CN105312028A - Zinc and copper bi-metal organic framework material and preparation method and application thereof - Google Patents
Zinc and copper bi-metal organic framework material and preparation method and application thereof Download PDFInfo
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- CN105312028A CN105312028A CN201510815135.8A CN201510815135A CN105312028A CN 105312028 A CN105312028 A CN 105312028A CN 201510815135 A CN201510815135 A CN 201510815135A CN 105312028 A CN105312028 A CN 105312028A
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Abstract
The invention belongs to the technical field of metal organic framework materials, and discloses a zinc and copper bi-metal organic framework material and a preparation method and application thereof. The preparation method comprises the steps that 1, soluble copper salt, soluble zinc salt and trimesic acid are added to mixed solvent of N,N'-dimethyl formamide, water and ethyl alcohol, even stirring and ultrasonic treatment are conducted, and reaction liquid is obtained; 2, the reaction liquid obtained in the first step is transferred into a polytef reaction kettle for a hydrothermal reaction, and a roughly prepared zinc and copper bi-metal organic framework material is obtained; 3, the material obtained in the second step is washed through the N,N'-dimethyl formamide firstly and then soaked through ethyl alcohol solvent, and the purified zinc and copper bi-metal organic framework material is obtained after activation is conducted. According to the zinc and copper bi-metal organic framework material, the framework structure of an original copper-based organic material is reserved; meanwhile, the prepared material is large in specific surface and developed in micro-pore structure and has higher adsorption capacity to low-concentration congo red dye molecules in water.
Description
Technical field
The present invention relates to the Congo red sorbing material of dye molecule in water, particularly a kind of zinc-copper bimetallic organic framework material and preparation method thereof.
Background technology
The development of society, promote the development of chemical industry, but industrial wastewater is also constantly increasing in evolution, and waste water from dyestuff is one of main noxious industry waste water.Dyestuff plays a very important role in daily life, is widely used in the various industry such as printing and dyeing, papermaking, paint, timber preservative.According to estimates, in some developing countries, the wastewater flow rate discharged by textile industry has more than ten hundred million tons 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, Cu
3(BTC)
2be a kind of MOFs material with high-ratio surface, but its water stability is bad, very easily reunites in aqueous phase, poor to the absorption property of low concentration dye molecule as Congo red in water, significantly limit the application of material environment remediation in water body.
Summary of the invention
The object of the invention is to the defect overcoming prior art, a kind of preparation method of Cu base organic framework material is provided.By means such as doping, heterogeneous combination and fabricated in situ, realize the high adsorption capacity Congo red to low concentration dye molecule in water.
Object of the present invention is achieved through the following technical solutions:
A preparation method for zinc-copper bimetallic organic framework material, comprises the following steps:
(1) soluble copper salt, soluble zinc salt and trimesic acid are joined N, in the mixed solvent of N '-dimethyl formamide, water and ethanol, uniform stirring ultrasonic process, obtain reactant liquor;
(2) reactant liquor of step (1) is transferred in polytetrafluoroethylene (PTFE) reactor carry out hydro-thermal reaction, obtain spelter copper bi-metal organic framework material;
(3) material that step (2) obtains first is used N, N '-dimethyl formamide rinses, then soaks with alcohol solvent, finally by activation, obtains the zinc-copper bimetallic organic framework material (blue colored crystal) of purifying.
The mol ratio of described soluble copper salt and soluble zinc salt, trimesic acid is 1:(0.1 ~ 0.3): (0.3 ~ 0.8).
The volume ratio of N, N in described mixed solvent '-dimethyl formamide and water, ethanol is 1:1:1.
In step (1), described soluble copper salt is 0.080 ~ 0.22mol/L with the molal volume ratio of mixed solvent.
The temperature programming of hydro-thermal reaction described in step (2) is: with the programming rate of 5 ~ 10 DEG C/h, the temperature of reactant liquor is risen to 85-125 DEG C, after constant temperature 12 ~ 24h, naturally cool to room temperature.
Described activation is keep 10 ~ 14h under 100 ~ 120 DEG C of vacuum conditions.
Described in step (1), soluble copper salt is copper nitrate, and the zinc salt of solubility is zinc nitrate.
Said method prepare zinc-copper bimetallic organic framework material dye molecule in adsorbed water Congo red in application.
