CN101575735B - Pyridine-2,4,6-triformate manganese ferro-electrical functional material and preparation method thereof - Google Patents
Pyridine-2,4,6-triformate manganese ferro-electrical functional material and preparation method thereof Download PDFInfo
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- CN101575735B CN101575735B CN2009100984457A CN200910098445A CN101575735B CN 101575735 B CN101575735 B CN 101575735B CN 2009100984457 A CN2009100984457 A CN 2009100984457A CN 200910098445 A CN200910098445 A CN 200910098445A CN 101575735 B CN101575735 B CN 101575735B
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- tricarboxylic acid
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Abstract
The present invention discloses a pyridine-2,4,6-triformate manganese ferro-electrical functional material and a preparation method thereof. Soluble divalent manganese salt, pyridine-2,4,6-triformic acid, an acidity regulator and a reaction auxiliary agent H2C2O4 are mixed according to the proportion; deionized water is added for carrying out the hydrothermal reaction, the filtration, the grinding, the screening by a 100-mesh sieve are carried out for obtaining brown monoclinic crystal system powder with the purity of being not lower than 99 percent; the powder is (Mn3(H2O)9(C8H2O6N)2) ferro-electrical material with a Cc space group structure; the ferro-electrical feature parameter Ps is equal to 0.40 (muC/cm<2>), and the variable-temperature magnetic susceptibility curve is in line with a Curie-Weiss equation which is as follows: Xm is equal to C/(T minus theta). The pyridine-2,4,6-triformate manganese ferro-electrical functional material has better compatibility of magnetic property and ferro-electrical property, and the preparation method has the advantages of simple and easy process, low equipment requirement, low material cost, high yield, no pollution and the like.
Description
Technical field
The present invention relates to ferroelectric function material, be specifically related to pyridine-2,4, the preparation method of 6-tricarboxylic acid manganese ferroelectric function material and this ferroelectric function material thereof.
Background technology
Ferroelectric material is the class in the pyroelectricity material, and its feature is not only to have spontaneous polarization, and in certain temperature range, the size and Orientation of its spontaneous polarization moment of dipole can change with the size and Orientation of extra electric field.The novel ferroelectric material is owing to be with a wide range of applications in modern electronic devices such as memory storage element, wave filter, High Performance Insulation body, thereby the novel ferroelectric material of developing excellent property in recent years causes that people study interest greatly.From present present Research, number of research projects is devoted to develop the mineral compound ferroelectric material, yet the research work of metal-organic coordination compound ferroelectric material is seemed relatively limited.Because the spacer of ferroelectric function material structure is necessary for one of following 10 polarity point groups: C
1, C
s, C
2, C
2v, C
3, C
3v, C
4, C
4v, C
6, C
6v, so ferroelectric material synthetic have challenge, selects suitable metal ion and organic ligand to realize the design of novel capabilities material and construct seeming particularly important.Based on above reason, people tend to select to have the chirality feature when synthetic metal-organic coordination compound ferroelectric material organic ligand improves and forms the probability with above polarity dots group structure, reported the ferroelectric function material that employing chiral ligand N-(4-cyanogen Bian Ji)-(S)-proline(Pro), (S)-4-(4 '-aminophenyl)-2-aminobutyric acid and quinine etc. and metal ion are constructed as people such as Xiong Rengen.On the contrary, it is very rare to adopt achirality organic ligand such as phenyl ring poly carboxylic acid, pyridine poly carboxylic acid to construct the example of metal-organic coordination compound ferroelectric function material.
