CN102766153A - Method for synchronizing microporous aluminum-base coordination polymers - Google Patents

Method for synchronizing microporous aluminum-base coordination polymers Download PDF

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Publication number
CN102766153A
CN102766153A CN2012102663560A CN201210266356A CN102766153A CN 102766153 A CN102766153 A CN 102766153A CN 2012102663560 A CN2012102663560 A CN 2012102663560A CN 201210266356 A CN201210266356 A CN 201210266356A CN 102766153 A CN102766153 A CN 102766153A
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China
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method
synchronizing
coordination polymers
temperature
microporous aluminum
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CN2012102663560A
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Chinese (zh)
Inventor
陈金喜
蒋婧
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东南大学
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Priority to CN2012102663560A priority Critical patent/CN102766153A/en
Publication of CN102766153A publication Critical patent/CN102766153A/en

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Abstract

The invention provides a method for synchronizing microporous aluminum-base coordination polymers. The method includes the following steps of utilizing Al(NO3)3 9H2O and ligand, 1,4-naphthalene diacid as raw materials and water as solvent, subjecting the raw materials to reaction for 2-32 hours at the temperature of 40-80 DEG C in 250W, filtering the obtained solution untile the temperature falls to the room temperature, and sequentially washing with deionized water, N,N-dimethylformamide and ethanol, drying at the room temperature and obtaining the microporous aluminum-base coordination polymers. The method for synchronizing microporous aluminum-base coordination polymers has the advantages of operable simplicity, high yield, simple posttreatment, fastness and environment-friendliness and the like.

Description

Aluminium base microporous coordination polymer compound method

Technical field

The present invention relates to the method that a kind of microwave method prepares aluminium base ligand polymer.That the present invention has is simple to operate, yield is high, aftertreatment simply reaches characteristics such as quick environmental protection.

Background technology

(metal-organic framework is to be formed through the supramolecule self-assembly by metals ion and organic ligand MOF) to the organic porous ligand polymer of metal.This title complex can through different metal ion and various rigidity organic ligands mutually complexing synthesize the metal-organic framework of Different Pore Structures, and can be with on the organic ligand some functional modifying factors (as Br ,-NH 2Deng), it is unique and functional that this title complex is structurally had more.As far back as the mid-90 in 20th century, first kind MOF just is synthesized out, but its porosity and chemicalstability are not high.Therefore, scientist's ligand polymer that novel positively charged ion, negatively charged ion and neutral ligand form that begins one's study.At present, there has been a large amount of metal-organic framework materials to be synthesized, mainly has been to be main, or uses jointly with the organic neutral ligand of nitrogen heterocyclic ring to contain carboxyl organic anion part.Majority all has the chemicalstability that high porosity is become reconciled in these metallic organic frameworks.Because the structure and the specific surface area of ability control punch are big, MOF has application prospect widely than other porous material, like fractionation by adsorption, catalyzer, magneticsubstance and optical material etc.In addition, MOF is as a kind of extremely-low density porous material, aspect the fuel gas such as a large amount of methane of storage and hydrogen very big potentiality arranged.

In general, the ligand polymer preparation direct synthesis techniques that adopt more, promptly metal salt solution and part are at the aqueous solution or organic solvent such as DMF (N; N '-N), DEF (N; N '-N,N-DIMETHYLACETAMIDE), methyl alcohol, ethanol etc., obtain the micropore coordinate complex that the duct is occupied by the solvent guest molecule through the reaction of methods such as hydrothermal method, solvent-thermal method, diffusion process, pass through pre-treatment again; Promptly with after lower boiling organic solvent such as the chloroform washing, heating, vacuum is drained and can be obtained poromerics.

UW is for the effect of chemical reaction, is considered to usually because ultrasonic cavitation causes.UW is incorporated into the preparation of synthetic, the nano material that has been widely used in organic reaction, polymkeric substance in the reaction process etc.; It is usually than traditional method high in efficiency and convenience more; But up to just having research that it is used for the ligand polymer field in recent years, and find that it has advantage efficiently equally.

