CN114524831B - Dysprosium complex and preparation method and application thereof - Google Patents
Dysprosium complex and preparation method and application thereof Download PDFInfo
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- 229910052692 Dysprosium Inorganic materials 0.000 title claims abstract description 62
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000010668 complexation reaction Methods 0.000 title description 2
- 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 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical compound CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- DCKWZDOAGNMKMX-UHFFFAOYSA-N dysprosium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DCKWZDOAGNMKMX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- -1 dysprosium metal hexahydrate Chemical class 0.000 claims description 16
- 239000004020 conductor Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000696 magnetic material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000005294 ferromagnetic effect Effects 0.000 claims description 3
- HFEOHRWLEGXZHW-UHFFFAOYSA-K trichlorodysprosium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Dy+3] HFEOHRWLEGXZHW-UHFFFAOYSA-K 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 101100153586 Caenorhabditis elegans top-1 gene Proteins 0.000 claims 1
- 101100370075 Mus musculus Top1 gene Proteins 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 230000005291 magnetic effect Effects 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000005307 ferromagnetism Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 26
- 239000001257 hydrogen Substances 0.000 description 8
- 150000000914 Dysprosium Chemical class 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002050 diffraction method Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000013354 porous framework Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- IOIFRTZBJMZZFO-UHFFFAOYSA-N dysprosium(3+) Chemical compound [Dy+3] IOIFRTZBJMZZFO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
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Abstract
The invention discloses a dysprosium complex and a preparation method and application thereof. The dysprosium complex has the structural formula: [ Hdmbpy ]][Dy(H 2 dobdc) 2 (H 2 O)]·3H 2 O，H 2 The dobdc ligand is a divalent anion of 2, 5-dihydroxyterephthalic acid losing two protons, and the Hdmbpy ligand represents a monovalent cation of 4,4 '-dimethyl-2, 2' -bipyridine yielding one proton. The dysprosium complex of the invention is prepared from H 4 The dobdc, dmbpy and the dysprosium nitrate hexahydrate are obtained through a hydrothermal reaction one-step method, the reaction raw materials are easy to obtain, the preparation method is simple, and the yield is high. The dysprosium complex has ferromagnetism and typical single-molecule magnet slow relaxation behavior under zero field, and the crystal structure of the dysprosium complex contains hydrophilic pore channels, so that the dysprosium complex can keep stable structure in water environment, can be used as a magnetic and proton conduction dual-functional material, and has higher application value.
Description
Technical Field
The invention relates to a dysprosium complex, a preparation method and application thereof, and belongs to the technical field of functional complexes.
Background
Metal organic framework complexes (MOFs) consisting of metal cations, secondary building units or clusters and multidentate organic ligands with coordinating terminal groups have the characteristics of diverse composition, diverse structure, and rich functional design, and nowadays have demonstrated great advantages in optical sensing, fuel cells, spintronics, drug delivery, heterogeneous catalysis, etc. (chem. Soc. Rev.2018,47,8611-8638; chord. Chem. Rev.2019,378, 365-381). The integration of two and more functional advanced materials in the same complex has attracted more and more researchers. In practice, a single material may perform a plurality of tasks (J.Am.chem.Soc.2020, 142,3970-3979;J.Mater.Chem.C 2020,8,16032-16041; inorg.chem.2021,60, 17487-17497).
On one hand, the MOFs constructed by the trivalent dysprosium ions and the organic ligands have larger ground spin and stronger intrinsic anisotropy of the dysprosium ions, are optimal candidates for molecular magnetic materials, and have potential application prospects in the aspects of high-density data storage and molecular spin electronic devices (chem.Commun.2016, 52,4804-4807; inorg.chem.2020,59, 11930-11934). On the other hand, the highly modifiable pore surfaces and precise crystal structures of MOFs offer great opportunities for improving proton conductivity properties, while providing ideal crystal models for in-depth understanding of proton transfer mechanisms, which may further facilitate the use of MOFs in fuel cells (Matter 2020,2,711-722;EnergyChem 2020,2,100029). The inventors of the present invention found that the existing research on magnetic and proton conducting dual-function materials based on MOFs still has the defects of poor water stability and low proton conductivity of the materials, so that the practicability of the materials is limited to a certain extent (Eur.J. Inorg. Chem.2021, 4610-4618; adv. Mater.2020,32, e 1907090). Therefore, the novel dysprosium complex with different topological structures is designed and synthesized, a channel beneficial to proton transfer is created, and the double-function material for realizing magnetism and proton conduction has very important significance.
