CN106699550A - Preparation method of nano Cu-CuBTC type metal organic framework material - Google Patents
Preparation method of nano Cu-CuBTC type metal organic framework material Download PDFInfo
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- CN106699550A CN106699550A CN201611141908.XA CN201611141908A CN106699550A CN 106699550 A CN106699550 A CN 106699550A CN 201611141908 A CN201611141908 A CN 201611141908A CN 106699550 A CN106699550 A CN 106699550A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/307—Monocyclic tricarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
Abstract
The invention discloses a preparation method of a nano Cu-CuBTC type metal organic framework material. The method takes a copper nanosheet as a template and 1,3,5-benzenetricarboxylic acid as an organic ligand, a characteristic that the copper nanosheet can slowly release copper ions in a high temperature solution is utilized, and the nano Cu-CuBTC type metal organic framework material is successfully prepared by a hydrothermal method. The method is simple in equipment, controllable in process parameters and extremely high in repeatability. The raw materials required for preparation are abundant, the energy consumption is low, and large-scale production is facilitated. The nano metal framework material is widely applied in catalysts, adsorption, separation and the like.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, it is related to a kind of preparation method of metal-organic framework materials.
Background technology
Metal-organic framework materials (Metal-organicframeworks, MOFs) are new as a class high-sequential
Type porous crystalline material, it has also become one of focus of technical field of material chemistry research.Because there is the hole similar to molecular sieve to tie for it
Structure, bigger serface, high porosity, chemistry can be modified and structure composition diversity, and they are in gas storage, adsorbing separation etc.
Field has broad application prospects.1,3,5- benzenetricarboxylic acids copper (II) (CuBTC) are a kind of typical MOFs materials.
There is unique cubic structure pattern in CuBTC, with multiple adsorption site, possess the pore passage structure and solely of three-dimensional orthogonal
The special string bag structure opened in face of duct, in larger specific surface area and pore volume, and the undersaturated metal active for enriching
The heart, illustrates excellent performance during catalysis, sorbent reactions, causes the widely studied of scientific worker.
Using soluble copper salt with organic ligand organic in current preparation process and technique, the preparation of CuBTC more
Under normal temperature and pressure or using the method for solvent thermal reaction in solvent.The CuBTC that the method is prepared mostly micrometer structures, it is desirable to
Then process is complicated to obtain nanometer materials, and energy consumption is larger.
Nanometer Copper slowly can discharge copper ion as a kind of copper source template in pyrosol, with solution in from
There is reaction in-situ in son, obtain required product.The method does not need additional other copper salt solutions, can efficiently control gained and produce
The size of thing.In addition, Nanometer Copper property is active, the Nanometer Copper not reacted completely also can participate in catalysis, focus as activated centre
The courses of reaction such as conduction.
However, Nanometer Copper prepares CuBTC materials as template and copper source being then rarely reported.Therefore, how using copper nanometer
The characteristic of piece, obtaining nano level CuBTC using simple, low energy consumption method will be significant.
The content of the invention
In order to solve the above problems, the invention provides a kind of method of brand-new preparation nanometer CuBTC materials, the method
Traditional mantoquita is substituted as reaction copper source using copper nanometer sheet, is effectively controlled the agglomeration of gained CuBTC products.
The present invention is achieved through the following technical solutions：
(1) water, glucose, polyvinylpyrrolidone are pressed into certain mass than mixing, is stirred more than 3 hours, obtain clarification mixed
Liquid；
(2) under conditions of stirring, to copper sulfate solution is added dropwise in the mixed liquid of clarification in step (1), it is stirred at room temperature
After 30-60min, it is transferred in hydrothermal reaction kettle in reacting 2.5-4h at 160-200 DEG C；
(3) after the product centrifugation obtained by step (2), using deionized water and absolute ethanol washing, vacuum drying successively
Obtain copper nanometer sheet；
(4) to step (3) gained copper nanometer sheet in add a certain amount of trimesic acid solution in hydrothermal reaction kettle, in baking oven
Middle insulation reaction；
(5) after room temperature cooling after, by products therefrom centrifugation, using absolute ethanol washing, vacuum drying after obtain a nanometer Cu-
CuBTC type metal-organic framework materials powders.
Resulting solution in step (1), water, glucose, the mass ratio of polyvinylpyrrolidone are controlled 25:0.5-1:0.2-
1。
Copper sulphate and the amount ratio of the material of glucose in step (1) are 1 in step (2): 2.5-5.
In step (4), copper nanometer sheet is 3-8 with the mol ratio of trimesic acid:0.25-5.
