CN107501565B - Rare earth metal-organic framework material Ho-MOF and preparation method and application thereof - Google Patents
Rare earth metal-organic framework material Ho-MOF and preparation method and application thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 183
- 239000000463 material Substances 0.000 title claims abstract description 93
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 86
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001868 water Inorganic materials 0.000 claims abstract description 37
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 33
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000013110 organic ligand Substances 0.000 claims abstract description 27
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- 238000000034 method Methods 0.000 claims description 36
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- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical group [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 claims description 12
- 230000000593 degrading effect Effects 0.000 claims description 9
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- 238000005406 washing Methods 0.000 claims description 7
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- -1 2, 5-dihydroxyterephthalate ions Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- MKPJADFELTTXAV-UHFFFAOYSA-H holmium(3+);trisulfate Chemical compound [Ho+3].[Ho+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MKPJADFELTTXAV-UHFFFAOYSA-H 0.000 claims description 3
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
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- 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 17
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- 239000000356 contaminant Substances 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
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Abstract
The invention relates to the technical field of metal organic framework materials, in particular to a rare earth metal-organic framework material Ho-MOF and a preparation method and application thereof. The rare earth metal-organic framework material Ho-MOF provided by the invention has a molecular formula of [ Ho (H)2‑DHBDC)0.5(DHBDC)0.5(H2O)2](H2O)nThe preparation method comprises the following steps: adding organic ligand 2, 5-dihydroxy terephthalic acid into water, adjusting the pH to 6.1-6.5, then adding water-soluble holmium salt and dimethylformamide, and carrying out hydrothermal reaction to obtain the rare earth metal-organic framework material Ho-MOF. The rare earth metal-organic framework material Ho-MOF provided by the invention has smaller optical energy gap and wider spectral response capability, and can be used as a photocatalytic material to rapidly and efficiently degrade waste water containing organic dye.
Description
Technical Field
The invention relates to the technical field of metal organic framework materials, in particular to a rare earth metal-organic framework material Ho-MOF and a preparation method and application thereof.
Background
The printing and dyeing industry is an industrial wastewater discharge consumer, and the produced dye wastewater has the characteristics of complex components, high organic matter content, high chromaticity, strong toxicity, large water quality change, large alkalinity, difficult biodegradation and the like, can cause serious pollution to water, and is one of the most main water pollution sources at present. Therefore, the comprehensive treatment of the printing and dyeing wastewater becomes a difficult problem to be solved urgently.
At present, the treatment means of the printing and dyeing wastewater in China mainly comprises a physical and chemical method and a biochemical method, but the methods have the problems of high operation cost, heavy secondary pollution, low adsorption capacity, difficult regeneration, no selectivity and the like. The photocatalytic treatment of the printing and dyeing wastewater is considered as a brand-new green treatment technology and has the advantages of environmental friendliness and mild reaction conditions.
Metal-Organic frameworks (MOFs) are crystalline porous materials with a periodic network structure formed by connecting inorganic Metal centers (Metal ions or Metal clusters) and bridged Organic ligands with each other through self-assembly, and are coordination polymers with a microporous network structure formed by self-assembly of transition Metal ions and polydentate Organic ligands (mostly aromatic polyacids and polybases) containing oxygen, nitrogen and the like. The metal organic framework material not only has infinitely variable topological structure, but also has attractive application potential in various aspects such as gas adsorption separation, catalysis, photoelectric and magnetic materials, sensors and the like, and is rapidly developing into research hotspots in many fields.
On one hand, MOFs have various nano and micro-scale framework type regular pore channel structures, ultra-large specific surface area and porosity (up to 0.9), and small solid density tradition, so that the MOFs have the advantages of large adsorption capacity, high selectivity, easiness in regeneration and recovery and the like, and show good treatment effect on the adsorption and separation of dye pollutants in a water phase. On the other hand, MOFs can also be used as a photocatalyst with adjustable energy band for degrading dye macromolecules in water by generating various different types of ligand-to-metal charge transfer transitions. Therefore, the novel metal-organic framework material is constructed, and the research on the photocatalytic performance of the dye wastewater is carried out, so that the method has important practical value and attractive application prospect.
