CN109535433A - Metal-organic framework material Ca3(BTC)2Preparation method and application of - Google Patents
Metal-organic framework material Ca3(BTC)2Preparation method and application of Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011575 calcium Substances 0.000 claims abstract description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 25
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000003755 preservative agent Substances 0.000 claims abstract description 4
- 230000002335 preservative effect Effects 0.000 claims abstract description 4
- 238000002604 ultrasonography Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- 230000000717 retained effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- -1 mono- acetate hydrate calcium Chemical compound 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 229940067460 calcium acetate monohydrate Drugs 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000010865 sewage Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 230000002124 endocrine Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Life Sciences & Earth Sciences (AREA)
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Abstract
Metal-organic boneScaffolding material Ca3(BTC)2Relates to the technical field of preparation and application of metal-organic framework materials. Dissolving calcium acetate monohydrate by using absolute ethyl alcohol and DMF (dimethyl formamide) and uniformly mixing to obtain a solution A; dissolving and uniformly mixing trimesic acid with DMF to obtain a solution B; placing the solution A and the solution B in a beaker A and uniformly mixing; placing DMF and triethylamine in a beaker B, uniformly mixing, and sealing the opening of the beaker through a preservative film; firstly, placing a beaker B in a beaker A, then placing the beaker A in an ultrasonic instrument, reacting under the ultrasonic condition to obtain a precipitate, filtering, washing and drying to obtain a metal-organic framework material Ca which takes Ca as a metal center and takes trimesic acid as a ligand3(BTC)2. The size and the shape of the product are correspondingly changed by regulating and controlling the ultrasonic time. The synthesized metal-organic framework material has stronger removal effect on most heavy metal ions.
Description
Technical field
The present invention relates to the preparation of metal-organic framework materials and applied technical field, being specifically related to a kind of metal-has
Machine framework material Ca3(BTC)2Preparation method and application.
Background technique
In the 1990s, first kind metal-organic framework materials are synthesized, nowadays development is more than 30 years existing,
In the meantime, metal-organic framework materials (Metal-Organic Frameworks, english abbreviation MOFs) are anticipated with one
Unimaginable speed rapidly develops.Metal-organic framework materials are a kind of novel porous crystalline materials, this polyporous materials be by
Coordination polymer made of metal ion or metal cluster and organic ligand self assembly.MOFs is mesh skeleton structure, is matched with organic
Body is bracket, metal ion or metal cluster are node, is attached to be formed by coordinate bond.Different organic ligands and gold
Belong to ion, can assemble to obtain the stephanoporate framework material with heterogeneous networks structure and different aperture size, it is identical organic to match
Body and metal ion can also obtain the framework material of the same race of different-shape by control synthetic method and condition.MOFs tool
There are special topological structure, biggish specific surface and porosity, pore size and reconfigurable, thermal stability good etc. many excellent
Point, therefore, it has extensive in fields such as hydrogen storage, catalysis, selective absorption, medicament slow release, fluorescence sense and magnetic materials
Using becoming a kind of new function material to attract attention, represent the new developing direction of material science.It is commonly used in preparation
The method of MOFs has: microwave-assisted reaction method, electrochemical synthesis, sonochemistry synthetic method, hydro-thermal method and solvent-thermal method etc..It passes
The synthesis metal-organic framework materials of system the most process of method is cumbersome, low yield, to pollute larger and waste of energy serious.
Since the 21th century, with the rapid development of human economy, environmental pollution has become increasingly serious, especially in water
Heavy metal pollution problem.Such as the discharge of mercury in Japanese Minamata bay industrial production in 1956, the body and mind for having seriously endangered locals is strong
Health.If heavy metal assembles the organs such as the nerve that can also injure people, digestion, immune, endocrine in vivo, or even influences newborn
Physical and intellectual development.How simple, the rapid heavy metal removed in water, is that researcher is paid close attention to and studied always
Important topic.There are many methods to can be used for removing the heavy metal in water such as: ion-exchange, coprecipitation, hyperfiltration
Deng.