On the other hand, find by former study, one of means that are hopeful most to obtain the novel capabilities material are exactly the compound that preparation contains two or more physical property, as far back as nineteen sixty USSR (Union of Soviet Socialist Republics) Smolenskii and two seminars of Venevtsev after deliberation contain simultaneously and be magnetic and the material of ferroelectric property, and shown novel mixed characteristic---many iron character.This class material is a kind of Multifunction material for showing the single-phase compound of ferroelectric property and magnetic simultaneously, permeates in the every field of modern technologies, as device miniaturization, aural detector and transmitter etc.Though there is such mixed characteristic in existing many compounds, the compatibility of magnetic and ferroelectric property is not fine, and up to the present some performance studies for multi-ferroic material still are in the starting stage.Therefore, contain the performance study of two kinds of physical properties compounds simultaneously, especially performance study and the application thereof to metal-organic coordination compound class mixing functions material remains a very challenging problem.
Summary of the invention
Technical problem to be solved by this invention provides a kind of pyridine-2,4,6-tricarboxylic acid manganese ferroelectric function material, and this ferroelectric function material has significant ferroelectric functional character, P
sValue is 0.40 (μ C/cm
2), also have the antiferromagnetism coupling, be the compatibility ferroelectric function material preferably of a kind of magnetic and ferroelectric property.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: pyridine-2,4, and 6-tricarboxylic acid manganese ferroelectric function material, the molecular formula of this ferroelectric function material is [Mn
3(H
2O)
9(C
8H
2O
6N)
2], this ferroelectric function material is that purity is not less than 99%, can pass through 100 mesh sieves, the oblique system powder of brown has the Cc spacer and (belongs to the C in top 10 point groups
sPoint group) structure, the unit cell parameters of crystallographic system is:
β=117.16 (3) °, the 2P of the ferroelectric hysteresis loop of this ferroelectric function material
r(remnant polarization) value is 0.78 (μ C/cm
2), 2E
c(coercive field) value is 117.90 (kV/cm), P
s(saturated polarization) value is 0.40 (μ C/cm
2), the alternating temperature susceptibility curve of this ferroelectric function material meets Curie-Wei Si equation χ
m=C/ (T-Θ), wherein C (Curie constant) is 11.606 (cm
3Mol
-1K), Θ (Wei Si constant) is-5.760 (K).
The preparation method of above-mentioned ferroelectric function material comprises the steps:
1) in the teflon-lined stainless steel cauldron, be 1: 0.8～1.5: 0.8～1.2: 0.8～1.2 ratio in molar ratio, with solubility manganous salt, pyridine-2,4,6-tricarboxylic acid (H
3Ptc), acidity regulator and auxiliary agent H
2C
2O
4Mix;
2) ratio in 0.25mmol solubility manganous salt admixture 5～20mL deionized water adds deionized water in above-mentioned stainless steel cauldron, after stirring, sealing was carried out hydro-thermal reaction in 3～10 days with the stainless steel cauldron heating under 150～200 ℃ of temperature condition; Synthetic by hydro-thermal like this, the Eo+ generation considerable change of hydrolysis reaction aggravation, material and reaction are quickened;
3) after hydro-thermal reaction is finished, allow described stainless steel cauldron naturally cool to room temperature, obtain the pyridine-2,4 of brown, 6-tricarboxylic acid manganese styloid;
4) to described pyridine-2,4,6-tricarboxylic acid manganese styloid grinds, with 100 mesh sieves screenings, by 100 mesh sieves be the pyridine-2,4 of brown, 6-tricarboxylic acid manganese oblique system powder.
Described solubility manganous salt is MnCl
24H
2O or MnCO
3Or Mn (ClO
4) 6H
2O or MnSO
4H
2O or Mn (CH
3CO
2) 4H
2O; Described acidity regulator is KHCO
3Or NaOH or KOH or Na
2CO
3Or K
2CO
3Or ammonia soln; Auxiliary agent is H
2C
2O
4
Solubility manganous salt, pyridine-2,4,6-tricarboxylic acid, acidity regulator and auxiliary agent H
2C
2O
4Mol ratio be 1: 1: 1: 1.