The invention is provided in view of the above.
Disclosure of Invention
The invention aims to provide a rare earth metal-organic framework material Ho-MOF, which has smaller optical energy gap and wider spectral response capability, can be used as a photocatalytic material to quickly and efficiently degrade waste water containing organic dye, and has the advantages of good degradation effect, mild reaction conditions and environmental friendliness.
The invention also aims to provide a preparation method of the rare earth metal-organic framework material Ho-MOF, which has the advantages of simple process, low production cost and good market application prospect.
In order to achieve the purpose, the invention adopts the technical scheme that:
a rare earth metal-organic framework material Ho-MOF having a molecular formula of [ Ho (H) ]2-DHBDC)0.5(DHBDC)0.5(H2O)2](H2O)n；
Wherein H2-DHBDC and DHBDC are 2, 5-dihydroxyterephthalate ions deprived of two protons and four protons, respectively; n is a natural number of 1 or more.
Wherein "-" in "rare earth metal-organic framework material" means that a rare earth metal and an organic ligand form a framework material by coordination.
Preferably, n is a natural number of 1 to 50.
More preferably, n is a natural number of2 to 20.
A preparation method of the rare earth metal-organic framework material Ho-MOF comprises the following steps:
adding organic ligand 2, 5-dihydroxy terephthalic acid into water, adjusting the pH to 6.1-6.5, then adding water-soluble holmium salt and dimethylformamide, and carrying out hydrothermal reaction to obtain the rare earth metal-organic framework material Ho-MOF.
Further, 5 to 8m L of water is added per mmol of2, 5-dihydroxyterephthalic acid, preferably 6 to 7m L of water per mmol of2, 5-dihydroxyterephthalic acid, and more preferably 6.5m L of water per mmol of2, 5-dihydroxyterephthalic acid.
Further, the pH is adjusted with a strongly alkaline solution, preferably with an aqueous solution of sodium hydroxide.
Further, the water-soluble holmium salt is holmium nitrate, holmium sulfate or holmium chloride, and is preferably holmium nitrate.
Further, the ratio of the water-soluble holmium salt to the mass of the organic ligand 2, 5-dihydroxyterephthalic acid is (2-4): 1, preferably 3: 1.
Further, the volume ratio of the dimethylformamide to the water is 1: (0.8-1.2), preferably 1:1.
Further, the temperature of the hydrothermal reaction is 100-.
Further, the hydrothermal reaction time is 20 to 30 hours, preferably 22 to 28 hours, and more preferably 24 hours.
Further, the preparation method comprises the steps of cooling to room temperature after the hydrothermal reaction is finished, washing, filtering and drying.
Further, the drying is carried out in vacuum, and the drying temperature is 50-80 ℃, preferably 60-70 ℃, and more preferably 65 ℃.
Further, the drying time is 20 to 36 hours, preferably 22 to 30 hours, and more preferably 24 hours.
The application of the rare earth metal-organic framework material Ho-MOF in degrading organic dye wastewater.
Compared with the prior art, the invention has the beneficial effects that:
1. the rare earth-metal organic framework material Ho-MOF provided by the invention has smaller optical energy gap and wider spectral response capability, and can be used as a photocatalytic material to rapidly and efficiently degrade waste water containing organic dye.