The a small amount of Zn of the present invention
2+the part that is incorporated to replace copper ion on paddlewheel configuration, hydrone coordinates the stable of zinc atom holding structure, even if can not be removed after activation, enhance the hydrogen bond action between adsorbent and target contaminant, improve absorption property, meanwhile, the shortcoming that copper base organic framework material is easily reunited in aqueous phase is overcome.Therefore, zinc-copper bimetallic organic framework material is relative to Cu
3(BTC)
2possesses better adsorption selectivity.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention is by adding zinc salt, Zn
2+replace a Cu on paddle wheel unit
2+, accelerate the crystal growth of metal-organic framework materials and the formation of pore structure.
(2) the material specific surface prepared of the present invention is large, there is flourishing micropore structure, compared with existing sorbing material, the congo red molecule of zinc-copper bimetallic organic framework material to low concentration in water that the present invention obtains has higher adsorption capacity.Under equal conditions, the adsorbance of zinc-copper bimetallic organic framework material of the present invention to the congo red molecule of low concentration is 10.84 times of active carbon.
(3) the zinc-copper bimetallic organic framework material that the present invention obtains remains the skeleton structure of original copper base organic material.Meanwhile, the shortcoming that copper base organic framework material is easily reunited in aqueous phase is overcome.
Accompanying drawing explanation
Fig. 1 is Zn prepared by embodiment 2,3,4
xthe powder X-ray RD spectrogram comparison diagram of Cu-BTC material prepared by/Cu-BTC material and embodiment 1.
Fig. 2 is Cu-BTC material (a) of embodiment 1 preparation and the Zn of embodiment 2 preparation
xthe SEM comparison diagram of/Cu-BTC composite (b).
Fig. 3 is Zn prepared by embodiment 2,3,4
xthe adsorption effect comparison diagram that/Cu-BTC composite and embodiment 1 Cu-BTC material, the active carbon prepared are Congo red to low concentration.
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
0.88g copper nitrate and 0.420g trimesic acid are dissolved into the deionization N that 45ml mixes by 1:1:1, uniform stirring in the mixed solution of N '-dimethyl formamide, water and ethanol ultrasonic process, the reactant liquor obtained rises to 120 DEG C with the speed of 5 DEG C/min from room temperature, constant temperature 24h, naturally cools to room temperature.Product after suction filtration first uses N, and N '-dimethyl formamide rinses 3 times, then soaks in ethanol after 3 days, under 120 DEG C of vacuum conditions, activate 12h, and marking this sample is Cu-BTC.
Embodiment 2: the preparation of zinc-copper bimetallic organic framework material
0.90g copper nitrate, 0.124g zinc nitrate and 0.50g trimesic acid are dissolved into the N that 22.5ml mixes by 1:1:1, uniform stirring in the mixed solution of N '-dimethyl formamide, deionized water and ethanol ultrasonic process, the reactant liquor obtained rises to 85 DEG C with the speed of 10 DEG C/min from room temperature, constant temperature 20h, naturally cools to room temperature.Product after suction filtration first uses N, and N '-dimethyl formamide rinses 3 times, then soaks in ethanol after 3 days, under 100 DEG C of vacuum conditions, activate 13h, and marking this sample is Zn10/Cu-BTC.
Embodiment 3: the preparation of zinc-copper bimetallic organic framework material
0.694g copper nitrate, 0.14g zinc nitrate and 0.420g trimesic acid are dissolved into the N that 22.5ml mixes by 1:1:1, uniform stirring in the mixed solution of N '-dimethyl formamide, deionized water and ethanol ultrasonic process, the reactant liquor obtained rises to 125 DEG C with the speed of 7 DEG C/min from room temperature, constant temperature 12h, naturally cools to room temperature.Product after suction filtration first uses N, and N '-dimethyl formamide rinses 3 times, then soaks in ethanol after 3 days, under 110 DEG C of vacuum conditions, activate 14h, and marking this sample is Zn20/Cu-BTC.
Embodiment 4: the preparation of zinc-copper bimetallic organic framework material
0.761g copper nitrate, 0.23g zinc nitrate and 0.630g trimesic acid are dissolved into the N that 45ml mixes by 1:1:1, uniform stirring in the mixed solution of N '-dimethyl formamide, deionized water and ethanol ultrasonic process, the reactant liquor obtained rises to 125 DEG C with the speed of 5 DEG C/min from room temperature, constant temperature 12h, naturally cools to room temperature.Product after suction filtration first uses N, and N '-dimethyl formamide rinses 3 times, then soaks in ethanol after 3 days, under 100 DEG C of vacuum conditions, activate 12h, and marking this sample is Zn30/Cu-BTC.
