CN116173917A - Preparation and application of arsenic and chromium bifunctional adsorbent lanthanum zirconium MOFs - Google Patents
Preparation and application of arsenic and chromium bifunctional adsorbent lanthanum zirconium MOFs Download PDFInfo
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- 239000011651 chromium Substances 0.000 title claims abstract description 71
- AZJLMWQBMKNUKB-UHFFFAOYSA-N [Zr].[La] Chemical compound [Zr].[La] AZJLMWQBMKNUKB-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 48
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 48
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 44
- 239000003463 adsorbent Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012621 metal-organic framework Substances 0.000 title claims abstract 13
- 230000001588 bifunctional effect Effects 0.000 title claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
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- 238000000034 method Methods 0.000 claims abstract description 14
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- 239000002243 precursor Substances 0.000 claims abstract description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000013110 organic ligand Substances 0.000 claims abstract description 6
- CWDUIOHBERXKIX-UHFFFAOYSA-K lanthanum(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] CWDUIOHBERXKIX-UHFFFAOYSA-K 0.000 claims abstract description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- OTJXRUHUGBSPCL-UHFFFAOYSA-N arsanylidynechromium Chemical compound [As]#[Cr] OTJXRUHUGBSPCL-UHFFFAOYSA-N 0.000 claims 2
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- RKYSWCFUYJGIQA-UHFFFAOYSA-H copper(ii) arsenate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RKYSWCFUYJGIQA-UHFFFAOYSA-H 0.000 description 2
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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Abstract
The invention discloses a preparation method and application of lanthanum zirconium MOFs serving as an arsenic and chromium dual-function adsorbent, wherein the preparation method comprises the following steps: adding lanthanum chloride hexahydrate and zirconium chloride metal salt with a certain molar ratio and a 2-amino terephthalic acid organic ligand into N, N-dimethylformamide, and fully stirring by using a magnetic stirrer to obtain a precursor mixture; transferring the precursor mixture into a high-pressure reaction kettle of polytetrafluoroethylene for reaction to obtain a crystallized product; and cleaning the obtained crystallized product by using N, N-dimethylformamide, and then placing the cleaned crystallized product in a constant-temperature drying oven for drying to obtain the lanthanum-zirconium MOFs adsorbent. The lanthanum-zirconium MOFs synthesized by the method are nearly spherical nano particles with high crystallinity, have larger specific surface area, show good arsenic and chromium adsorption performance in a wider concentration range in a pH=2 strong acid solution, overcome the defect of weak arsenic adsorption capability in the strong acid solution of the existing adsorbent, and can be applied to purification treatment of industrial wastewater containing arsenic and chromium.
Description
Technical Field
The invention belongs to the technical field of heavy metal arsenic and chromium adsorbents, and particularly relates to preparation and application of lanthanum zirconium MOFs (metal oxide semiconductor field effect transistors) serving as arsenic and chromium dual-function adsorbents.
Background
Arsenic (As) is a relatively rare but ubiquitous heavy metal-like element in the natural environment. Arsenic is classified by the world health organization as a first class of carcinogens. The long-term intake of As-containing water source with concentration above 50 mug/L will induce canceration of liver, kidney, lung and other organs. As is widely used As an alloying agent in various manufacturing industries, for example, arsenic-containing wastewater accompanied by high acidity is produced in nonferrous metal smelting process. As pollution in water is a global problem, and the As concentration in drinking water in nearly 50 countries exceeds the upper limit of 10 mug/L arsenic content in the drinking water and industrial wastewater discharge water quality standards commonly established in all countries of the world at present. In addition, although As (III) is 25 to 60 times As toxic As (V), as (III) is generally low in content in wastewater, and As (III) is mainly removed by oxidizing As pentavalent arsenic and further removing it, so removal of pentavalent arsenic in water has become an important research topic for water treatment.
Chromium (Cr), a silvery white shiny metal. Water-soluble Cr (VI) is listed as one of eight chemicals that are the most harmful to humans, and is one of three internationally recognized carcinogenic metals. It is accompanied by the exploitation of chromium, smelting, manufacturing of chromium salt, electroplating, metal processing, tanning, paint, pigment, dyeing industry, chromium-containing waste gas, waste water, waste residue and the like discharged by fuel combustion, and the like, which enter the environment and cause water pollution problems. Copper arsenate chromite is widely used for the anti-corrosion treatment of wood due to the characteristics of low price, easy painting after drying and strong corrosion resistance, but the service life of the wood is about 25 years, arsenic and chromium with strong fluidity in the waste wood enter a water body along with rainwater and the like to cause pollution, and in addition, the exploitation and the use process of copper arsenate chromite also can cause common pollution of arsenic and chromium in the water body. Therefore, research on simultaneous removal of arsenic and chromium in a water body is particularly important.
