CN110330661A - The preparation method of gradient copper cobalt dual-metal organic framework materials - Google Patents
The preparation method of gradient copper cobalt dual-metal organic framework materials Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of gradient copper cobalt dual-metal organic framework materials.Prepare 2-methylimidazole aqueous solution, cobalt saline solution, copper salt solution respectively first, then 2-methylimidazole aqueous solution is mixed with cobalt saline solution, copper salt solution is added in mixed liquor with certain rate of addition again and is stirred to react, is finally stood, isolated target product.The present invention regulates and controls the growth of cobalt metallic crystal by copper metal ion, and thus obtained gradient copper cobalt dual-metal organic framework materials partial size is smaller, has a variety of crystalline structures, and structure is adjustable and performance is stablized, and industrial applications prospect is preferable.
Description
Technical field
The present invention relates to technical field of function materials, and in particular to a kind of system of gradient copper cobalt dual-metal organic framework materials
Preparation Method.
Background technique
Metal-organic framework material (Metal-Organic Frameworks, abbreviation MOFs) is used as a kind of novel porous nothing
Machine-organic hybrid crystalline material, be widely used in gas storage with separate, shine, sense, be catalyzed, the fields such as magnetism.MOFs packet
Monometallic organic frame compound and bimetallic organic frame compound etc. are included, wherein the duct of bimetallic organic frame compound
Structure and frame are more flexible changeable, and function is more various, have outstanding not available for more monometallic organic frame compounds
Performance, therefore more and more attracted the concern of scientific research personnel.
CN105566654A discloses one-dimentional structure metal organic framework compound and preparation method thereof.This method includes matching
Oversaturated organic ligand solution is made, metal salt is then added and is reacted, being finally separating to obtain one-dimentional structure metal has machine frame
Frame compound.The target product of the program is a kind of monometallic organic frame compound, and toughness and mechanical strength are in certain journey
It is improved on degree.
CN109126885A discloses a kind of copper cobalt dual-metal organic frame/nano-fiber composite material and preparation method thereof
And application, the program prepare copper cobalt dual-metal organic framework using solvent-thermal method, it is double that copper cobalt then is made by electrostatic spinning
The efficiency of metal organic frame/nano-fiber composite material, the composite material catalytic degradation azo dyes is higher, and easily returns
It receives.
CN109647407A is related to a kind of for methane/nitrogen separation bimetallic organic framework material adsorbent and its system
Preparation Method, wherein organic ligand be HCOOH, two metal ion species be respectively Ni (II) and Mg (II) or Mn (II) or Fe (II) or
Co (II) or Cu (II) or Cd (II), when preparation, first mix a kind of metal with organic ligand solution, and another gold is then added
Belong to solution, bimetallic organic framework material adsorbent is made using solvent-thermal method after mixing, which has microcellular structure.
CN106673992A discloses a kind of conductor oxidate nanoparticle doped carbon nitrogen/MOF nanocomposite
Preparation method and its application for being catalyzed fixed nitrogen, the organic ligand of selection are 2, and dipicolimic acid 2 directly will at room temperature
The mixed solution and organic ligand solution hybrid reaction of two kinds of metals, are then calcined, in air to obtain oxide
Nanoparticle doped carbon nitrogen/MOF nanocomposite.
As the Typical Representative in metal-organic framework material, although most of cobalt-based metal MOFs materials are in catalytic performance
Etc. it is more prominent, but the cobalt ions contained by it is more toxic, and cobalt-based metal MOFs material is in application process not
It is enough to stablize, it is easy to pollute environment.Solve the method for this problem first is that introduce a kind of metallic element, form bimetallic cobalt-based
MOFs material.As described in patent document enumerated supra, the common methods for preparing bimetallic MOFs material include two kinds: a
Directly by two kinds of metal salt solutions simultaneously with ligand solution hybrid reaction；B first mixes a kind of metallic solution and organic ligand solution
It closes, adds another metallic solution and reacted.However it was verified that is deposited using bimetallic MOFs made from both methods
The disadvantages of structure is uncontrollable, property is unstable.