Summary of the invention

Technical problem: the purpose of this invention is to provide the high aluminium base microporous coordination polymer compound method of a kind of yield.

Technical scheme: for solving the problems of the technologies described above, the present invention provides a kind of aluminium base microporous coordination polymer compound method, and this method comprises the steps: the (NO with Al 3) 39H 2O and 1,4-H 2NDC (Al (NO 3) 39H 2O is an ANN aluminium nitrate nonahydrate, 1, and 4-H 2NDC is 1,4-naphthalene diacid) be raw material, water is made solvent, and reaction is 2~32 hours under 40~80 ℃, 250W; Treat that temperature reduces to room temperature, filter gained solution, and use deionized water, N successively; Dinethylformamide, washing with alcohol, normal temperature are dry down, obtain aluminium base microporous coordination polymer.

Preferably, Al (NO 3) 39H 2O and 1,4-H 2The mol ratio of NDC is 1:1.

Beneficial effect: this compound method simple and fast is environmentally friendly green synthesis method, and this method synthetic microporous coordination polymer is easy to preparation, and productive rate is higher, and cost of material is cheap.

Description of drawings

Fig. 1 is the x-ray diffraction pattern of the product of embodiment one preparation;

Fig. 2 is the x-ray diffraction pattern of the product of embodiment two preparations;

Fig. 3 a is that embodiment two is 80 ℃ in temperature, and the time is the sem photograph of the product that prepared under the situation in 2 hours;

Fig. 3 b is that embodiment three is 80 ℃ in temperature, and the time is the sem photograph of the product that prepared under the situation in 5 hours;

Fig. 3 c is that embodiment two is 80 ℃ in temperature, and the time is the sem photograph of the product that prepared under the situation in 7 hours;

Fig. 4 is the productive rate figure of the product of embodiment three preparations.

Embodiment

Below in conjunction with accompanying drawing the present invention is further specified.

The present invention is with the synthetic microporous ligand polymer of ultrasonic method: Al (NO 3) 39H 2O and ligand 1,4-H 2NDC (Al (NO 3) 39H 2O is an ANN aluminium nitrate nonahydrate, 1, and 4-H 2NDC is 1,4-naphthalene diacid) be raw material, water is made solvent; Reaction 2~32h under 40~80 ℃, 250W treats that temperature reduces to room temperature, filters gained solution; And use deionized water, DMF, washing with alcohol successively, normal temperature is dry down, finally obtains off-white powder shape product; Be a kind of aluminium base microporous coordination polymer Al (OH) (1,4-NDC) 2H 2O, 1,4-NDC 2-Be 1,4-naphthalene two acid groups.

Among the preparation method, Al (NO 3) 39H 2O and 1, the mol ratio of 4-naphthalene diacid is 1:1.

Among the preparation method, temperature of reaction is 40~80 ℃.

Among the preparation method, the reaction times is 2~32h.

The present invention as aluminium base microporous coordination polymer Al (OH) (1,4-NDC) 2H 2O (1,4-NDC 2-Be 1,4-naphthalene two acid groups) preparation method is a ultrasonic method, and preparation process is:

A). take by weighing Al (NO 3) 39H 2O 0.375g (1.0mmol) and 1,4-H 2NDC 0.216g (1.0mmol) (mol ratio Al 3+: 1,

4-NDC 2-=1:1, wherein 1,4-NDC 2Be 1,4-naphthalene two acid groups) place the beaker of 25mL, add the 15.0mL deionized water, stir it is mixed, obtain faint yellow turbid solution;

B). it is the ultrasonic cleaner of 250W that beaker is placed power, and ultrasonic certain hour obtains milky white precipitate under the certain temperature;

C). filter above-mentioned solution, and use deionized water, N successively, dinethylformamide, washing with alcohol, normal temperature is dry down, finally obtains off-white powder shape product.

