CN117024752A - Thorium-based metal organic framework material containing hexanuclear nickel clusters, and preparation method and application thereof - Google Patents
Thorium-based metal organic framework material containing hexanuclear nickel clusters, and preparation method and application thereof Download PDFInfo
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- 229910052776 Thorium Inorganic materials 0.000 title claims abstract description 70
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 69
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 title claims abstract description 68
- 150000002815 nickel Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000013078 crystal Substances 0.000 claims abstract description 43
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
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- 238000000634 powder X-ray diffraction Methods 0.000 description 10
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- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- 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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- 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
- 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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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/39—Actinides
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a thorium-based metal organic framework material containing hexanuclear nickel clusters, a preparation method and application thereof, and the chemical formula is [ Ni ] 6 Cl 10 (H 2 O) 6 Th 6 (μ 3 ‑O) 4 (μ 3 ‑OH) 4 (BPYDC) 6 (H 2 O) 6 ·Cl 2 ]·G 1 Wherein BPYDC is 2,2 '-bipyridine-4, 4' -dicarboxylic acid radical ion, G 1 Is a guest molecule; the thorium-based metal organic framework material containing the hexanuclear nickel cluster belongs to a cubic crystal system, the space group is Pa-3, and the unit cell parameters are as follows: α＝β＝γ＝90°，the metal organic framework material is prepared by impregnating a thorium-based metal organic framework with a solution containing NiCl 2 ·6H 2 And (3) reacting in diethylene glycol dimethyl ether solution of O at 90-110 ℃ to prepare the thorium-based metal organic framework material containing hexanuclear nickel clusters. The thorium-based metal organic framework material containing the hexanuclear nickel cluster has good chemical stability and thermal stability, simple synthesis process and mild condition, and the crystallization of the crystal is good, can be prepared in batches, and has good application prospect in the fields of catalysis, magnetic materials and the like.
Description
Technical Field
The invention relates to the technical field of metal organic frame materials, in particular to a thorium-based metal organic frame material containing hexanuclear nickel clusters, and a preparation method and application thereof.
Background
The development of thorium chemistry has important theoretical significance for uranium mining, nuclear fuel recycling and nuclear waste disposal, however, the research on thorium is less at present, and especially the structure and application research of thorium are more deficient. Thorium-based metal-organic frameworks (Th-MOFs) materials have received much attention in recent years, and the diversity of coordination chemistry and boundary orbitals that are rich in thorium elements compared to conventional transition metal or rare earth metal MOFs makes thorium-based MOFs have a rich secondary building block and structural complexity.
However, to date, thorium-based MOFs materials containing polynuclear transition metal clusters have not been reported, limiting the development of thorium-based MOFs materials. Jeffrey R.Long et al report the construction of polynuclear nickel clusters into zirconium-based MOFs materials such that the MOFs materials exhibit different magnetic behaviors, including the large spin ground state (Nature, 2020,577,64-68) that isolates ferromagnetic couplings by eliminating long-range interlayer magnetic ordering. Furthermore, luo Feng et al report that mononuclear nickel-modified thorium-based MOFs exhibit better electrocatalytic Oxygen Evolution (OER) performance (ACS Catal.2022,12, 9101-9113). Gao Zhi et al Ni 2+ Post-modification into Fe-MIL-53 greatly improves the OER performance of MOF materials (chem. Eng. J.2023,462, 142179). Synergistic effects among a plurality of nickel atoms of polynuclear nickel clusters have also been reported, and further improvement of OER performance is expected (chem. Soc. Rev.2022,51, 8923-8956).
