CN109317104A - A kind of mercapto-functionalized metal-organic framework materials, preparation and its application - Google Patents
A kind of mercapto-functionalized metal-organic framework materials, preparation and its application Download PDFInfo
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Abstract
A kind of mercapto-functionalized metal-organic framework materials, preparation and its application, belong to metal-organic framework materials technical field.Structural formula of compound isThe heavy metal ion being used for using UiO-66-SH as adsorbent for heavy metal in aqueous solution in Adsorption aqueous solution, adsorpting data show UiO-66-SH can mercury ion (Hg (II)) in good Adsorption aqueous solution, with UiO-66-NH2It compares, absorption property greatly improved, adsorbance is up to 490.98mg/g.In addition, UiO-66-SH being capable of selective absorption removal mercury ion under the conditions of polyion.
Description
Technical field
The invention belongs to adsorbent for heavy metal preparation technical fields in crystalline material and aqueous solution, and in particular to a kind of
The preparation method of the metal-organic framework (Metal-Organic Frameworks, abbreviation MOFs) of zirconium and its in aqueous solution
The application in heavy metal ion adsorbed removal field.
Technical background
Currently, with the fast development of Chinese national economy and the quickening of process of modernization, problem of environmental pollution is got over
Come more serious, more and more prominent, wherein heavy metal pollution is an extremely important problem of environmental pollution.Heavy metal ion is main
Come from the waste water discharged into natural environment during metallurgy, electrolysis, plating, chemical industry, printing and dyeing and various minings etc.,
Exhaust gas and waste residue equally exist a small amount of heavy metal ion in resident living sewage.
Currently, the method for common separation of heavy metal ions removal have separation by precipitation, electroosmose process, reverse osmosis method, from
Sub- exchange separation process and absorption method etc..It is in recent years, a kind of that emerging porous material --- metal-organic framework is as adsorbing separation
Medium shows great application potential in heavy metal ion adsorbed removal field.
Metal-organic framework is that one kind is had periodically infinitely by metal ion and organic ligand by what coordinate bond was formed
The crystalline state porous material of topological structure is a kind of special coordination polymer.Most metals-organic backbone hole with higher
The features such as gap rate, biggish specific surface area and various structures.By selecting different metal ion and organic ligand, Ke Yida
To topological structure, pore size and the shape of regulation metal-organic framework, to realize more function of large aperture, bigger serface
The building of energy metal-organic framework.Just because of the Modulatory character, modifiability and porosity of metal-organic framework, make it
Catalysis, gas storage with separate, heavy metal ion adsorbed removal, Subjective and Objective molecule (ion) in terms of with wide
Application prospect, it has also become the hot spot of people concern and research.
For now, domestic and international more and more researchers are to a utilization metal-organic framework Adsorption huge sum of money
Belong to ion and carried out research report, related research result is delivered in the form of paper, meeting report, patent etc..But due to metal-
Organic backbone lacks extra coordination site, causes it very weak to the active force of extraneous heavy metal ion, therefore metal-organic framework
Not high to the adsorbance of heavy metal ion, this significantly limits metal-organic framework answering as adsorbent for heavy metal
With.Therefore, how to improve metal-organic framework to the adsorption capacity of heavy metal ion, and assign metal-organic framework to have
The heavy metal ion such as lead, chromium, mercury, cadmium, arsenic in the removal aqueous solution of selective and high adsorption capacity, it has also become research hotspot and
Difficult point.
According to domestic and international researcher studies have shown that mercapto-functionalized metal-organic framework to mercury ion (Hg
(II)) adsorption capacity dramatically increases, and has thus highlighted mercapto groups to the coordination ability of mercury ion, to widen metal-
Organic backbone is in the application in heavy metal ion adsorbed removal field, and especially mercapto-functionalized metal-organic framework is in heavy metal
The application in ionic adsorption removal field.
Summary of the invention
The present invention provide it is a kind of after modify method synthesize mercapto-functionalized metal-organic framework method and its a huge sum of money
Belong to the application in ionic adsorption removal field.
