CN106669612A - Aluminum-based metal organic frame-graphene oxide composite material, as well as preparation method and application thereof - Google Patents
Aluminum-based metal organic frame-graphene oxide composite material, as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of material science and engineering, and discloses a method for preparing an Al-based metal organic frame-graphne oxide composite material and application thereof. The method comprises the following steps of: (1) adding an organic ligand and soluble aluminum salt into N,N'-dimethyl formamide, stirring and dissolving to obtain a reaction matrix solution; and (2) adding dried graphene oxide powder into the reaction matrix solution obtained in the step (1) to obtain a reaction mixed solution, heating to react to obtain a primary product of the aluminum-based metal organic frame-graphene oxide composite material, washing, heating and activating to obtain the aluminum-based metal organic frame-graphene oxide composite material. The method is simple and easy to operate, is short in time for the preparing process, can be product in large scale; the prepared material has excellent performance, and can be applied as an adsrobent to removal of methyl orange dye molecules in water.
Description
Technical field
The invention belongs to Materials Science and Engineering field, more particularly to a kind of Al Base Metals organic backbone@graphene oxides
The preparation method of composite and its application in methyl orange dye in absorption water.
Background technology
Azo dye is widely used in the industries such as weaving, papermaking, printing, foods and cosmetics, and the dyestuff of high chroma gives up
Water is discharged in environment and not only has a strong impact on water quality, and toxic action even " three cause " effect can be produced to organism.At present
The species of azo dye is increasingly sophisticated, and anti-light solution, antioxidation, antibiont degradation capability constantly strengthen, azo dye wastewater
Intractability is also continued to increase.For the treatment technology of water body middle and high concentration azo dye wastewater, existing method include coagulation,
Biodegradation, precipitation and chemical oxidization method etc..Comparatively, absorption method is considered as one kind quickly and effectively removes dye molecule
One of method, it can the selective compound molecule such as absorbing dye, it is outstanding for the process of difficult degradation azo dye wastewater
It is applicable.Traditional adsorbing material such as activated carbon, natural minerals and industrial residue etc., to waste water from dyestuff certain suction is shown
Attached capacity, but its adsorbance is limited, and it is not good for the waste water from dyestuff adsorption effect of low concentration.Therefore, research and develop
Low concentration dye molecule in water can be adsorbed, and there is high-adsorption-capacity novel absorption material to be very important again.
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) represent a class heterozygosis it is organic/
Inorganic supramolecular materials, are the ordered network structures consisted of the coordination of organic bridge ligand and inorganic metal ion.
MOFs materials have a specific surface area of superelevation, the advantages of relatively low crystalline density and hole size and function adjustability, in absorption
The fields such as separation show good potential application foreground.Although MOFs materials have lot of advantages, liquid phase is intended to apply to
Adsorbing separation, a factor that must take into is exactly water stability.At present overwhelming majority MOFs is served only for hydrogen storage or gas phase point
From reason is exactly to meet water back skeleton to cave in.Further, since MOFs material atom density is low, it is impossible to provide enough colors
Scattered power goes to capture small-molecule substance, therefore can be combined with carbon-based material, this deficiency is overcome or weaken, so as to improve
The absorption property of MOFs class materials.
Graphene is the carbon-based new material of discovered in recent years, possesses many excellent properties, such as higher mechanical strength, and heat is steady
Qualitative and electron mobility etc.；Additionally, Graphene also has regular two-dimensional structure, this makes it can be used as preparing composite
Ideal carrier.Graphene oxide (graphene oxide, GO) is the important derivatives of Graphene, containing substantial amounts of on GO monolithics
Epoxy radicals and hydroxyl, and contain carboxyl at monolithic edge, these features impart its good compound ability.These are graphene-based
Material had both possessed the excellent properties of Graphene itself with material obtained in organic or inorganic Material cladding, had organic or inorganic concurrently again
The self-characteristic of material, is that the preparation of specific function material opens new way.
MOFs materials prepare composite and are typically matched somebody with somebody with the oxygen-containing functional group on GO surfaces by metal ion with GO
Position reaction.And in MOFs material formation process, often containing a large amount of carboxyls or amino, these groups may for organic ligand
Directly with GO on oxygen-containing functional group occur dehydration and prevent GO and metallic ion coordination, so as to cause the system of composite
Standby failure.