The thorium-based MOFs have higher stability and larger monocrystal size, so that the crystal structure characterization after the nickel cluster is modified is facilitated, and the preparation of the thorium-based MOFs with polynuclear nickel cluster modification is expected, so that the application of the thorium-based MOFs in the aspects of electrocatalysis and magnetic materials is promoted.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a thorium-based metal organic framework material containing hexanuclear nickel clusters, a preparation method and application thereof, wherein the thorium-based metal organic framework material is immersed in a metal-organic framework material containing NiCl 2 ·6H 2 The thorium-based metal organic framework material crystal containing the hexanuclear nickel cluster can be prepared by reaction in a specific solvent of O, has good crystallinity and repeatability, can be prepared in batches, has outstanding chemical stability and thermal stability, and has good application prospect in the aspects of photoelectrocatalysis, magnetic materials and the like.
In order to solve the technical problems, the invention provides the following technical scheme:
the first aspect of the invention provides a thorium-based metal organic framework material containing hexanuclear nickel clusters, which has the chemical formula of [ Ni ] 6 Cl 10 (H 2 O) 6 Th 6 (μ 3 -O) 4 (μ 3 -OH) 4 (BPYDC) 6 (H 2 O) 6 ·Cl 2 ]·G 1 Wherein BPYDC is 2,2 '-bipyridine-4, 4' -dicarboxylic acid radical ion, G 1 Is a guest molecule;
the thorium-based metal organic framework material containing the hexanuclear nickel cluster belongs to a cubic crystal system, the space group is Pa-3, and the unit cell parameters are as follows:α＝β＝γ＝90°，/>
further, the guest molecule is diethylene glycol dimethyl ether and water; specifically, in some preferred embodiments of the invention, the G 1 Is (C) 6 H 14 O 3 ) 7 (H 2 O) 36 。
The second aspect of the invention provides a preparation method of the thorium-based metal organic framework material containing the hexanuclear nickel cluster, which comprises the steps ofSingle crystal impregnated with NiCl-containing material 2 ·6H 2 In diethylene glycol dimethyl ether solution of O, reacting to prepare the thorium-based metal organic framework material containing the hexanuclear nickel cluster;
the chemical formula of the thorium metal organic framework material is [ Th ] 6 (μ 3 -O) 4 (μ 3 -OH) 4 (BPYDC) 6 (H 2 O) 6 ]·G 2 Wherein BPYDC is 2,2 '-bipyridine-4, 4' -dicarboxylic acid radical ion, G 2 Is a guest molecule; the thorium-based metal organic framework material belongs to a cubic crystal system, the space group is Fm-3m, and the unit cell parameters are as follows:α＝β＝γ＝90°，/>
further, the G 2 Can be (DMF) x (H 2 O) y ，x、y≥0。
The inventors have unexpectedly found during the course of experiments that single crystals of thorium-based metal organic framework materials were impregnated with NiCl-containing materials 2 ·6H 2 O in diethylene glycol dimethyl ether solution, and reacting at a certain temperature, thus obtaining the thorium-based metal organic framework material containing hexanuclear nickel clusters; and when the solvent diethylene glycol dimethyl ether is replaced by solvents such as methanol, ethanol, tetrahydrofuran, N-dimethylformamide, acetonitrile and the like, the thorium-based metal organic framework material containing the hexanuclear nickel cluster cannot be obtained. In addition, the inventor verifies for tens times that the thorium-based metal organic framework material containing the hexanuclear nickel cluster can be stably prepared by the method, and the obtained crystal has good crystallinity and good repeatability.
Further, during the impregnation process, the NiCl-containing material 2 ·6H 2 NiCl in diethylene glycol dimethyl ether solution of O 2 ·6H 2 O remains supersaturated, i.e. always present in solutionUndissolved NiCl 2 ·6H 2 O solid.
Further, the temperature of the reaction is preferably 90 to 110 ℃, for example 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, etc., including but not limited to the temperature values listed above; the reaction time is preferably 30 to 40 days. The inventor finds through a comparison experiment that if the reaction temperature is reduced to below 90 ℃, the reaction is shorter than 30 days, and the post-modified nickel clusters cannot form hexanuclear nickel clusters; if the reaction temperature is set above 110 ℃, the organic solution is overheated, which is unfavorable for the reaction under normal pressure, and the reaction glass bottle is extremely easy to explode. Therefore, the reaction temperature needs to be controlled to a suitable range, for example, 90 to 110 ℃.