Technical scheme is as follows:
A kind of mercapto-functionalized metal-organic framework UiO-66-SH, which is characterized in that chemical structural formula is as follows:
A method of above-mentioned mercapto-functionalized metal-organic framework UiO-66-SH, feature are synthesized by rear modification method
It is, includes the following steps:
(1) amino functional metal-organic framework UiO-66-NH2Synthesis:
Zirconium chloride, 2- amino terephthalic acid (TPA), n,N-Dimethylformamide solution and concentrated hydrochloric acid solution are mixed, at ultrasound
It is transferred to after reason in the reaction kettle with polytetrafluoroethyllining lining, it is small to react 8-20 after tightening in 200 DEG C -250 DEG C of baking oven
When, preferably 220 DEG C and 16 hours；
It is preferred that the molar ratio of the zirconium chloride and 2- amino terephthalic acid (TPA) is 1:(15-25)；
It is preferred that the molar ratio of the zirconium chloride and N,N-dimethylformamide is 1:(75-85)；
It is preferred that the molar ratio of the zirconium chloride and concentrated hydrochloric acid is 1:(1-5).
(2) synthesis of mercapto-acetaldehyde:
A, under condition of ice bath, chloroacetaldehyde solution is added in zero degrees celsius deionized water, adjusts pH with sodium carbonate liquor
It is worth to 1-5, preferably 3；
B, under condition of ice bath, NaHS hydrate is dissolved completely in zero degrees celsius deionized water；
C, the sodium hydrosulfide of step B is added slowly in the chloroacetaldehyde solution of step A, whole process stirring, until white is solid
Body no longer generates；
It is preferred that the molar ratio of the chloroacetaldehyde of the step A and zero degrees celsius deionized water is 1:(25-35)；
It is preferred that the molar ratio of the NaHS hydrate of the step B and zero degrees celsius deionized water is 1:(15-25)；
The molar ratio (1-3) of the NaHS and chloroacetaldehyde: (1-3).
(3) synthesis of mercapto-functionalized metal-organic framework UiO-66-SH:
By UiO-66-NH2It is blended in methanol solution with mercapto-acetaldehyde, 65 DEG C is heated under the conditions of oil bath, is condensed back to
Stream, is stirred to react 24 hours；
It is preferred that the UiO-66-NH2With the molar ratio (1-5) of mercapto-acetaldehyde: (1-5).
The application of heavy metal ion, side in mercapto-functionalized metal-organic framework UiO-66-SH Adsorption aqueous solution
Method is as follows:
A certain amount of UiO-66-SH is weighed, is added in the solution containing heavy metal ion, due to UiO-66-SH tool one
By the way of being put into shaking table after magneton is added, it is more abundant to be allowed to stirring for fixed hydrophobicity；It is stirred to react 24 hours.
The application of above-mentioned mercapto-functionalized metal-organic framework UiO-66-SH is used for selective absorption mercury ion (Hg
(II))。
The supernatant after absorption is extracted by centrifugation, it is dense using inductively coupled plasma body test heavy metal ion residue
The volume of heavy metal ion solution is added according to the quality of weighed UiO-66-SH in degree, heavy metal ion solution it is initial dense
Degree and residual concentration calculate adsorbance of the UiO-66-SH to heavy metal ion of unit mass, in terms of milligrams per gram (mg/g).
It is an advantage of the invention that successfully finding out the side of a mercapto-functionalized metal-organic framework UiO-66-SH of synthesis
Method, and using the mercury ion in UiO-66-SH Adsorption aqueous solution, it has widened metal-organic framework and has been inhaled in heavy metal ion
The application in attached removal field.
Using UiO-66-SH as adsorbent for heavy metal in aqueous solution be used for the heavy metal in Adsorption aqueous solution from
Son, adsorpting data show UiO-66-SH can mercury ion in good Adsorption aqueous solution, with UiO-66-NH2It compares,
Absorption property greatly improved, adsorbance is up to 490.98mg/g.In addition, UiO-66-SH can be selected under the conditions of polyion
Property Adsorption mercury ion.
Detailed description of the invention
The synthetic route chart and structure chart of Fig. 1 UiO-66-SH of the present invention
Fig. 2 UiO-66-SH of the present invention is under the conditions of single ionic to the absorption figure of heavy metal ion
Fig. 3 UiO-66-SH of the present invention is under the conditions of hybrid ionic to the absorption figure of heavy metal ion
Fig. 4 UiO-66-SH of the present invention and UiO-66-NH2Adsorption of Mercury ion comparison diagram
Adsorption isotherm of Fig. 5 UiO-66-SH of the present invention to mercury ion
Specific embodiment
The reagent that the present invention uses:
Zirconium chloride, 2- amino terephthalic acid (TPA), n,N-Dimethylformamide solution, concentrated hydrochloric acid solution, chloroacetaldehyde solution, zero
Degree Celsius deionized water, sodium carbonate, NaHS hydrate, methanol solution, dimethyl sulphoxide solution, lead standard liquid, chromium standard liquid, mercury
Standard liquid, cadmium standard liquid, arsenic standard liquid, mercury chloride, deionized water.
