CN114672036A - Metal organic framework material with basic functional group and preparation method thereof - Google Patents
Metal organic framework material with basic functional group and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 24
- 125000000524 functional group Chemical group 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 121
- 239000013096 zirconium-based metal-organic framework Substances 0.000 claims abstract description 67
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000001179 sorption measurement Methods 0.000 claims abstract description 37
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 26
- 239000011630 iodine Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims description 143
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 74
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000013110 organic ligand Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- FYEKGZUXGKAJJQ-UHFFFAOYSA-N 3-amino-4-(4-carboxyphenyl)benzoic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C1=CC=C(C(O)=O)C=C1 FYEKGZUXGKAJJQ-UHFFFAOYSA-N 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- 229910007926 ZrCl Inorganic materials 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005538 encapsulation Methods 0.000 abstract description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000002285 radioactive effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000013208 UiO-67 Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000012922 MOF pore Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SVKHKEDVAHYEBY-UHFFFAOYSA-N n-iodocyclohexanamine Chemical compound INC1CCCCC1 SVKHKEDVAHYEBY-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 208000024770 Thyroid neoplasm Diseases 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XMBWDFGMSWQBCA-RNFDNDRNSA-M iodine-131(1-) Chemical compound [131I-] XMBWDFGMSWQBCA-RNFDNDRNSA-M 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 201000002510 thyroid cancer Diseases 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- 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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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract
The invention discloses a metal organic framework material with basic functional groups and a preparation method thereof. And respectively washing the obtained product by DMF and acetone in centrifugal separation to obtain the Zr-MOFs material of the invention. The Zr-MOFs material prepared by the method has the adsorption rate of 1.5-2.5 g/g (48h) for gaseous iodine and the adsorption rate of 80-95% (24h) for iodine in a solution. The Zr-MOFs material of the invention not only has higher thermal stability, but also has higher porosity and alkaline sites, which are beneficial to encapsulation and adsorption of iodine, and improves the adsorption capacity to iodine.
Description
Technical Field
The invention relates to the technical field of MOFs materials, in particular to a preparation method and performance characterization of a metal organic framework material with a basic functional group.
Background
Metal-Organic Frameworks (MOFs), which are Organic-inorganic hybrid materials with intramolecular pores formed by self-assembly of Organic ligands and Metal ions or clusters through coordination bonds.
One of the main safety issues with respect to nuclear power is the management of nuclear waste and its possible leaks in the event of a catastrophic failure. In chernobiles and fukushima accidents, the uncontrolled diffusion of dangerous radionuclides into the air, soil and ocean poses a serious threat to the environment and human health. Among the radioactive species, the species of the radioactive species,129i and131the I isotope is of particular concern. Although it is used for129The half-life of I is relatively long (t)1/2＝1.57×107Year) challenging, but short half-life131I(t1/2Day 8) due to its high ionizing radiation (energy of beta particles is 606 keV; the energy of the gamma particles is 364keV) is also threatening the environmental safety. In addition, the two iodine isotopes are highly volatile and easily bioaccumulate in the thyroid gland of human, which may cause thyroid cancer. Therefore, there is an urgent need to remove radioactive iodine from nuclear waste streams.
Adsorption is an important process for capturing radioactive iodine from plant off-gases and liquid streams. Therefore, various adsorbents have been developed and effective capture of I has been carried out2The test of (1). Currently, Activated Carbon (AC) is widely used as an adsorbent in nuclear power plants. However, it should be noted that the AC must be impregnated with metal compounds (e.g., KI, PI) prior to use2) Or organic amines (e.g., diethanolamine, triethylenediamine). Due to precipitation of AgI (K)sp＝8.52×10－17) Formation of Ag exchanged zeolites in Capture I2The method has a good prospect in aspects. But I2Has an absorption capacity of less than 200mg/g and Ag+Random distribution of ions limits I2The absorption rate of (c). In recent years, MOFs materials have been considered as promising I due to their high specific surface area, uniform pore distribution and multiple functionalities2The candidate material is captured.