At present, the common techniques for removing As (V) and Cr (VI) from water body include a chemical precipitation method, a membrane separation method, an ion exchange method and an adsorption method. The adsorption method has the advantages of high removal efficiency, good stability, no or little secondary pollution, economy, green, high efficiency, reproducibility and the like, is favored, and becomes one of the most promising removal technologies. By implementing the adsorption technology, heavy metal pollutants can be attached to the surface of a solid object through intermolecular forces or bonding effects of chemical bonds, so that the pollutants are efficiently removed from the water body. The adsorption technology has strong enrichment capability on As (V) and Cr (VI) in water, and the concentration range for treating wastewater containing As (V) and Cr (VI) is wide, and is suitable for developing countries lacking electric facilities.
The choice of the adsorbent material is a key factor in the efficient application of the adsorbent to treat arsenic and chromium containing wastewater. Currently, common As (V) and Cr (VI) adsorbents include mineral adsorbents, activated carbon, metal oxides, metal hydroxides, and adsorbents made of various agricultural and industrial wastes, and the like. Research results show that most of the existing desorbing agents can effectively remove As (V) substances in alkaline and neutral wastewater, but the removing effect on the strong acidity, especially the removing effect on As (V) in the wastewater with pH=2, is not ideal; when arsenic and chromium are co-present, competition makes their co-removal undesirable because both are in anionic form.
Disclosure of Invention
Aiming at the problems of weak adsorption capacity and poor effect of the existing adsorption material for jointly removing As (V) and Cr (VI) in strong acid wastewater, the invention provides the preparation and application of the lanthanum zirconium MOFs serving As the arsenic and chromium dual-function adsorbent.
The preparation method of the arsenic and chromium bifunctional adsorbent lanthanum zirconium MOFs comprises the following steps:
(1) Adding lanthanum metal salt, zirconium metal salt and 1.0mmol of 2-amino terephthalic acid organic ligand into N, N-dimethylformamide according to a certain molar ratio;
(2) Thoroughly stirring the precursor mixture obtained in the step (1) by using a magnetic stirrer;
(3) Transferring the uniform precursor mixture obtained in the step (2) into a polytetrafluoroethylene high-pressure reaction kettle, and placing the polytetrafluoroethylene high-pressure reaction kettle in a constant-temperature drying oven at 120 ℃ for a certain period of time to obtain a crystallized product;
(4) And (3) cleaning the crystallized product obtained in the step (3) by using N, N-dimethylformamide, and then placing the cleaned crystallized product in a constant-temperature drying oven for drying to obtain the dual-function adsorbent lanthanum zirconium MOFs with arsenic and chromium removed together.
The lanthanum metal salt and the zirconium metal salt in the step (1) are lanthanum chloride hexahydrate and zirconium chloride.
The molar ratio of the lanthanum metal salt to the zirconium metal salt in the step (1) is 0.2-2:1mmol.
And (3) stirring in the step (2) for 30min.
And (3) maintaining the constant temperature drying oven for a certain period of time, namely 2-12 hours.
And (3) drying the constant-temperature drying oven in the step (4) at the temperature of 60 ℃ for 12 hours.
The dual-function adsorbent lanthanum zirconium MOFs of arsenic and chromium is prepared by the preparation method. The application of the arsenic and chromium bifunctional adsorbent lanthanum zirconium MOFs in high-efficiency adsorption in a water body containing arsenic and chromium.
Compared with the prior art, the invention has the advantages that:
1. the arsenic and chromium dual-function adsorbent lanthanum zirconium MOFs has the advantages of environment-friendly raw materials, simple and convenient preparation process, strong operability, mild reaction conditions, high repeatability, large-scale production and prospect of industrialization.
2. The lanthanum-zirconium MOFs prepared by the invention is a topological nano material with high crystallinity, has a nearly spherical morphology and has a larger specific surface area (453 m 2 /g) and has a strong stability in acidic aqueous solutions.
