CN104710303A - Spherical coordination polymer material and preparation method thereof - Google Patents
Spherical coordination polymer material and preparation method thereof Download PDFInfo
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- CN104710303A CN104710303A CN201310691036.4A CN201310691036A CN104710303A CN 104710303 A CN104710303 A CN 104710303A CN 201310691036 A CN201310691036 A CN 201310691036A CN 104710303 A CN104710303 A CN 104710303A
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Abstract
The invention relates to a spherical coordination polymer material and a preparation method thereof, wherein the material is polymerized from metal ions and an organic ligand containing a carboxyl group. The coordination polymer material has a spherical shape, has a particle size of 50-1000 nm, and provides wide application prospects in the fields of gas storage, separation, drug release, catalysis materials, and the like.
Description
Technical field
The invention belongs to nano material and preparation method thereof, specifically a kind of metal organic coordination polymer material.
Background technology
Coordination polymer material is the organic-inorganic hybrid material be polymerized by metal ion and organic ligand, and its structure composition can be controlled by the structure of metal species and part.By the structure of the geometric configuration control mesh of part, utilize organic bridge receipts or other documents in duplicate unit to assemble with metal ion the solid obtaining measurable geometry, and these solids reflect the function of anticipation.Because, in catalysis, biological medicine, environment, gas storage and be separated, the field such as fluorescence, energy has a wide range of applications, and causes the extensive concern of people.Recently, the size of coordination polymer material and morphology control, become the focus of research.Compare inorganic materials and organic polymer material, people to the crystallization behavior understanding of coordination polymer material seldom.To the pattern of coordination polymer material and size control also more difficult.The current pattern of control coordination polymer material and the method for size, Ligand Competition coordination mainly by introducing another organic ligand and bridging affects crystallization behavior, or introduce tensio-active agent and limit the growth of crystal, or by some any special measures and technology.
The polymer materials that metal ion and Carboxylic acid ligand are formed is the coordination polymer materials extensively studied at present.At present, take carboxylic acid as the coordination polymer material of organic ligand, cube, sheet, pattern that is bar-shaped, wire had report (J.Am.Chem.Soc.2012,134,1317; J.Am.Chem.Soc.2011,133,15506; J.Am.Chem.Soc.2010,132,10391; J.Am.Chem.Soc.2008,130,14358.).But these coordination polymer materials are generally by adding some additives, such as tensio-active agent, organic ligand etc.; Or adopt some new technologies, such as ultrasonic, microwave etc.; Or adopt the part of some more complicated.And these ligand polymer are that one has polyhedral crystal mostly.Preparation has the ligand polymer of regular spherical pattern, and realizes the controlled modulation of size and chemical constitution, remains a huge challenge.
The present invention has developed a kind of new synthetic method, can synthesize the material of the ligand polymer with regular spherical pattern, and can realize the controllable adjustment of size and composition.This material has a wide range of applications in fields such as catalysis, biology, medicine, fluorescence.
Summary of the invention
Object of the present invention provides a kind of spherical coordination polymer materials and preparation method thereof, is exactly that under certain solvent and temperature, polycoordination forms with metal ion and organic carboxyl acid for construction unit specifically.The well-regulated spherical morphology of this material tool, particle diameter is 50-1000nm.
A kind of spherical coordination polymer materials, metal ion is Mg
2+, Ni
2+, Zn
2+, In
3+, Y
3+, Pm
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+in one or more.Metal ion is highly dispersed among material.The precursor of described metal ion is its nitrate, vitriol, chlorate, one or more in acetate.
A kind of spherical coordination polymer materials, organic ligand is the rigidity organic molecule containing two carboxylic groups, the m-phthalic acid referred to and fragrant cyclosubstituted derivative thereof, 3, the derivative of 5-pyridine dicarboxylic acid and replacement thereof, with one or more (Fig. 1) in 1,5-naphthalene diacid and fragrant cyclosubstituted derivative thereof.Substituting group (R
1-R
6) be F, Cl, Br, I, NO
2, CH
3, OH, OCH
3, NH
2in one or more.
In order to make organic molecule and the full and uniform hybrid reaction of metal salt ligands, need to use suitable dissolution with solvents organic molecule monomer, homogeneous reaction.Described organic solvent is one or more in acetonitrile, dimethyl sulfoxide (DMSO), dioxane, toluene, tetrahydrofuran (THF) and diformamide.
