different anions.
FIG. 6 shows an adsorbent MnO2Adsorption isotherm of/FeOOH/KIT-6 on arsenic.
FIG. 7 shows an adsorbent MnO2Experimental graphs for the cyclic elution of/FeOOH/KIT-6.
Detailed Description
Practice ofExample 1 manganese dioxide/ferric oxide hydroxide Supported three-dimensional silica adsorbent MnO2The preparation method of/FeOOH/KIT-6 (I) is as follows
1. Preparation of three-dimensional mesoporous material KIT-6
Mixing 4g of triblock copolymer P123, 120g of deionized water and 20mL of concentrated hydrochloric acid, stirring overnight at 35-45 ℃ until the triblock copolymer P123, adding 4g of n-butyl alcohol, continuously stirring for 1-3 h, dropwise adding 8.6g of ethyl orthosilicate, continuously stirring for 24-48 h, transferring the obtained mixture into a stainless steel reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 24h, naturally cooling the obtained product to room temperature, filtering, washing with water and ethanol to be neutral, drying, and roasting in a muffle furnace at 550 ℃ for 12h to obtain the three-dimensional mesoporous material KIT-6.
2. Preparation of FeOOH/KIT-6
5g of three-dimensional mesoporous material KIT-6 is added, and the concentration of 30mL is 0.05 mol.L-1FeCl of3Solution and 5mL of 3 mol. L-1The obtained HCl solution is mixed, stirred for 2 hours at room temperature, then transferred to a reaction kettle, subjected to hydrothermal reaction for 7 hours at 100 ℃, washed to be neutral by deionized water, and dried for 24 hours at 80 ℃ to obtain an intermediate product FeOOH/KIT-6.
3、MnO2Preparation of/FeOOH/KIT-6
73.40g, 32.18g, 11.48g, 4.59g and 1.15g of MnSO were weighed out respectively4·H2Mixing O and 8.85g FeOOH/KIT-6, condensing and refluxing at 80 deg.C for 15min, and then weighing 50.59g, 22.13g, 7.91g, 3.16g, 0.79g KMnO4KMnO formed by dissolving in 5mL water4Adding the solution into the above reaction, continuously refluxing for 1.5h, washing the obtained product with deionized water to neutrality, drying to obtain MnSO4·H2MnO with the molar ratio of Fe to Mn of 1:8 in O and FeOOH/KIT-62the/FeOOH/KIT-6 adsorbent is marked as 8MnO2/FeOOH/KIT-6；MnSO4·H2MnO with Fe and Mn molar ratio of 2:7 in O and FeOOH/KIT-62the/FeOOH/KIT-6 adsorbent, labelled 3.5MnO2/FeOOH/KIT-6；MnSO4·H2MnO with Fe and Mn molar ratio of 4:5 in O and FeOOH/KIT-62/FeOOH/KIT-6 adsorbentMarked 1.25MnO2/FeOOH/KIT-6；MnSO4·H2MnO with Fe and Mn molar ratio of 6:3 in O and FeOOH/KIT-62the/FeOOH/KIT-6 adsorbent, labelled 0.5MnO2/FeOOH/KIT-6；MnSO4·H2MnO with Fe and Mn molar ratio of 8:1 in O and FeOOH/KIT-62the/FeOOH/KIT-6 adsorbent, labeled 0.125MnO2/FeOOH/KIT-6。
(II) detection
FIG. 2 shows KIT-6(A), FeOOH/KIT-6(B) and MnO2Transmission electron microscope of/FeOOH/KIT-6 (C). FIG. 3 shows an adsorbent MnO2X-ray diffraction pattern of/FeOOH/KIT-6. From A in FIG. 2, it can be seen that KIT-6 has a large number of regular and ordered pores. As can be seen from B in FIG. 2, a clear ordered pore structure still exists after FeOOH loading, which indicates that the ordered structure of the material is not damaged, probably because FeOOH is loaded in the pores of KIT-6. However, as can be seen from C in FIG. 2, via MnO2After loading, the original ordered pore channel structure of the material completely disappears, and a completely disordered macroporous structure is presented, which shows that MnO is2The introduction of (2) causes the ordered structure of the material to be completely destroyed. This is consistent with the X-ray diffraction pattern of FIG. 3, showing the manganese dioxide/ferric oxide hydroxide loaded three-dimensional silica adsorbent MnO2the/FeOOH/KIT-6 was successfully synthesized.