Summary of the invention
In view of the above problems and insufficient, the structure that the present invention overcomes existing bimetallic MOFs synthetic method generally existing can not
Control, the problems such as property is unstable, by improve synthesis technology develop it is a kind of it is simple and reliable, environmentally protective, convenient for industrialized
Gradient copper cobalt dual-metal MOFs new synthetic method, the specific steps of which are as follows: (a) prepares 2-methylimidazole aqueous solution, cobalt salt respectively
Aqueous solution, copper salt solution are spare；(b) 2-methylimidazole aqueous solution is mixed with cobalt saline solution, after reaction a period of time again
Copper salt solution is added drop-wise in mixed solution to the reaction was continued, stands, isolated gradient copper cobalt dual-metal organic framework materials.
Further, cobalt salt used in cobalt saline solution is prepared in cobalt nitrate, cobalt chloride, cobaltous sulfate, cobalt acetate
Any one.
Further, mantoquita used in copper salt solution is prepared in copper nitrate, copper chloride, copper sulphate, copper acetate
Any one.
Further, the concentration of 2-methylimidazole aqueous solution is 150-250g/L, and the concentration of cobalt saline solution is 50-70g/
L, the concentration of copper salt solution are 5-15g/L.
Further, the molar ratio of mantoquita needed for reacting and cobalt salt is 1:4-9, the sum of mantoquita, cobalt salt needed for reacting and 2-
The molar ratio of methylimidazole is 1:6-10.
Further, detailed process is as follows for step (b): cobalt saline solution being added to 2-methylimidazole aqueous solution in proportion
In, 10-30min is stirred with the revolving speed of 500-1000rpm；It is kept stirring that speed is constant, with the rate of addition of 20-40mL/h by copper
Saline solution is slowly dropped in mixed solution, and 8-12h is stood after being added dropwise to complete, and is finally centrifugated, is washed, is dry, obtaining
Gradient copper cobalt dual-metal organic framework materials.
Further, all operations in step (b) carry out at room temperature.
The pore structure of gradient CuCo-ZIF produced by the present invention is mainly micropore, and increasing hole type along with Cu content has increasing
The trend added；Compared to Co monometallic organic frame compound ZIF-67, gradient CuCo-ZIF is in addition to the tradition with ZIF-67
Outside crystal form, also possess the diffraction maximum of a variety of crystal faces such as a variety of copper cobalt hydrates (001), (220), (221), (210), this explanation should
Gradient CuCo-ZIF crystalline structure multiplicity, it is more complicated.
The present invention use by copper salt solution with certain rate be added drop-wise to mode in cobalt salt and organic ligand mixed liquor into
Row reaction, principle is to make itself and cobalt ions competitive coordination using copper salt solution as regulator, to control the molding of crystal
Journey, the crystal being consequently formed have different pore structures.Additionally due to the adjustment effect of copper ion, gradient CuCo-ZIF obtained
With different crystal structures, cellular structure is more rich and varied.
Compared with prior art, the invention has the following advantages: preparation process is simple, environmentally protective, reaction condition
Mildly, it is suitble to industrialization large-scale promotion；Product has different crystal structures, compared to monometallic organic frame compound,
Surface cellular structure and function of the present invention are more various, compared to common bimetallic organic frame compound, product of the present invention
Pore-size distribution and pore structure are adjustable, and stability is more preferable.
Detailed description of the invention
Fig. 1 is the XRD comparison diagram of metal-organic framework material made from embodiment 1,3 and comparative example 1；
Fig. 2 is embodiment 2, bimetallic organic framework materials SEM comparison diagram made from comparative example 2；
Fig. 3 is the graph of pore diameter distribution of gradient copper cobalt dual-metal organic framework materials made from embodiment 1,3；
Fig. 4 is the specific surface area figure of gradient copper cobalt dual-metal organic framework materials made from embodiment 1,3.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further described.
Embodiment 1
A kind of preparation method of gradient copper cobalt dual-metal organic framework materials, includes the following steps:
1) 0.04mol 2-methylimidazole is added in 20mL deionized water, stirring (500-1000rpm, similarly hereinafter) makes it
It is completely dissolved, obtains 2-methylimidazole aqueous solution.
2) 5mmol cobalt nitrate is added in 20mL deionized water, stirring, which dissolves it sufficiently, obtains cobalt nitrate aqueous solution,
Cobalt nitrate aqueous solution is added in the prepared 2-methylimidazole aqueous solution of step (1), stirring is uniformly mixed it.
3) 1.25mmol copper nitrate is added in 20mL deionized water, stirring makes it completely dissolved, and obtains nitric acid copper water
Solution.After mixed solution stir about 30min in step (2), using syringe pump with the rate of addition of 40mL/h within 30min
Copper nitrate aqueous solution is all added drop-wise in mixed solution, entire dropwise addition process is kept stirring state.After being added dropwise, stand
10h obtains suspension.