2. The preparation method of the rare earth metal-organic framework material Ho-MOF provided by the invention has the advantages of simple process, mild reaction conditions, environmental friendliness, low production cost and good market application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a diagram of coordination environment of rare earth metal-organic framework material Ho-MOF;
FIG. 2 is a schematic diagram of a three-dimensional framework structure of a rare earth metal-organic framework material Ho-MOF;
FIG. 3 is an X-ray powder diffraction pattern of a rare earth metal-organic framework material Ho-MOF;
FIG. 4 is a graph of the UV-visible diffuse reflectance spectrum of a rare earth metal-organic framework material Ho-MOF, wherein (a) the UV-vis spectrum of the rare earth metal-organic framework material Ho-MOF; (b) a Kubelka-Munk transition diffuse reflection spectrogram of a rare earth metal-organic framework material Ho-MOF;
FIG. 5 is a UV-Vis spectrum of a methylene blue solution as a target contaminant in example 1;
FIG. 6 is a quasi-first order kinetic fit spectrum of the photocatalytic reaction in example 1;
FIG. 7 is a UV-Vis spectrum of a comparative example degrading methylene blue, a target contaminant.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments and the accompanying drawings, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
On one hand, the MOFs has various nano and micro-scale framework type regular pore channel structures, an ultra-large specific surface area, a porosity (which can reach 0.9) and a small solid density, so that the MOFs has the advantages of large adsorption capacity, high selectivity, easiness in regeneration and recovery and the like, and shows a good treatment effect on the adsorption and separation of dye pollutants in a water phase. On the other hand, MOFs can also be used as a photocatalyst with adjustable energy band for degrading dye macromolecules in water by generating various different types of ligand-to-metal charge transfer transitions.
The invention provides a rare earth metal-organic framework material Ho-MOF, wherein the molecular formula of the rare earth metal-organic framework material is [ Ho (H)2-DHBDC)0.5(DHBDC)0.5(H2O)2](H2O)n；
Wherein H4-DHBDC is 2, 5-dihydroxyterephthalic acid; h2-DHBDC and DHBDC are 2, 5-dihydroxyterephthalate ions deprived of two protons and four protons, respectively; n is a natural number of 1 or more.
In an alternative embodiment of the invention, n is a natural number from 1 to 50.
In a preferred embodiment of the invention, n is a natural number from 2 to 20.
As shown in FIG. 1, in the asymmetric unit of the rare earth metal-organic framework material Ho-MOF, Ho adopts an eight-coordination mode and five carboxyl oxygen atoms from four organic ligands (wherein O4, O4B and O5B adopt mu)2:η1:η2A coordination mode; o1 and O2A are mu2:η1:η1Coordination mode) and one phenolic oxygen atom (O6), and two water molecules (O7, O8) to H2-a DHBDC ligand, the two carboxylic acid groups of which adopt the same coordination mode, the two oxygen atoms of each carboxylic acid group forming a coordination with two metal ions, respectively; whereas for DHBDC ligands, one oxygen atom of each carboxylic acid group coordinates to one metal ion, the remaining one oxygen atom chelates one metal ion to the adjacent oxyhydroxy oxygen atom.
As shown in FIG. 2, two organic ligands are connected Ho3+Ions form one-dimensional rare earth chains along the c axis, and adjacent one-dimensional chains are connected through two organic ligands to form a three-dimensional organic framework.
The rare earth metal-organic framework material Ho-MOF belongs to a monoclinic system, P21The space group of/c, the unit cell parameters are respectively:
α＝90°，β＝103.067(4)°，γ＝90°。
2, 5-dihydroxyterephthalic acid can form various coordination modes of monodentate, bidentate, bridging and chelation due to introduction of an auxiliary functional group hydroxyl group in the phthalic acid, and further form a complex with a stable structure by combining with rare earth metal ions, thereby being beneficial to synthesis of a coordination polymer with a novel structure and performance.
The invention also provides a preparation method of the rare earth metal-organic framework material Ho-MOF, which comprises the following steps:
adding organic ligand 2, 5-dihydroxy terephthalic acid into water, adjusting the pH to 6.1-6.5, then adding water-soluble holmium salt and dimethylformamide, and carrying out hydrothermal reaction to obtain the rare earth metal-organic framework material Ho-MOF.
According to the invention, the rare earth metal-organic framework material Ho-MOF can be obtained by carrying out hydrothermal reaction on organic ligand 2, 5-dihydroxy terephthalic acid and water-soluble holmium salt under the action of specific pH and solvent dimethylformamide.
The pH value of the solution can influence the structure of growth elements in the solution, and the specific pH value is 6.1-6.5, so that the organic ligand and the water-soluble holmium salt can obtain the rare earth metal-organic framework material Ho-MOF. The purpose of adding the dimethylformamide is to increase the solubility of the system, so that crystals can easily grow out, and if other solvents are used, the crystals are difficult to grow out and are only powder. Meanwhile, the preparation method provided by the invention is simple in process, mild in reaction conditions, environment-friendly, low in production cost and good in market application prospect.