Example 2 manganese dioxide/ferric oxide hydroxide loaded three-dimensional silica adsorbent MnO2Application of/FeOOH/KIT-6 in adsorption of As (III)
(one) MnO2Adsorption effect of FeOOH/KIT-6 on arsenic under different acidity
The method comprises the following steps: 10mg of MnO of example 1 having different Fe/Mn molar ratios were weighed out separately2the/FeOOH/KIT-6 is added into 10mL of the mixture with the concentration of 20 mg.L-1The As (III) solution of (2) is subjected to shaking adsorption for 24 hours in a shaking box at 30 ℃ and 180r/min, wherein the pH values of the solution are respectively adjusted to 1, 3, 5, 7, 9 and 11. The results are shown in FIGS. 4a and 4 b.
As can be seen from FIG. 4a, the adsorption capacity of the adsorbent to As (III) gradually decreases as the Fe/Mn molar ratio increases, and the adsorption rate of the adsorbent to arsenic is the greatest at pH 1. The adsorbing capacity of the adsorbent to As (III) is the strongest and reaches 92% when the pH is 1 and the Fe/Mn molar ratio is 4: 5.
As can be seen from fig. 4b, all adsorbents have the highest adsorption rate for arsenic at pH 1. As can be seen, KIT-6 has little or no adsorption capacity on arsenic ions; the adsorption effect of the intermediate product FeOOH/KIT-6 on arsenic ions is small; MnO2the/KIT-6 has certain adsorption on arsenic ions, the adsorption rate can reach 90 percent when the pH value is 1, and the adsorbent is 1.25MnO2The adsorption capacity of the/FeOOH/KIT-6 to arsenic ions is obviously improved, thereby realizing the recovery of As (III).
(II) adsorption Effect of different anions on As (III)
The method comprises the following steps: at 10 mg.L-1While adding the solution of (A) and (III) to the solution of (A) and (B) at a final concentration of 10 mg. L-1Cl of-、NO3 -、SO4 2-、SiO3 2-And PO4 3-. Prepared by the same method until the final concentration is 100 mg.L-1、500mg·L-1Containing Cl-、NO3 -、SO4 2-、SiO3 2-And PO4 3-Anionic as (iii) solution.
10mg of 1.25MnO having a Fe/Mn molar ratio of 4:5 prepared in example 1 were added to 10mL of As (III) solutions having different anion concentrations2And the/FeOOH/KIT-6 is subjected to oscillation adsorption for 24 hours in an oscillation box at the temperature of 30 ℃ and at the speed of 180 r/min. The results are shown in FIG. 5.
As can be seen from FIG. 5, the anion concentration was 10 mg.L-1～500mg·L-1In the range of (1), Cl-、NO3 -、SO4 2-And SiO3 2-Has no obvious influence on the adsorption of As (III). However, PO4 3-Has more remarkable influence on the adsorption of As (III), particularly under the condition of high concentration, the order of the magnitude of the influence is Cl-≈NO3 -≈SO4 2-≈SiO3 2-<PO4 3-。
(III) MnO2/FeOOH/KIT-6Adsorption isotherm for As (III) adsorption
The method comprises the following steps: respectively prepared at a concentration of 10 mg.L-1，20mg·L-1，30mg·L-1，40mg·L-1，50mg·L-1The pH of the arsenic ion solution was adjusted to 1. 10mg of 1.25MnO having a Fe/Mn molar ratio of 4:5 prepared in example 1 were weighed out separately2the/FeOOH/KIT-6 is respectively added into the 10mL of As (III) solution prepared above, and the solution is vibrated and adsorbed for 24h in a shaking box with the temperature of 30 ℃ and the speed of 180 r/min. The results are shown in FIG. 6.
As can be seen from FIG. 6, the linear correlation coefficient R2The largest value is the Langmuir adsorption isotherm model, R2Is 0.91, which indicates MnO2The adsorption of the/FeOOH/KIT-6 to As (III) belongs to monomolecular adsorption, and the maximum saturated adsorption quantity obtained by fitting a Langmuir adsorption isotherm model is 39.77mg g-1。
(IV) selection of eluent
The method comprises the following steps: taking 10mL of the solution with the concentration of 20 mg.L-1Adjusted to pH 1, 10mg of 1.25MnO with Fe/Mn molar ratio of 4:5 prepared in example 1 was added to the arsenic ion solution of (1)2And the/FeOOH/KIT-6 is subjected to oscillation adsorption for 24 hours in an oscillation box at the temperature of 30 ℃ and at the speed of 180 r/min.
