CN114380869A - Metal-organic framework material and preparation method and application thereof - Google Patents
Metal-organic framework material and preparation method and application thereof Download PDFInfo
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- CN114380869A CN114380869A CN202210033593.6A CN202210033593A CN114380869A CN 114380869 A CN114380869 A CN 114380869A CN 202210033593 A CN202210033593 A CN 202210033593A CN 114380869 A CN114380869 A CN 114380869A
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- 239000000463 material Substances 0.000 title claims abstract description 160
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 36
- 239000010935 stainless steel Substances 0.000 claims abstract description 36
- 238000005554 pickling Methods 0.000 claims abstract description 35
- 239000002351 wastewater Substances 0.000 claims abstract description 33
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 3
- 238000001514 detection method Methods 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 239000011550 stock solution Substances 0.000 claims description 7
- 238000000825 ultraviolet detection Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 3
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 18
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- 238000004519 manufacturing process Methods 0.000 description 6
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- 238000001878 scanning electron micrograph Methods 0.000 description 5
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- 150000007522 mineralic acids Chemical class 0.000 description 4
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
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- 239000002699 waste material Substances 0.000 description 3
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- 238000001728 nano-filtration Methods 0.000 description 1
- 239000013265 porous functional material Substances 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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Abstract
The invention belongs to the technical field of a preparation method of a metal-organic framework material and recycling of pickling wastewater in stainless steel industry, and particularly relates to a metal-organic framework material and a preparation method and application thereof. For solving the problem of stainless steel pickling wasteThe recycling of water and the high cost of the metal-organic framework material which is FexCr3‑xFy(BTC)zWherein BTC is trimesic acid, x is 2.0-2.8, y is 0.5-1.0, and z is 1.5-3.0. The material consists of blocky particles, and the particle size is 0.3-2.0 mu m; the BET specific surface area is 1192 to 1870m2Per gram, the pore volume is 0.6608-1.8323 cm3(ii) in terms of/g. The material is prepared by using stainless steel pickling wastewater, the stainless steel pickling wastewater and trimesic acid are mixed, stirred uniformly at room temperature and then put into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and the reaction is carried out at high temperature.
Description
Technical Field
The invention belongs to the technical field of a preparation method of a metal-organic framework material and recycling of pickling wastewater in stainless steel industry, and particularly relates to a metal-organic framework material and a preparation method and application thereof.
Background
The smelting, casting, hot rolling, heat treatment, welding and other processes in the production process of stainless steel can generate compact oxide skin on the surface of steel, and the subsequent treatment process of the steel needs to keep the surface smooth, so that the acid cleaning treatment is needed to remove the oxide skin so as to achieve the purpose of smooth surface. In the pickling process, about 0.8-2 tons of pickling wastewater is generated per ton of steel, wherein the pickling wastewater contains high-concentration heavy metals such as iron, chromium, nickel and the like besides inorganic acids such as nitric acid and hydrofluoric acid. Therefore, the resource utilization of the metal in the pickling wastewater has important practical significance.
At present, stainless steel pickling wastewater is mainly utilized in two aspects, one of the two aspects is to realize metal recovery through methods such as selective precipitation and nanofiltration crystallization, and although part of the technologies are already industrially applied, the problems of high energy consumption, large investment and high operation cost still exist. The other method is to prepare the functional material by taking the pickling wastewater as a raw material, but the method is mainly limited to metal oxides or salts, and few researches are made on the preparation of novel materials with high added values.
Metal-organic frameworks (MOFs) are a new type of porous functional material that has emerged in recent years. Based on the characteristics of regular pore channel structure, ultra-large specific surface area, porosity, low solid density and the like, the MOF material has excellent performance in a plurality of fields such as separation, energy storage, catalysis, biomedicine, sensing and the like, but the high cost becomes a core problem limiting the popularization of the MOF material. Raw materials for preparing the MOF material comprise a metal source, a ligand, a solvent, other regulators and the like, and the large-scale production process of the MOF material can be promoted by greatly reducing the cost of any raw material. The stainless steel pickling wastewater contains high-concentration Fe, Cr and Ni, nitric acid, hydrofluoric acid and the like, which are raw materials for preparing various classical MOF materials, such as MIL-53, MIL-100, MIL-101 and the like. At present, the preparation of MOF materials with high added value by taking stainless steel pickling wastewater as a raw material is not reported at home and abroad.