Temperature of reaction and time directly affect the speed of polycoordination and growth, thus affect the size of material.In order to control material size at nano level to micron order, optimal conditions is: temperature of reaction is 30-200 DEG C, and the reaction times is 10 minutes-72 hours;
The concentration of metal-salt and organic molecule monomer directly affects speed of reaction, and speed of reaction speed also directly affects the size of material, simultaneously the final pattern of metal-salt and organic molecule monomer mole ratio meeting direct relation material.In polyreaction, in added raw material, optimal conditions is: the volumetric molar concentration of metal and organic molecule is 0.1-100mM; Metal is 0.5-2 with the organic molecule mol ratio containing hydroxy-acid group.
The coordination polymer material of the present invention's synthesis, the well-regulated spherical morphology of tool, have that granular size can regulate and control, uniform particle sizes, good dispersity, the feature such as simple to operate.
Accompanying drawing explanation
The carboxylic organic ligand structural representation of Fig. 1.
Fig. 2 materials A stereoscan photograph.
Embodiment
By finite concentration, and the organic molecule of certain metal-salt and organic carboxyl acid small molecules ratio is dissolved among solvent, certain temperature and under the time, and reactive polymeric forms.Metal ion in metal-salt is Mg
2+, Ni
2+, Zn
2+, In
3+, Y
3+, Pm
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+in one or more; The presoma of metal ion is one or more in nitrate, vitriol, chlorate, acetate.Organic carboxyl acid molecule is m-phthalic acid and fragrant cyclosubstituted derivative thereof, the derivative of 3,5-pyridine dicarboxylic acid and replacement thereof, and one or more in 1,5-naphthalene diacid and fragrant cyclosubstituted derivative thereof.Described organic solvent is one or more in acetonitrile, dimethyl sulfoxide (DMSO), dioxane, toluene, tetrahydrofuran (THF) and diformamide.Reaction optimal conditions is: the volumetric molar concentration of metal-salt and organic molecule is 0.1-100mM; Metal is 0.5-2 with the organic molecule mol ratio containing hydroxy-acid group.Temperature of reaction is 30-200 DEG C, and the reaction times is 10 minutes-72 hours.
Below by embodiment, method provided by the invention is described in detail, but do not limit the present invention in any form.
The preparation of embodiment 1 materials A
Get 0.1mmol m-phthalic acid and 0.1mmol Yttrium trinitrate is dissolved in 20mL dimethyl sulfoxide (DMSO).100 DEG C of reaction 48h.After being cooled to room temperature, centrifugal, the 50mL acetonitrile cleaning of gained solid, dry 24h at 100 DEG C.As shown in Figure 1, can find out that made material particle size is even from scanning electron microscope, the well-regulated spherical morphology of tool, particle diameter is about 300nm.
The preparation of embodiment 2 material B-L
The same materials A of preparation method of material B-L, difference is source metal and organic ligand and concentration thereof and mol ratio, temperature of reaction, reaction times and organic solvent.Organic ligand is the substituting group derivative of m-phthalic acid, and table 1 listed in by preparation condition and the material obtained.
Table 1 material B-L and preparation condition thereof
The preparation of embodiment 3 material M
Get 0.2mmol3,5-pyridine dicarboxylic acid and 0.2mmol europium nitrate are dissolved in 20mL dioxane.160 DEG C of reaction 1h.After being cooled to room temperature, centrifugal, the 50mL acetonitrile cleaning of gained solid, dry 24h at 100 DEG C.
The preparation of embodiment 4 material N-S
The preparation method of material N-S is with material M, and difference is source metal and organic ligand and concentration thereof and mol ratio, temperature of reaction and reaction times.Organic ligand is the substituting group derivative of 3,5-pyridine dicarboxylic acid, and table 2 listed in by preparation condition and the material obtained.
Table 2 material N-S and preparation condition thereof
The preparation of embodiment 5 material T
Get 0.5mmol1,5-naphthalene diacid and 0.5mmol ytterbium nitrate are dissolved in 20mL diformamide.140 DEG C of reaction 2h.After being cooled to room temperature, centrifugal, the 50mL acetonitrile cleaning of gained solid, dry 24h at 100 DEG C.
The preparation of embodiment 6 material U-Z
The preparation method of material U-Z is with material T, and difference is source metal and organic ligand and concentration thereof and mol ratio, temperature of reaction and reaction times.Organic ligand is the substituting group derivative of 1,5-naphthalene diacid, and table 3 listed in by preparation condition and the material obtained.
Table 3 material U-Z and preparation condition thereof
Embody rule purposes:
Because this material has metal ion, active centre can be provided in catalyzed reaction; Can as the catalyzer of acid catalyzed reaction, particularly catalyst for oxidation reaction.The nitrile Silanization reaction of phenyl aldehyde is ion:
0.5mmol phenyl aldehyde, 0.05g catalyzer and 5mL methylene dichloride join in reactor, stirred at ambient temperature reaction 6h.Product gas chromatographic analysis.Reaction result is in table 1.As can be seen from Table 4, the spherical coordination polymer materials of the present invention's synthesis is a kind of extraordinary acid catalyst, in the nitrile Silanization reaction of phenyl aldehyde, show good catalytic effect.