Will adsorb saturated 1.25MnO2the/FeOOH/KIT-6 is placed in a stoppered vial, 10mL NaOH aqueous solution with different mass fractions shown in the table 1 is added, the mixture is shaken for 24 hours in a shaking box under the condition of 303K, the filtration is carried out, the concentration of As (III) in the obtained filtrate is measured, and then the elution rate of different eluents is calculated. The results are shown in Table 1.
TABLE 1 elution Effect of eluents of different concentrations on arsenic ions
Figure BDA0003266998340000061
As can be seen from table 1, the elution effect of 0.30% and 1.0% NaOH is the best, and the eluent with a smaller concentration (0.30% NaOH) is selected as the best eluent from the viewpoint of saving raw materials and environmental protection.
(V) MnO2Regeneration of/FeOOH/KIT-6
The method comprises the following steps: 100mg of 1.25MnO 4:5 Fe/Mn molar ratio prepared in example 1 were weighed out2the/FeOOH/KIT-6 was added to a 150mL conical flask in 100mL of 20 mg. multidot.L-1Adjusting the pH of the As (III) solution to 1, and oscillating and adsorbing the solution for 24 hours in an oscillating box at 30 ℃ and 180 r/min. The concentration of As (III) in the filtrate was measured, and then the above adsorbent was eluted with 0.30% NaOH as an eluent, and the elution was repeated five times in succession, as shown in FIG. 7.
It can be seen from FIG. 7 that the adsorbent MnO was subjected to five cycles2The adsorption capacity of the/FeOOH/KIT-6 to As (III) can still reach more than 98 percent, and the stability for adsorbing As (III) is better.

Claims (10)

1. A preparation method of a manganese dioxide/ferric oxide hydroxide loaded three-dimensional silicon dioxide adsorbent is characterized by comprising the following steps:
1) three-dimensional mesoporous materials KIT-6 and FeCl3Mixing the solution and the HCl solution, stirring uniformly at room temperature, transferring to a reaction kettle for hydrothermal reaction, washing the obtained product to be neutral by using deionized water, and drying to obtain an intermediate product FeOOH/KIT-6;
2) mixing MnSO4·H2Mixing O and FeOOH/KIT-6, adding KMnO after reflux reaction4And (3) continuously carrying out reflux reaction on the aqueous solution, washing the obtained product to be neutral by using deionized water, and drying to obtain the manganese dioxide/ferric oxide hydroxide-loaded three-dimensional silicon dioxide adsorbent.
2. The preparation method according to claim 1, wherein in the step 1), the preparation method of the three-dimensional mesoporous material KIT-6 comprises the following steps: mixing 2-6 g of triblock copolymer P123, 100-140 g of deionized water and 20mL of concentrated hydrochloric acid, stirring at 35-45 ℃ for dissolution, adding 2-6 g of n-butyl alcohol, continuously stirring for 1-3 h, dropwise adding 6.6-10.6 g of ethyl orthosilicate, continuously stirring for 24-48 h, transferring the obtained mixture into a stainless steel reaction kettle, carrying out hydrothermal reaction at 80-120 ℃ for 24-48 h, naturally cooling the obtained product to room temperature, filtering, washing with water and ethanol to be neutral, drying, and roasting in a muffle furnace at 400-700 ℃ for 6-12 h to obtain the three-dimensional mesoporous material KIT-6.
3. The preparation method according to claim 1, wherein step 1) is specifically: 3-7 g of three-dimensional mesoporous material KIT-6 is added to 20-50 mL of the three-dimensional mesoporous material KIT-6, wherein the concentration of the three-dimensional mesoporous material KIT-6 is 0.03-0.07 mol.L-1FeCl of3The solution and 1-10 mL of the solution with the concentration of 2-5 mol.L-1Mixing the HCl solutions, stirring for 1-3 h at room temperature, transferring to a reaction kettle, carrying out hydrothermal reaction for 6-12 h at 80-120 ℃, washing the obtained product to be neutral by deionized water, and drying to obtain an intermediate product FeOOH/KIT-6.
4. The preparation method according to claim 1, wherein the step 2) is specifically: mixing MnSO4·H2Mixing O and FeOOH/KIT-6, performing reflux reaction at the temperature of 60-100 ℃ for 10-20 min, and adding KMnO4And (3) continuously carrying out reflux reaction on the aqueous solution for 1-3 h, washing the obtained product to be neutral by using deionized water, and drying to obtain the manganese dioxide/ferric oxide hydroxide-loaded three-dimensional silicon dioxide adsorbent.