Disclosure of Invention
The invention aims to prepare a novel Zr-MOFs material and a preparation method thereof aiming at the problem of radioactive iodine adsorption. The method for preparing the Zr-MOFs material has the advantages that the steps are easy to control and simple to operate, and the prepared Zr-MOFs material is applied to radioactive iodine adsorption, so that the adsorption effect is good.
The equilibrium adsorption rate of the Zr-MOFs material prepared by the method on solid iodine is 1.5-2.5 g/g; the equilibrium adsorption rate of the liquid iodine is 80-95%.
The invention relates to a method for preparing a metal organic framework material with a basic functional group, which comprises the following steps:
firstly, ultrasonically dissolving in a reaction kettle of a solvothermal method to prepare a mixed solution;
putting a zirconium source, an organic ligand, an organic solvent and an acid liquor into a reaction kettle, performing ultrasonic treatment for 30-100 min, then fully dissolving, and then heating and reacting at 60-120 ℃ for 24-72 h to prepare a mixed solution containing Zr-MOFs solid;
the dosage is as follows: adding 0.2-0.9 g of zirconium source, 0.5-0.7 g of organic ligand and 1.5-4.5 mL of acid solution into 100mL of organic solvent;
the source of zirconium being zirconium tetrachloride (ZrCl)4) Zirconium dioxide (ZrO)2) Or zirconium nitrate (Zr (NO)3)4)；
The organic ligand is 2-amino-4, 4' -biphenyldicarboxylic acid (C)14H11NO4)；
The organic solvent is DMF (N, N-dimethylformamide, C)3H7NO), N-diethylformamide (C)5H11NO) or acetone (C)6H6O)；
The acid solution is hydrochloric acid or sulfuric acid; the mass fraction concentration of the hydrochloric acid (HCl) is 37 wt%; the sulfuric acid (H)2SO4) The mass fraction concentration of (A) is 98 wt%;
step two, centrifugally separating and taking precipitate;
step 21, transferring the mixed liquid of the Zr-MOFs solid prepared in the step one to a centrifugal tube for centrifugal separation, and taking a precipitate to obtain a precipitate AA;
centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 22, adding 60-80 mL of DMF into the precipitate AA, performing centrifugal separation, and taking the precipitate to obtain a precipitate AB;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 23, adding 60-80 mL of DMF into the precipitate AB, performing centrifugal separation, and taking the precipitate to obtain a precipitate AC;
centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 24, adding 60-80 mL of DMF into the precipitate AC, performing centrifugal separation, and taking the precipitate to obtain a precipitate AD;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step three, carrying out second centrifugal separation to obtain a precipitate;
31, transferring the mixed solution prepared in the second step to a centrifugal tube for centrifugal separation, and taking a precipitate to obtain a precipitate BA;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 32, adding 60-80 mL of acetone into the precipitate BA, performing centrifugal separation, and taking the precipitate to obtain a precipitate BB;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 33, adding 60-80 mL of acetone into the precipitate BB, performing centrifugal separation, and taking the precipitate to obtain a precipitate BC;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 34, adding 60-80 mL of acetone into the precipitate BC, then carrying out centrifugal separation, and taking the precipitate to obtain a precipitate BD;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 35, transferring the precipitate BD back to the reaction kettle, adding 80-100 mL of acetone, and heating and reacting at 60-120 ℃ for 24-72 h to obtain a mixed solution containing the Zr-MOFs material;
step four, drying treatment;
step 41, transferring the mixed liquid containing the Zr-MOFs material prepared in the step three to a centrifugal tube, centrifuging for 3-10 min at the rotating speed of 5000-12000 r/min, standing for 30-100 min, and separating to obtain a solid product;
and step 42, drying the solid product at the temperature of 80-100 ℃ for 24-72 h to obtain the zirconium-based metal organic framework material, namely the Zr-MOFs material.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of the Zr-MOFs material prepared in example 1.
FIG. 2 is a graph of the pore size distribution of the powder of the zirconium-based metal organic framework material prepared in example 1.