The nitrile Silanization reaction result of table 4 phenyl aldehyde
| Catalyzer | Yield/% |
| A | 90 |
| B | 99 |
| C | 98 |
| D | 91 |
| E | 88 |
| F | 99 |
| G | 96 |
| H | 94 |
| I | 92 |
Claims (6)
1. a spherical coordination polymer materials, is characterized in that: this material is that polycoordination forms in a solvent by metal ion and the organic molecule containing carboxylic group; This material has spherical morphology, and particle diameter is 50-1000nm.
2. according to spherical coordination polymer materials described in claim 1, it is characterized in that: described metal ion is Mg
2+, Ni
2+, Zn
2+, In
3+, Y
3+, Pm
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+in one or more than two kinds;
The described organic molecule containing carboxylic group, refers to the one in m-phthalic acid and fragrant cyclosubstituted derivative, 3,5-pyridine dicarboxylic acids and fragrant cyclosubstituted derivative thereof and 1,5-naphthalene diacid and fragrant cyclosubstituted derivative thereof or more than two kinds;
Substituting group in the cyclosubstituted derivative of described virtue on aromatic ring is F, Cl, Br, I, NO
2, CH
3, OH, OCH
3, NH
2in one or more than two kinds, substituent number is 1-6.
3. a preparation method for spherical coordination polymer materials described in claim 1 or 2, is characterized in that:
This material is that polycoordination forms in a solvent by metal ion and the organic molecule containing carboxylic group; Temperature of reaction is 30-200 DEG C, and the reaction times is 10 minutes-72 hours.
4. according to preparation method according to claim 3, it is characterized in that: organic solvent is one or two or more kinds in acetonitrile, dimethyl sulfoxide (DMSO), dioxane, toluene, tetrahydrofuran (THF) and diformamide.
5., according to preparation method according to claim 3, it is characterized in that:
Described metal ion is Mg
2+, Ni
2+, Zn
2+, In
3+, Y
3+, Pm
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+in one or more than two kinds;
The metal ion presoma that polymerization process adopts is the nitrate of metal, vitriol, chlorate, the one in acetate or more than two kinds;
The described organic molecule containing carboxylic group, refers to the one in m-phthalic acid and fragrant cyclosubstituted derivative, 3,5-pyridine dicarboxylic acids and fragrant cyclosubstituted derivative thereof and 1,5-naphthalene diacid and fragrant cyclosubstituted derivative thereof or more than two kinds;
Substituting group in the cyclosubstituted derivative of described virtue on aromatic ring is F, Cl, Br, I, NO
2, CH
3, OH, OCH
3, NH
2in one or more than two kinds, substituent number is 1-6.
6. according to preparation method according to claim 1, it is characterized in that: in added raw material, the volumetric molar concentration of metal and organic molecule is respectively 0.1-100mM; Metal is 0.5-2 with the organic molecule mol ratio containing carboxylic group.
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| CN107286184A (en) * | 2017-07-10 | 2017-10-24 | 肇庆学院 | A kind of zinc metal-organic framework materials and preparation method thereof |
| CN108070090A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of sugar-metal coordinating polymer material and preparation method thereof |
| CN108070091A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of chirality sugar-metal coordinating polymer material and preparation method thereof |
| CN110787790A (en) * | 2019-11-13 | 2020-02-14 | 武汉纺织大学 | Sea urchin-shaped metal oxide porous photocatalytic material and preparation method and application thereof |
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| CN108070090A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of sugar-metal coordinating polymer material and preparation method thereof |
| CN108070091A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of chirality sugar-metal coordinating polymer material and preparation method thereof |
| CN107286184A (en) * | 2017-07-10 | 2017-10-24 | 肇庆学院 | A kind of zinc metal-organic framework materials and preparation method thereof |
| CN107286184B (en) * | 2017-07-10 | 2019-05-28 | 肇庆学院 | A kind of zinc metal-organic framework materials and preparation method thereof |
| CN110787790A (en) * | 2019-11-13 | 2020-02-14 | 武汉纺织大学 | Sea urchin-shaped metal oxide porous photocatalytic material and preparation method and application thereof |
| CN110787790B (en) * | 2019-11-13 | 2022-04-29 | 武汉纺织大学 | Sea urchin-shaped metal oxide porous photocatalytic material and preparation method and application thereof |
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