Embodiments of the invention 1 and the material obtained by embodiment 2, its characterization result is as follows with the Congo red performance of absorption:
(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 embodiment of the present invention 1 and 2,3,4 porous material prepared characterizes, 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, Zn/Cu-BTC bimetallic material prepared by embodiment 2,3,4 shows the characteristic peak consistent with Cu-BTC material prepared by embodiment 1, and peak is strong and sharp-pointed, shows that it has good Cu-BTC crystal framework structure.
(2) 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 2, sample all presents octahedral crystal structure to result, shows that mixing of Zn does not destroy the original structure of Cu-BTC.
(3) Congo red 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, and Cu-BTC material prepared by embodiment 1 and Zn/Cu-BTC bimetallic material prepared by embodiment 2,3,4, and the absorption property curve map that charcoal absorption low concentration is Congo red, by sample vacuum activating 12h under 110 DEG C of conditions before test.
As shown in Figure 4, Zn
x/ Cu-BTC bimetallic material to Congo red adsorbance at more than 40mg/g, higher than the 26.7mg/g of Cu-BTC material under equal experiment condition.This shows, due to the introducing of Zn, contributes to the raising of absorption property.
Table 3 is Congo red desorption balance data on different sorbing material.As can be seen from the table, under equal experiment condition, the Zn/Cu-BTC bimetallic material equilibrium adsorption capacity Congo red to low concentration is about 1.74 times of Cu-BTC, 10.84 times of active carbon.
Table 3
Claims (9)
1. a preparation method for zinc-copper bimetallic organic framework material, is characterized in that, comprises the following steps:
(1) soluble copper salt, soluble zinc salt and trimesic acid are joined N, in the mixed solvent of N '-dimethyl formamide, water and ethanol, uniform stirring ultrasonic process, obtain reactant liquor;
(2) reactant liquor of step (1) is transferred in polytetrafluoroethylene (PTFE) reactor carry out hydro-thermal reaction, obtain spelter copper bi-metal organic framework material;
(3) material that step (2) obtains first is used N, N '-dimethyl formamide rinses, then soaks with alcohol solvent, finally by activation, obtains the zinc-copper bimetallic organic framework material of purifying.
2. preparation method according to claim 1, is characterized in that, the mol ratio of described soluble copper salt and soluble zinc salt, trimesic acid is 1:(0.1 ~ 0.3): (0.3 ~ 0.8).
3. preparation method according to claim 1, is characterized in that, in described mixed solvent, the volume ratio of N, N '-dimethyl formamide and water, ethanol is 1:1:1.
4. preparation method according to claim 1, is characterized in that, in step (1), described soluble copper salt is 0.080 ~ 0.22mol/L with the molal volume ratio of mixed solvent.
5. the preparation method according to any one of Claims 1 to 4, it is characterized in that, the temperature programming of hydro-thermal reaction described in step (2) is: with the programming rate of 5 ~ 10 DEG C/h, the temperature of reactant liquor is risen to 85-125 DEG C, after constant temperature 12 ~ 24h, naturally cool to room temperature.
6. preparation method according to claim 5, is characterized in that, described activation is keep 10 ~ 14h under 100 ~ 120 DEG C of vacuum conditions.
7. the preparation method according to any one of Claims 1 to 4, is characterized in that, described in step (1), soluble copper salt is copper nitrate, and the zinc salt of solubility is zinc nitrate.
8. the zinc-copper bimetallic organic framework material prepared of any one of claim 1 ~ 7 method.
9. zinc-copper bimetallic organic framework material according to claim 8 dye molecule in adsorbed water Congo red in application.
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| CN105693750A (en) * | 2016-03-01 | 2016-06-22 | 青岛大学 | Rapid preparation method of environment-friendly metal-organic framework material |
| CN105713208A (en) * | 2016-04-15 | 2016-06-29 | 中国科学院上海高等研究院 | CuZn bi-metal organic framework material and preparing method thereof |
| CN105797157A (en) * | 2016-04-26 | 2016-07-27 | 中国科学技术大学 | Preparation method and application of porous core-shell double-metal organic framework nano drug carrier |
| CN105854944A (en) * | 2016-03-31 | 2016-08-17 | 华南理工大学 | Copper doped ferrous metal organic framework material as well as preparation method and method for activating persulfate to treat organic wastewater by using same |
| CN105884576A (en) * | 2016-04-15 | 2016-08-24 | 中国科学院上海高等研究院 | Copper-based catalyst with Cu and Zn Bi-MOF (bi-metal organic framework) as precursor as well as preparation method and application of copper-based catalyst |
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