MIL-68 (Al) is MILs (Materials of the Institut Lavoisier) series metal organic backbone
In one kind, its good hydrothermal stability and with high specific surface area.Space structure is by MO4(OH)2Octahedral unit with to benzene
The mutual bridging of dioctyl phthalate part is formed, and tridimensional network is characterized in that it has trigonometric sum hexagonal duct, opening diameter point simultaneously
It is notWithPossesses good separation basic condition.
The content of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, the primary and foremost purpose of the present invention is to provide a kind of aluminium based metal
The preparation method of organic backbone@graphene oxide composite materials.
Another object of the present invention is to provide aluminium based metal organic backbone@graphene oxide composite woods prepared by said method
Material.
Still a further object of the present invention is to provide above-mentioned aluminium based metal organic backbone@graphene oxide composite materials in absorption water
Application in middle methyl orange dye molecule.
The purpose of the present invention is realized by following proposal：
A kind of preparation method of aluminium based metal organic backbone@graphene oxide composite materials, it specifically includes following steps：
(1) organic ligand and aluminum soluble salt are added to into N, in N '-dimethylformamide, stirring ultrasound dissolves it,
Obtain reactive matrix solution；
(2) dried graphene oxide powder is added in the reactive matrix solution of step (1), ultrasound makes oxidation stone
Black alkene is uniformly dispersed, and obtains reaction mixture, then temperature reaction, obtains aluminium based metal organic backbone@graphene oxides and answers
Condensation material head product；
(3) the aluminium based metal organic backbone@graphene oxide composite material head products for obtaining step (2) are washed,
Then heat-activated obtains aluminium based metal organic backbone@graphene oxide composite material end-products.
Organic ligand described in step (1) is p-phthalic acid；
Aluminum soluble salt described in step (1) is aluminum nitrate or aluminum chloride；
Aluminum soluble salt used and the mol ratio of organic ligand are 1 in step (1)：(1~4)；N used, N '-diformazan
It is 0.008~0.019g/mL that the amount of base Methanamide is concentration of the aluminum soluble salt in N, N '-dimethylformamide.
The amount of graphene oxide powder used and reactive matrix solution is in the reaction mixture for obtaining in step (2)
The concentration of graphene oxide is 0.4mg/mL~1.5mg/mL.
Temperature reaction described in step (2) to be referred to and react 12~20h at 100~150 DEG C.
Washing described in step (3) is referred to first with N, N '-dimethylformamide flushing 3 times, again with methanol or deionization
Water is cleaned 3 times.
Heat-activated described in step (3) refers to 8~12h of holding under 80~110 DEG C of vacuum conditions.
A kind of aluminium based metal organic backbone@graphene oxide composite materials prepared by said method.
Above-mentioned aluminium based metal organic backbone@graphene oxide composite materials are in dye molecule methyl orange in absorption water
Using.
The present invention mechanism be：
Graphene oxide maintains six regular ring carbon planar structures of Graphene and has abundant oxygen-containing on its surface
Functional group, including hydroxyl, carboxyl and epoxy radicals etc..It is designed with MOFs Material claddings so that oxygen-containing functional group can be with gold
Category center produces coordination, makes it be stacked with forming new duct by chemical bond, while also using Graphene
Fine and close carbon atom surface can be between reinforcing material and guest molecule dispersion force the characteristics of make the absorption property of MOFs composites
It is significantly improved, and its mechanical property also can be improved.
The present invention has the following advantages and beneficial effect relative to prior art：
(1) the unsatuated metal position in the present invention is enriched using surface of graphene oxide oxygen-containing functional group and MOFs units
There is complexation reaction in point aluminium ion, accelerate the crystal growth of metal-organic framework materials and the formation of pore structure and in oxidation stone
New duct is formed between black alkene and MOFs crystal units；Simultaneously as the introducing of graphene oxide so that material has higher
Atomic density, and dispersion force can be produced on the interface of MOFs units and graphene oxide, so as to give material excellent suction
Attached performance.