As an alternative embodiment of the invention, 5 to 8m L of water is added per mmol of2, 5-dihydroxyterephthalic acid the volume of water added per mmol of2, 5-dihydroxyterephthalic acid is typically, but not limited to, 5m L, 5.5m L, 6m L, 6.5m L, 7m L, 7.5m L or 8m L. as a preferred embodiment of the invention, 6.5m L of water is added per mmol of2, 5-dihydroxyterephthalic acid.
As an alternative embodiment of the invention, the pH is adjusted with strongly alkaline solutions, preferably with aqueous sodium hydroxide.
As an alternative embodiment of the present invention, the water-soluble holmium salt is holmium nitrate, holmium sulfate or holmium chloride. As a preferred embodiment of the present invention, the water-soluble holmium salt is holmium nitrate.
As an alternative embodiment of the invention, the mass ratio of the water-soluble holmium salt to the organic ligand 2, 5-dihydroxyterephthalic acid is (2-4): 1. the mass ratio of the water soluble holmium salt to the organic ligand 2, 5-dihydroxyterephthalic acid is typically, but not limited to, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, or 4: 1. As a preferred embodiment of the present invention, the mass ratio of the water-soluble holmium salt to the organic ligand 2, 5-dihydroxyterephthalic acid is 3: 1. Crystals can grow only if the dosage of the water-soluble holmium salt and the organic ligand is within a certain range, and otherwise, the crystals are clear liquid or powder.
As an alternative embodiment of the invention, the volume ratio of dimethylformamide to water is 1: (0.8-1.2) in a typical but non-limiting amount of 1:0.8, 1:0.9, 1:1, 1:1.1 or 1:1.2 by volume. As a preferred embodiment of the present invention, the volume ratio of dimethylformamide to water is 1:1. Too little dimethylformamide will affect the amount of organic ligand dissolved, making it less likely to form crystals.
As an alternative embodiment of the present invention, the temperature of the hydrothermal reaction is 100-120 ℃. The temperature of the hydrothermal reaction is typically, but not limited to: 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃ or 120 ℃. In a preferred embodiment of the present invention, the hydrothermal reaction temperature is 110 ℃. Under general conditions, the growth rate of crystals increases with the hydrothermal reaction temperature, but too high a reaction rate causes non-uniformity in crystal size. The hydrothermal reaction temperature is 100-120 ℃, so that high-yield and high-quality crystals can be obtained.
As an alternative embodiment of the present invention, the hydrothermal reaction time is 20 to 30 hours. Typical single non-limiting times for the hydrothermal reaction are 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, or 30 hours. In a preferred embodiment of the present invention, the hydrothermal reaction is carried out for 24 hours. The hydrothermal reaction time is too short, the crystal does not form a complete structure yet and the yield is low; the hydrothermal reaction time is too long, the reaction efficiency is low, and the energy consumption is high.
In an alternative embodiment of the invention, the hydrothermal synthesis reaction is carried out in a polytetrafluoroethylene-lined reaction vessel.
Further, the preparation method comprises the steps of cooling to room temperature after the hydrothermal reaction is finished, washing, filtering and drying.
As an alternative embodiment of the invention, deionized water is used for washing 3 to 5 times.
As an optional embodiment of the invention, the drying adopts vacuum drying, and the drying temperature is 50-80 ℃. The drying temperature is typically, but not limited to: 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃. As a preferred embodiment of the present invention, the drying temperature is 65 ℃. The drying temperature of 50-80 ℃ is selected to ensure that the crystal structure of Ho-MOF is not damaged and the Ho-MOF can be dried quickly.
As an alternative embodiment of the invention, the drying time is from 20 to 36 hours. Drying times are typically, but not limited to: 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, or 36 hours. In a preferred embodiment of the present invention, the drying time is 24 hours.
The application of the rare earth metal-organic framework material Ho-MOF in degrading organic dye wastewater. In an alternative embodiment of the present invention, the organic dye wastewater comprises a cationic dye and a heterocyclic dye. In a preferred embodiment of the present invention, the organic dye wastewater is a cationic dye represented by methylene blue. The invention uses methylene blue solution to simulate organic dye wastewater and investigates the performance of rare earth metal-organic framework material Ho-MOF in degrading organic dye wastewater.