Further, the preparation method of the thorium-based metal organic framework material comprises the following steps: will H 2 BPYDC and Th (NO) 3 ) 4 ·6H 2 O reacts in the presence of an acidic regulator and an organic solvent to obtain the thorium metal organic framework.
Further, the H 2 BPYDC and Th (NO) 3 ) 4 ·6H 2 The feeding mole ratio of O is 1:2-1:3; the acidity regulator is one or more of trifluoroacetic acid, formic acid or nitric acid; adding water while adding an acid regulator, wherein the volume ratio of the acid regulator to the water is 0.8-1.2: 0.3 to 0.5. In the process of preparing the thorium-based metal organic framework material, on one hand, an acid regulator is added to slow down the growth of single crystals, so that large-size high-quality single crystals are obtained; meanwhile, a small amount of water is added into the system to regulate the size and yield of the crystals, and if no water is added, the prepared crystals have smaller size and low yield.
Further, H 2 BPYDC and Th (NO) 3 ) 4 ·6H 2 The reaction temperature of O in the presence of an acid regulator and an organic solvent is 100-120 ℃, and the reaction time is 3-5 days.
In some embodiments of the invention, H 2 BPYDC and Th (NO) 3 ) 4 ·6H 2 O is dissolved in 5-10 mL of DMF, after ultrasonic homogenization, 0.8-1.2 mL of trifluoroacetic acid and 0.3-0.5 mL of water are added to obtain a mixed solution, and the mixed solution is added in an amount of 100And (3) reacting for 3-5 days at 120 ℃, cooling and filtering to obtain crystals of the thorium-based metal organic framework material after the reaction is completed.
The third aspect of the invention provides the application of the thorium-based metal organic framework material containing the hexanuclear nickel cluster in catalysis and magnetic materials.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a novel thorium-based metal organic framework material containing hexanuclear nickel clusters, which is prepared from thorium-based metal organic framework material (Th-MOF) with specific crystal structure and NiCl 2 ·6H 2 The method is characterized in that the O is synthesized in a specific solvent (diethylene glycol dimethyl ether) by a one-step solvent method, the reaction condition of the synthesis method is mild, nickel ions can be quickly modified into a thorium-based metal organic frame material to form a single thorium-based metal organic frame material containing hexanuclear nickel clusters, the morphology of the monocrystal after the modification of the nickel clusters is basically kept unchanged, and only the color of the monocrystal is changed from colorless to grey green. The prepared crystal has good crystallinity and can accurately control Th 4+ And Ni 2+ Has good repeatability and can be prepared in batches.
2. The thorium-based metal organic framework material containing the hexanuclear nickel cluster prepared by the invention contains one kind of thorium ion and two kinds of nickel ions, th1 and BPYDC from four ligands 2- And two mu are selected from the group consisting of carboxylic acid O atoms and two mu 3 -O, two mu 3 -OH, O atom of a water molecule coordinates to form Th 6 (μ 3 -O) 4 (μ 3 -OH) 4 (H 2 O) 6 (-CO 2 ) 6 A secondary construction unit; ni1 and a ligand BPYDC 2- Two pyridine N atoms and two mu 2 -Cl and one μ 3 Cl atoms of-Cl, O atoms of one coordinated water molecule, ni2 and two μ 2 -Cl, three μ 3 The Cl atom of Cl, the O atom of one coordinated water molecule coordinates to form Ni 6 (μ 3 -Cl) 4 (μ 2 -Cl) 6 (H 2 O) 6 Is a hexagonal nickel cluster of (c). Further such secondary building units, hexanuclear nickel clusters and BPYDC 2- The ligands are linked to form threeAnd a vitamin frame, wherein free chloride ions are also present in the pore canal to maintain the charge balance of the structure. The material has the porosity of 47.2%, excellent chemical stability and thermal stability, can be used under extreme conditions such as acid, alkali, high temperature and the like, has better acid resistance compared with thorium-based metal organic framework materials, and has good application prospect in catalysis and magnetic materials due to the fact that the material contains polynuclear nickel clusters.