(2) the MOFs materials in the present invention are MIL-68 (Al) material, and in its Al-O-Al crystal unit μ is contained2- OH, no
Be only capable of and on GO oxygen-containing functional group produce hydrogen bond action, and can with GO hexagonal carbons atomic plane produce π-π effects, increase GO with
The chance of metallic ion coordination.
(3) the Al Base Metal organic backbone@graphene oxide composite materials that the present invention is obtained are compared to single MIL-68
(Al) material has bigger pore volume.
(4) the Al Base Metal organic backbone@graphene oxide composite materials that the present invention is obtained remain original Al Base Metals
The framing structure of organic material, and it has been successfully introduced into graphene oxide.Compared with matrix MIL-68 (Al), MIL-68 (Al)@GO
Composite enhances the absorption to methyl orange in water.
(5) preparation method of the invention is simple and easy to operate, and preparation process takes short, easy large-scale production.
Description of the drawings
The powder xrd pattern of samples of the Fig. 1 to prepare in raw materials used graphene oxide in embodiment and embodiment 1~5.
Fig. 2 is the N of sample prepared by embodiment 2~52Adsorption isotherm comparison diagram.
Fig. 3 is the SEM figures of MIL-68 (Al) sample prepared in embodiment 2.
Fig. 4 is the SEM figures of MIL-68 (Al) the@GO-2 samples prepared in embodiment 4.
Fig. 5 is the adsorption effect comparison diagram of methyl orange dye in the sample adsorption water prepared in embodiment 2~5.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Agents useful for same can routinely be buied if no special instructions from market in embodiment.Graphite oxide used in embodiment
Alkene powder is purchased from Shanghai Aladdin biochemical technology limited company.
Embodiment 1：
7.60g aluminum nitrates and 5.0g p-phthalic acids are dissolved in into 300mLN, in N '-dimethylformamide, uniform stirring makes
It is completely dissolved, and stirring reaction 12 hours, naturally cools to room temperature under 130 DEG C of constant temperatures.Product after filtration first use N, N '-
Dimethylformamide is rinsed 3 times, and methanol is cleaned 3 times, and under vacuum condition 12h is activated, and obtains sample and this sample of labelling is MIL-
68(Al)-1。
Embodiment 2：
5.00g aluminum chloride and 5.0g p-phthalic acids are dissolved in into 300mLN, in N '-dimethylformamide, uniform stirring makes
It is completely dissolved, and stirring reaction 12 hours, naturally cools to room temperature under 130 DEG C of constant temperatures.Product after filtration first use N, N '-
Dimethylformamide is rinsed 3 times, and methanol is cleaned 3 times, and under vacuum condition 12h is activated, and obtains sample and this sample of labelling is MIL-
68(Al)。
Embodiment 3：The preparation of Al Base Metal organic backbone@graphene oxide composite materials
5.00g aluminum chloride and 5.0g p-phthalic acids are dissolved in into 300mLN, in N '-dimethylformamide, uniform stirring makes
It is completely dissolved.It is subsequently adding 0.23g graphene oxide powders and supersound process, reaction mixture；Stir under 130 DEG C of constant temperatures
Reaction 12 hours is mixed, room temperature is naturally cooled to.Product after filtration first uses N, N '-dimethylformamide to rinse 3 times, deionized water
Cleaning 3 times, activates 12h under 110 DEG C of vacuum conditions, and this sample of labelling is MIL-68 (Al)@GO-1.
Embodiment 4：The preparation of Al Base Metal organic backbone@graphene oxide composite materials
5.00g aluminum chloride and 5.0g p-phthalic acids are dissolved in into 300mLN, in N '-dimethylformamide, uniform stirring makes
It is completely dissolved.It is subsequently adding 0.45g graphene oxide powders and supersound process, reaction mixture；Stir under 130 DEG C of constant temperatures
Reaction 12 hours is mixed, room temperature is naturally cooled to.Product after filtration first uses N, N '-dimethylformamide to rinse 3 times, methanol cleaning
3 times, 12h is activated under 110 DEG C of vacuum conditions, this sample of labelling is MIL-68 (Al)@GO-2.