Example 1
The method for preparing rare earth metal-organic framework material Ho-MOF of example 1, comprising the steps of:
(a) weighing 0.198g of organic ligand 2, 5-dihydroxy terephthalic acid, adding into 6.5m L deionized water, uniformly stirring, dropwise adding 0.1 mol/L sodium hydroxide aqueous solution under the stirring condition, monitoring the pH value of the system to be 6.4 by using an acidimeter, and uniformly stirring to obtain a light green mixed solution;
(b) weighing 0.951g of holmium nitrate solid, adding the holmium nitrate solid into the mixed solution obtained in the step (a), adding 6.5m L of dimethylformamide, stirring and mixing uniformly, and then transferring the mixture into a reaction kettle for hydrothermal reaction at the temperature of 105 ℃ for 24 hours;
(c) and after the hydrothermal reaction is finished, cooling to room temperature, washing with deionized water, filtering for 4 times to obtain orange-red columnar crystals, and drying in vacuum at 65 ℃ for 24 hours to obtain the rare earth metal-organic framework material Ho-MOF.
Example 2
The method for preparing rare earth metal-organic framework material Ho-MOF of example 2, comprising the steps of:
(a) weighing 0.198g of organic ligand 2, 5-dihydroxy terephthalic acid, adding into 6m L deionized water, uniformly stirring, dropwise adding 0.1 mol/L of sodium hydroxide aqueous solution under the stirring condition, monitoring the pH value of the system to be 6.2 by using an acidimeter, and uniformly stirring to obtain a light green mixed solution;
(b) weighing 0.634g of holmium nitrate solid, adding the holmium nitrate solid into the mixed solution obtained in the step (a), adding 5m L of dimethylformamide, stirring and mixing uniformly, and then transferring the mixture into a reaction kettle for hydrothermal reaction at the temperature of 100 ℃ for 30 hours;
(c) and after the hydrothermal reaction is finished, cooling to room temperature, washing with deionized water, filtering for 3 times to obtain orange-red columnar crystals, and drying in vacuum at 50 ℃ for 36 hours to obtain the rare earth metal-organic framework material Ho-MOF.
Example 3
The method for preparing rare earth metal-organic framework material Ho-MOF of example 3, comprising the steps of:
(a) weighing 0.198g of organic ligand 2, 5-dihydroxy terephthalic acid, adding the organic ligand into 4m L deionized water, uniformly stirring, dropwise adding 0.1 mol/L sodium hydroxide aqueous solution under the stirring condition, monitoring the pH value of a system to be 6.4 by using an acidimeter, and uniformly stirring to obtain a light green mixed solution;
(b) weighing 1.2g of holmium nitrate solid, adding the holmium nitrate solid into the mixed solution obtained in the step (a), adding 5m L of dimethylformamide, stirring and mixing uniformly, and then transferring the mixture into a reaction kettle for hydrothermal reaction at the temperature of 110 ℃ for 20 hours;
(c) and after the hydrothermal reaction is finished, cooling to room temperature, washing with deionized water, filtering for 5 times to obtain orange-red columnar crystals, and drying in vacuum at the temperature of 80 ℃ for 20 hours to obtain the rare earth metal-organic framework material Ho-MOF.
Test example 1 determination of Crystal Structure of rare earth Metal-organic framework Material Ho-MOF
The crystal structure of the rare earth metal-organic framework material Ho-MOF provided in example 1 was measured using a Bruker Smart apex ii X-ray single crystal diffractometer, using molybdenum target Mo-K α rays monochromated by a graphite monochromator as a radiation source, collecting diffraction points using an ω -2 θ scanning method at a temperature of 296K, obtaining the crystal structure using the SHE L XT L-97 package direct method, determining all non-oxygen atom coordinates using a difference function method and a least square method, obtaining hydrogen atom positions using a theoretical hydrogenation method, and then correcting the crystal structure using a least square method.
