CN102924486A - Phenanthroline copper malonate ferroelectric functional material and preparation method thereof - Google Patents
Phenanthroline copper malonate ferroelectric functional material and preparation method thereof Download PDFInfo
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- CN102924486A CN102924486A CN2012104009538A CN201210400953A CN102924486A CN 102924486 A CN102924486 A CN 102924486A CN 2012104009538 A CN2012104009538 A CN 2012104009538A CN 201210400953 A CN201210400953 A CN 201210400953A CN 102924486 A CN102924486 A CN 102924486A
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Abstract
The invention discloses a phenanthroline copper malonate ferroelectric functional material with a molecular formula of [Cu2(phen)2(H2O)3(mal)(ClO4)](ClO4). Phen is phenanthroline; mal is malonic acid; the ferroelectric functional material is blue powder and belongs to a P21 space group crystal structure; cell parameters of the ferroelectric functional material are shown in the specification; and ferroelectric characteristic parameters of the ferroelectric functional material are respectively that: the saturated polarization Ps is 0.25mu C.cm<-2>, the remanent polarization 2Pr is 0.20mu C.cm<-2>, and a coercive electric field value 2Ec is 3.59kv.cm<-1>. The material is a metal-organic complex which is constructed by using a flexible malonic acid organic ligand, Cu<2+> ions, perchlorate ions and phenanthroline, and has good ferroelctric characteristics, and the saturated polarization is equivalent to that of Rochelle salt. The ferroelectric functional material is prepared by mixing a copperperchlorate hydrate solution and a malonic acid solution, and then mixing the mixed solution and a phenanthroline solution; and the flow and the process are simple, and equipment requirements are low.
Description
Technical field
The present invention relates to ferroelectric function material, be specifically related to phenanthroline propanedioic acid copper ferroelectric function material and preparation method thereof.
Background technology
Ferroelectric function material refers to that its crystalline structure just has the spontaneous polarization phenomenon when not adding external electric field, the class functional materials that the direction of spontaneous polarization can be reversed by extra electric field or redirect.It has the characteristics such as good ferroelectric, dielectric, pyroelectricity and piezoelectricity, thereby be widely used in the solid unit aspects such as the modern electronic technologies such as ferroelectric memory, infrared eye, surface acoustic wave and integrated optoelectronic device and micro mechanical technology, ferroelectric material and applied research thereof have become one of Condensed Matter Physics, research topic that the Solid State Electronics field is the most popular.
As far back as 18 to 19 Shi Ji, scientist just studies the ferroelectric properties of material, the ferroelectric material that obtains the earliest to use is sieve breath salt (Seignette salt), Pockels in 1894 has reported that sieve breath salt has unusual large piezoelectric constant, and nineteen twenty, the Valasek of France observed the ferroelectric hysteresis loop that sieve ceases salt crystal (rhombic system); Nineteen thirty-five, nineteen forty-two have been found again potassium primary phosphate (KH
2PO
4) and similar crystal in ferroelectricity, and barium titanate (BaTiO
3) ceramic ferroelectricity.From present present Research, still be in developmental stage for the research and development application with high performance ferroelectric material.The design that develops into the novel ferroelectric functional materials of metal organic coordination chemistry is synthesized and is prepared and exploitation provides brand-new thinking, and has greatly promoted the development of Materials science.Its main policies is by selecting suitable metal ion and organic ligand, by the cooperate and bond function between metal ion and the organic ligand, realizes the design of novel capabilities material and constructs.Because the spacer of the microcosmic crystalline structure of ferroelectric function material is one of 10 polarity point groups, therefore ferroelectric material synthetic had challenge, the metal ion that How to choose is suitable and organic ligand are realized the design of novel capabilities material and are constructed the particularly key that seems.
Summary of the invention
Technical problem to be solved by this invention provides a kind of phenanthroline propanedioic acid copper ferroelectric function material, and phenanthroline propanedioic acid copper is new ferroelectric function material, has preferably ferroelectric properties, and saturated polarization is suitable with sieve breath salt.The present invention also provides the preparation method of phenanthroline propanedioic acid copper, and it is few that this preparation method has flow process, and technique is simple, and is pollution-free, and cost is low, is easy to the advantages such as industrialization.
The present invention solves the problems of the technologies described above the technical scheme that adopts: phenanthroline propanedioic acid copper ferroelectric function material, the molecular formula of phenanthroline propanedioic acid copper is [Cu
2(phen)
2(H
2O)
3(mal) (ClO
4)] (ClO
4), wherein phen is phenanthroline, and mal is propanedioic acid, and this ferroelectric function material is blue powder, and purity is not less than 99%, belongs to P2
1The spacer crystalline structure, its unit cell parameters is:
Its ferroelectric characteristics parameter is respectively: saturated polarization Ps=0.25 μ Ccm
-2, remnant polarization 2Pr=0.20 μ Ccm
-2, coercive electric field 2Ec=3.59kvcm
-1This material is by flexible propanedioic acid organic ligand and Cu
2+Ion, perchlorate and phenanthroline are built into Metal-organic complex, have preferably ferroelectric properties.