Embodiment 5：The preparation of Al Base Metal organic backbone@graphene oxide composite materials
5.00g aluminum chloride and 5.0g p-phthalic acids are dissolved in into 300mLN, in N '-dimethylformamide, uniform stirring makes
It is completely dissolved.It is subsequently adding 0.90g graphene oxide powders and supersound process, reaction mixture；Stir under 130 DEG C of constant temperatures
Reaction 12 hours is mixed, room temperature is naturally cooled to.Product after filtration first uses N, N '-dimethylformamide to rinse 3 times, deionized water
Cleaning 3 times, activates 12h under 110 DEG C of vacuum conditions, and this sample of labelling is MIL-68 (Al)@GO-3.
As a result characterize：
(1) XRD phenetic analysis
The sharp shadow X-ray diffractometers of Empyrean produced using Dutch PANalytical company are made to the embodiment of the present invention 1~5
The standby porous material for obtaining is characterized, and graphene oxide (GO) is as blank, wherein operating condition：Copper target, 40KV,
40mA, 0.0131 degree of step-length, 9.664 seconds/step of scanning speed.As a result as shown in figure 1, it will be seen from figure 1 that embodiment 1 and reality
The MIL-68 (Al) for applying the preparation of example 2 has identical diffraction maximum, illustrates that aluminum nitrate and aluminum chloride could act as synthesizing MIL-68
(Al) raw metal.MIL-68 (Al) GO composites prepared by embodiment 3,4,5 show the MIL- prepared with embodiment 2
The consistent characteristic peak of 68 (Al) materials, but peak intensity is different, shows to include complete MIL-68 (Al) crystal in composite.
(2) pore structure is characterized
The hole knot of the sample prepared using ASAP2020 specific surface areas and distribution of pores structural test machines embodiment 2~5
Structure is tested, the N of gained2Adsorption isotherm comparison diagram is as shown in Fig. 2 design parameter is as shown in table 1.
The porous material structural parameters of table 1
From figure 2 it can be seen that the N of material prepared by embodiment 2~52Adsorption isotherm belongs to Ι class isothermal lines, table
Bright its has microcellular structure.As shown in Table 1, the specific surface area of composite prepared by embodiment 3~5 is with graphene-supported amount
Increase is gradually lowered, and the below specific surface area of MIL-68 (Al) material prepared by embodiment 2, but total pore volume is both greater than
MIL-68 (Al) prepared by embodiment 2, this shows that the addition of graphene oxide has certain bearing to the specific surface area of composite
Face rings, but has active influence to total pore volume.
(3) SEM phenetic analysis
Using MERLIN field emission scanning electron microscopes (Carl Zeiss companies, Germany) to embodiment 2 and embodiment 4
The surface topography of the sample of preparation is characterized.As a result distinguish as shown in Figure 3 and Figure 4, from figure 3, it can be seen that embodiment 2 is made
Standby MIL-68 (Al) sample is in strip and crystal is stacked with figure 4, it is seen that the MIL-68 of the preparation of embodiment 4
(Al) MIL-68 (Al) crystal growths can be substantially observed in@GO-2 composites on the Graphene of lamella, shows graphite oxide
Alkene and MIL-68 (Al) are not simply physical mixed, but are together with each other by chemical bond.
(4) to the measure of Adsorption of Methyl Orange performance
Adsorption of Methyl Orange experiment adopts shake flat experiment, i.e., appropriate methyl orange solution is added in 250mL conical flasks, then
A certain amount of adsorbent is added, constant-temperature table is placed in, 25 DEG C, adsorption experiment is carried out under the conditions of 150 revs/min, timing sampling is carried out
Analysis.
The model DR5000 ultraviolet spectrophotometer produced using HACH companies of the U.S. determines the extinction of solution after absorption
Degree, then calculates adsorbance, before test by adsorbent under the conditions of 100 DEG C vacuum activation 12h.Concrete operations are：In 250mL
The methyl orange solution of 100mL, 60mg/L is added in conical flask, the adsorbent of 0.02g is then added, constant-temperature table is placed in, 25 DEG C,
Adsorption experiment is carried out under the conditions of 150 revs/min, timing sampling is analyzed.In sample adsorption water prepared in embodiment 2~5
The adsorption effect comparison diagram of methyl orange dye is as shown in figure 5, the prepared specimen material in embodiment 2~5 of methyl orange molecule
On desorption balance data it is as shown in table 2.
