CN105170095A - In-based organic framework-graphene oxide composite material as well as preparation method and application thereof - Google Patents
In-based organic framework-graphene oxide composite material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of metal organic framework materials, and discloses an In-based organic framework-graphene oxide composite material as well as a preparation method and application thereof. The preparation method comprises the following steps: dispersing graphene oxide powder in N,N'-dimethylformamide and carrying out ultrasonic processing to obtain a dispersion agent; adding soluble indium salt and 2-amino terephthalic acid to the dispersing agent, stirring uniformly, carrying out ultrasonic processing to obtain a reaction solution, and reacting under the condition of temperature programming to obtain a rough composite material; and washing and soaking the rough composite material with N,N'-dimethylformamide and a methanol solvent sequentially, and activating to finally obtain a target composite material. The material prepared according to the invention is large in specific surface, has a developed micropore pore structure, is high in adsorption capacity for low-concentration Rhodamine B dye molecules in water, and has the adsorption capacity for Rhodamine B, which is 2.24 times that of activated carbon and 20.1 times that of a ZSM-5 molecular sieve, in same conditions.
Description
Technical field
The present invention relates to dye molecule rhodamine B sorbing material in water, particularly a kind of In base organic backbone-graphene oxide composite material and preparation method thereof.
Background technology
Dyestuff is widely used in the various industry such as printing and dyeing, papermaking, paint, timber preservative.In some developing countries, the wastewater flow rate discharged by textile industry has more than ten hundred million tons according to estimates every year.The waste water from dyestuff of high chroma has a strong impact on water quality, and can produce toxic action even " three cause " effect to organism.In view of toxicity and the feature such as complex structure, biodegradability difference thereof of dye molecule, for the effective and safe Adsorption of dyes molecule, for solution water body environment safety problem, there is important scientific meaning and realistic meaning.
For the treatment technology of water body middle and high concentration waste water from dyestuff, existing method comprises coagulation, biodegradation, precipitation and chemical oxidization method.But, even if after adopting said method process, water body also fails to decolour completely, still remains the soluble ion dyestuff of low concentration in water.Adsorption technology is the high and feature that cost benefit is good because of its feasibility, is widely used in processing large-scale industrial wastewater.Traditional material, as active carbon, natural minerals and industrial residue etc., all demonstrate high adsorption capacity, but adsorption efficiency is then not good when being applied to the process of low concentration waste water from dyestuff to the waste water of high concentration.Therefore, the novel absorption material researched and developed low concentration dye molecule in water has high Adsorption usefulness is very important.
In recent years, metal-organic framework compound (metalorganicframeworks, MOFs) because its specific area is huge, physicochemical property is adjustable, the advantage such as easy functionalization and synthesis strategy variation shows good potential application foreground in fields such as adsorbing separation.Wherein, MIL-68 (In)-NH
2be a kind of good hydrothermal stability and there is the MOFs material of high-ratio surface, and its with free amino group group towards pore passage structure center, and due to the confinement effect in duct, large-sized substrate can not enter duct, and small size substrate then can enter and reacts with amino active sites in duct and adsorbed.So, MIL-68 (In)-NH
2metal-organic framework materials possesses good adsorption selectivity.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is the preparation method providing a kind of In base organic backbone-graphene oxide composite material.By means such as modified with functional group, heterogeneous combination and fabricated in situ, realize the high adsorption capacity to low concentration dye molecule rhodamine B in water.
Object of the present invention is achieved through the following technical solutions:
A preparation method for In base organic backbone-graphene oxide composite material, comprises the following steps:
(1) graphene oxide powder dispersion is carried out ultrasonic process in N, N '-dimethyl formamide, obtain the dispersion liquid of graphene oxide;
(2) solubility indium salt and the amino terephthalic acid (TPA) of 2-are joined in the graphene oxide dispersion of step (1), uniform stirring ultrasonic process, obtain reactant liquor, react under temperature programming condition, obtain rough In base organic backbone-graphene oxide composite material;
(3) rough In base organic backbone step (2) obtained-graphene oxide composite material successively uses N, N '-dimethyl formamide and methanol solvate rinse and soak, activation, finally obtains the In base organic backbone-graphene oxide composite material of purifying.
The amount of graphene oxide used is 2 ~ 7% of the amino terephthalic acid (TPA) gross mass of solubility indium salt and 2-.
