CN101768433B - Thermochromic organic cobalt phosphonate material Cox[R(PO3)m]y(H2O)z - Google Patents
Thermochromic organic cobalt phosphonate material Cox[R(PO3)m]y(H2O)z Download PDFInfo
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- CN101768433B CN101768433B CN200910028634.7A CN200910028634A CN101768433B CN 101768433 B CN101768433 B CN 101768433B CN 200910028634 A CN200910028634 A CN 200910028634A CN 101768433 B CN101768433 B CN 101768433B
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- compound
- phospho acid
- organic phospho
- temperature
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- 239000000463 material Substances 0.000 title claims abstract description 19
- LWJGSVGLOAZBQT-UHFFFAOYSA-L [Co+2].[O-]P([O-])=O Chemical compound [Co+2].[O-]P([O-])=O LWJGSVGLOAZBQT-UHFFFAOYSA-L 0.000 title abstract 2
- -1 2-pyridylmethylene cobalt phosphonate compound Chemical class 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 19
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 101100006982 Mus musculus Ppcdc gene Proteins 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002178 crystalline material Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- 125000000962 organic group Chemical group 0.000 abstract description 6
- 238000006297 dehydration reaction Methods 0.000 abstract description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000004700 cobalt complex Chemical group 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
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Abstract
The invention provides novel organic cobalt phosphonate coordination compounds serving as thermochromic materials with composition of Cox[R(PO3)m]y(H2O)z (wherein R is an organic group). The modulation of the composition structure of the materials is realized by changing the R organic group in the organic phosphonic acid so as to adjust the color change temperature of the material and improve the sensitivity. A preparation method adopts low-temperature and low-pressure hydrothermal synthesis technology with low cost, the yield is high and the purity is high. An obtained 2-pyridylmethylene cobalt phosphonate compound with a laminated structure is dehydrated and discolored in two steps at two different temperature regions, and the water re-absorption-re-dehydration process is reversible. Therefore, the material synthesized by the method has better reversible color change performance and can be used for detecting two different temperatures.
Description
Technical field
The present invention relates to the structure that a class has the organic phospho acid cobalt material of reversible thermochromic character forms and preparation method thereof.
Background technology
Thermochromic material produces the novel intelligent material of response as a kind of to external world environmental change, has extremely wide application prospect.Cause the reason of thermochromism to generally include: intermolecular chemical reaction occurs in (1); (2) metallic ion coordination environmental change; (3) crystalline structure changes; (4) thermolysis etc.Wherein a class inorganic thermochromic material commonly used be Cu, Co, Ni etc. with the colored compound of crystal water, as be usually used in cobalt chloride in the discolour silica gel.But the general temperature-sensitive scope of these thermochromatic materials is all narrow, and temperature susceplibility is not high enough.The Low-temperature Thermochromic material of development of new improves variable color stability and temperature susceplibility, will greatly widen Application Areas and the application mode of this class material.
Summary of the invention
The object of the invention is to propose a class and consist of Co
x[R (PO
3)
m]
y(H
2O)
zThe novel organic phospho acid cobalt coordination compound of (wherein R=organic group) is as thermochromic material, with and low-temperature hydro-thermal synthesis.
Technical scheme of the present invention is as follows:
Novel organic phospho acid cobalt coordination compound Co
x[R (PO
3)
m]
y(H
2O)
zAs thermochromic material, it is characterized in that: form structure and mainly include machine phosphonic acid R (PO
3H
2)
n, cobalt metal ion and water molecules three parts.
Described organic phospho acid cobalt coordination compound Co
x[R (PO
3)
m]
y(H
2O)
z, it is characterized in that: organic phospho acid R (PO
3H
2)
nBe different from inorganic phosphate radical PO
4 3-Be that a R organic group (R=CH is arranged
2, CH
3C (OH), C
6H
6, C
5H
5N, C
5H
5NCH
2Deng), n PO
3H
2Link to each other RPO when n=1 with the C atom among the organic group R
3H
2Be organic mono phosphonic acid, R (PO when n=2
3H
2)
2Be organic diphosphonic acid, by that analogy.
Described organic phospho acid cobalt coordination compound Co
x[R (PO
3)
m]
y(H
2O)
zLow-temperature hydro-thermal synthesis, it is characterized in that: described hydrothermal synthesis method is comprised of the following step
Step 1. is dissolved in organic phospho acid in an amount of water, with the cobalt metal salt solution mix of the amount of suitable substance, and the suitable pH value of conditioned reaction thing, stir about is 0.5 hour at ambient temperature,
Step 2. is packed the solution of step 1 gained into and is sealed in the teflon-lined hydrothermal reaction kettle of suitable volumes, temperature programming (5 ℃/minute) is to suitable temp (140～180 ℃), isothermal reaction (0.5 ℃ of the positive negative error of temperature) certain hour (2～7 days), final program cooling (5 ℃/minute) is to normal temperature
Step 3. is filtered the product of step 2 gained, and the solids that obtains cleans vacuum-drying with deionized water, ethanol, the acetone of appropriate amount respectively.