FIG. 1 is a diagram of coordination environment of rare earth metal-organic framework material Ho-MOF. FIG. 2 is a schematic diagram of a three-dimensional crystal structure of a rare earth metal-organic framework material Ho-MOF.
As shown in FIG. 1, in the asymmetric unit of the rare earth metal-organic framework material Ho-MOF, Ho adopts an eight-coordination mode and five carboxyl oxygen atoms from four organic ligands (wherein O4, O4B and O5B adopt mu)2:η1:η2A coordination mode; o1 and O2A are mu2:η1:η1Coordination mode) and one phenolic oxygen atom (O6), and two water molecules (O7, O8) to H2-a DHBDC ligand, the two carboxylic acid groups of which adopt the same coordination mode, the two oxygen atoms of each carboxylic acid group forming a coordination with two metal ions, respectively; whereas for DHBDC ligands, one oxygen atom of each carboxylic acid group coordinates to one metal ion, the remaining one oxygen atom chelates one metal ion to the adjacent oxyhydroxy oxygen atom.
As shown in FIG. 2, two organic ligands are connected Ho3+Ions form one-dimensional rare earth chains along the c axis, and adjacent one-dimensional chains are connected through two organic ligands to formA three-dimensional organic framework.
The rare earth metal-organic framework material Ho-MOF belongs to a monoclinic system, P21The space group of/c, the unit cell parameters are respectively:
α＝90°，β＝103.067(4)°，γ＝90°。
experimental example 2X-ray powder diffraction Pattern determination of Ho-MOF
The phase of the rare earth metal-organic framework material Ho-MOF provided in example 1 was determined by means of a Powder X-Ray diffractometer (Powder X-Ray Diffraction, PXRD, instrument model: RigakuDMAX-IIIA, Cu K α radiation). the X-Ray Powder Diffraction pattern of the rare earth metal-organic framework material Ho-MOF is shown in FIG. 3.
As can be seen from FIG. 3, the diffraction peaks in the X-ray powder diffraction experimental spectrogram and the simulated spectrogram are basically consistent, no obvious impurity peak is observed, which indicates that the phase purity of the complex is very high, and the material structure is [ Ho (H)2-DHBDC)0.5(DHBDC)0.5(H2O)2](H2O)n。
Experimental example 3 UV-visible diffuse reflectance Spectroscopy assay of Ho-MOF
The diffuse reflection data of the rare earth metal-organic framework material Ho-MOF sample provided in example 1 in the range of 200-800nm was measured using an L ambda 650 UV-visible-near infrared spectrophotometer with an integrating sphere diameter of 90cm, BaSO4For reference (reflectance 100%).
And calculating a Kubelka-Munk function corresponding to the incident wavelength through UV-vis reflection spectrum data, and plotting Kubelka-Munk (F) against the incident photon energy eg (eV) to obtain an F-E curve so as to represent the light absorption characteristic of the sample. And the F-E curve has an absorption peak in the UV-vis area, a tangent is drawn along the edge of the absorption peak, and the energy corresponding to the intersection point of the tangent and the E axis is the energy gap (Eg) of the sample.
FIG. 4 is a chart of UV-visible diffuse reflectance spectra of rare earth metal-organic framework material Ho-MOF, wherein (a) UV-vis spectra of rare earth metal-organic framework material Ho-MOF; (b) Kubelka-Munk transition diffuse reflection spectrogram of rare earth metal-organic framework material Ho-MOF.
As can be seen from fig. 4 combining (a) and (b), the rare earth metal-organic framework material Ho-MOF of the present invention has a wide spectral response capability and a small optical energy gap (Eg ═ 2.16eV), and is a novel photocatalyst with potential.
Experimental example 4 degradation of methylene blue-containing wastewater by rare earth metal-organic framework material Ho-MOF prepared in example 1
And (3) simulating organic dye wastewater by using a methylene blue solution, and investigating the performance of degrading the organic dye wastewater by using the rare earth metal-organic framework material Ho-MOF.