4) suspension is centrifugally separating to obtain solid product, is washed with deionized and dries afterwards for several times, and it is double to obtain gradient copper cobalt
Metal-organic framework material (Cu, Co molar ratio are 1:4), is denoted as 1-CuCo-ZIF.
Embodiment 2
A kind of preparation method of gradient copper cobalt dual-metal organic framework materials, includes the following steps:
1) 0.04mol 2-methylimidazole is added in 20mL deionized water, stirring makes it completely dissolved, and obtains 2- first
Base imidazoles aqueous solution.
2) 5mmol cobalt nitrate is added in 20mL deionized water, stirring, which dissolves it sufficiently, obtains cobalt nitrate aqueous solution,
Cobalt nitrate aqueous solution is added in the prepared 2-methylimidazole aqueous solution of step (1), stirring is uniformly mixed it.
3) 0.830mmol copper nitrate is added in 20mL deionized water, stirring makes it completely dissolved, and obtains nitric acid copper water
Solution.After mixed solution stir about 30min in step (2), using syringe pump with the rate of addition of 40mL/h within 30min
Copper nitrate aqueous solution is all added drop-wise in mixed solution, entire dropwise addition process is kept stirring state.After being added dropwise, stand
10h obtains suspension.
4) suspension is centrifugally separating to obtain solid product, is washed with deionized and dries afterwards for several times, and it is double to obtain gradient copper cobalt
Metal-organic framework material (Cu, Co molar ratio are 1:6), is denoted as 2-CuCo-ZIF.
Embodiment 3
A kind of preparation method of gradient copper cobalt dual-metal organic framework materials, includes the following steps:
1) 0.04mol 2-methylimidazole is added in 20mL deionized water, stirring makes it completely dissolved, and obtains 2- first
Base imidazoles aqueous solution.
2) 5mmol cobalt nitrate is added in 20mL deionized water, stirring, which dissolves it sufficiently, obtains cobalt nitrate aqueous solution,
Cobalt nitrate aqueous solution is added in the prepared 2-methylimidazole aqueous solution of step (1), stirring is uniformly mixed it.
3) 0.556mmol copper nitrate is added in 20mL deionized water, stirring makes it completely dissolved, and obtains nitric acid copper water
Solution.After mixed solution stir about 30min in step (2), using syringe pump with the rate of addition of 40mL/h within 30min
Copper nitrate aqueous solution is all added drop-wise in mixed solution, entire dropwise addition process is kept stirring state.After being added dropwise, stand
10h obtains suspension.
4) suspension is centrifugally separating to obtain solid product, is washed with deionized and dries afterwards for several times, and it is double to obtain gradient copper cobalt
Metal-organic framework material (Cu, Co molar ratio are 1:9), is denoted as 3-CuCo-ZIF.
Comparative example 1
A kind of preparation method of cobalt monometallic organic framework materials, includes the following steps:
1) 0.04mol 2-methylimidazole is added in 20mL deionized water, stirring makes it completely dissolved, and obtains 2- first
Base imidazoles aqueous solution.
2) 5mmol cobalt nitrate is added in 20mL deionized water, stirring, which dissolves it sufficiently, obtains cobalt nitrate aqueous solution,
Cobalt nitrate aqueous solution is added in the prepared 2-methylimidazole aqueous solution of step (1), 10h is stood after stirring 1h, is hanged
Supernatant liquid.
3) suspension is centrifugally separating to obtain solid product, is washed with deionized and dries afterwards for several times, and obtaining cobalt monometallic has
Machine frame frame material, is denoted as Co-ZIF.
Comparative example 2
A kind of preparation method of copper cobalt dual-metal organic framework materials, includes the following steps:
1) 0.04mol 2-methylimidazole is added in 20mL deionized water, stirring makes it completely dissolved, and obtains 2- first
Base imidazoles aqueous solution.
2) 5mmol cobalt nitrate, 0.830mmol ferric nitrate are added in 40mL deionized water, stirring dissolves it sufficiently
Cobalt nitrate-copper nitrate mixed aqueous solution is obtained, is added it in the prepared 2-methylimidazole aqueous solution of step (1), is stirred
10h is stood after 1h, obtains suspension.