The preparation method of above-mentioned phenanthroline propanedioic acid copper ferroelectric function material, its step is as follows:
A, cupric perchlorate is dissolved in the deionized water, being made into volumetric molar concentration is the cupric perchlorate solution for later use of 0.2～0.6mol/L;
B, propanedioic acid is dissolved in the deionized water, be stirred to fully dissolving, being made into volumetric molar concentration is the propanedioic acid solution of 0.1～0.3mol/L, in the ratio of the mol ratio 1:2 of propanedioic acid and cupric perchlorate, described propanedioic acid solution and described cupric perchlorate solution are mixed, obtain light blue solution;
C, phenanthroline is dissolved in the ethanol, being made into volumetric molar concentration is the phenanthroline solution of 0.2～0.6mol/L, then in the ratio of the mol ratio 1:1 of phenanthroline and cupric perchlorate, described phenanthroline solution and above-mentioned light blue solution are mixed, blue suspension liquid to be formed, remove by filter insolubles, filtrate is statically placed in room temperature, treat that mazarine shape crystal separates out complete, filter, mazarine shape crystal was ground to form the powder of 100 mesh sieves, and obtained purity and be not less than 99% phenanthroline propanedioic acid copper ferroelectric function material.The molecular formula of phenanthroline propanedioic acid copper is through analysis of components and be determined as [Cu
2(phen)
2(H
2O)
3(mal) (ClO
4)] (ClO
4), powder obtains the powder crystalline phase of PXRD collection of illustrative plates as shown in Figure 2 through X-ray diffraction.
Compared with prior art, the invention has the advantages that phenanthroline propanedioic acid copper ferroelectric function material, its molecular formula is [Cu
2(phen)
2(H
2O)
3(mal) (ClO
4)] (ClO
4), wherein phen is phenanthroline, and mal is propanedioic acid, and this ferroelectric function material is blue powder, and purity is not less than 99%, belongs to P2
1The spacer crystalline structure, its unit cell parameters is:
Its ferroelectric characteristics parameter is respectively: saturated polarization Ps=0.25 μ Ccm
-2, remnant polarization 2Pr=0.20 μ Ccm
-2, coercive electric field 2Ec=3.59kvcm
-1This material is by flexible propanedioic acid acid organic ligand and Cu
2+The Metal-organic complex that ion, perchlorate and phenanthroline are constructed has preferably ferroelectric properties, and is suitable with the saturated polarization of sieve breath salt.This ferroelectric function material preparation method mixes with propanedioic acid solution with cupric perchlorate solution, prepare with phenanthroline solution hybrid mode again, has flow process few, technique is simple, low for equipment requirements, raw material uses cheap cupric perchlorate and propanedioic acid and phenanthroline, and is pollution-free, cost is low, is easy to the advantages such as industrialization.
Description of drawings
Fig. 1 is the molecular structure of phenanthroline propanedioic acid copper ferroelectric function material;
Fig. 2 is PXRD and the monocrystalline simulation PXRD comparison diagram of phenanthroline propanedioic acid copper ferroelectric function material;
Fig. 3 is the ferroelectric hysteresis loop figure of phenanthroline propanedioic acid copper ferroelectric function material.
Embodiment
Embodiment is described in further detail the present invention below in conjunction with accompanying drawing.
0.4 mole cupric perchlorate is dissolved in 1 liter of deionized water, and being made into volumetric molar concentration is the cupric perchlorate solution for later use of 0.4mol/L; 0.2 mole of propanedioic acid is joined in 1 liter of deionized water, be stirred to fully dissolving, being made into volumetric molar concentration is the propanedioic acid solution of 0.2mol/L, joins in the cupric perchlorate solution, mixes, and obtains light blue propanedioic acid copper solutions; 0.4 mole of phenanthroline is dissolved in 1 liter of ethanol, being made into volumetric molar concentration is the phenanthroline solution of 0.4mol/L, join in the light blue propanedioic acid copper solutions and mix, blue suspension liquid to be formed, remove by filter insolubles, filtrate is statically placed in room temperature, after several days, mazarine shape crystal is separated out complete, mazarine shape crystal ground to form the powder of 100 mesh sieves, obtain purity and be not less than 99% phenanthroline propanedioic acid copper ferroelectric function material, the molecular formula of this phenanthroline propanedioic acid copper ferroelectric function material is [Cu
2(phen)
2(H
2O)
3(mal) (ClO
4)] (ClO
4), wherein phen is phenanthroline, mal is propanedioic acid.Its microcosmic crystalline structure is P2
1Spacer, powder obtain the as shown in Figure 2 powder crystalline phase of PXRD collection of illustrative plates through X-ray diffraction; This powder ferroelectric hysteresis loop as shown in Figure 3, as can be seen from Figure 3 its ferroelectric properties characteristic parameter is respectively: Ps=0.25 μ Ccm
-2, 2Pr=0.20 μ Ccm
-2, 2Ec=3.59kvcm
-1Illustrate to have preferably ferroelectric properties, the Ps value 0.25 μ Ccm of its Ps value and sieve breath salt
-2Quite, be preferably ferroelectrics of ferroelectric properties.