Disclosure of Invention
In view of the above problems in the prior art, a first object of the present invention is to provide a dysprosium complex with dual properties of magnetism and high proton conductivity, which is structurally stable and can be widely used as a novel multifunctional material with both magnetism and conductivity for information storage and fuel cells.
The second aim of the invention is to provide a preparation method of the dysprosium complex, which uses simple and easily available raw materials to synthesize the dysprosium complex in one step, and has the advantages of simplicity, easy implementation, high yield and low cost.
The third object of the present invention is to provide an application of the dysprosium complex as a ferromagnetic material, which shows a slow relaxation behavior of a single-molecule magnet in zero field; the proton conducting material can show very high proton conductivity in a high-temperature and high-humidity environment.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention is thatThe dysprosium complex has a structural formula as follows: [ Hdmbpy ]][Dy(H 2 dobdc) 2 (H 2 O)]·3H 2 O, wherein: h 2 dobdc ligand expresses 2, 5-dihydroxyterephthalic acid (H) 4 dobdc) a divalent anion that loses both protons; hdmbpy ligand means a monovalent cation of 4,4 '-dimethyl-2, 2' -bipyridine (dmbpy) to give one proton; dy represents trivalent dysprosium ions.
The dysprosium complex is crystallized in a triclinic system, belongs to the P-1 space group and has unit cell parameters of
α＝110.0330(10)°，β＝106.1880(10)°，γ＝95.7150(10)，/>
The invention selects H 4 The dobdc is used as a ligand, the structure of the dobdc contains carboxyl-COOH and hydroxyl-OH functional groups, so that on one hand, the dobdc shows various coordination modes, and on the other hand, the dobdc is used as a donor and a receptor of hydrogen bonds to provide a hydrophilic environment; the dmbpy is selected as an auxiliary ligand, a pyridine group in the structure is used as a hydrogen bond acceptor, counter ions are provided after protonation, the hydrophilicity is improved, and the formed dysprosium complex has good water stability.
The dysprosium complex is formed by H 2 The three-dimensional porous structure formed by the dobdc ligand, the Hdmbpy ligand, the dysprosium (III) metal center and the water molecules together contains hydrophilic triangular pore channels, wherein Hdmbpy and a large number of water molecules occupy the pore channels, and rich hydrogen bond channels are formed between the Hdmbpy and the framework, so that a path is provided for proton transfer, and the porous structure can be used as a potential proton conducting material.
The preparation method of the dysprosium complex provided by the invention comprises the following specific steps:
stirring and mixing 2, 5-dihydroxyterephthalic acid, 4 '-dimethyl-2, 2' -bipyridine, dysprosium metal hexahydrate and deionized water to obtain an aqueous solution; uniformly mixing, reacting for 60-84 hours at a constant temperature of 135-145 ℃, and cooling to 25-35 ℃ after 12-20 hours to obtain the dysprosium complex.
The solution is kept at the temperature of 140 ℃ for more than 60 hours to provide proper energy, so that ligand and dysprosium ion are easier to form coordination bond; the solution is slowly cooled to about 30 ℃ over 12 hours to better produce single crystals.
Preferably, the concentration of 2, 5-dihydroxyterephthalic acid in the aqueous solution is 0.009-0.011 mmol/mL, the concentration of 4,4 '-dimethyl-2, 2' -bipyridine is 0.01-0.011 mmol/mL, and the concentration of dysprosium metal salt hexahydrate is 0.007-0.011 mmol/mL.