3) suspension is centrifugally separating to obtain solid product, is washed with deionized and dries afterwards for several times, obtains copper cobalt dual-metal
Organic framework materials (Cu, Co molar ratio are 1:6), are denoted as CuCo-ZIF.
To fully understand the performance difference between each embodiment and comparative example products therefrom, corresponding test is carried out, has been tied
Fruit difference is as shown in Figs 1-4.
Fig. 1 is that XRD compares photo.As can be seen from Figure, the gradient CuCo- that embodiment 1 and 3 is prepared by dripping method
ZIF preferably remains the frame of Co-ZIF, and the concentration gradient distribution due to Cu element in frame, forms a variety of crystal forms
CuCo/ZIF frame structure；1 product of comparative example does not observe the above results, spectrogram and ZIF-67 standard spectrogram basic one
It causes.Furthermore compared with Example 1, the intensity at 3 product peak of embodiment slightly weakens, and illustrates the reduction with Cu content, formation
Polymorphic structures are reduced, and the formation that side demonstrates this polymorphic structures is caused by the influence of Cu metallic element.
Fig. 2 is that SEM compares photo.It can be seen from the figure that compared to 2 products therefrom CuCo-ZIF (b) of comparative example, this reality
It is smaller to apply products therefrom 2-CuCo-ZIF (a) particle size, while various sizes of particle is distributed with.This is because Cu gradient
The influence of concentration forms the CuCo/ZIF frame object of different crystal forms structure.
Fig. 3 and Fig. 4 is respectively graph of pore diameter distribution and specific surface area figure.By Fig. 3-4 it is found that the aperture of the product of embodiment 1 and 3
Respectively in 20nm, 10nm hereinafter, in embodiment 1 aperture multiplicity and pore size is comparatively single in embodiment 3.This is because
For embodiment 3, Cu constituent content increases embodiment 1, increased the size in its product aperture, type all,
Thus pore-size distribution is wider.Relative complex pore structure, but also the specific surface area of product is greater than in embodiment 3 in embodiment 1
The specific surface area of product.
Claims (8)
1. a kind of preparation method of gradient copper cobalt dual-metal organic framework materials, it is characterised in that the following steps are included:
(a) it is spare that 2-methylimidazole aqueous solution, cobalt saline solution, copper salt solution are prepared respectively；
(b) 2-methylimidazole aqueous solution is mixed with cobalt saline solution, is again added drop-wise to copper salt solution after reacting a period of time
The reaction was continued in mixed solution, stands, isolated gradient copper cobalt dual-metal organic framework materials.
2. preparation method as described in claim 1, it is characterised in that: prepare cobalt salt used in cobalt saline solution and be selected from nitric acid
Cobalt, cobalt chloride, cobaltous sulfate, any one in cobalt acetate.
3. preparation method as described in claim 1, it is characterised in that: prepare mantoquita used in copper salt solution and be selected from nitric acid
Copper, copper chloride, copper sulphate, any one in copper acetate.
4. preparation method as described in claim 1, it is characterised in that: the concentration of 2-methylimidazole aqueous solution is 150-250g/
L, the concentration of cobalt saline solution are 50-70g/L, and the concentration of copper salt solution is 5-15g/L.
5. preparation method as described in claim 1, it is characterised in that: the molar ratio of mantoquita needed for reacting and cobalt salt is 1:4-9.
6. preparation method as described in claim 1, it is characterised in that: the sum of mantoquita, cobalt salt needed for reacting and 2-methylimidazole
Molar ratio be 1:6-10.
7. preparation method as described in claim 1, it is characterised in that detailed process is as follows for step (b): in proportion by cobalt saline
Solution is added in 2-methylimidazole aqueous solution, stirs 10-30min with the revolving speed of 500-1000rpm；It is kept stirring speed not
Become, copper salt solution be slowly dropped in mixed solution with the rate of addition of 20-40mL/h, stands 8-12h after being added dropwise to complete,
It is finally centrifugated, washs, is dry, obtaining gradient copper cobalt dual-metal organic framework materials.
8. preparation method as claimed in claim 1 or 7, it is characterised in that: all operations in step (b) at room temperature into
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| CN114835913A (en) * | 2022-05-24 | 2022-08-02 | 扬州大学 | Colorimetric analysis method of copper-cobalt bimetallic organic framework nanoenzyme and organophosphorus colorimetric sensor thereof |
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