Embodiment one:

Divide another name Al (NO 3) 39H 2O 0.375g (1.0mmol) and 1,4-H 2NDC 0.216g (1.0mmol) (mol ratio Al 3+: 1,4-NDC 2-=1:1, wherein 1,4-NDC 2Be 1,4-naphthalene two acid groups) placing volume is the 25mL beaker, adds the 15.0mL deionized water; Stirring mixes it, obtains faint yellow turbid solution, and beaker is placed ultrasonic cleaning machine; Keep 4h down at 60 ℃, close instrument and be cooled to room temperature, obtain milky white precipitate; Filter and use successively deionized water, DMF, washing with alcohol, normal temperature is dry down, finally obtains off-white powder shape product.

Embodiment two:

Take by weighing Al (NO respectively 3) 39H 2O 0.375g (1.0mmol) and 1,4-H 2NDC 0.216g (1.0mmol) (mol ratio Al 3+: 1,4-NDC 2-=1:1, wherein 1,4-NDC 2Be 1,4-naphthalene two acid groups) placing volume is the 25mL beaker, adds the 15.0mL deionized water; Stirring mixes it, obtains faint yellow turbid solution, and beaker is placed ultrasonic cleaner; Under 80 ℃, keep 2h, 5h and 7h respectively, close instrument and be cooled to room temperature, obtain oyster white look deposition; Filter and use successively deionized water, DMF, washing with alcohol, normal temperature is dry down, finally obtains off-white powder shape product.

Embodiment three:

Take by weighing Al (NO respectively 3) 39H 2O 0.375g (1.0mmol) and 1,4-H 2NDC 0.216g (1.0mmol) (mol ratio Al 3+: 1,4-NDC 2-=1:1, wherein 1,4-NDC 2Be 1,4-naphthalene two acid groups) placing volume is the 25mL beaker, adds the 15.0mL deionized water; Stirring mixes it, obtains faint yellow turbid solution, and beaker is placed ultrasonic cleaner; Under 40 ℃, 60 ℃ and 80 ℃, keep different time respectively, close instrument and be cooled to room temperature, obtain milky white precipitate; Filter and use successively deionized water, DMF, washing with alcohol, normal temperature is dry down, finally obtains off-white powder shape product.

The above is merely preferred embodiments of the present invention; Protection scope of the present invention is not exceeded with above-mentioned embodiment; As long as the equivalence that those of ordinary skills do according to disclosed content is modified or changed, all should include in the protection domain of putting down in writing in claims.

Claims (2)

1. an aluminium base microporous coordination polymer compound method is characterized in that, this method comprises the steps: the (NO with Al 3) 39H 2O and ligand 1,4-naphthalene diacid is a raw material, and water is made solvent, and reaction is 2 ~ 32 hours under 40 ~ 80 ℃, 250W; Treat that temperature reduces to room temperature, filter gained solution, and use deionized water, N successively; Dinethylformamide, washing with alcohol, normal temperature are dry down, obtain aluminium base microporous coordination polymer.
2. aluminium base microporous coordination polymer compound method according to claim 1 is characterized in that Al (NO 3) 39H 2O and 1, the mol ratio of 4-naphthalene diacid is 1:1.
CN2012102663560A 2012-07-30 2012-07-30 Method for synchronizing microporous aluminum-base coordination polymers CN102766153A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101379072A (en) * 2006-02-07 2009-03-04 韩国化学研究院 A preparation method of porous hybrid inorganic-organic materials
CN101531672A (en) * 2008-03-12 2009-09-16 安徽大学 Metal-organic framework material with nano pores and preparation method and application thereof
CN102329333A (en) * 2011-06-24 2012-01-25 东南大学 Preparation method of aluminum-based organic microporous coordination polymer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101379072A (en) * 2006-02-07 2009-03-04 韩国化学研究院 A preparation method of porous hybrid inorganic-organic materials
CN101531672A (en) * 2008-03-12 2009-09-16 安徽大学 Metal-organic framework material with nano pores and preparation method and application thereof
CN102329333A (en) * 2011-06-24 2012-01-25 东南大学 Preparation method of aluminum-based organic microporous coordination polymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ANGIOLINA COMOTTI ET AL.: "Nanochannels of Two Distinct Cross-Sections in a Porous Al-Based Coordination Polymer", 《JOURNAL OF AMERICAN CHEMISTRY》 *

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