Described in step (2), solubility indium salt is indium nitrate.
In step (2), the mol ratio of solubility indium salt used and the amino terephthalic acid (TPA) of 2-is (2 ~ 4): 1.
The concentration of described solubility indium salt in N, N '-dimethyl formamide is 0.093 ~ 0.120g/mL.
Described in step (2), temperature programming is: with the programming rate of 5 ~ 10 DEG C/h, the temperature of reactant liquor is risen to 150-170 DEG C, after constant temperature 5 ~ 6h, naturally cools to room temperature.
Step (3) described activation is keep 8 ~ 12h under 100 ~ 150 DEG C of vacuum conditions.
The application of In base organic backbone-graphene oxide composite material in adsorbed water in dye molecule rhodamine B prepared by said method.
Graphene by carbon atom with alveolate texture (similar benzene ring structure) the tightly packed two-dimensional material formed, it has specific area and the hydrophobic property of superelevation, itself and MOFs Material cladding are designed, the carbon atom of Graphene densification surface also can be utilized simultaneously the feature of dispersion force between reinforcing material and guest molecule the absorption property of MOFs composite to be significantly improved, and its mechanical property also can be improved.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention is by adding graphene oxide, the unsatuated metal site In in the abundant oxygen-containing functional group utilizing graphene oxide to have and MOFs unit
3+there is bonding, accelerate the crystal growth of metal-organic framework materials and the formation of pore structure; Meanwhile, due to the introducing of graphene oxide, make material have higher atomic density, and dispersion force can be produced on the interface of MOFs unit and graphene oxide, thus give the absorption property of material excellence.
(2) compared with existing sorbing material, the rhdamine B molecule of In base organic backbone-graphene oxide composite material to low concentration in water that the present invention obtains has higher adsorption capacity.Under equal conditions, the adsorbance of In base organic backbone-graphene oxide composite material of the present invention to the rhdamine B molecule of low concentration is 2.24 times of active carbon, 20.1 times of ZSM-5 molecular sieve.
(3) In base organic backbone-graphene oxide composite material that the present invention obtains remains the skeleton structure of original In base organic material, and successfully introduces graphene oxide.Meanwhile, micro-double-pore structure during In base organic backbone-graphene oxide composite material that the present invention obtains has.
Accompanying drawing explanation
Fig. 1 is MIL-68 (In)-NH prepared by embodiment 2,3,4
2mIL-68 (In)-NH prepared by@GO composite and embodiment 1
2the powder X-ray RD spectrogram contrast of material, and the XRD spectra of graphene oxide.
Fig. 2 is MIL-68 (In)-NH prepared by embodiment 2
2mIL-68 (In)-NH prepared by@GO-1 composite and embodiment 1
2the N of material
2adsorption isotherm contrasts.
Fig. 3 is MIL-68 (In)-NH prepared by embodiment 1
2mIL-68 (In)-NH prepared by material (a) and embodiment 2
2the SEM comparison diagram of@GO-1 composite (b).
Fig. 4 is MIL-68 (In)-NH prepared by embodiment 2,3,4
2mIL-68 (In)-NH prepared by@GO composite and embodiment 1
2material, active carbon and ZSM-5 molecular sieve contrast the adsorption effect of low concentration rhodamine B.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, but enforcement of the present invention is not limited thereto, and change is included in technical scope of the present invention.
Embodiment 1: comparative example
Amino to 1.49g indium nitrate and 0.230g2-terephthalic acid (TPA) is dissolved in 12.4mLN, and in N '-dimethyl formamide, uniform stirring ultrasonic process, the reactant liquor obtained rises to 150 DEG C with the speed of 10 DEG C/h from room temperature, and constant temperature 5h, naturally cools to room temperature.Product after suction filtration first uses N, and N '-dimethyl formamide rinses 3 times, then is immersed in methyl alcohol after 3 days, through tube furnace at N
2the lower 200 DEG C of roasting 5h of atmosphere, activate 12h under 150 DEG C of vacuum conditions, and marking this sample is MIL-68 (In)-NH
2.