3. The lanthanum-zirconium MOFs prepared by the method have high adsorption capacity to As (V) and Cr (VI) solutions in a wider initial concentration range by virtue of the advantages of strong coordination capability of hydroxyl functional groups on lanthanum and zirconium metal with As (V) and Cr (VI) and the like in a pH=2 strong acid solution, and the synthesis of the adsorbent has important significance for purifying high-concentration As (V) and Cr (VI) containing strong acid wastewater.
Drawings
FIG. 1 is a schematic view showing the microstructure of lanthanum zirconium MOFs prepared in example 1 under an electron scanning microscope.
Fig. 2 is an XRD spectrum of lanthanum zirconium MOFs prepared in example 1.
Fig. 3 is an XRD spectrum of lanthanum zirconium MOFs prepared in example 2.
Fig. 4 is an XRD spectrum of lanthanum zirconium MOFs prepared in example 3.
FIG. 5 is a schematic diagram showing adsorption capacities of lanthanum zirconium MOFs prepared in example 1 for As (V) and Cr (VI).
FIG. 6 is a schematic diagram showing adsorption capacities of lanthanum zirconium MOFs prepared in example 2 for As (V) and Cr (VI).
Detailed Description
The invention is further illustrated by the following examples.
Example 1:
the example prepares the arsenic and chromium bifunctional adsorbents lanthanum zirconium MOFs according to the following steps.
(1) Adding 1:1 mol ratio of lanthanum metal salt and zirconium metal salt, and 1.0mmol of 2-amino terephthalic acid organic ligand into N, N-dimethylformamide;
(2) Thoroughly stirring the precursor mixture obtained in the step (1) for 30min by using a magnetic stirrer;
(3) Transferring the uniform precursor mixture obtained in the step (2) into a polytetrafluoroethylene high-pressure reaction kettle, and placing the polytetrafluoroethylene high-pressure reaction kettle in a constant-temperature drying oven at 120 ℃ for 12 hours to obtain a crystallized product;
(4) And (3) cleaning the crystallized product obtained in the step (3) by using N, N-dimethylformamide, and then placing the cleaned crystallized product in a constant-temperature drying oven for drying at a drying temperature of 60 ℃ for 12 hours to obtain the arsenic and chromium bifunctional adsorbent lanthanum zirconium MOFs.
The obtained arsenic and chromium bifunctional adsorbents lanthanum zirconium MOFs are placed under an electronic scanning electron microscope, and the morphology of the MOFs is observed, as shown in figure 1. The resultant arsenic and chromium bifunctional adsorbents lanthanum zirconium MOFs were analyzed using XRD equipment and their structures were analyzed as shown in fig. 2.
As can be seen from fig. 1, the lanthanum zirconium MOFs have a nearly spherical morphology. As can be seen from fig. 2, the lanthanum zirconium MOFs have distinct crystal diffraction peaks, indicating that the material is present in crystalline form.
The physical and surface properties of the arsenic and chromium bifunctional adsorbents lanthanum zirconium MOFs prepared in example 1 are shown in Table 1:
TABLE 1
Example 2:
the example prepares the arsenic and chromium bifunctional adsorbents lanthanum zirconium MOFs according to the following steps.
(1) Adding 0.2:1 molar ratio of lanthanum metal salt and zirconium metal salt, and 1.0mmol of 2-amino terephthalic acid organic ligand into N, N-dimethylformamide;
(2) Thoroughly stirring the precursor mixture obtained in the step (1) for 30min by using a magnetic stirrer;
(3) Transferring the uniform precursor mixture obtained in the step (2) into a polytetrafluoroethylene high-pressure reaction kettle, and placing the polytetrafluoroethylene high-pressure reaction kettle in a constant-temperature drying oven at 120 ℃ for 12 hours to obtain a crystallized product;
(4) And (3) cleaning the crystallized product obtained in the step (3) by using N, N-dimethylformamide, and then placing the cleaned crystallized product in a constant-temperature drying oven for drying at a drying temperature of 60 ℃ for 12 hours to obtain the arsenic and chromium bifunctional adsorbent lanthanum zirconium MOFs.
The resultant arsenic and chromium bifunctional adsorbents lanthanum zirconium MOFs were analyzed using XRD equipment and their structures were analyzed as shown in fig. 3.
As can be seen from fig. 3, the lanthanum zirconium MOFs have distinct crystal diffraction peaks, indicating that the material is present in crystalline form.