Currently, China pays much attention to environmental protection, develop the very simple and convenient method of one kind for heavy metal in solution
Processing, detection have very important practical significance, develop heavy metal processing, detection system and the dress being of great significance
It sets, will be widely used in that there is very important value and application prospect in heavy metal processing for future.
Summary of the invention
The technical problem to be solved in the present invention be provide it is a kind of prepare be applicable to heavy metal ions removal metal-it is organic
Framework material Ca3(BTC)2Method.
To achieve the goals above, the technical scheme adopted by the invention is as follows:
A kind of metal-organic framework materials Ca3(BTC)2Preparation method, steps are as follows:
1), an acetate hydrate calcium utilization dehydrated alcohol and n,N-Dimethylformamide are dissolved and are uniformly mixed, solution is obtained
A；
2) trimesic acid is mixed using N,N-dimethylformamide dissolution, and obtains solution B；
3), solution A and solution B are placed in beaker A and mixed, is retained spare；
4), n,N-Dimethylformamide and triethylamine are placed in beaker B and are uniformly mixed, and beaker is sealed by preservative film
Mouthful, it retains spare；
5), beaker B is placed in beaker A first, then beaker A is put into Ultrasound Instrument, is reacted under ultrasound condition
It to precipitating, is finally filtered, washed, obtains metal-organic framework materials Ca through dry3(BTC)2。
As metal-organic framework materials Ca of the invention3(BTC)2Preparation method optimal technical scheme, one hydration
The molar ratio of calcium acetate, trimesic acid and triethylamine is 1.5-1.7:1:1.4-1.6.Every mono- acetate hydrate calcium of 1g in step 1)
It is dissolved using the dehydrated alcohol of 30-50mL and the N,N-dimethylformamide of 30-50mL.Every 1g trimesic acid benefit in step 2)
It is dissolved with the N,N-dimethylformamide of 80-120mL.Every 1mL triethylamine utilizes the N of 5-15mL, N- dimethyl methyl in step 4)
Amide mixing.It is 40-60W that ultrasonic power is adjusted in step 5), and the ultrasound condition lower reaction time is 1-30min, and reaction temperature is
60-80℃。
The present invention is prepared for by simple and quick ultrasound diffusion combination method using Ca as metal center, trimesic acid be with
The metal-organic framework materials Ca of body3(BTC)2.Ultrasound diffusion combination method is a kind of high efficient cryogenic synthesis metal-organic framework material
The method of material mainly the mixed solution of metal ion and organic ligand is added in large beaker, and triethylamine is added in small beaker,
Small beaker is put into large beaker, under the action of Ultrasound Instrument, three reacts into metal-organic framework materials.Such method tool
Have the advantages that generated time is short, high-efficient, easy to operate.Pass through the structure of XRD analysis sample, the results showed that pass through such method
The product of acquisition is target product.By the regulation to ultrasonic time, it is found that Product size, pattern have corresponding change, it can
To analyze the forming process that ultrasonic method prepares metal-organic framework materials based on this.
The features such as metal-organic framework materials prepared by the present invention are due to its big specific surface area, stable structure, is used for
In the purified treatment of water.The present invention utilizes synthesized metal-organic framework materials Ca3(BTC)2, it is had studied to a huge sum of money in water
The removal of category acts on.The results showed that the metal-organic framework materials to most of heavy metal ion such as:52Cr、55Mn
、59Co、60Ni、63Cu、66Zn、75As、111Cd、137Ba and208Pb has stronger removal effect, therefore, the organic bone of the metal-
Frame material Ca3(BTC)2It is worth with important research and development.
Compared with prior art, it also have the advantage that
1) and the most process of conventional synthesis metal-organic framework materials method is cumbersome, low yield, pollution is larger, wastes
The disadvantages of energy, is compared, and the present invention may be implemented rapid synthesis and largely prepare metal-organic framework materials, and preparation method has
It imitates, is quick, succinct and pollution-free, having important practical significance.