FIG. 3 shows powder N of a zirconium-based metal organic framework material prepared in example 12Adsorption-desorption isotherms.
FIG. 4 is an adsorption curve of gaseous iodine by the Zr-MOFs material prepared in example 1.
FIG. 5 is a powder X-ray diffraction pattern of the Zr-MOFs material prepared in example 2.
FIG. 6 is an adsorption curve of Zr-MOFs material prepared in example 2 for iodine in solution.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The preparation method of the Zr-MOFs material comprises the following steps:
firstly, ultrasonically dissolving in a reaction kettle of a solvothermal method to prepare a mixed solution;
putting a zirconium source, an organic ligand, an organic solvent and an acid liquor into a reaction kettle, carrying out ultrasonic treatment for 30-100 min, then fully dissolving, and then heating and reacting at 60-120 ℃ for 24-72 h to obtain a mixed solution containing Zr-MOFs solids.
The dosage is as follows: adding 0.2-0.9 g of zirconium source, 0.5-0.7 g of organic ligand and 1.5-4.5 mL of acid solution into 100mL of organic solvent.
In the present invention, the zirconium source is zirconium tetrachloride (ZrCl)4) Zirconium dioxide (ZrO)2) Or zirconium nitrate (Zr (NO)3)4)。
In the present invention, the organic ligand is 2-amino-4, 4' -biphenyldicarboxylic acid (C)14H11NO4)。
In the present invention, the organic solvent is DMF (N, N-dimethylformamide, C)3H7NO), N-diethylformamide (C)5H11NO) or acetone (C)6H6O)。
In the present invention, the acid solution is hydrochloric acid or sulfuric acid; the mass fraction concentration of the hydrochloric acid (HCl) is 37 wt%; the sulfuric acid (H)2SO4) The mass fraction concentration of (D) is 98 wt%.
Step two, centrifugally separating and taking precipitate;
step 21, transferring the mixed liquid of the Zr-MOFs solid prepared in the step one to a centrifugal tube for centrifugal separation, and taking a precipitate to obtain a precipitate AA;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 22, adding 60-80 mL of DMF into the precipitate AA, performing centrifugal separation, and taking the precipitate to obtain a precipitate AB;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 23, adding 60-80 mL of DMF into the precipitate AB, performing centrifugal separation, and taking the precipitate to obtain a precipitate AC;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 24, adding 60-80 mL of DMF into the precipitate AC, performing centrifugal separation, and taking the precipitate to obtain a precipitate AD;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
in the present invention, the precipitate extracted by the separation technique of centrifugation with DMF addition 3 or more times is to remove the unreacted 2-amino-4, 4' -biphenyldicarboxylic acid (C)14H11NO4)。
And step 25, transferring the precipitate AD back to the reaction kettle, adding 60-80 mL of DMF, and heating and reacting at 60-120 ℃ for 24-72 h to obtain a mixed solution.
Step three, carrying out second centrifugal separation to obtain a precipitate;
31, transferring the mixed solution prepared in the second step to a centrifugal tube for centrifugal separation, and taking a precipitate to obtain a precipitate BA;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 32, adding 60-80 mL of acetone into the precipitate BA, performing centrifugal separation, and taking the precipitate to obtain a precipitate BB;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 33, adding 60-80 mL of acetone into the precipitate BB, performing centrifugal separation, and taking the precipitate to obtain a precipitate BC;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 34, adding 60-80 mL of acetone into the precipitate BC, then carrying out centrifugal separation, and taking the precipitate to obtain a precipitate BD;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
in the present invention, the precipitate is extracted by a separation technique of 3 or more times of centrifugation with acetone added thereto in order to remove DMF molecules coated in the MOF pore channels.
And step 35, transferring the precipitate BD back to the reaction kettle, adding 80-100 mL of acetone, and heating and reacting at 60-120 ℃ for 24-72 h to obtain a mixed solution containing the Zr-MOFs material.