Compared with prior art, the invention has the advantages that pyridine-2,4,6-tricarboxylic acid manganese ferroelectric function material, the molecular formula of this ferroelectric function material is [Mn
3(H
2O)
9(C
8H
2O
6N)
2], this ferroelectric function material is that purity is not less than 99%, can pass through 100 mesh sieves, and the oblique system powder of brown has Cc spacer structure, and the unit cell parameters of crystallographic system is:
β=117.16 (3) °, the 2P of the ferroelectric hysteresis loop of this ferroelectric function material
rValue is 0.78 (μ C/cm
2), 2E
cValue is 117.90 (kV/cm), P
sValue is 0.40 (μ C/cm
2), the alternating temperature susceptibility curve of this ferroelectric function material meets Curie-Wei Si equation χ
m=C/ (T-Θ), wherein C is 11.606 (cm
3Mol
-1K), Θ is-5.760 (K); This ferroelectric function material has the Cc spacer structure that meets ferroelectric function material, and saturated polarization P
s=0.400.25 μ Ccm
-2, obvious saturated polarization P greater than sieve breath salt
s=0.25 μ Ccm
-2, illustrate that this ferroelectric function material has significant ferroelectric functional character; The alternating temperature susceptibility curve of this ferroelectric function material meets Curie-Wei Si equation χ in addition
m=C/ (T-Θ), wherein C is 11.606 (cm
3Mol
-1K), Θ is-5.760 (K), therefore has the antiferromagnetism coupling, so the present invention is the compatibility pyridine-2 preferably of a kind of magnetic and ferroelectric property, 4,6-tricarboxylic acid manganese ferroelectric function material has potential application foreground in modern electronic devices such as transmitter, infrared eye, surface acoustic wave and integrated optoelectronic device.Preparation method of the present invention is included in the stainless steel cauldron in proportion with solubility manganous salt, H
3Ptc, KHCO
3And H
2C
2O
4Mix, add deionized water and carry out hydro-thermal reaction, obtain pyridine-2 after reacting the filtration that finishes, 4,6-tricarboxylic acid manganese styloid grinds the back of sieving and just is the pyridine of brown of the present invention-2,4,6-tricarboxylic acid manganese oblique system powder ferroelectric function material, that preparation method of the present invention has is simple for process, low for equipment requirements, raw materials cost is low, productive rate is high, advantage such as pollution-free.
Description of drawings
Fig. 1 is a pyridine of the present invention-2,4, the molecular structure of 6-tricarboxylic acid manganese ferroelectric function material;
Fig. 2 is a pyridine of the present invention-2,4, the comparison diagram of the PXRD collection of illustrative plates of 6-tricarboxylic acid manganese ferroelectric function material and monocrystalline simulation PXRD collection of illustrative plates;
Fig. 3 is a pyridine of the present invention-2,4, the TG-DTA graphic representation of 6-tricarboxylic acid manganese ferroelectric function material;
Fig. 4 is a pyridine of the present invention-2,4, the alternating temperature susceptibility curve figure of 6-tricarboxylic acid manganese ferroelectric function material;
Fig. 5 is a pyridine of the present invention-2,4, the ferroelectric hysteresis loop figure of 6-tricarboxylic acid manganese ferroelectric function material.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment
The MnCl that in the polytetrafluoroethyllining lining stainless steel cauldron, adds 0.25mmol successively
24H
2The H of O, 0.25mmol
3The KHCO of ptc, 0.25mmol
3H with 0.25mmol
2C
2O
4, add the 13mL deionized water then, after stirring, sealing is heated 5 days and carries out hydro-thermal reaction under 170 ℃ of temperature condition, and the hydro-thermal reaction equation is as follows:
Synthetic by hydro-thermal like this, the Eo+ generation considerable change of hydrolysis reaction aggravation, material and reaction are quickened; After hydro-thermal reaction finishes, allow stainless steel cauldron naturally cool to room temperature, obtain the pyridine-2,4 of brown, 6-tricarboxylic acid manganese styloid; To pyridine-2,4,6-tricarboxylic acid manganese styloid grinds, and with 100 mesh sieves screenings, the purity that obtains by 100 mesh sieves is not less than 99%, the pyridine of brown-2,4, and 6-tricarboxylic acid manganese oblique system powder, this powder has Cc spacer structure as shown in Figure 1.