Preferably, the ratio of the amounts of the substances added to the reaction 2, 5-dihydroxyterephthalic acid and 4,4 '-dimethyl-2, 2' -bipyridine is 1 to 1.2:1.
preferably, the ratio of the amounts of the materials of 2, 5-dihydroxyterephthalic acid and dysprosium metal salt hexahydrate that are charged to the reaction is 1:0.76 to 1.2. The crystals precipitated at this ratio are purer.
Preferably, the dysprosium metal salt hexahydrate is dysprosium nitrate hexahydrate or dysprosium chloride hexahydrate.
The invention also provides application of the dysprosium complex as a magnetic material and/or a proton conducting material.
The dysprosium complex has ferromagnetic interactions and can show slow relaxation behavior of a single-molecule magnet under zero field.
The dysprosium complex as a proton conducting material can exhibit good stability and high proton conductivity over different relative humidity ranges and a wide temperature range.
Preferably, the dysprosium complex has a proton conductivity of 1.86×10 at 30 ℃ and a relative humidity of 75-100% -6 ～1.70×10 -4 S cm -1 Within the range. At 30-70 ℃ and relative humidity of 100%, the proton conductivity is 1.70X10 -4 ～1.20×10 -3 S cm -1 Within the range. In particular, the dysprosium complex has a proton conductivity of 1.20X10 at 70 ℃ and a relative humidity of 100% -3 S cm -1 。
The dysprosium complex has double performances of magnetism and proton conduction, can be used as a magnetic material or a proton conduction material for single application, and can also be used as the magnetic material and the proton conduction material for simultaneous application.
Compared with the prior art, the invention has the beneficial effects that: the dysprosium complex has definite microstructure information, presents a specific connection mode of hydrogen bonds, and is favorable for understanding proton conduction mechanism; the dysprosium complex provided by the invention has the advantages of simple preparation method, easily obtained reaction raw materials, high yield and low cost, and is obtained through one-step reaction, thereby being beneficial to industrial production; the dysprosium complex prepared by the invention has the characteristics of ferromagnetism and single-molecule magnet, shows good stability and high proton conductivity in a wider temperature range and a higher humidity environment, belongs to a super-ion conductor, and can be used as a proton conducting material to be applied to an extreme working environment.
Drawings
FIG. 1 is a crystal structure diagram of dysprosium complex in example 1 of the invention;
FIG. 2 is a schematic representation of the three-dimensional porous structure of dysprosium complexes of example 1 of the invention;
FIG. 3 is an infrared spectrum of dysprosium complex in example 1 of the invention;
FIG. 4 is a powder diffraction pattern of dysprosium complex of example 1 of the invention under various conditions;
FIG. 5 is a graph showing DC susceptibility testing of dysprosium complex in example 1 of the invention;
FIG. 6 is a graph of the imaginary AC susceptibility of dysprosium complex of example 1 according to the invention as a function of temperature at zero field;
FIG. 7 is a graph showing the impedance of dysprosium complexes of example 1 of the present invention at 75% and 100% relative humidity;
FIG. 8 is a graph showing the impedance of dysprosium complexes of example 1 of the present invention at various temperatures at 100% relative humidity;
FIG. 9 is an Arrhenius diagram of dysprosium complex of example 1 of the invention at various temperatures at 100% relative humidity.
Detailed Description
The present invention will be further described in detail with reference to specific examples for the purpose of making the objects, technical solutions and advantages of the present invention more clear, but the purpose of these exemplary embodiments is to be construed as merely illustrative and not limitative of the actual scope of the present invention in any way.