Step four, drying treatment;
step 41, transferring the mixed liquid containing the Zr-MOFs material prepared in the step three to a centrifugal tube, centrifuging for 3-10 min at the rotating speed of 5000-12000 r/min, standing for 30-100 min, and separating to obtain a solid product;
and step 42, drying the solid product at the temperature of 80-100 ℃ for 24-72 h to obtain the zirconium-based metal organic framework material, namely the Zr-MOFs material.
Iodine adsorption Properties
In the invention, the Zr-MOFs material and the solid iodine are placed in a reagent bottle, a cover is covered, and then the reagent bottle is placed in an oven to carry out an adsorption test at the temperature of 80 ℃. After a plurality of tests (the adsorption time is respectively 2h, 4h, 8h, 12h, 16h, 24h and 48h), the equilibrium adsorption rate of the Zr-MOFs material to the solid iodine is 1.5-2.5 g/g. Putting the Zr-MOFs material in a brown centrifugal tube, adding an iodocyclohexylamine solution, and sealing. And (3) performing an adsorption experiment on an oscillator platform shaker, and obtaining the equilibrium adsorption rate of the Zr-MOFs material to the liquid iodine of 80-95% after a plurality of experiments (the adsorption time is respectively 2h, 4h, 8h, 12h and 24 h).
Example 1
Firstly, ultrasonically dissolving in a reaction kettle of a solvothermal method to prepare a mixed solution;
0.447g of ZrCl4(Shanghai Michelin Biochemical technology Ltd.) 0.613g of C14H11NO4Subjecting 100mL of DMF (Shanghai Qianling Biotechnology Co., Ltd.), and 3.3mL of hydrochloric acid (37 wt% in terms of mass fraction, modern east (Beijing) science and technology development Co., Ltd.) to ultrasonic treatment in a reaction kettle for 50min to dissolve completely, and heating at 80 deg.C for 24h to obtain the final productObtaining mixed liquid containing Zr-MOFs solid.
Organic ligand C used in example 114H11NO4The structural formula of (A) is:
step two, centrifuging and taking a precipitate;
step 21, transferring the mixed liquid of the Zr-MOFs solid prepared in the step one to a centrifugal tube for centrifugal separation, and taking a precipitate to obtain a precipitate AA;
centrifugal separation conditions: centrifuging at 10000r/min for 5min, and standing for 30 min;
step 22, adding 70mL of DMF into the precipitate AA, performing centrifugal separation, and taking the precipitate to obtain a precipitate AB;
and (3) centrifugal separation conditions: centrifuging at 12000r/min for 3min, and standing for 30 min;
step 23, adding 70mL of DMF into the precipitate AB, and then carrying out centrifugal separation to obtain a precipitate, namely a precipitate AC;
and (3) centrifugal separation conditions: centrifuging at a rotation speed of 5000r/min for 10min, and standing for 50 min;
step 24, adding 70mL of DMF into the precipitate AC, performing centrifugal separation, and taking the precipitate to obtain a precipitate AD;
and (3) centrifugal separation conditions: centrifuging at a rotation speed of 5000r/min for 10min, and standing for 50 min;
Step three, carrying out second centrifugal separation to obtain a precipitate;
31, transferring the mixed solution prepared in the second step to a centrifugal tube for centrifugal separation to obtain a precipitate BA;
step 32, adding 70mL of acetone (Beijing chemical plant) into the precipitate BA, then carrying out centrifugal separation, and taking the precipitate to obtain a precipitate BB;
step 33, adding 70mL of acetone into the precipitate BB, and then performing centrifugal separation to obtain a precipitate BC;
step 34, adding 70mL of acetone into the precipitate BC, and then carrying out centrifugal separation to obtain a precipitate BD;
step 31 to step 34 adopt the same centrifugal separation condition, namely centrifugal separation is carried out for 5min at the rotating speed of 10000r/min, and standing is carried out for 30 min;
and step 35, transferring the precipitate BD back into the reaction kettle, adding 100mL of acetone, and heating at 60 ℃ for reaction for 72 hours to obtain a mixed solution containing the Zr-MOFs material.