The metal-organic framework material is prepared by utilizing metal ions and inorganic acid in the stainless steel pickling wastewater and combining with a conventional low-cost organic ligand through a hydrothermal method, so that the industrial wastewater is converted into a high-added product (organic-metal framework), and the metal-organic framework material has good value in the fields of stainless steel pickling wastewater recycling and MOF material large-scale popularization.
Disclosure of Invention
In order to solve the problems of recycling of stainless steel pickling wastewater and high cost of metal-organic framework materials, the invention provides a metal-organic framework material prepared from stainless steel pickling wastewater, a preparation method and application of the prepared metal-organic framework material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the metal-organic framework material is FexCr3-xFy(BTC)zWherein BTC is trimesic acid, x is 2.0-2.8, y is 0.5-1.0, and z is 1.5-3.0.
Further, the material consists of blocky particles, and the particle size is 0.3-2.0 mu m; the BET specific surface area is 1192 to 1870m2Per gram, the pore volume is 0.6608-1.8323 cm3(ii) in terms of/g. The larger specific surface area and pore volume are favorable for the adsorption of guest molecules by the material.
Further, the structure of the material is still stable after the material is soaked in an aqueous solution with the pH value of 1.0-12.0 for 10 days. The excellent long-period acid-base stability can ensure the application of the material in a complex water body environment.
A preparation method of a metal-organic framework material by using stainless steel pickling wastewater comprises the following steps:
mixing the stainless steel pickling wastewater with trimesic acid, stirring uniformly at room temperature, putting into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at high temperature to obtain the material.
Further, the volume ratio of the mass of the trimesic acid to the stainless steel pickling wastewater is as follows: 15-250 g/L.
Further, the stirring time at room temperature is 30 min; the high-temperature reaction is carried out at the temperature of 180-220 ℃ for 12 hours.
An application of a metal-organic framework material is applied to the adsorption and removal of methylene blue aqueous solution. The adsorption of the dye shows that the dye can effectively treat the printing and dyeing industrial wastewater.
A method for applying a metal-organic framework material, comprising the following steps:
and 3, carrying out ultraviolet detection on the filtrate and the stock solution together.
Further, the mass of the metal-organic framework material in the step 1 is 20 mg; the volume of the methylene blue aqueous solution is 10mL, and the concentration is 100 mg/L; the stirring time at room temperature is 720 min; the pore size of the filter membrane in the step 2 is 0.22 mu m.
A stability test method of a metal-organic framework material comprises the following steps:
and 3, carrying out XRD detection on the solid obtained by drying.
Compared with the prior art, the invention has the following advantages:
the raw materials for making MOF materials include metals, inorganic acids, solvents, and organic ligands. The raw materials for MOF synthesis at present are generally from commercial reagents and have high cost. In the method, the stainless steel pickling wastewater is used, and metal ions (Fe and Cr), inorganic acid (nitric acid and hydrofluoric acid) and water in the stainless steel pickling wastewater are fully utilized, so that the material preparation cost can be greatly reduced. Meanwhile, the prepared material has good porosity and dye removal performance, and has good practical application value. Can realize changing waste into valuable and promote the treatment of waste by waste.
Drawings
FIG. 1 is an XRD pattern of a metal-organic framework material according to example 1 of the present invention;
FIG. 2 is an SEM image of a metal-organic framework material according to example 1 of the present invention;
FIG. 3 is a nitrogen adsorption and desorption curve of the metal-organic framework material at 77K according to example 1 of the present invention;
FIG. 4 is an XRD pattern of the metal-organic framework material of example 1 after being soaked in different pH solutions for 10 days;
FIG. 5 is an XRD pattern of a metal-organic framework material according to example 2 of the present invention;
FIG. 6 is an SEM image of a metal-organic framework material according to example 2 of the present invention;
FIG. 7 is a nitrogen adsorption and desorption curve of the metal-organic framework material at 77K according to example 2 of the present invention;
FIG. 8 is an XRD pattern of the metal-organic framework material of example 2 after being soaked in different pH solutions for 10 days;
FIG. 9 is an XRD pattern of a metal-organic framework material according to example 3 of the present invention;
FIG. 10 is an SEM image of a metal-organic framework material according to example 3 of the present invention;
FIG. 11 is a nitrogen adsorption and desorption curve of the metal-organic framework material at 77K according to example 3 of the present invention;
FIG. 12 is an XRD pattern of the metal-organic framework material of example 3 after being soaked in different pH solutions for 10 days;
FIG. 13 is an XRD pattern of a metal-organic framework material according to example 4 of the present invention;
FIG. 14 is an SEM image of a metal-organic framework material according to example 4 of the present invention;
FIG. 15 is a nitrogen adsorption and desorption curve at 77K for the metal-organic framework material in example 4 of the present invention;
FIG. 16 is an XRD pattern of the metal-organic framework material of example 4 after being soaked in different pH solutions for 10 days;
FIG. 17 is an XRD pattern of a metal-organic framework material according to example 5 of the present invention;
FIG. 18 is an SEM image of a metal-organic framework material according to example 5 of the present invention;
FIG. 19 is a nitrogen adsorption and desorption curve at 77K for the metal-organic framework material in example 5 of the present invention;
fig. 20 is an XRD pattern after soaking the metal-organic framework material in solution of different pH for 10 days according to example 5 of the present invention.