Example 1: dysprosium complex [ Hdmbpy ]][Dy(H 2 dobdc) 2 (H 2 O)]·3H 2 Preparation of O (also abbreviated as Dy-MOF in the present application)
0.1mmol of dysprosium nitrate hexahydrate (0.0457 g), 0.103mmol of 2, 5-dihydroxyterephthalic acid (0.0204 g, abbreviated as H in this application) 4 dobdc) and 0.104mmol of 4,4 '-dimethyl-2, 2' -bipyridine (0.0192 g, abbreviated as dmbpy in the present application) were added to 10mL of deionized water, mixed uniformly under stirring, then placed in a polytetrafluoroethylene reaction vessel for sealing, reacted at a constant temperature in an oven at 140 ℃ for 72 hours, and cooled slowly to 30 ℃ over 15 hours, thus obtaining pale yellow bulk crystal Dy-MOF with a yield of 72.0% (based on H 4 dobdc)。
The crystals obtained in this example were selected and tested using a Bruker Smart-APEXII CCD X-ray single crystal diffractometer. The resulting crystallographic structure refinement data are shown in table 1 below, the partial bond lengths are shown in table 2, and the hydrogen bond configurations are shown in table 3.
Table 1: structural refinement data for Dy-MOF
Table 2: partial bond length of Dy-MOF
Table 3: hydrogen bond configuration of Dy-MOF
The single crystal structure of Dy-MOF has two Dy (III) centers connected by a carboxylic acid group to form [ Dy ] 2 (CO 2 ) 4 ]Binuclear structural unit (FIG. 1), the binuclear unit is further modified by four different coordination modes of H 2 The dobdc ligand is connected to form a three-dimensional porous framework, free Hdmbpy and water molecules occupy pore channels, and abundant hydrogen bond interaction exists between the porous framework and the free Hdmbpy (figure 2)
Dy-MOF of this example was characterized using an IRAfforescence-1S infrared spectrometer, with the following results: 3515.33 (w), 1639.52 (m), 1599.98 (w), 1580.69 (w), 1495.82 (m), 1448.57(s), 1355.98 (m), 1242.18 (vs), 1113.91 (w), 922.95 (w), 910.42 (w), 875.70 (w), 814.94(s), 796.61 (m), 783.11 (w), 759.00 (w), 610.48 (w), 551.65 (m), 518.86 (w), 416.63 (w) (fig. 3).
The phase purity and stability of the Dy-MOF of this implementation were characterized using a Bruker D8 ADVANCE powder diffractometer. As shown in fig. 4, comparing the curve obtained by the experiment with the curve obtained by the simulated crystal data, it can be seen that Dy-MOF prepared by the above method is a pure phase. In addition, after being soaked in the aqueous solution for 7 days, the curves still keep consistent, which shows that Dy-MOF has good water stability and provides guarantee for the application of the Dy-MOF in proton conducting materials.
Comparative examples 1 to 1
The water added in example 1 was replaced with N, N-dimethylformamide or a mixed solvent of water and N, N-dimethylformamide, and the remaining conditions were unchanged; as a result, no crystals or powder products were produced.
Comparative examples 1 to 2
The reaction temperature in example 1 was changed to 125℃or less, and the remaining conditions were unchanged; as a result, no crystals or powder products were produced.
Comparative examples 1 to 3
The reaction time in example 1 was changed to 60 hours or less, and the remaining conditions were unchanged; as a result, no crystals or powder products were produced.
As is clear from a comparison of examples 1 to comparative examples 1 to 3, the target dysprosium complex cannot be obtained in the present invention if water is exchanged for another solvent, which is caused by the solvent effect. If the reaction temperature is lowered or the reaction time is shortened, the target dysprosium complex cannot be obtained. The present invention therefore uses water as a solvent and requires sufficient reaction temperature and reaction time to provide the energy required for the reaction.
Example 2: dy-MOF preparation
0.1mmol of dysprosium chloride hexahydrate (0.0377 g), 0.099mmol of H 4 dobdc (0.0196 g) and 0.1mmol dmbpy (0.0184 g) were added to 10mL deionized water, mixed well under stirring, then placed in a polytetrafluoroethylene reaction vessel, sealed, reacted at constant temperature in an oven at 140℃for 72 hours, cooled slowly to 30℃over 15 hours to give pale yellow bulk crystals with a yield of 61.6% (based on H) 4 dobdc)。
The crystals obtained in this example were subjected to single crystal diffraction analysis, and the pale yellow bulk crystals were confirmed to be Dy-MOF, which was the same as that obtained by the preparation method of example 1.