Step four, drying treatment;
step 41, transferring the mixed liquid containing the Zr-MOFs material prepared in the step three to a centrifugal tube, centrifuging for 10min at the rotating speed of 10000r/min, standing for 30min, and separating to obtain a solid product;
and 42, drying the solid product at the temperature of 80 ℃ for 24 hours to obtain the zirconium-based metal organic framework material, namely the Zr-MOFs material.
In the invention, the prepared Zr-MOFs material is also commonly known as UiO-67-NH2。
Characterization of Properties
The Zr — MOFs material obtained in example 1 was subjected to X-ray examination, and the powder X-ray diffraction pattern shown in fig. 1 had characteristic peaks at 2 θ of 5.73 °,6.61 °,9.35 °,10.97 ° and 11.48 °, respectively.
The obtained Zr-MOFs material is further subjected to a total micropore specific surface area test by adopting a BET (BET surface area) test method, and the measured specific surface area is 863m2(ii) in terms of/g. As shown in fig. 2, there are 2 pore sizes with 1.25nm and 2.2 nm.
UiO-67-NH as shown in FIG. 32Material powder N2Adsorption-desorption isotherms, which show the UiO-67-NH prepared by the method of example 12Micropores and mesopores exist in the material.
Iodine adsorption Property
300mg of the Zr-MOFs material of the present invention and 30mg of solid iodine were placed in a reagent bottle, the lid was closed, and then the reagent bottle was placed in an oven to perform an adsorption test at 80 ℃. After a plurality of tests (the adsorption time is respectively 2h, 4h, 8h, 12h, 16h, 24h and 48h), the equilibrium adsorption rate performance of the Zr-MOFs material is obtained. As shown in FIG. 4, the equilibrium adsorption ratio of the Zr-MOFs material was 1.91 g/g. Compared with the organic ligand without-NH2The UiO-67 of (A) improves the equilibrium adsorption rate by about 0.62 g/g.
The molecular formula of UiO-67 is C84H52O32Zr6. UiO-67 is a metal organic framework material. UiO is an abbreviation for Norway language of the university of Oslo (Universal site i Oslo). It can be obtained by reacting 4, 4' -biphenyldicarboxylic acid with zirconium tetrachloride in N, N-dimethylformamide solvent at 120 ℃.
UiO-67-NH prepared in example 12The coordination polymerization organic material is formed by self-assembly of Zr metal center and multidentate organic ligand through coordination bond connection. UiO-67-NH2Has extremely high specific surface area (up to 863 m)2/g) and porosity, and has the characteristics of adjustable pore channels and structural diversity, and is easy to design, assemble and structurally adjust, so that the catalyst has unique advantages in the selective adsorption of gaseous iodine or liquid iodine, and UiO-67-NH under high temperature and high acid atmosphere2The structure can not be collapsed and damaged, and the adsorption performance of the structure to iodine is not influenced. In addition, the preparation process provided by the invention can realize large-scale production, the process operation is controllable, and the production cost is low.
Example 2
Firstly, ultrasonically dissolving in a reaction kettle of a solvothermal method to prepare a mixed solution;
0.82g of Zr (NO)3)4(Shanghai Michelin Biochemical technology Ltd.) 0.613g of C14H11NO4100mL of DMF and 1.6mL of sulfuric acid (with a mass fraction concentration of 98 wt%, from the modern east (Beijing) science and technology development Co., Ltd.) were placed in a reaction vessel for ultrasonic treatment for 30min and then sufficiently dissolved, followed by heating reaction at 60 deg.CAnd preparing a mixed solution containing Zr-MOFs solid after 70 hours.
Step two, centrifugally separating and taking precipitate;
step 21, transferring the mixed liquid of the Zr-MOFs solid prepared in the step one to a centrifugal tube for centrifugal separation, and taking a precipitate to obtain a precipitate AA;
centrifugal separation conditions: centrifuging at 8000r/min for 5min, and standing for 30 min;
step 22, adding 70mL of DMF into the precipitate AA, performing centrifugal separation, and taking the precipitate to obtain a precipitate AB;
and (3) centrifugal separation conditions: centrifuging at 10000r/min for 8min, and standing for 40 min;
after repeating step 22 twice, the obtained precipitate was transferred back to the reaction kettle, and 100mL of DMF was added, followed by heating at 80 ℃ for 36h to obtain a mixed solution.