The purity of the zirconium chloride is 98%；
The 2- amino terephthalic acid (TPA) purity is 99%；
The concentration of the N,N-dimethylformamide is 99.5%；
The concentration of the concentrated hydrochloric acid solution is 36%-38%；
The concentration of the chloroacetaldehyde solution is 40%；
The purity of the sodium carbonate is 99.8%；
The purity of the NaHS hydrate is 68%~72%；
The concentration of the methanol solution is 99.5%；
The concentration of the dimethyl sulphoxide solution is 99.0%；
The concentration of the lead standard liquid is 1000 μ g/mL；
The concentration of the chromium standard liquid is 1000 μ g/mL；
The concentration of the mercury standard liquid is 1000 μ g/mL；
The concentration of the cadmium standard liquid is 1000 μ g/mL；
The concentration of the arsenic standard liquid is 1000 μ g/mL；
The purity of the mercury chloride is 99.5%.
Embodiment 1
1.1. the 2- amino terephthalic acid (TPA) of the zirconium chloride and 1.45g that weigh 931mg is added to the N of 24mL, N- dimethyl
In formamide solution, 670 μ L concentrated hydrochloric acid solutions are added, are transferred to the reaction kettle with polytetrafluoroethyllining lining after ultrasonic treatment
In, it is reacted 16 hours in 220 DEG C of baking oven after tightening.Taken out from baking oven after the reaction was completed, after being cooled to room temperature by from
The heart collects solid, impregnates solid 4-5 times in 60 DEG C of environment with n,N-Dimethylformamide solution, and 12 hours every time, to remove
Remove unreacted 2- amino terephthalic acid (TPA)；Again with acetone soak solid 4-5 times, every time 12 hours, to replace N, N- dimethyl
Formamide；Drying solid is obtained finally by degassing to get amino functional metal-organic framework UiO-66-NH is arrived2。
1.2. under condition of ice bath, the chloroacetaldehyde solution of 19.5mL is added in 58.8mL zero degrees celsius deionized water,
PH value is adjusted to 3 or so with the sodium carbonate liquor of 2mol/L；Under condition of ice bath, the NaHS hydrate of 5.6g is dissolved in
In 33mL zero degrees celsius deionized water.
1.3. sodium hydrosulfide is added slowly in chloroacetaldehyde solution, whole process stirring, until white solid no longer generates.It is logical
It crosses and solid is collected by centrifugation, solid is washed with deionized 4-5 times to get mercapto-acetaldehyde is arrived.Natural air drying.
1.3. the UiO-66-NH of 274mg is weighed2It is blended in 50mL methanol solution with the mercapto-acetaldehyde of 380mg, in oil bath
Under the conditions of heated constant temperature at 65 DEG C, be condensed back under the conditions of air-tightness is good, under the conditions of magnetic agitation react 24 hours.
After the reaction was completed by the way that solid is collected by centrifugation, impregnated solid 4-5 times in 60 DEG C of environment with dimethyl sulphoxide solution, 12 is small every time
When, to remove unreacted mercapto-acetaldehyde；It is impregnated solid 4-5 times in 60 DEG C of environment with n,N-Dimethylformamide solution again,
12 hours every time, to replace dimethyl sulfoxide；Solid 4-5 times is impregnated in room temperature environment with acetone again, 12 hours every time, to set
Change N,N-dimethylformamide；Drying solid is obtained finally by degassing to get mercapto-functionalized metal-organic framework UiO- is arrived
66-SH。
1.4. the UiO-66-SH for weighing 5mg, being added to equipped with 3mL concentration is the leaded of 100 μ g/mL, chromium, mercury, cadmium, arsenic
Single ionic solution or concentration be that the leaded of 100 μ g/mL, chromium, mercury, cadmium, the mixed ion solutions of arsenic or concentration are
50 μ g/mL, 100 μ g/mL, 150 μ g/mL, 200 μ g/mL, 300 μ g/mL, 500 μ g/mL, 600 μ g/mL, 700 μ g/mL, 800 μ g/
ML, 900 μ g/mL, 1000 μ g/mL, the mercurous solion of 1200 μ g/mL, since UiO-66-SH has certain hydrophobicity, because
After this is using magneton is added, it is put into the mode of shaking table, it is more abundant to be allowed to stirring.After stirring 24 hours, extracted by centrifugation
Clear liquid tests heavy metal ion residual concentration using inductively coupled plasma body, according to the matter of weighed metal-organic framework
Amount, is added the volume of heavy metal ion solution, and the initial concentration and residual concentration of heavy metal ion calculate unit mass
UiO-66-SH is shown in attached drawing 2-5 in terms of milligrams per gram (mg/g) to the adsorbance of heavy metal ion.