Detailed Description
Example 1
A preparation method of a metal-organic framework material, which is prepared by using stainless steel pickling wastewater from a certain stainless steel production enterprise in Shanxi jin, comprises the following steps:
0.3g of trimesic acid is mixed with 20mL of stainless steel pickling wastewater (solid-to-liquid ratio: 15g/L), stirred for 30min at room temperature and then reacted for 12 hours at 180 ℃ in a high-temperature high-pressure reaction kettle to obtain the material.
The material can be used for adsorbing an aqueous solution containing methylene blue, and the specific method comprises the following steps:
and 2, filtering the mixture by using a filter membrane with the diameter of 0.22 mu m to obtain a clear and transparent solution after the reaction is finished.
And 3, carrying out ultraviolet detection on the adsorbed solution and the stock solution together, wherein the removal rate of the methylene blue is 93.2% according to the detection result of an ultraviolet-visible spectrophotometer.
XRD detection is carried out on the prepared material, and the result is shown in figure 1, and the material has characteristic diffraction peaks at 6.4 degrees, 10.4 degrees, 11.2 degrees, 12.7 degrees, 20.2 degrees, 24.2 degrees and 28.2 degrees.
SEM detection is carried out on the prepared material, and the result is shown in figure 2, wherein the material consists of blocky particles, and the particle size is about 0.3-2 μm.
Performing energy spectrum detection on the prepared material, and speculating from a scanning energy spectrum detection result that the main elements of the material are as follows: C. o, Cr, Fe and F, and judging the material composition according to the content: fe2.0Cr1.0F0.5(BTC)2.0。
The nitrogen adsorption and desorption curve of the prepared material at 77K is shown in figure 3, and the BET specific surface area of the material is 1341.0m2Per g, pore volume 0.8733cm3/g。
XRD detection is carried out on a sample after the material is soaked in aqueous solutions with different pH values for 10 days, as shown in figure 4, the XRD spectrogram of the material is basically kept unchanged, and good stability of the material is proved.
Example 2
A preparation method of a metal-organic framework material, which is prepared by using stainless steel pickling wastewater from a certain stainless steel production enterprise in Shanxi jin, comprises the following steps:
0.7g of trimesic acid is mixed with 20mL of stainless steel pickling wastewater (solid-to-liquid ratio: 35g/L), stirred for 30min at room temperature and then reacted for 12 hours at 180 ℃ in a high-temperature high-pressure reaction kettle to obtain the material.
The material can be used for adsorbing methylene blue in aqueous solution, and the specific method is as follows:
and 2, filtering the mixture by using a filter membrane with the diameter of 0.22 mu m to obtain a clear and transparent solution after the reaction is finished.
And 3, carrying out ultraviolet detection on the adsorbed solution and the stock solution together, wherein the removal rate of the methylene blue is 99.2% according to the detection result of an ultraviolet-visible spectrophotometer.
XRD detection is carried out on the prepared material, and the result is shown in figure 5, and the material has characteristic diffraction peaks at 6.4 degrees, 10.4 degrees, 11.2 degrees, 12.7 degrees, 20.2 degrees, 24.2 degrees and 28.2 degrees.
SEM detection is carried out on the prepared material, and the result is shown in figure 6, wherein the material consists of blocky particles, and the particle size is about 0.5-1.5 mu m.