Step three, carrying out second centrifugal separation to obtain a precipitate;
31, transferring the mixed solution prepared in the second step to a centrifugal tube for centrifugal separation, and taking a precipitate to obtain a precipitate BA;
and (3) centrifugal separation conditions: centrifuging at 6000r/min for 10min, and standing for 50 min;
step 32, adding 70mL of acetone into the precipitate BA, performing centrifugal separation, and taking the precipitate to obtain a precipitate BB;
and (3) centrifugal separation conditions: centrifuging at 12000r/min for 3min, and standing for 30 min;
after the step 32 is repeatedly executed twice, the obtained precipitate is transferred back to the reaction kettle, 100mL of acetone is added, and then the mixture is heated and reacted for 24 hours at 80 ℃ to obtain a mixed solution containing the Zr-MOFs material.
Step four, drying treatment;
step 41, transferring the mixed liquid containing the Zr-MOFs material prepared in the step three to a centrifuge tube, centrifuging for 5min at the rotating speed of 7000r/min, standing for 50min, and separating to obtain a solid product;
and 42, drying the solid product at the temperature of 80 ℃ for 60 hours to obtain the zirconium-based metal organic framework material, namely the Zr-MOFs material.
As shown in the powder X-ray diffraction pattern of FIG. 5, the zeolite molecular sieve prepared in example 2 had characteristic peaks at 5.73 °,6.61 °,9.35 °,10.97 ° and 11.48 °, respectively, and the specific surface area of the thus-prepared zirconium-based metal-organic framework material was further measured by the BET method to obtain a specific surface area of 860m2(ii) in terms of/g. The material structure has 2 kinds of pore canals with the sizes of 1.30nm and 2.30nm respectively.
Iodine adsorption Property
As shown in FIG. 6, 450mg of the Zr-MOFs material of the present invention was put into a 10mL brown centrifuge tube, 10mL of iodocyclohexylamine solution (concentration: 0.001mol/L) was added, and the tube was sealed with a sealing film. And (3) transversely placing the brown centrifugal tube on an oscillator platform shaker, shaking at room temperature at the rotating speed of 250r/min, and respectively adsorbing for 2h, 4h, 8h, 12h and 24 h. Finally, the adsorption rate of 89.71% is obtained after 24 h.
Example 3
Firstly, ultrasonically dissolving in a reaction kettle of a solvothermal method to prepare a mixed solution;
0.236g of ZrO2(Shanghai Maxin Biochemical technologies, Ltd.) 0.613g of C14H11NO4And then 100mL of acetone and 3.3mL of hydrochloric acid (the mass fraction concentration is 37 wt%) are placed in a reaction kettle for ultrasonic treatment for 40min to be fully dissolved, and then the mixture is heated and reacted for 36h at the temperature of 100 ℃ to prepare a mixed solution containing Zr-MOFs solids.
Step two, centrifuging and taking a precipitate;
step 21, transferring the mixed liquid of the Zr-MOFs solid prepared in the step one to a centrifugal tube for centrifugal separation, and taking a precipitate to obtain a precipitate AA;
centrifugal separation conditions: centrifuging at a rotation speed of 5000r/min for 10min, and standing for 30 min;
step 22, adding 80mL of DMF into the precipitate AA, then carrying out centrifugal separation, and taking the precipitate to obtain a precipitate AB;
and (3) centrifugal separation conditions: centrifuging at 6000r/min for 8min, and standing for 30 min;
step 23, adding 70mL of DMF into the precipitate AB, and then carrying out centrifugal separation to obtain a precipitate, namely a precipitate AC;
and (3) centrifugal separation conditions: centrifuging at 7000r/min for 6min, and standing for 30 min;
step 24, adding 60mL of DMF into the precipitate AC, performing centrifugal separation, and taking the precipitate to obtain a precipitate AD;
and (3) centrifugal separation conditions: centrifuging at 8000r/min for 3min, and standing for 30 min;
in the present invention, the precipitate extracted by the separation technique of centrifugation with DMF addition 3 times or more is to remove the unreacted 2-amino-4, 4' -biphenyldicarboxylic acid.