The preparation of embodiment 2:In base organic backbone-graphene oxide composite material
0.0965g graphene oxide powder dispersion is carried out ultrasonic process in 11.0mLN, N '-dimethyl formamide, obtains the dispersion liquid of graphene oxide; 1.148g indium nitrate and the amino terephthalic acid (TPA) of 0.230g2-are joined in above-mentioned graphene oxide dispersion, stir and ultrasonic process, the reactant liquor obtained rises to 160 DEG C with the speed of 5 DEG C/h from room temperature, and constant temperature 6h, naturally cools to room temperature.Product after suction filtration first uses N, and N '-dimethyl formamide rinses 3 times, then is immersed in methyl alcohol after 3 days, through tube furnace at N
2the lower 180 DEG C of roasting 5h of atmosphere, activate 12h under 130 DEG C of vacuum conditions, and marking this sample is MIL-68 (In)-NH
2@GO-1.
The preparation of embodiment 3:In base organic backbone-graphene oxide composite material
0.0722g graphene oxide powder dispersion is carried out ultrasonic process in 10.1mLN, N '-dimethyl formamide, obtains the dispersion liquid of graphene oxide; Join in above-mentioned graphene oxide dispersion by amino to 1.207g indium nitrate and 0.237g2-terephthalic acid (TPA), uniform stirring ultrasonic process, the reactant liquor obtained rises to 170 DEG C with the speed of 8 DEG C/h from room temperature, and constant temperature 5h, naturally cools to room temperature.Product after suction filtration first uses N, and N '-dimethyl formamide rinses 3 times, then is immersed in methyl alcohol after 3 days, through tube furnace at N
2the lower 150 DEG C of roasting 5h of atmosphere, activate 12h under 100 DEG C of vacuum conditions, and marking this sample is MIL-68 (In)-NH
2@GO-2.
The preparation of embodiment 4:In base organic backbone-graphene oxide composite material
0.0340g graphene oxide powder dispersion is carried out ultrasonic process in 12.4mLN, N '-dimethyl formamide, obtains the dispersion liquid of graphene oxide; Join in above-mentioned graphene oxide dispersion by amino to 1.49g indium nitrate and 0.230g2-terephthalic acid (TPA), uniform stirring ultrasonic process, the reactant liquor obtained rises to 150 DEG C with the speed of 10 DEG C/h from room temperature, and constant temperature 6h, naturally cools to room temperature.Product after suction filtration first uses N, and N '-dimethyl formamide rinses 3 times, then is immersed in methyl alcohol after 3 days, through tube furnace at N
2the lower 200 DEG C of roasting 5h of atmosphere, activate 12h under 150 DEG C of vacuum conditions, and marking this sample is MIL-68 (In)-NH
2@GO-3.
Embodiments of the invention 1 and the material obtained by embodiment 2, its characterization result is as follows with absorption rhodamine B performance:
(1) XRD phenetic analysis
The crystal structure of the sharp shadow X-ray diffractometer of the Empyrean adopting Dutch PANalytical company to produce to the porous material that the embodiment of the present invention 1 and 2 prepares characterizes, graphene oxide (GO) is as blank, as shown in Figure 1, wherein operating condition is: copper target, 40KV, 40mA, step-length 0.0131 degree, sweep speed 9.664 seconds/step.
As can be seen from Figure 1, MIL-68 (the In)-NH of embodiment 2,3,4 preparation
2@GO composite shows MIL-68 (the In)-NH prepared with embodiment 1
2the characteristic peak that material is consistent, peak is strong and sharp-pointed, shows that it has good MIL-68 (In)-NH
2crystal framework structure.
(2) pore structure characterizes
Application ASAP2020 specific area and distribution of pores structural test machines test the pore structure of material prepared by embodiment 1 and embodiment 2, and the material that in Fig. 2 prepared by two embodiments is labeled as MIL-68 (In)-NH respectively
2with MIL-68 (In)-NH
2@GO-1.Test result is as shown in table 1.
Table 1
The pore volume of table 2 porous material and aperture parameters
As seen from Figure 2, MIL-68 (the In)-NH of embodiment 2 preparation
2the N of@GO-1 composite
2adsorption isotherm belongs to Ι class thermoisopleth, shows that it has microcellular structure.As shown in Table 1, MIL-68 (the In)-NH of embodiment 2 preparation
2the specific surface of@GO-1 composite is 493.1m
2/ g, lower than MIL-68 (In)-NH prepared by embodiment 1
2material 579.6m
2/ g, this shows that adding of graphene oxide has a certain impact to the specific area of composite.Table 2 shows, micro-double-pore structure during In base organic backbone-graphene oxide composite material has, and micro-porous adsorption gesture and the adsorption of absorption pore volume to composite thereof have material impact, and meso-hole structure is then conducive to the rapid diffusion of adsorption molecule in hole.