Example 3:
the example prepares the arsenic and chromium bifunctional adsorbents lanthanum zirconium MOFs according to the following steps.
(1) Adding 2:1 mol ratio of lanthanum metal salt and zirconium metal salt, and 1.0mmol of 2-amino terephthalic acid organic ligand into N, N-dimethylformamide;
(2) Thoroughly stirring the precursor mixture obtained in the step (1) for 30min by using a magnetic stirrer;
(3) Transferring the uniform precursor mixture obtained in the step (2) into a polytetrafluoroethylene high-pressure reaction kettle, and placing the polytetrafluoroethylene high-pressure reaction kettle in a constant-temperature drying oven at 120 ℃ for 2 hours to obtain a crystallized product;
(4) And (3) cleaning the crystallized product obtained in the step (3) by using N, N-dimethylformamide, and then placing the cleaned crystallized product in a constant-temperature drying oven for drying at a drying temperature of 60 ℃ for 12 hours to obtain the arsenic and chromium bifunctional adsorbent lanthanum zirconium MOFs.
The resultant arsenic and chromium bifunctional adsorbents lanthanum zirconium MOFs were analyzed using XRD equipment and their structures were analyzed as shown in fig. 4.
As can be seen from fig. 4, the lanthanum zirconium MOFs have distinct crystal diffraction peaks, indicating that the material is present in crystalline form.
Application example 1:
(1) At a constant temperature of 25 ℃, 0.01g of lanthanum zirconium MOFs prepared in example 1 is respectively placed in 20mL of wastewater containing As (V) and Cr (VI), and the initial concentrations of Cr (VI) and As (V) in the mixed solution are respectively As follows: 21.02mg/L,17.79mg/L;53.61mg/L,63.26mg/L;86.29mg/L,83.73mg/L;103.6mg/L,105.7mg/L;158.6mg/L,144.5mg/L;216.2mg/L,215.9mg/L; the initial pH value of the wastewater is 2;
(2) Carrying out oscillation reaction on the mixed solution in the step (1), wherein the rotating speed is 200rpm;
(3) After the reaction in the step (2) is carried out for 12 hours, the supernatant is extracted and solid-liquid separation is carried out again.
The residual arsenic concentration in the filtrate was measured with an atomic absorption spectrophotometer, and the residual chromium concentration was measured with an ultraviolet spectrophotometer, thereby calculating the equilibrium adsorption capacities of lanthanum zirconium MOFs to As (V) and Cr (VI), and the experimental results are shown in FIG. 5.
As shown in FIG. 5, at a solution pH of 2, the equilibrium adsorption capacities of lanthanum zirconium MOFs for As (V) with initial concentrations of 17.79mg/L, 63.26mg/L, 83.73mg/L, 105.7mg/L, 144.5mg/L, 215.9mg/L were 32.8mg/g, 97.9mg/g, 120.6mg/g, 136.6mg/g, 145.4mg/g, 159.6mg/g, respectively; the equilibrium adsorption capacities of the lanthanum-zirconium MOFs on Cr (VI) with initial concentrations of 21.02mg/L, 53.61mg/L, 86.29mg/L, 103.6mg/L, 158.6mg/L and 216.2mg/L are 24.3mg/g, 48.1mg/g, 68.4mg/g, 77.0mg/g, 94.6mg/g and 108.8mg/g respectively, which indicates that the lanthanum-zirconium MOFs have stronger adsorption capacity on As (V) and Cr (VI) in a strong acid aqueous solution.
Application example 2:
(1) At a constant temperature of 25 ℃, 0.01g of lanthanum zirconium MOFs prepared in example 2 is respectively placed in 20mL of wastewater containing As (V) and Cr (VI), and the initial concentrations of Cr (VI) and As (V) in the mixed solution are respectively As follows: 21.02mg/L,17.79mg/L;53.61mg/L,63.26mg/L;86.29mg/L,83.73mg/L;103.6mg/L,105.7mg/L;216.2mg/L,215.9mg/L; the initial pH value of the wastewater is 2;
(2) Carrying out oscillation reaction on the mixture obtained in the step (1), wherein the rotation speed is 200rpm;
(3) After the reaction in the step (2) is carried out for 12 hours, the supernatant is extracted and solid-liquid separation is carried out again.
The residual arsenic concentration in the filtrate was measured with an atomic absorption spectrophotometer, and the residual chromium concentration was measured with an ultraviolet spectrophotometer, thereby calculating the equilibrium adsorption capacities of lanthanum zirconium MOFs to As (V) and Cr (VI), and the experimental results are shown in FIG. 6.