Step three, carrying out second centrifugal separation to obtain a precipitate;
31, transferring the mixed solution prepared in the second step to a centrifugal tube for centrifugal separation, and taking a precipitate to obtain a precipitate BA;
and (3) centrifugal separation conditions: centrifuging at 12000r/min for 3min, and standing for 30 min;
step 32, adding 60mL of acetone into the precipitate BA, performing centrifugal separation, and taking the precipitate to obtain a precipitate BB;
and (3) centrifugal separation conditions: centrifuging at 10000r/min for 5min, and standing for 50 min;
step 33, adding 60mL of acetone into the precipitate BB, and then performing centrifugal separation to obtain a precipitate BC;
and (3) centrifugal separation conditions: centrifuging at 8000r/min for 7min, and standing for 50 min;
step 34, adding 60mL of acetone into the precipitate BC, and then carrying out centrifugal separation to obtain a precipitate BD;
and (3) centrifugal separation conditions: centrifuging at a rotation speed of 5000r/min for 10min, and standing for 50 min;
in the present invention, the precipitate is extracted by a separation technique of 3 or more times of centrifugation with acetone added thereto in order to remove DMF molecules coated in the MOF pore channels.
And step 35, transferring the precipitate BD back to the reaction kettle, adding 100mL of acetone, and heating at 100 ℃ for reaction for 36 hours to obtain a mixed solution containing the Zr-MOFs material.
Step four, drying treatment;
step 41, transferring the mixed liquid containing the Zr-MOFs material prepared in the step three to a centrifuge tube, centrifuging for 5min at the rotating speed of 8000r/min, standing for 40min, and separating to obtain a solid product;
and 42, drying the solid product at the temperature of 100 ℃ for 40 hours to obtain the zirconium-based metal organic framework material, namely the Zr-MOFs material.
Iodine adsorption Property
In the present invention, 300mg of the Zr-MOFs material of the present invention and 30mg of solid iodine were placed in a reagent bottle, the lid was closed, and then the reagent bottle was placed in an oven to perform an adsorption test at 80 ℃. After a plurality of tests (the adsorption time is respectively 2h, 4h, 8h, 12h, 16h, 24h and 48h), the equilibrium adsorption rate of the Zr-MOFs material is 1.89 g/g.
Among the numerous metal organic framework Materials (MOFs), Zr-based MOFs are a promising radioiodine capture material for the following reasons. First, Zr-MOFs exhibit high thermal and mechanical stability due to their high number of metal coordination bonds. For example, the UiO series of Zr-MOFs (e.g., UiO-66) not only maintain structural integrity at 500 ℃ but are also stable in aqueous and acidic solutions. And secondly, the Zr-MOFs has large porosity, is beneficial to encapsulation of iodine and improves the adsorption capacity. Third, the carboxylic acid ligands may be modified with different electron donating groups (e.g., -NH)2SH, pyridine), enhance the interaction between host and object, accelerate I2And (4) an adsorption process.
The above description is only for the purpose of illustrating the embodiments of the present invention, and the scope of protection is not limited thereto, and any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of protection of the present invention.
Claims (6)
1. A metal-organic framework material having basic functional groups, characterized by: the metal organic framework material with basic functional groups is UiO-67-NH2And (4) preparing the system.