Principle of the present invention
Inorganic thermochromic material commonly used is generally by preparations such as solid phase method, liquid-phase precipitation method, chemical Vapor deposition process, sol-gel technique, magnetron sputtering methods, and the composition structure is not easy regulation and control.And synthetic metal organic phospho acid title complex can realize that material forms the modulation of structure by the R organic group that changes in the organic phospho acid.The Hydrothermal Synthesis of metal organic phospho acid title complex then is to utilize the viscosity at 140～180 ℃ of interval water significantly to descend, separate out so that metal ion and organic phospho acid are easy to form high-purity crystal sedimentation from solution, thereby realize obtaining target substance under lesser temps and the lower pressure condition.
Advantage of the present invention
1, by changing the R group of organic phospho acid, can realize the modulation that organic phospho acid cobalt complex structure forms.
2, by modulation metal-organic phospho acid hydridization main structure, the temperature of adjustable material variable color improves sensitivity.
3, the hydrothermal synthesizing condition of low-temp low-pressure is easy to realize, and is with low cost.
4, the product yield that obtains of this synthetic method is high, and the crystal purity of generation can reach more than 99.9%.
Embodiment
The organic phospho acid of selecting in the embodiment of the invention is 2-pyridine methylene phosphonic acids, and molecular formula is C
5H
4CH
2PO
3H
2, structural formula is as follows:
Embodiment 1, Co (C
5H
4CH
2PO
3) (H
2O)
2Synthetic
CoAc
24H
2O 0.025g (0.1mmol), 2-pyridine methylene phosphonic acids C
5H
4CH
2PO
3H
20.017g (0.1mmol) and 8mLH
2O mixes, stirring at room 0.5 hour, mixture is packed in the teflon-lined stainless steel cauldron, sealing, temperature programming to 140 ℃, isothermal reaction 2 days, programmed cooling filters deionized water, ethanol, washing with acetone to room temperature, vacuum-drying obtains pure red-purple spiculation compound 11mg.Productive rate 41%.Chemical formula C
6H
10NO
5PCo, ultimate analysis calculated value (%): C, 27.09; H, 3.79; N, 5.26; Experimental value (%): C, 27.07; H, 3.78; N, 5.21.
Infrared spectra: (KBr, cm
-1): 3596 (m), 3439 (br), 3096 (br), 2943 (w), 2365 (w), 2344 (w), 1647 (m), 1604 (m), 1568 (m), 1478 (m), 1447 (m), 1397 (w), 1315 (m), 1269 (m), 1216 (m), 1170 (w), 1143 (s), 1116 (s), 1058 (s), 1018 (w), 981 (s), 836 (m), 798 (s), 766 (w), 730 (m), 681 (m), 641 (w), 622 (m), 572 (m), 457 (m), 422 (w).
Crystal parameters: asymmetric cell chemical formula C
6H
10NO
5PCo; Crystallographic system Monoclinic; Spacer P2
1/ c; A=10.697 (2), b=7.346 (1), c=12.439 (2)
, β=110.358 (3) °, V=916.5 (3)
Z=4; D
c=1.928g cm
-3F (000) value 540; GOF value 1.004; R
1=0.0366,, wR
2=0.0931[I＞2 σ (I)]; (Δ ρ)
Max=0.512, e
(Δ ρ)
Min=-0.348e
Co (C
5H
4CH
2PO
3) (H
2O)
2Slough a coordinated water at 50-120 ℃ after the crystalline material heating, obtain purple Compound C o (C
5H
4CH
2PO
3) (H
2O), continue heating and slough second coordinated water at 160-220 ℃, obtain mazarine powdered product Co (C
5H
4CH
2PO
3).
Co (C
5H
4CH
2PO
3) can again absorb water, obtain Co (C
5H
4CH
2PO
3) (H
2O)
2Red powder.Slough a coordinated water at 40-80 ℃ after this powdered material heating, obtain purple Compound C o (C
5H
4CH
2PO
3) (H
2O), continue heating and slough second coordinated water at 140-180 ℃, obtain mazarine Compound C o (C
5H
4CH
2PO
3).After this suction-dehydration can reversiblely be carried out again, and two step dehydration temperaturres are almost constant.