(3) SEM phenetic analysis
MERLIN field emission scanning electron microscope (CarlZeiss company, Germany) is adopted to characterize the surface topography of sample.As shown in Figure 3, sample all presents bar-shaped crystal structure to result, and MIL-68 (In)-NH prepared by embodiment 2
2the crystalline size of@GO composite is obviously greater than MIL-68 (the In)-NH of embodiment 1 preparation
2the crystalline size of material, shows that adding of graphene oxide has a certain impact to the crystal growing process of composite.
(4) rhodamine B absorption property measures
The model adopting HACH company of the U.S. to produce is that DR5000 ultraviolet specrophotometer measures absorption property.Fig. 4 is under 298K, MIL-68 (In)-NH prepared by embodiment 1
2mIL-68 (In)-NH prepared by material and embodiment 2,3,4
2@GO composite, and active carbon, ZSM-5 molecular sieve adsorption of Low Concentration rhodamine B absorption property curve map, test before by sample vacuum activating 12h under 150 DEG C of conditions.
As shown in Figure 4, MIL-68 (In)-NH
2@GO composite to the adsorbance of rhodamine B at about 55mg/g, higher than MIL-68 (In)-NH
2the 40.7mg/g of material under equal experiment condition.This shows, due to the introducing of graphene oxide, makes full use of the functional group on it, contributes to the raising of absorption property; Simultaneously, the dispersion force that the individual layer interface of MOF unit and graphene oxide produces, too increase the interaction force between the unsatuated metal adsorption site in rhodamine B molecule and MOF skeleton and the functional group on organic ligand, thus improve In base organic backbone-graphene oxide composite material to the absorption property of low concentration rhodamine B molecule.
Table 3 is rhodamine B desorption balance data on different sorbing material.As can be seen from the table, under equal experiment condition, MIL-68 (In)-NH
2the equilibrium adsorption capacity of@GO composite to low concentration rhodamine B is about MIL-68 (In)-NH
21.37 times, 2.24 times of active carbon, 20.1 times of ZSM-5 molecular sieve.
Table 3
Claims (9)
1. a preparation method for In base organic backbone-graphene oxide composite material, is characterized in that, comprise the following steps:
(1) graphene oxide powder dispersion is carried out ultrasonic process in N, N '-dimethyl formamide, obtain the dispersion liquid of graphene oxide;
(2) solubility indium salt and the amino terephthalic acid (TPA) of 2-are joined in the graphene oxide dispersion of step (1), uniform stirring ultrasonic process, obtain reactant liquor, react under temperature programming condition, obtain rough In base organic backbone-graphene oxide composite material;
(3) rough In base organic backbone step (2) obtained-graphene oxide composite material successively uses N, N '-dimethyl formamide and methanol solvate rinse and soak, activation, finally obtains the In base organic backbone-graphene oxide composite material of purifying.
2. preparation method according to claim 1, is characterized in that, the amount of graphene oxide used is 2 ~ 7% of the amino terephthalic acid (TPA) gross mass of solubility indium salt and 2-.
3. preparation method according to claim 1, is characterized in that, described in step (2), solubility indium salt is indium nitrate.
4. preparation method according to claim 1, is characterized in that, in step (2), the mol ratio of solubility indium salt used and the amino terephthalic acid (TPA) of 2-is (2 ~ 4): 1.
5. preparation method according to claim 1, is characterized in that, the concentration of described solubility indium salt in N, N '-dimethyl formamide is 0.093 ~ 0.120g/mL.
6. the preparation method according to any one of Claims 1 to 5, it is characterized in that, described in step (2), temperature programming is: with the programming rate of 5 ~ 10 DEG C/h, the temperature of reactant liquor is risen to 150-170 DEG C, after constant temperature 5 ~ 6h, naturally cools to room temperature.
7. preparation method according to claim 6, is characterized in that, described activation is keep 8 ~ 12h under 100 ~ 150 DEG C of vacuum conditions.
8. In base organic backbone-graphene oxide composite material of preparing of any one of claim 1 ~ 7 method.
9. the application of In base organic backbone-graphene oxide composite material according to claim 8 in adsorbed water in dye molecule rhodamine B.
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