5. The method according to claim 1, wherein in step 2), MnSO4·H2In the molar ratio of O to FeOOH/KIT-6, Fe and Mn are 1: 8-8: 1.
6. Use of a manganese dioxide/ferric oxide hydroxide loaded three-dimensional silica adsorbent prepared according to the method of claim 1 As an adsorbent for adsorbing As (iii).
7. Use according to claim 6, characterized in that the method is as follows: after the solution containing As (III) is adjusted to pH 1-4, a three-dimensional silica adsorbent loaded with manganese dioxide/ferric oxide hydroxide is added, and the mixture is vibrated and adsorbed in a shaking box for 24 hours.
8. Use according to claim 7, wherein the pH of the solution containing As (III) is adjusted to 1.
9. The use of claim 7, comprising an elution step of adding an eluent to the manganese dioxide/ferric oxide hydroxide loaded three-dimensional silica adsorbent after adsorption of As (III).
10. The application of the eluent as claimed in claim 9, wherein the eluent is NaOH solution with the mass percentage concentration of 0.30-1.0%.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471605A (en) * 2022-02-10 2022-05-13 辽宁大学 Ellipsoidal iron oxyhydroxide/manganese dioxide core-shell structure catalyst and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101024160A (en) * 2006-02-21 2007-08-29 中国科学院生态环境研究中心 Preparation of iron-managanese compounded oxide/diatomite adsorbant, its using and regenerating method
US20100181258A1 (en) * 2007-07-13 2010-07-22 Research Center for Eco-Enviromental Sciences Chinese Academy of Sciences The ferric and manganese binary oxide based adsorbent, and the methods for the preparation and applicaiton of the adsorbent
CN105289493A (en) * 2015-11-17 2016-02-03 辽宁大学 Ferromanganese modified straw active carbon adsorbent for As (III) adsorption, and applications thereof
CN105771878A (en) * 2016-03-31 2016-07-20 辽宁大学 Ferro-manganese modified aluminum oxide adsorbent and application thereof in As (III) adsorption
CN107281999A (en) * 2017-05-26 2017-10-24 北京工业大学 A kind of ferriferous oxide/manganese dioxide nano-composite material and preparation method and application
CN108970574A (en) * 2018-08-13 2018-12-11 辽宁大学 FeOOH/MnO2/ KIT-6 adsorbent and its preparation method and application
CN112452302A (en) * 2020-11-06 2021-03-09 辽宁大学 Three-dimensional gallium imprinted Chinese gall tannin silicon-based composite material and application thereof in gallium recovery

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101024160A (en) * 2006-02-21 2007-08-29 中国科学院生态环境研究中心 Preparation of iron-managanese compounded oxide/diatomite adsorbant, its using and regenerating method
US20100181258A1 (en) * 2007-07-13 2010-07-22 Research Center for Eco-Enviromental Sciences Chinese Academy of Sciences The ferric and manganese binary oxide based adsorbent, and the methods for the preparation and applicaiton of the adsorbent
CN105289493A (en) * 2015-11-17 2016-02-03 辽宁大学 Ferromanganese modified straw active carbon adsorbent for As (III) adsorption, and applications thereof
CN105771878A (en) * 2016-03-31 2016-07-20 辽宁大学 Ferro-manganese modified aluminum oxide adsorbent and application thereof in As (III) adsorption
CN107281999A (en) * 2017-05-26 2017-10-24 北京工业大学 A kind of ferriferous oxide/manganese dioxide nano-composite material and preparation method and application
CN108970574A (en) * 2018-08-13 2018-12-11 辽宁大学 FeOOH/MnO2/ KIT-6 adsorbent and its preparation method and application
CN112452302A (en) * 2020-11-06 2021-03-09 辽宁大学 Three-dimensional gallium imprinted Chinese gall tannin silicon-based composite material and application thereof in gallium recovery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王丹丹: "功能化三维双连续立方体结构硅基材料构筑及对As(Ⅲ)、Pb(Ⅱ)、Cr(Ⅵ)去除研究" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471605A (en) * 2022-02-10 2022-05-13 辽宁大学 Ellipsoidal iron oxyhydroxide/manganese dioxide core-shell structure catalyst and preparation method and application thereof
CN114471605B (en) * 2022-02-10 2024-01-12 辽宁大学 Ellipsoidal iron oxyhydroxide/manganese dioxide core-shell structure catalyst and preparation method and application thereof

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