The rare earth metal-organic framework material Ho-MOF 40mg prepared in example 1 was weighed out and added as a catalyst to a concentration of 40m L of 3.12 × 10-2magnetically stirring in the dark for 20min to ensure the completion of adsorption balance, analyzing 2m L solution at30min intervals under the irradiation of ultraviolet light, measuring the ultraviolet absorption spectrum of the solution, detecting the concentration of methylene blue by using absorbance, and adopting the concentration ratio of C/C0Adding 40 mu L hydrogen peroxide into the reaction system after the reaction time reaches 120min, every time at an interval of 15min, taking 2m L solution for analysis, measuring the ultraviolet absorption spectrum of the solution, detecting the concentration of methylene blue by using absorbance, and adopting the concentration ratio C/C0The degradation efficiency is measured and plotted against time t.
FIG. 5 is a UV-Vis spectrum of a methylene blue solution as a degradation target contaminant in example 1. Wherein-20 min in FIG. 5 refers to the UV-Vis spectrum of the methylene blue solution without the addition of Ho-MOF material, and after the measurement Ho-MOF is added; 0min refers to the ultraviolet-visible spectrogram of the solution 20min after the addition of Ho-MOF (i.e. when the Ho-MOF completes the adsorption), Cat30min, Cat 60min, Cat 75min, Cat 90min, Cat 105min and Cat 120min refer to the ultraviolet-visible spectrogram of the solution 30min, 60min, 75min, 90min, 105min and 120min after the completion of the adsorption, respectively, and H is added 120min after the completion of the adsorption2O2；Cat/H2O2135min，Cat/H2O2150min，Cat/H2O2165min and Cat/H2O2Adding H in 180min2O2Ultraviolet-visible spectrum of the solution at 15min, 30min, 45min and 60 min.
FIG. 6 is a quasi-first order kinetic fit spectrum of the photocatalytic reaction in example 1.
Combining the absorbance values of the graph 5 and calculating, after the reaction time reaches 120min, the removal rate of the target pollutant methylene blue solution is 35.0%, then adding 40 mu L hydrogen peroxide solution, and after 60min, the removal rate of the target pollutant methylene blue solution is 83.0%.
From FIG. 6, it can be seen that the photocatalytic reaction using the rare earth metal-organic framework material Ho-MOF conforms to the quasi-first order kinetic equation with a rate constant of 4.33 × 10-3min-1After the hydrogen peroxide is added, the photocatalytic reaction conforms to a quasi first order kinetic equation, and the rate constant is 2.57 × 10-2min-1The degradation rate is obviously increased, and the rare earth metal-organic framework material Ho-MOF can rapidly and efficiently degrade the organic dye wastewater in the presence of hydrogen peroxide.
The rare earth metal-organic framework material Ho-MOF obtained in example 2 and example 3 was used for degrading methylene blue-containing wastewater according to the method of test example 4, and higher degradation efficiency was also obtained.
Comparative test example
Instead of using the rare earth metal-organic framework material Ho-MOF prepared in example 1, only 40. mu. L of hydrogen peroxide were added to a concentration of 40m L of 3.12 × 10-2In a methylene blue solution of mmol/L, under the irradiation of ultraviolet light, every 30min, taking a solution of 2m L for analysis, measuring the ultraviolet absorption spectrum of the solution, detecting the concentration of the methylene blue by using absorbance, and adopting the concentration ratio C/C0The degradation efficiency is measured and plotted against time t.
FIG. 7 is a UV-Vis spectrum of a methylene blue solution as a degradation target contaminant in example 1. As can be seen from fig. 7, the removal rate of methylene blue, which is a target pollutant, is only 36.0% after the reaction time reaches 120 min.
As shown by comparing the test example 4 with the comparative test example, the rare earth metal-organic framework material Ho-MOF can rapidly and efficiently degrade organic dye wastewater.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (25)
1. A rare earth metal-organic framework material Ho-MOF is characterized in that the molecular formula of the rare earth metal-organic framework material is [ Ho (H)2-DHBDC)0.5(DHBDC)0.5(H2O)2](H2O)n；
Wherein H2-DHBDC and DHBDC are 2, 5-dihydroxyterephthalate ions deprived of two protons and four protons, respectively; n is a natural number of 1 or more.