Employing Bruker D8 Focus powder diffractometer with the sweep velocity of 6 °/min, is at room temperature collected the powder diffraction spectrum (PXRD) of sample in 5-50 ° 2 θ angular ranges, and contrasts (Fig. 2) with monocrystalline simulation PXRD figure.Adopt Seiko TG/DTA 6300 type partial heat analysers, with α-Al
2O
3Be reference substance, at the N2 of 200ml/min air-flow protection, temperature rise rate is to measure crystalline TG-DTA curve (Fig. 3) under the condition of 10 ℃/min.Adopt SQUID Quantum Design Model MPMS-7 type magnetic intensity meter to carry out the test of alternating temperature susceptibility, temperature range is 5-300K (Fig. 4).。Adopt the ferroelectric hysteresis loop of the U.S. ferroelectric material test macro Premier II of Lipton company specimen.It is last that sample is pulverized, and is pressed into the sheet that diameter is 15mm, and the two-sided elargol that is coated with dries naturally, measures ferroelectric hysteresis loop then and obtain ferroelectric properties parameter (remnant polarization Pr and coercive field E
c) numerical value (Fig. 5).Product as can be seen from Figure 2 of the present invention is a pure phase, and its PXRD and monocrystalline simulation are basic identical, so product purity of the present invention is not less than 99%; Gained crystal as can be seen from Figure 3 of the present invention can stable existence in room temperature to 130 ℃ temperature range; Product as can be seen from Figure 4 of the present invention has magnetic function; Product as can be seen from Figure 5 of the present invention has more significant ferroelectric functional performance.
MnCl in the foregoing description
24H
2O, H
3Ptc, KHCO
3, H
2C
2O
4Between mol ratio can be 1: 0.8: 0.8: 0.8, also can be 1: 1.5: 1.2: 1.2, also can be 1: 0.9: 1.2: 1.1 etc.; Hydrothermal temperature also can be for 150 ℃ or 200 ℃ or 180 ℃ etc., under 150～200 ℃ of temperature condition, and pyridine-2,4, the productive rate of 6-tricarboxylic acid manganese styloid can reach 86.%; The hydro-thermal reaction time can be 3 days, 7 days or 10 days etc.; Do not enumerate one by one at this.
MnCl in the foregoing description
24H
2O can use MnCO
3Or Mn (ClO
4) 6H
2O or MnSO
4H
2O or Mn (CH
3CO
2) 4H
2Solubility manganous salts such as O substitute; KHCO
3Also can be with NaOH or KOH or Na
2CO
3Or K
2CO
3Or alkaline matter such as ammonia soln substitutes.
Claims (4)
1. pyridine-2,4,6-tricarboxylic acid manganese ferroelectric function material is characterized in that the molecular formula of this ferroelectric function material is [Mn
3(H
2O)
9(C
8H
2O
6N)
2], this ferroelectric function material is that purity is not less than 99%, can pass through 100 mesh sieves, and the oblique system powder of brown has Cc spacer structure, and the unit cell parameters of crystallographic system is: a=19.824 (4)
B=6.848 (1)
C=19.765 (4)
β=117.16 (3) °, the ferroelectric characteristics parameter of this ferroelectric function material is respectively: 2P
r=0.78 μ C/cm
2, 2E
c=117.90kV/cm, P
s=0.40 μ C/cm
2, the alternating temperature susceptibility curve of this ferroelectric function material meets Curie-Wei Si equation χ
m=C/ (T-Θ), wherein C is 11.606cm
3Mol
-1K, Θ is-5.760K.