From figure 5 it can be seen that MIL-68 (Al)@GO-1 and MIL-68 (Al)@GO-2 composites are to methyl orange in water
Adsorbance in 117mg/g or so, higher than 99mg/g of MIL-68 (Al) materials under equal experiment condition.This shows, in right amount
The introducing of graphene oxide, makes full use of functional group thereon, contributes to the raising of absorption property；Meanwhile, MOF units with oxidation
The dispersion force produced on the monolayer interface of Graphene, also increases methyl orange molecule and inhales with the unsatuated metal in MOF skeletons
The interaction force between functional group on attached site and organic ligand, so as to improve aluminium based metal organic backbone@oxidation stones
The absorption property of methyl orange dye molecule in black alkene composite water.
Desorption balance data on the prepared specimen material in embodiment 2~5 of the methyl orange molecule of table 2
From Table 2, it can be seen that under equal experiment condition, MIL-68 (Al)@GO-1 and MIL-68 (Al)@GO-2 are combined
The equilibrium adsorption capacity of methyl orange is about 1.18 times of MIL-68 (Al), the methyl orange solution for 60mg/L, MIL- in material water
The clearance of 68 (Al)@GO-1 and MIL-68 (Al)@GO-2 composites is 97% or so, hence it is evident that higher than MIL-68 (Al) material
Equal clearance 82%.But MIL-68 (Al)@GO-3 composites are not but lifted to the absorption property of methyl orange, and this can
A large amount of introducings of graphene oxide can be because reduces the ratio of MOF materials.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of aluminium based metal organic backbone@graphene oxide composite materials, it is characterised in that including following step
Suddenly：
(1) organic ligand and aluminum soluble salt are added to into N, in N '-dimethylformamide, stirring ultrasound dissolves it, obtains
Reactive matrix solution；
(2) dried graphene oxide powder is added in the reactive matrix solution of step (1), ultrasound makes graphene oxide
It is uniformly dispersed, obtains reaction mixture, then temperature reaction, obtains aluminium based metal organic backbone@graphene oxide composite woods
Material head product；
(3) the aluminium based metal organic backbone@graphene oxide composite material head products for obtaining step (2) are washed, then
Heat-activated obtains aluminium based metal organic backbone@graphene oxide composite material end-products.
2., according to the preparation method of the aluminium based metal organic backbone@graphene oxide composite materials described in claim 1, it is special
Levy and be：
Organic ligand described in step (1) is p-phthalic acid；
Aluminum soluble salt described in step (1) is aluminum nitrate or aluminum chloride.
3., according to the preparation method of the aluminium based metal organic backbone@graphene oxide composite materials described in claim 1, it is special
Levy and be：
Aluminum soluble salt used and the mol ratio of organic ligand are 1 in step (1)：(1~4)；N used, N '-dimethyl methyl
It is 0.008~0.019g/mL that the amount of amide is concentration of the aluminum soluble salt in N, N '-dimethylformamide.
4., according to the preparation method of the aluminium based metal organic backbone@graphene oxide composite materials described in claim 1, it is special
Levy and be：
The amount of graphene oxide powder used and reactive matrix solution is to aoxidize in the reaction mixture for obtaining in step (2)
The concentration of Graphene is 0.4mg/mL~1.5mg/mL.
5., according to the preparation method of the aluminium based metal organic backbone@graphene oxide composite materials described in claim 1, it is special
Levy and be：
Temperature reaction described in step (2) to be referred to and react 12~20h at 100~150 DEG C.
6., according to the preparation method of the aluminium based metal organic backbone@graphene oxide composite materials described in claim 1, it is special
Levy and be：
Washing described in step (3) is referred to and first use N, and N '-dimethylformamide is rinsed 3 times, and again with methanol or deionized water are clear
Wash 3 times.
7., according to the preparation method of the aluminium based metal organic backbone@graphene oxide composite materials described in claim 1, it is special
Levy and be：
Heat-activated described in step (3) refers to 8~12h of holding under 80~110 DEG C of vacuum conditions.
8. the aluminium based metal organic backbone@graphene oxides that prepared by a kind of method by described in any one of the claims 1~7
Composite.
9. aluminium based metal organic backbone@graphene oxide composite materials according to claim 8 absorption water in methyl orange
Application in dye molecule.
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