As shown in FIG. 6, lanthanum zirconium MOFs show good adsorption performance for As (V) and Cr (VI) in a strong acid water body, the adsorption capacity for Cr (VI) is kept in the range of 12.5 mg/g-88.2 mg/g, and the adsorption capacity for As (V) is kept in the range of 23.8 mg/g-142.6 mg/g.
Application example 3:
(1) At a constant temperature of 25 ℃, 0.01g of lanthanum zirconium MOFs prepared in example 3 is respectively placed in 20mL of wastewater containing As (V) and Cr (VI), and the initial concentrations of Cr (VI) and As (V) in the mixed solution are respectively As follows: 21.02mg/L,17.79mg/L;53.61mg/L,63.26mg/L;86.29mg/L,83.73mg/L;103.6mg/L,105.7mg/L;216.2mg/L,215.9mg/L; the initial pH value of the wastewater is 2;
(2) Carrying out oscillation reaction on the mixture obtained in the step (1), wherein the rotation speed is 200rpm;
(3) After the reaction in the step (2) is carried out for 12 hours, the supernatant is extracted and solid-liquid separation is carried out again.
The residual arsenic concentration in the filtrate was measured by an atomic absorption spectrophotometer, and the residual chromium concentration was measured by an ultraviolet spectrophotometer, thereby calculating the equilibrium adsorption capacity of lanthanum zirconium MOFs to As (V) and Cr (VI), wherein the adsorption capacity to Cr (VI) was maintained in the range of 18.3mg/g to 92.3mg/g, and the adsorption capacity to As (V) was maintained in the range of 27.3mg/g to 150.3 mg/g. This demonstrates that lanthanum zirconium MOFs exhibit good adsorption properties for As (V) and Cr (VI) in strongly acidic water bodies.
Claims (8)
1. The preparation method of the lanthanum zirconium MOFs serving as the arsenic and chromium bifunctional adsorbents is characterized by comprising the following steps of:
(1) Adding lanthanum metal salt, zirconium metal salt and 1.0mmol of 2-amino terephthalic acid organic ligand into N, N-dimethylformamide according to a certain molar ratio;
(2) Fully stirring the precursor mixture obtained in the step (1);
(3) Transferring the uniform precursor mixture obtained in the step (2) into a polytetrafluoroethylene high-pressure reaction kettle, and placing the polytetrafluoroethylene high-pressure reaction kettle in a constant-temperature drying oven at 120 ℃ for a certain period of time to obtain a crystallized product;
(4) And (3) cleaning the crystallized product obtained in the step (3) by using N, N-dimethylformamide, and then placing the cleaned crystallized product in a constant-temperature drying oven for drying to obtain the dual-function adsorbent lanthanum zirconium MOFs with arsenic and chromium removed together.
2. The method for preparing the arsenic-chromium bifunctional adsorbent lanthanum-zirconium MOFs according to claim 1, wherein the lanthanum metal salt and the zirconium metal salt in the step (1) are lanthanum chloride hexahydrate and zirconium chloride.
3. The method for preparing the arsenic-chromium bifunctional adsorbent lanthanum-zirconium MOFs according to claim 1, wherein the molar ratio of the lanthanum metal salt to the zirconium metal salt in the step (1) is 0.2-2:1mmol.
4. The method for preparing the lanthanum zirconium MOFs serving as the arsenic and chromium dual-function adsorbent, according to claim 1, wherein the stirring in the step (2) is performed by using a magnetic stirrer for 30min.
5. The method for preparing the lanthanum zirconium MOFs serving as the arsenic and chromium dual-function adsorbent, according to claim 1, wherein the period of time in the constant-temperature drying oven in the step (3) is 2-12 hours.
6. The method for preparing the lanthanum zirconium MOFs serving as the arsenic and chromium dual-function adsorbent, according to claim 1, wherein the drying condition in the constant-temperature drying oven in the step (4) is that the temperature is 60 ℃ and the time is 12 hours.
7. A dual function adsorbent lanthanum zirconium MOFs of arsenic and chromium, characterized by being prepared by the preparation method of any one of claims 1-6.
8. The application of the dual-function adsorbent lanthanum zirconium MOFs of arsenic and chromium in high-efficiency adsorption in a water body containing arsenic and chromium according to claim 7.
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