Performing energy spectrum detection on the prepared material, and speculating from a scanning energy spectrum detection result that the main elements of the material are as follows: C. o, Cr, Fe and F, and judging the material composition according to the content: fe2.4Cr0.6F0.8(BTC)3.0。
The nitrogen adsorption and desorption curve of the prepared material at 77K is shown in figure 7, and the BET specific surface area of the material is 1870.0m2Per g, pore volume 0.8969cm3/g。
XRD detection is carried out on a sample after the material is soaked in aqueous solutions with different pH values for 10 days, as shown in figure 8, the XRD spectrogram of the material is basically kept unchanged, and good stability of the material is proved.
Example 3
A preparation method of a metal-organic framework material, which is prepared by using stainless steel pickling wastewater from a certain stainless steel production enterprise in Shanxi jin, comprises the following steps:
1.4g of trimesic acid and 20mL of stainless steel pickling wastewater are mixed (solid-to-liquid ratio: 70g/L), stirred for 30min at room temperature and reacted for 12 hours at 200 ℃ in a high-temperature high-pressure reaction kettle to obtain the material.
The material can be used for adsorbing methylene blue in aqueous solution, and the specific method is as follows:
and 2, filtering the mixture by using a filter membrane with the diameter of 0.22 mu m to obtain a clear and transparent solution after the reaction is finished.
And 3, carrying out ultraviolet detection on the adsorbed solution and the stock solution together, wherein the removal rate of the methylene blue is 91.4% according to the detection result of an ultraviolet-visible spectrophotometer.
XRD detection is carried out on the prepared material, and the result is shown in figure 9, and the material has characteristic diffraction peaks at 6.4 degrees, 10.4 degrees, 11.2 degrees, 12.7 degrees, 20.2 degrees, 24.2 degrees and 28.2 degrees.
SEM detection is carried out on the prepared material, and the result is shown in figure 10, wherein the material is composed of blocky particles, and the particle size is about 0.3-2.0 μm.
Performing energy spectrum detection on the prepared material, and speculating from a scanning energy spectrum detection result that the main elements of the material are as follows: C. o, Cr, Fe and F, and judging the material composition according to the content: fe2.8Cr0.2F1.0(BTC)2.4。
The nitrogen adsorption and desorption curve of the prepared material at 77K is shown in FIG. 11, and the BET specific surface area of the material is 1572m2Per g, pore volume 0.9255cm3/g。
XRD detection is carried out on a sample after the material is soaked in aqueous solutions with different pH values for 10 days, as shown in figure 12, the XRD spectrogram of the material is basically kept unchanged, and good stability of the material is proved.
Example 4
A preparation method of a metal-organic framework material, which is prepared by using stainless steel pickling wastewater from a certain stainless steel production enterprise in Shanxi jin, comprises the following steps:
3.0g of trimesic acid is mixed with 20mL of stainless steel pickling wastewater (solid-to-liquid ratio: 150g/L), stirred for 30min at room temperature and then reacted for 12 hours at 220 ℃ in a high-temperature high-pressure reaction kettle to obtain the material.
The material can be used for adsorbing methylene blue in aqueous solution, and the specific method is as follows:
and 2, filtering the mixture by using a filter membrane with the diameter of 0.22 mu m to obtain a clear and transparent solution after the reaction is finished.
And 3, carrying out ultraviolet detection on the adsorbed solution and the stock solution together, wherein the removal rate of the methylene blue is 97.4% according to the detection result of an ultraviolet-visible spectrophotometer.
XRD detection is carried out on the prepared material, and the result is shown in figure 13, and the material has characteristic diffraction peaks at 6.4 degrees, 10.4 degrees, 11.1 degrees, 12.7 degrees, 20.2 degrees, 24.2 degrees and 28.2 degrees.
SEM detection is carried out on the prepared material, and the result is shown in figure 14, wherein the material is composed of blocky particles, and the particle size is about 0.3-2.0 μm.
Performing energy spectrum detection on the prepared material, and speculating from a scanning energy spectrum detection result that the main elements of the material are as follows: C. o, Cr, Fe and F, and judging the material composition according to the content: fe2.5Cr0.5F0.8(BTC)1.5。
The nitrogen adsorption and desorption curve of the prepared material at 77K is shown in FIG. 15, and the BET specific surface area of the material is 1354m2Per g, pore volume 1.8323cm3/g。
XRD detection is carried out on a sample after the material is soaked in aqueous solutions with different pH values for 10 days, as shown in figure 16, the XRD spectrogram of the material is basically kept unchanged, and good stability of the material is proved.