Drawings
FIG. 1 is a crystal structure diagram of a thorium-based metal organic framework material containing hexanuclear nickel clusters prepared in example 1 of the present invention;
FIG. 2 is a crystal structure diagram of hexanuclear nickel clusters in the thorium-based metal organic framework material containing hexanuclear nickel clusters prepared in example 1 of the present invention;
FIG. 3 is an X-ray powder diffraction Pattern (PXRD) of a thorium-based metal-organic framework material containing hexanuclear nickel clusters prepared in example 1 of the present invention;
FIG. 4 is an infrared spectrum of a thorium-based metal organic framework material containing hexanuclear nickel clusters prepared in example 1 of the present invention;
FIG. 5 is a thermogravimetric analysis of a thorium-based metal organic framework material containing hexanuclear nickel clusters prepared in example 1 of the present invention;
FIG. 6 is a graph showing the nitrogen adsorption of thorium-based metal organic framework material containing hexanuclear nickel clusters prepared in example 1 of the present invention;
FIG. 7 is a PXRD stack of a hexanuclear nickel cluster-containing thorium-based metal organic framework material prepared in example 1 of the present invention after 24h immersion in aqueous solutions of different pH (1-12);
FIG. 8 is a PXRD stack of a thorium-based metal-organic framework material prepared in example 1 of the present invention after 24h immersion in aqueous solutions of different pH (1-12).
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The test equipment and parameters involved in the following examples are as follows:
characterization test by X-ray powder diffraction: the X-ray powder diffraction data collection was done on a Bruker D8 Advance diffractometer, operating at 40KV, current at 40mA, using graphite-monochromatized copper target X-rays (cukα,) The continuous scanning is completed in the range of 3 ° to 40 °.
Characterization and structural analysis of X-ray single crystal diffraction: selecting single crystals of appropriate size under a microscope, and using Mo-K alpha on a Germany Bruker D8 VENTURE CMOS photon 100diffractometer with helios mxmultilayer single crystal diffractometerAnd collecting at 120K radiation, wherein all crystal data are subjected to Lp factor correction and empirical absorption correction, the absorption correction uses SADABS program, the structure is analyzed by a direct method, then all non-hydrogen atoms on a framework are subjected to anisotropic correction by a full matrix least square method, the coordinates of the hydrogen atoms on all carbons are obtained by theoretical hydrogenation, and then the isotropy correction is performed on the hydrogen atoms.
Simulation of transformation of X-ray powder diffraction spectrum of single crystal structure: mercury software.
Infrared Spectroscopy (IR) using a Thermo Nicolet 6700FTIR spectrometer equipped with a diamond Attenuated Total Reflectance (ATR) accessory, test range 400-4000cm -1 。
Thermogravimetric analysis (TGA) was performed using NETZSCH STA 449F 3 under a nitrogen atmosphere at a heating rate of 10 ℃/min and a test temperature of 30 ℃ to 800 ℃.
The nitrogen adsorption test uses a microphone ASAP 2020 specific surface area and porosity analyzer, N at 77K 2 Adsorption isotherms.
Examples
The embodiment relates to preparation of a thorium-based metal organic framework material (Th-MOF) and a thorium-based metal organic framework material (ThNi-MOF-1) containing hexanuclear nickel clusters, which comprises the following specific operations:
preparation of Th-MOF: the preparation method is the same as that of the embodiment 1 of the patent CN115490872A, and the preparation method is as follows:
(1) Will H 2 BPYDC (19.5 mg,0.08 mmol) and Th (NO) 3 ) 4 ·6H 2 O (94 mg,0.16 mmol) is dissolved in 5mL of N, N-Dimethylformamide (DMF), after ultrasonic homogenization, 0.8mL of trifluoroacetic acid and 0.3mL of water are added to the solution, and ultrasonic treatment is carried out to obtain a mixed solution;
(2) Placing the mixed solution into a reaction kettle, reacting for 5 days at 120 ℃, cooling, and filtering to obtain crystals and filtrate; and collecting crystals, washing the crystals with DMF for three times, and washing the crystals with ethanol for three times to obtain the thorium-based metal organic framework named Th-MOF.