In step (4), the concentration of trimesic acid solution is 5-25 mmol/L；Preferably, stating trimesic acid solution is
It is the trimesic acid ethanol solution prepared with absolute ethyl alcohol.
In step (4), the reaction temperature of baking oven is 100-150 DEG C, and the reaction time is 2-10h.
In step (5), nanometer Cu-CuBTC materials'use absolute ethyl alcohols are washed.
The beneficial effects of the invention are as follows：The present invention successfully synthesizes a nanometer Cu-CuBTC type metal organic framework materials first
Material, this method equipment is simple, and technological parameter is controllable, and repeatability is high.
Brief description of the drawings
Fig. 1（a）It is the SEM pictures of nanometer Cu-CuBTC materials of the present invention；
Fig. 1（b）It is Fig. 1（a）Partial enlarged drawing；
Fig. 2 is the XRD piece of nanometer Cu-CuBTC materials of the present invention；
Fig. 3 is the TEM pictures of nanometer Cu-CuBTC materials of the present invention；
Fig. 4 is the SEM pictures of copper nanometer sheet template of the present invention.
Specific embodiment
With reference to specific embodiment, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member makes various changes or modifications to the present invention, and these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Embodiment 1
The deionized water of 0.4g glucose, 0.2g polyvinylpyrrolidones and 16mL is stirred into 4h at ambient temperature, obtains clear
Liquid mixed clearly.It is added thereto to the copper-bath of 0.8mmoL, is transferred to after stirring 1h in hydrothermal reaction kettle in being reacted at 160 DEG C
3h, product centrifugation, successively with deionized water, absolute ethanol washing three times, products therefrom is dried to obtain in vacuum drying chamber
Copper nanometer sheet.0.025g copper nanometer sheets are dispersed in 10mL, in the trimesic acid ethanol solution of 10mmoL, hydro-thermal reaction is put into
Kettle insulation reaction 6h in 120 DEG C of baking oven.By products therefrom centrifugation, with absolute ethanol washing, vacuum drying after obtain a nanometer Cu-
CuBTC type metal-organic framework materials powders.
The SEM pictures of copper nanometer sheet are as shown in Figure 4；
SEM, XRD, TEM picture of nanometer Cu-CuBTC materials are respectively such as Fig. 1（a）, Fig. 1（b）, shown in Fig. 2 and Fig. 3.From figure
As can be seen that copper nanometer sheet area load has the nanometer CuBTC materials of column, cylindricality pattern is clear, favorable dispersibility, without substantially
Agglomeration produce.
Embodiment 2
The deionized water of 1.5g glucose, 1g polyvinylpyrrolidones and 40mL is stirred into 4h at ambient temperature, is clarified
Mixed liquid.It is added thereto to the copper-bath of 1.5mmoL, is transferred to after stirring 1h in hydrothermal reaction kettle in reacting 3h at 180 DEG C,
Product is centrifuged, and successively with deionized water, absolute ethanol washing three times, products therefrom is dried to obtain into copper in vacuum drying chamber and is received
Rice piece.0.05g copper nanometer sheets are dispersed in 5mL, in the trimesic acid ethanol solution of 25mmoL, hydrothermal reaction kettle is put into baking
Insulation reaction 4h in 100 DEG C of case.By products therefrom centrifugation, with absolute ethanol washing, vacuum drying after obtain a nanometer Cu-CuBTC
Type metal-organic framework materials powder.
Embodiment 3
The deionized water of 1g glucose, 0.4g polyvinylpyrrolidones and 20mL is stirred into 4h at ambient temperature, is clarified
Mixed liquid.It is added thereto to the copper-bath of 1mmoL, is transferred to after stirring 1h in hydrothermal reaction kettle in 4h is reacted at 170 DEG C, produces
Thing is centrifuged, and successively with deionized water, absolute ethanol washing three times, products therefrom is dried to obtain copper nanometer in vacuum drying chamber
Piece.0.04g copper nanometer sheets are dispersed in 10mL, in the trimesic acid ethanol solution of 15mmoL, hydrothermal reaction kettle is put into baking
Insulation reaction 3h in 130 DEG C of case.By products therefrom centrifugation, with absolute ethanol washing, vacuum drying after obtain a nanometer Cu-CuBTC
Type metal-organic framework materials powder.