Example 3: dy-MOF preparation
0.076mmol of dysprosium nitrate hexahydrate (0.0457 g), 0.1mmol of 2, 5-dihydroxyterephthalic acid (0.0198 g, abbreviated as H in this application) 4 dobdc) and 0.1mmol of 4,4 '-dimethyl-2, 2' -bipyridine (0.0184 g, abbreviated as dmbpy in this application) were added to 10mL of deionized water, mixed uniformly with stirring, then placed in a polytetrafluoroethylene reaction vessel and sealed, reacted at a constant temperature in an oven at 135℃for 84 hours, and cooled slowly to 30℃over 12 hours to give pale yellow bulk crystals with a yield of 63.5% (based on H) 4 dobdc)。
The crystals obtained in this example were subjected to single crystal diffraction analysis, and the pale yellow bulk crystals were confirmed to be Dy-MOF, which was the same as that obtained by the preparation method of example 1.
Example 4: dy-MOF preparation
0.11mmol of dysprosium nitrate hexahydrate (0.0502 g), 0.092mmol of 2, 5-dihydroxylTerephthalic acid (0.0182 g, abbreviated as H in this application) 4 dobdc) and 0.11mmol of 4,4 '-dimethyl-2, 2' -bipyridine (0.0203 g, abbreviated as dmbpy in the present application) were added to 10mL of deionized water, mixed uniformly under stirring, then placed in a polytetrafluoroethylene reaction vessel for sealing, reacted at a constant temperature of 145 ℃ for 60 hours and then cooled slowly to 35 ℃ over 20 hours to obtain pale yellow bulk crystals with a yield of 67.2% (based on H) 4 dobdc)。
The crystals obtained in this example were subjected to single crystal diffraction analysis, and the pale yellow bulk crystals were confirmed to be Dy-MOF, which was the same as that obtained by the preparation method of example 1.
In order to examine the magnetic properties and proton conductivity properties of dysprosium complexes prepared in accordance with the invention.
Application example 1
The dysprosium complex prepared in example 1 of the invention has direct current magnetic susceptibility (χ) under the conditions of field intensity of 1kOe and temperature of 1.8-300K M ) Is a test of (2). As shown in FIG. 5, at 300K, the product of DC magnetic susceptibility and temperature (T) is 14.31cm 3 K mol -1 . When the temperature starts to decrease, the value of the product slowly decreases to 12.39cm at 10K 3 K mol -1 Continuing to decrease the temperature, the product starts to increase rapidly, reaching 13.62cm at 1.8K 3 K mol -1 Shows that the binuclear dysprosium ions in Dy-MOF have ferromagnetic interaction.
Application example 2
The dysprosium complex prepared in example 1 of the present invention was tested for imaginary alternating current magnetic susceptibility (χ ") under conditions of field strength of 0Oe, temperature of 1.8-5.0K, and frequency of 1-707 Hz. The imaginary part alternating current magnetic susceptibility of Dy-MOF gradually decreases along with the rise of temperature, and the obvious temperature dependence phenomenon is shown (figure 7), and the curves at different frequencies are not coincident with each other, so that the Dy-MOF has typical slow relaxation characteristics of a single-molecule magnet.
Application example 3
The dysprosium complex prepared in example 1 of the present invention was subjected to proton conductivity test at 30℃and Relative Humidity (RH) of 75% and 100%, respectively. With the increase of relative humidity, the proton conductivity (sigma) of dysprosium complex is from 1.87×10 -6 S cm -1 Up to 1.70X10 -4 S cm -1 The dysprosium complex can be used as a proton conducting material in environments with different humidity.