Description of drawings
Fig. 1. Co (C in the example 1
5H
4CH
2PO
3) (H
2O)
2The two-dimensional layer structure
Fig. 2. Co (C in the example 1
5H
4CH
2PO
3) (H
2O)
2Three-dimensional structure
Fig. 3. Co (C in the example 1
5H
4CH
2PO
3) (H
2O)
2Thermogravimetric curve with the product that again absorbs water after the dehydration
Fig. 4. Co (C in the example 1
5H
4CH
2PO
3) (H
2O)
2The colour-change of substep dehydration and the after product that again absorbs water.1：Co(C
5H
4CH
2PO
3)(H
2O)
2；2：Co(C
5H
4CH
2PO
3)(H
2O)；3：Co(C
5H
4CH
2PO
3)。
Claims (2)
1. metal organic phospho acid cobalt coordination compound as thermochromic material, its chemical formula is Co (C
5H
4NCH
2PO
3) (H
2O)
2Perhaps Co (C
5H
4NCH
2PO
3) (H
2O) or Co (C
5H
4NCH
2PO
3), wherein the synthetic middle organic phospho acid that uses of above-mentioned metal organic phospho acid cobalt coordination compound is 2-pyridine methylene phosphonic acids, structural formula is:
2. preparation method of compound as claimed in claim 1 is characterized in that described preparation method is:
Steps A is with CoAc
24H
2O0.025g, 2-pyridine methylene phosphonic acids 0.017g and 8mLH
2O mixes, stirring at room 0.5 hour, mixture is packed in the teflon-lined stainless steel cauldron, sealing, temperature programming to 140 ℃, isothermal reaction 2 days, programmed cooling filters deionized water, ethanol, washing with acetone to room temperature, vacuum-drying obtains pure red-purple spiculation compound Co (C
5H
4NCH
2PO
3) (H
2O)
211mg;
Step B is with the red-purple spiculation compound Co (C of steps A gained
5H
4NCH
2PO
3) (H
2O)
2Slough a coordinated water at 50-120 ℃ after the crystalline material heating, obtain purple Compound C o (C
5H
4NCH
2PO
3) (H
2O), continue heating and slough second coordinated water at 160-220 ℃, obtain mazarine powdered product Co (C
5H
4NCH
2PO
3).
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|---|---|---|---|
| CN200910028634.7A CN101768433B (en) | 2009-01-07 | 2009-01-07 | Thermochromic organic cobalt phosphonate material Cox[R(PO3)m]y(H2O)z |
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|---|---|---|---|
| CN200910028634.7A CN101768433B (en) | 2009-01-07 | 2009-01-07 | Thermochromic organic cobalt phosphonate material Cox[R(PO3)m]y(H2O)z |
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| Publication Number | Publication Date |
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| CN101768433B true CN101768433B (en) | 2013-05-29 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103242382B (en) * | 2013-04-24 | 2016-01-06 | 南京大学 | Chiral rare-earth organic phosphoric acid macroscopic spirochete material |
| CN104789206B (en) * | 2015-04-30 | 2016-12-07 | 浙江大学 | A kind of low-temp reversible thermochromic material and its production and use |
| CN105950131B (en) * | 2016-05-11 | 2018-06-05 | 山西师范大学 | Light heat based on iodine cuprate hybrid causes off-color material and its preparation |
| CN114621298B (en) * | 2022-03-25 | 2024-04-19 | 宿迁学院 | Cobalt organic phosphonic acid compound with high ferrimagnetism order temperature and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260123A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院大连化学物理研究所 | Novel metal organic phosphonate crystal material and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260123A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院大连化学物理研究所 | Novel metal organic phosphonate crystal material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Klaui,W ,et al..[(C5H5Co{P(O)(OH)(2)(3)H]:A novel organometallic tris-phosphonic acid that dissolves glass to form a six-coordinate silicon complex.《CHEMISTRY-A-EUROPEAN JOURNAL》.2002,第8卷(第10期),第2335-2340页. |
| Klaui,W,et al..[(C5H5Co{P(O)(OH)(2)(3)H]:A novel organometallic tris-phosphonic acid that dissolves glass to form a six-coordinate silicon complex.《CHEMISTRY-A-EUROPEAN JOURNAL》.2002,第8卷(第10期),第2335-2340页. * |
| 李子峰等.钴(Ⅱ)和铜(Ⅱ)膦酸配位聚合物的热、磁性能.《化学研究与应用》.2008,第20卷(第9期),第1154-1157页. * |
| 李锦堂、曹登科、郑丽敏.[M(OOCC6H4PO3H)(H2O)](M(Ⅱ)＝Mn,Co,Ni)：表现出金属粒子相关的可变磁性的层状金属有机膦酸化合物.《中国化学会2008年中西部地区无机化学、化工学术交流会会议论文集》.2008,第148页. * |
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