Embodiment 2
Substantially the same manner as Example 1, difference is that 0.2 mole cupric perchlorate is dissolved in 1 liter of deionized water, and 0.1 mole of propanedioic acid joins in 1 liter of deionized water, and 0.2 mole of phenanthroline is dissolved in 1 liter of ethanol.
Embodiment 3
Substantially the same manner as Example 1, difference is that 0.6 mole cupric perchlorate is dissolved in 1 liter of deionized water, and 0.3 mole of propanedioic acid joins in 1 liter of deionized water, and 0.6 mole of phenanthroline is dissolved in 1 liter of ethanol.
Claims (2)
1. phenanthroline propanedioic acid copper ferroelectric function material is characterized in that the molecular formula of phenanthroline propanedioic acid copper is [Cu
2(phen)
2(H
2O)
3(mal) (ClO
4)] (ClO
4), wherein phen is phenanthroline, and mal is propanedioic acid, and this ferroelectric function material is blue powder, and purity is not less than 99%, belongs to P2
1The spacer crystalline structure, its unit cell parameters is:
Its ferroelectric characteristics parameter is respectively: saturated polarization Ps=0.25 μ Ccm
-2, remnant polarization 2Pr=0.20 μ Ccm
-2, coercive electric field 2Ec=3.59kvcm
-1
2. the preparation method of phenanthroline propanedioic acid copper ferroelectric function material claimed in claim 1 is characterized in that step is as follows:
A, cupric perchlorate is dissolved in the deionized water, being made into volumetric molar concentration is the cupric perchlorate solution for later use of 0.2～0.6mol/L;
B, propanedioic acid is dissolved in the deionized water, be stirred to fully dissolving, being made into volumetric molar concentration is the propanedioic acid solution of 0.1～0.3mol/L, in the ratio of the mol ratio 1:2 of propanedioic acid and cupric perchlorate, described propanedioic acid solution and described cupric perchlorate solution are mixed, obtain light blue solution;
C, phenanthroline is dissolved in the ethanol, being made into volumetric molar concentration is the phenanthroline solution of 0.2～0.6mol/L, then in the ratio of the mol ratio 1:1 of phenanthroline and cupric perchlorate, described phenanthroline solution and above-mentioned light blue solution are mixed, blue suspension liquid to be formed, remove by filter insolubles, filtrate is statically placed in room temperature, treat that mazarine shape crystal separates out complete, filter, mazarine shape crystal was ground to form the powder of 100 mesh sieves, and obtained purity and be not less than 99% phenanthroline propanedioic acid copper ferroelectric function material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254218A (en) * | 2013-04-24 | 2013-08-21 | 宁波大学 | O-phenanthroline m-hydroxybenzoic acid copper ferroelectric function material and preparation method thereof |
| CN105017289A (en) * | 2014-04-17 | 2015-11-04 | 宁波大学 | Ferroelectric functional material of copper 4, 4-dipyridyl o-chloromandelic acid hydrate and preparation method of ferroelectric functional material |
| CN105839187A (en) * | 2016-05-06 | 2016-08-10 | 华侨大学 | Organic-inorganic hybridization semiconductor crystal material and synthesis method and application thereof |
| CN106929007A (en) * | 2017-03-10 | 2017-07-07 | 宁波大学 | A kind of cyanic colours fluorescent material and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254218A (en) * | 2013-04-24 | 2013-08-21 | 宁波大学 | O-phenanthroline m-hydroxybenzoic acid copper ferroelectric function material and preparation method thereof |
| CN103254218B (en) * | 2013-04-24 | 2015-09-30 | 宁波大学 | O-phenanthroline m-hydroxybenzoic acid copper ferroelectric function material and preparation method thereof |
| CN105017289A (en) * | 2014-04-17 | 2015-11-04 | 宁波大学 | Ferroelectric functional material of copper 4, 4-dipyridyl o-chloromandelic acid hydrate and preparation method of ferroelectric functional material |
| CN105017289B (en) * | 2014-04-17 | 2017-11-10 | 宁波大学 | One kind 4,4 ' bipyridyl o-chloromandelic acid copper and iron sulfate ferroelectric functional materials of hydration and preparation method thereof |
| CN105839187A (en) * | 2016-05-06 | 2016-08-10 | 华侨大学 | Organic-inorganic hybridization semiconductor crystal material and synthesis method and application thereof |
| CN105839187B (en) * | 2016-05-06 | 2018-07-20 | 华侨大学 | A kind of hybrid inorganic-organic semiconductor crystalline material and its synthetic method and application |
| CN106929007A (en) * | 2017-03-10 | 2017-07-07 | 宁波大学 | A kind of cyanic colours fluorescent material and preparation method thereof |
| CN106929007B (en) * | 2017-03-10 | 2019-01-22 | 宁波大学 | A kind of cyanic colours fluorescent material and preparation method thereof |
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