Claims (7)
1. a kind of nanometer of preparation method of Cu-CuBTC type metal-organic framework materials, it is characterised in that the method includes following
Step：
(1) water, glucose, polyvinylpyrrolidone are pressed into certain mass than mixing, is stirred more than 3 hours, obtain clarification mixed
Liquid；
(2) under conditions of stirring, to copper sulfate solution is added dropwise in the mixed liquid of clarification in step (1), it is stirred at room temperature
After 30-60min, it is transferred in hydrothermal reaction kettle in reacting 2.5-4h at 160-200 DEG C；
(3) after the product centrifugation obtained by step (2), using deionized water and absolute ethanol washing, vacuum drying successively
Obtain copper nanometer sheet；
(4) to step (3) gained copper nanometer sheet in add a certain amount of trimesic acid solution in hydrothermal reaction kettle, in baking oven
Middle insulation reaction；
(5) after after room temperature cooling, by step（4）Products therefrom centrifugation, using absolute ethanol washing, vacuum drying after obtain nanometer
Cu-CuBTC type metal-organic framework materials powders.
2. the according to claim 1 nanometer of preparation method of Cu-CuBTC type metal-organic framework materials, it is characterised in that：
Resulting solution in step (1), water, glucose, the mass ratio of polyvinylpyrrolidone are controlled 25:0.5-1:0.2-1.
3. the according to claim 1 nanometer of preparation method of Cu-CuBTC type metal-organic framework materials, it is characterised in that：
Copper sulphate and the amount ratio of the material of glucose in step (1) are 1 in step (2): 2.5-5.
4. the according to claim 1 nanometer of preparation method of Cu-CuBTC type metal-organic framework materials, it is characterised in that：
In step (4), the concentration of trimesic acid solution is 5-25 mmol/L；It is with absolute ethyl alcohol that the trimesic acid solution is
The trimesic acid ethanol solution of preparation.
5. the according to claim 1 nanometer of preparation method of Cu-CuBTC type metal-organic framework materials, it is characterised in that：
In step (4), copper nanometer sheet is 3-8 with the mol ratio of trimesic acid:0.25-5.
6. the according to claim 1 nanometer of preparation method of Cu-CuBTC type metal-organic framework materials, it is characterised in that：
In step (4), the reaction temperature of baking oven is 100-150 DEG C, and the reaction time is 2-10h.
7. the preparation method of Cu-CuBTC types metal-organic framework materials according to claim 1, it is characterised in that：Step
(5) in, nanometer Cu-CuBTC materials'use absolute ethyl alcohols are washed.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610489A (en) * | 2018-06-21 | 2018-10-02 | 福州大学 | The preparation method of the nano material of different dimensions based on metal-organic framework material |
| CN109293940A (en) * | 2018-11-22 | 2019-02-01 | 苏州大学 | One-dimensional HKUST-1 nanobelt and preparation method thereof |
| CN111013543A (en) * | 2019-12-12 | 2020-04-17 | 同济大学 | Porous CuBTC ligand assembly synthesis method |
| CN115490868A (en) * | 2021-06-17 | 2022-12-20 | 上海科技大学 | Preparation method of HKUST-1 crystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170647A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Method for forming copper nanometer sheet through self-assembly |
| CN104892518A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Preparation method and application of porous nano metal organic framework material |
-
2016
- 2016-12-12 CN CN201611141908.XA patent/CN106699550B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170647A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Method for forming copper nanometer sheet through self-assembly |
| CN104892518A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Preparation method and application of porous nano metal organic framework material |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610489A (en) * | 2018-06-21 | 2018-10-02 | 福州大学 | The preparation method of the nano material of different dimensions based on metal-organic framework material |
| CN108610489B (en) * | 2018-06-21 | 2023-10-20 | 福州大学 | Preparation method of nano material based on metal organic framework material and with different dimensions |
| CN109293940A (en) * | 2018-11-22 | 2019-02-01 | 苏州大学 | One-dimensional HKUST-1 nanobelt and preparation method thereof |
| CN109293940B (en) * | 2018-11-22 | 2020-10-16 | 苏州大学 | One-dimensional HKUST-1 nanobelt and preparation method thereof |
| CN111013543A (en) * | 2019-12-12 | 2020-04-17 | 同济大学 | Porous CuBTC ligand assembly synthesis method |
| CN111013543B (en) * | 2019-12-12 | 2021-04-09 | 同济大学 | Porous CuBTC ligand assembly synthesis method |
| CN115490868A (en) * | 2021-06-17 | 2022-12-20 | 上海科技大学 | Preparation method of HKUST-1 crystal |
| CN115490868B (en) * | 2021-06-17 | 2023-12-01 | 上海科技大学 | Preparation method of HKUST-1 crystal |
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