Preparation of ThNi-MOF-1:
impregnating the prepared thorium-based metal organic framework material (Th-MOF) with a solution containing NiCl 2 ·6H 2 O in diethylene glycol dimethyl ether solution, reacting for 30 days at 100 ℃, cooling, filtering to obtain a grey green octahedral monocrystal and filtrate, washing the crystal with acetone, and drying to obtain the thorium-based metal organic framework material containing hexanuclear nickel clusters, which is named as ThNi-MOF-1.
X-ray single crystal diffraction characterization is carried out on the prepared ThNi-MOF-1, and partial parameters of corresponding crystallographic diffraction point data collection and structure refinement are shown in table 1:
TABLE 1 parameters of ThNi-MOF-1 single crystals
The crystal structure analysis result of ThNi-MOF-1 prepared in this example is as follows: thNi-MOF-1 contains one kind of thorium ion and two kinds of nickel ions, and its crystal structure is shown in FIG. 1, th1 and BPYDC from four ligands 2- And two mu are selected from the group consisting of carboxylic acid O atoms and two mu 3 -O, two mu 3 -OH, O atom of a water molecule coordinates to form Th 6 (μ 3 -O) 4 (μ 3 -OH) 4 (H 2 O) 6 (-CO 2 ) 6 A secondary construction unit; ni1 and a ligand BPYDC 2- Two pyridine N atoms and two mu 2 -Cl and one μ 3 Cl atoms of-Cl, O atoms of one coordinated water molecule, ni2 and two μ 2 -Cl, three μ 3 The Cl atom of Cl, the O atom of one coordinated water molecule coordinates to form Ni 6 (μ 3 -Cl) 4 (μ 2 -Cl) 6 (H 2 O) 6 Is shown (fig. 2). Further such secondary building units, hexanuclear nickel clusters and BPYDC 2- The ligands are connected into a three-dimensional framework, free chloride ions are also present in the pore canal to maintain the charge balance of the structure, and the porosity of the material is 47.2%. As shown in FIG. 3, the X-ray powder diffraction spectrum obtained by single crystal data simulation is consistent with the PXRD spectrum actually measured by ThNi-MOF-1, which shows that the crystal structure of the synthesized ThNi-MOF-1 is consistent with the analyzed structure.
The infrared spectrogram of the ThNi-MOF-1 material prepared in the embodiment is shown in FIG. 4, and FIG. 5 is a thermogravimetric analysis chart, and it is known from the chart that the ThNi-MOF-1 material prepared in the embodiment has good thermal stability within 400 ℃. FIG. 6 is a nitrogen adsorption isotherm at 77K for ThNi-MOF-1, which is a first type of adsorption curve, showing that it has a microporous structure with a specific surface area of 51.8m 2 And/g, has application prospect in catalysis and adsorption materials.
In addition, the invention further researches the chemical resistance of ThNi-MOF-1 and starting material Th-MOF, two single crystals with equal amounts are respectively placed in aqueous solutions with different pH values (pH=1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11 and 12) for soaking for 24 hours, and then the single crystals are taken out for testing PXRD.
The chemical resistance test results of the ThNi-MOF-1 and the starting material Th-MOF are shown in figures 7 and 8 respectively, and the diffraction peak positions of the ThNi-MOF-1 after being treated by water solutions with different pH values are all attributed to the initial crystal form of the ThNi-MOF-1, namely the crystal form is unchanged, the intensity of the characteristic diffraction peak is not changed obviously, and the phenomenon shows that the prepared ThNi-MOF-1 has good structural stability under the acidic or alkaline condition with the pH value of 1-12; while the original crystal structure of the Th-MOF of the unmodified nickel cluster can be maintained under the acidic or alkaline condition with pH=2-12, after soaking for 24 hours under the acidic condition with pH=1, the diffraction peak of the Th-MOF disappears, namely the crystal structure of the Th-MOF collapses, so that the acid resistance of the MOF is further improved after the nickel cluster is modified.