Application example 4
The dysprosium complex prepared in example 1 of the present invention was subjected to proton conductivity testing at 100% RH and a temperature range of 30 to 70 ℃. The proton conductivity of dysprosium complexes gradually increases with increasing temperature, reaching a maximum of 1.20X10 at 70℃due to the thermal activation mechanism -3 S cm -1 Far exceeding 10 -4 S cm -1 Belongs to a super ion conductor, and illustrates that the dysprosium complex can be used as a proton conducting material at different temperatures.
Application example 5
Dysprosium complexes prepared in example 1 of the present invention have activation energies (E) in the temperature range of 30-70℃and 100% RH a ) From arrhenius formula σt=σ 0 exp(E a /k B T) is calculated. Linear fitting ln (σT) to 1000/T data to obtain E a The value of (a) is 0.37eV (fig. 9), which shows that proton conduction of the dysprosium complex follows a hopping mechanism, and protons received on a group hop to another adjacent group through an infinite hydrogen bond network, so that rapid proton transfer is realized.
The dysprosium complex can keep stable structure in a high humidity environment, has ferromagnetism and slow relaxation behavior of a single-molecule magnet under a zero field, shows high proton conductivity in a wider temperature range, can be used as a potential magnetic and proton conducting dual-functional material, and has higher application value. The preparation method is simple, high in yield and low in cost, and is suitable for large-scale popularization and application.
Claims (8)
1. A dysprosium complex characterized by: the structure is as follows: [ Hdmbpy ]][Dy(H 2 dobdc) 2 (H 2 O)]·3H 2 O, where H 2 dobdc ligand indicates loss of 2, 5-dihydroxyterephthalic acidDivalent anions of two protons; the Hdmbpy ligand represents a monovalent cation of 4,4 '-dimethyl-2, 2' -bipyridine to a proton;
the dysprosium complex is crystallized in a triclinic system and belongs toP-1 space group, unit cell parameters of a= 10.5170 (8) a, b= 11.1467 (8) a, c= 14.8120 (11) a, α= 110.0330 (10) °, β= 106.1880 (10) °, γ= 95.7150 (10), v=1529.6 (2) a 3 。
2. The method of preparing a dysprosium complex as defined in claim 1, wherein: stirring and mixing 2, 5-dihydroxyterephthalic acid, 4 '-dimethyl-2, 2' -bipyridine, dysprosium metal hexahydrate and water to obtain an aqueous solution; uniformly mixing, reacting for 60-84 hours at a constant temperature of 135-145 ℃, and cooling to 25-35 ℃ after 12-20 hours to obtain the dysprosium complex.
3. The method for preparing the dysprosium complex according to claim 2, wherein: the concentration of the 2, 5-dihydroxyterephthalic acid in the aqueous solution is 0.009-0.011 mmol/mL, the concentration of the 4,4 '-dimethyl-2, 2' -bipyridine is 0.01-0.011 mmol/mL, and the concentration of the dysprosium metal salt hexahydrate is 0.007-0.011 mmol/mL.
4. The method for preparing the dysprosium complex according to claim 2, wherein: the ratio of the amounts of the 2, 5-dihydroxyterephthalic acid and 4,4 '-dimethyl-2, 2' -bipyridine added to the reaction is 1 to 1.2:1.
5. the method for preparing the dysprosium complex according to claim 2, wherein: the ratio of the amounts of the materials of 2, 5-dihydroxyterephthalic acid and dysprosium metal salt hexahydrate charged to the reaction was 1:0.76 to 1.2.
6. The method for preparing the dysprosium complex according to claim 2, wherein: the dysprosium metal salt hexahydrate is dysprosium nitrate hexahydrate or dysprosium chloride hexahydrate.
7. The use of a dysprosium complex as defined in claim 1, characterized in that: as magnetic materials and proton conducting materials; it is ferromagnetic and exhibits typical single-molecule magnet slow relaxation behavior at zero field.
8. The use of a dysprosium complex as defined in claim 7, characterized in that: the dysprosium complex has proton conductivity of 1.70X10 at 30-70deg.C and relative humidity of 100% -4 ～1.20×10 -3 S cm -1 Within the range.
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