Claims (9)
1. a kind of mercapto-functionalized metal-organic framework UiO-66-SH, which is characterized in that chemical structural formula is as follows:
2. a kind of side modified method after and synthesize mercapto-functionalized metal-organic framework UiO-66-SH described in claim 1
Method, which comprises the steps of:
(1) amino functional metal-organic framework UiO-66-NH2Synthesis:
Zirconium chloride, 2- amino terephthalic acid (TPA), n,N-Dimethylformamide solution and concentrated hydrochloric acid solution are mixed, after ultrasonic treatment
It is transferred in the reaction kettle with polytetrafluoroethyllining lining, is reacted 8-20 hours in 200 DEG C -250 DEG C of baking oven after tightening, it is excellent
Select 220 DEG C and 16 hours.
It is preferred that the molar ratio of the zirconium chloride and 2- amino terephthalic acid (TPA) is 1:(15-25)；
It is preferred that the molar ratio of the zirconium chloride and N,N-dimethylformamide is 1:(75-85)；
It is preferred that the molar ratio of the zirconium chloride and concentrated hydrochloric acid is 1:(1-5).
(2) synthesis of mercapto-acetaldehyde:
A, under condition of ice bath, chloroacetaldehyde solution is added in zero degrees celsius deionized water, with sodium carbonate liquor adjust pH value to
1-5, preferably 3；
B, under condition of ice bath, NaHS hydrate is dissolved completely in zero degrees celsius deionized water；
C, the sodium hydrosulfide of step B is added slowly in the chloroacetaldehyde solution of step A, whole process stirring, until white solid is not
It generates again；
(3) synthesis of mercapto-functionalized metal-organic framework UiO-66-SH:
By UiO-66-NH2It is blended in methanol solution with mercapto-acetaldehyde, 65 DEG C is heated under the conditions of oil bath, be condensed back, stir
Mix reaction 24 hours.
3. according to the method for claim 2, which is characterized in that the preferred chloroacetaldehyde rubs with zero degrees celsius deionized water
You are than being 1:(25-35).
4. according to the method for claim 2, which is characterized in that the preferred NaHS hydrate and zero degrees celsius go from
The molar ratio of sub- water is 1:(15-25).
5. according to the method for claim 2, which is characterized in that the molar ratio (1- of the preferred NaHS and chloroacetaldehyde
3):(1-3)。
6. according to the method for claim 2, which is characterized in that the preferred UiO-66-NH2With the molar ratio of mercapto-acetaldehyde
(1-5):(1-5)。
7. the application of mercapto-functionalized metal-organic framework UiO-66-SH described in claim 1, in Adsorption aqueous solution
Heavy metal ion.
8. the application of mercapto-functionalized metal-organic framework UiO-66-SH as claimed in claim 7 is used for selective absorption mercury
Ion (Hg (II)).
9. the method for the application of mercapto-functionalized metal-organic framework UiO-66-SH described in claim 1, weighs a certain amount of
UiO-66-SH, be added in the solution containing heavy metal ion, since UiO-66-SH has certain hydrophobicity, using addition
It is put into the mode of shaking table after magneton, it is more abundant to be allowed to stirring；It is stirred to react 24 hours.
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| CN112934204A (en) * | 2021-02-23 | 2021-06-11 | 上海交通大学 | Heavy metal mercury adsorbent and preparation method thereof |
| CN113293621A (en) * | 2021-04-23 | 2021-08-24 | 中交天津港湾工程研究院有限公司 | Preparation method of hydrophobic thiolated Zr-MOFs modified non-woven fabric, prepared modified non-woven fabric and application thereof |
| CN114196032A (en) * | 2021-10-22 | 2022-03-18 | 广东工业大学 | Tetrathiol functionalized UiO-66 type metal organic framework material and preparation method and application thereof |
| CN115216022A (en) * | 2021-04-16 | 2022-10-21 | 香港科技大学 | Thiolated Zr-based metal organic framework and preparation method and application thereof |
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Application publication date: 20190212 |