2. The rare earth metal-organic framework material Ho-MOF of claim 1, wherein n is a natural number from 1 to 50.
3. The rare earth metal-organic framework material Ho-MOF of claim 1, wherein n is a natural number from 2 to 20.
4. A process for the preparation of a rare earth metal-organic framework material Ho-MOF according to any one of claims 1 to 3, comprising the steps of:
adding organic ligand 2, 5-dihydroxy terephthalic acid into water, adjusting the pH to 6.1-6.5, then adding water-soluble holmium salt and dimethylformamide, and carrying out hydrothermal reaction to obtain the rare earth metal-organic framework material Ho-MOF.
5. The method of claim 4, wherein 5-8m L of water is added per mmol of2, 5-dihydroxyterephthalic acid, and/or the pH is adjusted with a strongly basic solution.
6. The method of claim 5, wherein 6-7m L of water is added per mmol of2, 5-dihydroxyterephthalic acid, and/or the pH is adjusted with a strongly basic solution.
7. The method of claim 5, wherein 6.5m L of water is added per mmol of2, 5-dihydroxyterephthalic acid.
8. The method for preparing rare earth metal-organic framework material Ho-MOF according to claim 5, wherein the pH is adjusted with aqueous sodium hydroxide solution.
9. The method for preparing a rare earth metal-organic framework material Ho-MOF according to claim 4, wherein the water-soluble holmium salt is holmium nitrate, holmium sulfate or holmium chloride;
and/or the mass ratio of the water-soluble holmium salt to the organic ligand 2, 5-dihydroxyterephthalic acid is (2-4): 1.
10. the method for preparing a rare earth metal-organic framework material Ho-MOF according to claim 9, wherein the water-soluble holmium salt is holmium nitrate.
11. The method for preparing a rare earth metal-organic framework material Ho-MOF according to claim 9, wherein the mass ratio of the water-soluble holmium salt to the organic ligand 2, 5-dihydroxyterephthalic acid is 3: 1.
12. The method for preparing a rare earth metal-organic framework material Ho-MOF according to claim 4, wherein the volume ratio of the dimethylformamide to the added water is 1: (0.8-1.2).
13. The method of preparing a rare earth metal-organic framework material Ho-MOF according to claim 12, wherein the volume ratio of dimethylformamide to added water is 1:1.
14. The method for preparing rare earth metal-organic framework material Ho-MOF according to claim 4, wherein the temperature of the hydrothermal reaction is 100-120 ℃;
and/or the hydrothermal reaction time is 20-30 hours.
15. The method for preparing rare earth metal-organic framework material Ho-MOF according to claim 14, wherein the temperature of the hydrothermal reaction is 105-115 ℃.
16. The method for preparing a rare earth metal-organic framework material Ho-MOF according to claim 14, wherein the temperature of the hydrothermal reaction is 110 ℃.
17. The method for preparing a rare earth metal-organic framework material Ho-MOF according to claim 14, wherein the time of hydrothermal reaction is 22-28 hours.
18. The method for preparing a rare earth metal-organic framework material Ho-MOF according to claim 14, wherein the time of hydrothermal reaction is 24 hours.
19. The method for preparing a rare earth metal-organic framework material Ho-MOF according to claim 4, further comprising cooling to room temperature, washing, filtering and drying after the hydrothermal reaction is completed.
20. The method for preparing the rare earth metal-organic framework material Ho-MOF according to claim 19, wherein the drying is vacuum drying at 50-80 ℃;
and/or the drying time is 20-36 hours.
21. The method for preparing a rare earth metal-organic framework material Ho-MOF according to claim 20, wherein the drying temperature is 60-70 ℃.
22. The method of making a rare earth metal-organic framework material Ho-MOF of claim 20, wherein the drying temperature is 65 ℃.
23. The method for preparing a rare earth metal-organic framework material Ho-MOF according to claim 20, wherein the drying time is 22-30 hours.
24. The method for preparing a rare earth metal-organic framework material Ho-MOF according to claim 20, wherein the drying time is 24 hours.
25. Use of the rare earth metal-organic framework material Ho-MOF according to any one of claims 1 to 3 for degrading organic dye wastewater.
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