According to the results of the performance study, the prepared ThNi-MOF-1 has high specific surface area, good chemical stability and thermal stability, and good application prospect in the field of catalytic and adsorption materials, and the MOF material has a certain application prospect in the field of magnetic materials due to the modification of polynuclear nickel clusters.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A thorium-based metal organic framework material containing hexanuclear nickel clusters is characterized in that the chemical formula is [ Ni ] 6 Cl 10 (H 2 O) 6 Th 6 (μ 3 -O) 4 (μ 3 -OH) 4 (BPYDC) 6 (H 2 O) 6 ·Cl 2 ]·G 1 Wherein BPYDC is 2,2 '-bipyridine-4, 4' -dicarboxylic acid radical ion, G 1 Is a guest molecule;
the thorium-based metal organic framework material containing the hexanuclear nickel cluster belongs to a cubic crystal system, the space group is Pa-3, and the unit cell parameters are as follows:α＝β＝γ＝90°，/>
2. the thorium-based metal organic framework material containing hexanuclear nickel clusters of claim 1, wherein the guest molecules are diethylene glycol dimethyl ether and water.
3. The thorium-based metal organic framework material containing hexanuclear nickel clusters of claim 1, wherein the G 1 Is (C) 6 H 14 O 3 ) 7 (H 2 O) 36 。
4. A process for producing a thorium-based metal organic framework material containing a hexanuclear nickel cluster as claimed in any one of claims 1 to 3, characterized in that a single crystal of the thorium-based metal organic framework material is immersed in a solution containing NiCl 2 ·6H 2 In diethylene glycol dimethyl ether solution of O, reacting to prepare the thorium-based metal organic framework material containing the hexanuclear nickel cluster;
the chemical formula of the thorium metal organic framework material is [ Th ] 6 (μ 3 -O) 4 (μ 3 -OH) 4 (BPYDC) 6 (H 2 O) 6 ]·G 2 Wherein BPYDC is 2,2 '-bipyridine-4, 4' -dicarboxylic acid radical ion, G 2 Is a guest molecule; the thorium-based metal organic framework material belongs to a cubic crystal system, the space group is Fm-3m, and the unit cell parameters are as follows:α＝β＝γ＝90°，
5. the method according to claim 4, wherein during the impregnation, the NiCl-containing material is 2 ·6H 2 NiCl in diethylene glycol dimethyl ether solution of O 2 ·6H 2 O remains supersaturated.
6. The method according to claim 4, wherein the reaction temperature is 90 to 110℃and the reaction time is 30 to 40 days.
7. The preparation method of claim 4, wherein the preparation method of the thorium-based metal organic framework material comprises the following steps: will H 2 BPYDC and Th (NO) 3 ) 4 ·6H 2 O reacts in the presence of an acidic regulator and an organic solvent to obtain the thorium metal organic framework.
8. The method of claim 7, wherein the H is 2 BPYDC and Th (NO) 3 ) 4 ·6H 2 The feeding mole ratio of O is 1:2-1:3; the acidity regulator is one or more of trifluoroacetic acid, formic acid or nitric acid; adding water while adding an acid regulator, wherein the volume ratio of the acid regulator to the water is 0.8-1.2: 0.3 to 0.5.
9. The process according to claim 7, wherein H 2 BPYDC and Th (NO) 3 ) 4 ·6H 2 The reaction temperature of O in the presence of an acid regulator and an organic solvent is 100-120 ℃, and the reaction time is 3-5 days.
10. Use of a thorium-based metal organic framework material comprising hexanuclear nickel clusters according to any one of claims 1-3 in catalytic, magnetic materials.
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