2. A method for preparing a metal organic framework material having a basic functional group, comprising the steps of:
firstly, ultrasonically dissolving in a reaction kettle of a solvothermal method to prepare a mixed solution;
putting a zirconium source, an organic ligand, an organic solvent and an acid liquor into a reaction kettle, performing ultrasonic treatment for 30-100 min, then fully dissolving, and then heating and reacting at 60-120 ℃ for 24-72 h to prepare a mixed solution containing Zr-MOFs solid;
the dosage is as follows: adding 0.2-0.9 g of zirconium source, 0.5-0.7 g of organic ligand and 1.5-4.5 mL of acid liquor into 100mL of organic solvent;
the source of zirconium being zirconium tetrachloride (ZrCl)4) Zirconium dioxide (ZrO)2) Or zirconium nitrate (Zr (NO)3)4)；
The organic ligand is 2-amino-4, 4' -biphenyldicarboxylic acid (C)14H11NO4)；
The organic solvent is DMF (N, N-dimethylformamide, C)3H7NO), N-diethylformamide (C)5H11NO) or acetone (C)6H6O)；
The acid solution is hydrochloric acid or sulfuric acid; the mass fraction concentration of the hydrochloric acid (HCl) is 37 wt%; the sulfuric acid (H)2SO4) The mass fraction concentration of (A) is 98 wt%;
step two, centrifugally separating and taking precipitate;
step 21, transferring the mixed liquid of the Zr-MOFs solid prepared in the step one to a centrifugal tube for centrifugal separation, and taking a precipitate to obtain a precipitate AA;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 22, adding 60-80 mL of DMF into the precipitate AA, performing centrifugal separation, and taking the precipitate to obtain a precipitate AB;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 23, adding 60-80 mL of DMF into the precipitate AB, performing centrifugal separation, and taking the precipitate to obtain a precipitate AC;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 24, adding 60-80 mL of DMF into the precipitate AC, performing centrifugal separation, and taking the precipitate to obtain a precipitate AD;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 25, transferring the precipitate AD back to the reaction kettle, adding 60-80 mL of DMF, and heating and reacting at 60-120 ℃ for 24-72 h to obtain a mixed solution;
step three, carrying out second centrifugal separation to obtain a precipitate;
step 31, transferring the mixed solution prepared in the step two to a centrifugal tube for centrifugal separation, and taking a precipitate to obtain a precipitate BA;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 32, adding 60-80 mL of acetone into the precipitate BA, performing centrifugal separation, and taking the precipitate to obtain a precipitate BB;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 33, adding 60-80 mL of acetone into the precipitate BB, performing centrifugal separation, and taking the precipitate to obtain a precipitate BC;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 34, adding 60-80 mL of acetone into the precipitate BC, then carrying out centrifugal separation, and taking the precipitate to obtain a precipitate BD;
and (3) centrifugal separation conditions: carrying out centrifugal separation for 3-10 min at the rotating speed of 5000-12000 r/min, and standing for 30-100 min;
step 35, transferring the precipitate BD back into a reaction kettle, adding 80-100 mL of acetone, and heating and reacting at 60-120 ℃ for 24-72 h to obtain a mixed solution containing the Zr-MOFs material;
step four, drying treatment;
step 41, transferring the mixed liquid containing the Zr-MOFs material prepared in the step three to a centrifugal tube, centrifuging for 3-10 min at the rotating speed of 5000-12000 r/min, standing for 30-100 min, and separating to obtain a solid product;
and step 42, drying the solid product at the temperature of 80-100 ℃ for 24-72 h to obtain the zirconium-based metal organic framework material, namely the Zr-MOFs material.
3. The metal-organic framework material having basic functional groups and the method for preparing the same according to claim 1, wherein: the prepared metal organic framework material with basic functional groups is UiO-67-NH2And (4) preparing the system.
4. The metal-organic framework material having basic functional groups and the method for preparing the same according to claim 1, wherein: the equilibrium adsorption rate of the prepared metal organic framework material with basic functional groups to solid iodine is 1.0-2.5 g/g.
5. The metal-organic framework material having basic functional groups and the method for preparing the same according to claim 1, wherein: the equilibrium adsorption rate of the prepared metal organic framework material with the basic functional group to liquid iodine is 80-95%.
6. The metal-organic framework material having basic functional groups and the method for preparing the same according to claim 1, wherein: micropores and mesopores exist in the prepared metal organic framework material with the basic functional group.
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