Example 5
A preparation method of a metal-organic framework material, which is prepared by using stainless steel pickling wastewater from a certain stainless steel production enterprise in Shanxi jin, comprises the following steps:
5.0g of trimesic acid is mixed with 20mL of stainless steel pickling wastewater (solid-to-liquid ratio: 250g/L), stirred for 30min at room temperature and then reacted for 12 hours at 220 ℃ in a high-temperature high-pressure reaction kettle to obtain the material.
The material can be used for adsorbing methylene blue in aqueous solution, and the specific method is as follows:
and 2, filtering the mixture by using a filter membrane with the diameter of 0.22 mu m to obtain a clear and transparent solution after the reaction is finished.
And 3, carrying out ultraviolet detection on the adsorbed solution and the stock solution together, wherein the removal rate of the methylene blue is 96.7 percent according to the detection result of an ultraviolet-visible spectrophotometer.
XRD detection is carried out on the prepared material, and the result is shown in figure 17, and the material has characteristic diffraction peaks at 6.4 degrees, 10.4 degrees, 11.1 degrees, 12.7 degrees, 20.2 degrees, 24.2 degrees and 28.2 degrees.
SEM detection is carried out on the prepared material, and the result is shown in figure 18, wherein the material is composed of blocky particles, and the particle size is about 0.3-2.0 μm.
Performing energy spectrum detection on the prepared material, and speculating from a scanning energy spectrum detection result that the main elements of the material are as follows: C. o, Cr, Fe and F, and judging the material composition according to the content: fe2.8Cr0.2F0.5(BTC)2.0。
The nitrogen adsorption and desorption curve of the prepared material at 77K is shown in figure 19, and the BET specific surface area of the material is 1192m2Per g, pore volume 0.6608cm3/g。
XRD detection is carried out on a sample after the material is soaked in aqueous solutions with different pH values for 10 days, as shown in figure 20, the XRD spectrogram of the material is basically kept unchanged, and good stability of the material is proved.
Claims (10)
1. A metal-organic framework material, characterized in that the material is FexCr3-xFy(BTC)zWherein BTC is trimesic acid, x is 2.0-2.8, y is 0.5-1.0, and z is 1.5-3.0.
2. The metal-organic framework material according to claim 1, wherein the material is composed of bulk particles having a particle size of 0.3-2.0 μm and a BET specific surface area of 1192-1870 m2Per gram, the pore volume is 0.6608-1.8323 cm3/g。
3. The metal-organic framework material according to claim 1, wherein the structure of the material remains stable after being soaked in an aqueous solution with a pH of 1.0-12.0 for 10 days.
4. A method for preparing a metal-organic framework material according to any one of claims 1 to 3, wherein the metal-organic framework material is prepared by using stainless steel pickling wastewater, and comprises the following steps:
mixing the stainless steel pickling wastewater with trimesic acid, stirring uniformly at room temperature, putting into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at high temperature to obtain the material.
5. The method for preparing a metal-organic framework material according to claim 4, wherein the volume ratio of the mass of the trimesic acid to the stainless steel pickling wastewater is as follows: 15-250 g/L.
6. The method for preparing a metal-organic framework material according to claim 4, wherein the stirring time at room temperature is 30 min; the high-temperature reaction is carried out at the temperature of 180-220 ℃ for 12 hours.
7. Use of a metal-organic framework material according to any of claims 1 to 3 for the adsorptive removal of aqueous methylene blue solutions.
8. A method for using a metal-organic framework material according to any one of claims 1 to 3, comprising the steps of:
step 1, mixing a metal-organic framework material with a methylene blue aqueous solution, and stirring at room temperature;
step 2, after stirring, filtering with a filter membrane to obtain clear and transparent filtrate;
and 3, carrying out ultraviolet detection on the filtrate and the stock solution together.
9. The method for applying a metal-organic framework material according to claim 8, wherein the mass of the metal-organic framework material in the step 1 is 20 mg; the volume of the methylene blue aqueous solution is 10mL, and the concentration is 100 mg/L; the stirring time at room temperature is 720 min; the pore size of the filter membrane in the step 2 is 0.22 mu m.
10. A method for testing the stability of a metal-organic framework material according to any one of claims 1 to 3, comprising the steps of:
step 1, taking 200mg of metal-organic framework material, respectively adding the metal-organic framework material into aqueous solutions with pH values of 1, 6 and 12, and standing for 10 days at room temperature;
step 2, sucking out supernatant in the solution after being placed for 10 days, putting the solid at the bottom into a drying box, and drying for 12 hours at the temperature of 120 ℃;
and 3, carrying out XRD detection on the solid obtained by drying.
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