2. the preparation method of the described ferroelectric function material of claim 1 is characterized in that comprising the steps:
1) in the teflon-lined stainless steel cauldron, be 1: 0.8～1.5: 0.8～1.2: 0.8～1.2 ratio in molar ratio, with solubility manganous salt, pyridine-2,4,6-tricarboxylic acid, acidity regulator and auxiliary agent H
2C
2O
4Mix, described acidity regulator is KHCO
3Or NaOH or KOH or Na
2CO
3Or K
2CO
3
2) ratio in 0.25mmol solubility manganous salt admixture 5～20mL deionized water adds deionized water in above-mentioned stainless steel cauldron, after stirring, with its sealing, under 150～200 ℃ of temperature condition,, carry out hydro-thermal reaction with mixture heating up 3～10 days;
3) after hydro-thermal reaction is finished, allow described stainless steel cauldron naturally cool to room temperature, obtain the pyridine-2,4 of brown, 6-tricarboxylic acid manganese styloid;
4) to described pyridine-2,4,6-tricarboxylic acid manganese styloid grinds, with 100 mesh sieves screenings, by 100 mesh sieves be the pyridine-2,4 of brown, 6-tricarboxylic acid manganese oblique system powder.
3. the preparation method of ferroelectric function material as claimed in claim 2 is characterized in that described solubility manganous salt is MnCl
24H
2O or MnCO
3Or MnSO
4H
2O.
4. the preparation method of ferroelectric function material as claimed in claim 2 is characterized in that in step 1, solubility manganous salt, pyridine-2,4,6-tricarboxylic acid, acidity regulator and auxiliary agent H
2C
2O
4Mol ratio be 1: 1: 1: 1.
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| CN102153591B (en) * | 2011-01-17 | 2013-11-06 | 天津师范大学 | Manganese (II) complex containing 2-(1H-tetrazole-5-methyl) pyridine and 5-nitroisophthalic acid mixed ligand and preparation method and application of manganese (II) complex |
| CN102134752B (en) * | 2011-03-08 | 2012-11-28 | 宁波大学 | Preparation method of organic eutectic ferroelectric and organic eutectic ferroelectric |
| CN102425010A (en) * | 2011-11-28 | 2012-04-25 | 宁波大学 | 1, 2, 3, 4-butane manganese tetracarboxylate ferroelectric material and preparation method thereof |
| CN103450228B (en) * | 2013-07-23 | 2016-04-20 | 宁波大学 | Terpyridyl-4 '-carboxylic acid hydrogen sulfate copper ferroelectric function material and preparation method |
| CN108191892A (en) * | 2018-01-19 | 2018-06-22 | 安庆师范大学 | A kind of cadmium complex based on phthalic acid and the double imidazoles ylidene ligands of biphenyl and preparation method thereof |
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Non-Patent Citations (9)
| Title |
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| 63• |
| 63)2(46• |
| 84)(43• |
| 86)2 topology network built up from the highly connective pyridine-2,4,6-tricarboxylate ligand.《Inorganic Chemistry Communications》.2007,第10卷第836-838页. |
| Hong-Ling Gao et al.Syntheses and structures of 1D and 2D coordination polymers derived from pyridine-2,4,6-tricarboxylic acid.《Inorganic Chemistry Communications》.2004,第8卷第151-154页. * |
| Madhab C. Das et al.Coordination polymers with pyridine-2,4,6-tricarboxylic acid and alkaline-earth/lanthanide/transition metals: synthesis and X-ray structures.《Dalton Transactions》.2009,第1644-1658页. * |
| Peng Ren et al.Novel (42• |
| Peng Ren et al.Novel (42•84)(43•63)2(46•63•86)2 topology network built up from the highly connective pyridine-2,4,6-tricarboxylate ligand.《Inorganic Chemistry Communications》.2007,第10卷第836-838页. * |
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