2), the present invention passes through ultrasonic diffusion method rapid synthesis using calcium constituent as metal center ion, and trimesic acid is
The metal-organic framework materials Ca of ligand3(BTC)2, and can be obtained by regulation ultrasonic time and have different-shape and size
Product.
3), metal-organic framework materials prepared by the present invention have removing speed for the removal of heavy metal in sewage
Fastly, the good feature of removal effect.Being applied to sewage treatment field for future has important value, and this material can be with
Realize quick, mass production, being applied to environment protection field for future has potential application prospect.
Detailed description of the invention
With reference to embodiments with attached drawing to a kind of metal-organic framework materials Ca of the invention3(BTC)2Preparation method
And application is made and being discussed further.
Fig. 1 is the XRD spectra that embodiment 1 prepares product.
Fig. 2 is the scanning electron microscope (SEM) photograph for regulating and controlling the different resulting products of ultrasonic time in embodiment 1.
Fig. 3 is Ca3(BTC)2Remove concentration-adsorption time curve of each heavy metal ion in sewage.
Fig. 4 is Ca3(BTC)2Remove Pb in chlorination lead solution2+Concentration-adsorption time curve.
Specific embodiment
Embodiment 1
Metal-organic framework materials Ca3(BTC)2Preparation method, steps are as follows:
1) an acetate hydrate calcium (Ca (CH of 0.1233g (0.78mmol), is weighed3COO)2·H2O) in the beaker of 25mL
In, the dehydrated alcohol of 5mL and the n,N-Dimethylformamide (DMF) of 5mL is added, sufficiently shakes up rear spare.
2) 0.1g (0.48mmol) trimesic acid (H, is weighed3BDC) it is dissolved in the N,N-dimethylformamide (DMF) of 10mL
In, it mixes spare.
3), by above-mentioned steps 1) and the prepared two kinds of solution of step 2) be transferred in the beaker of 50mL together, sufficiently shake
It is retained after even spare.
4) triethylamine of the n,N-Dimethylformamide (DMF) and 0.1mL that, pipette 1mL is placed in the beaker of 25mL, mixing
Uniformly, and by preservative film beaker mouth is sealed, retained spare.
5), the small beaker of 25mL is placed in 50mL large beaker first, then 50mL large beaker is put into Ultrasound Instrument,
Adjusting ultrasonic power is 50W, and control bath temperature is 70 DEG C, and ultrasonic reaction 5min, 10min, 15min, 20min, obtain respectively
White precipitate, finally filtering, alcohol are washed, 70 DEG C of vacuum drying 4h.
Fig. 1 is the XRD spectra that embodiment 1 prepares product.A is monocrystalline fit standard Ca in Fig. 13(BTC)2XRD spectra, b
For the XRD spectra of ultrasonic 10min products therefrom.As shown in Figure 1, the single crystal diffraction peak of the two is completely the same, without other miscellaneous peaks
It generates, shows that by the product of ultrasonic method diffusion method rapid synthesis be exactly target product Ca3(BTC)2Metal-organic framework materials.
According to Debye-Scherrer formula:
Wherein k is constant (k=0.89), and λ is wavelength (λ=1.54178nm), and β and θ are half-peak breadth and the angle of diffraction respectively.
Grain size obtained by calculation is consistent with grain morphology size shown by SEM.
Fig. 2 is the scanning electron microscope (SEM) photograph for regulating and controlling the different resulting products of ultrasonic time, as can be seen from Figure 2: ultrasonic 5min
When (Fig. 2 a) there is rodlike product, length is about 50 μm, this rodlike crystal structure be quickly and a large amount of ion exchange
Provide possibility.Continuing growing ultrasonic time is 10min (Fig. 2 b), and rodlike product has the tendency that gradually shortening, when ultrasound
Between when increasing to 15min (Fig. 2 c), rodlike product gradually disintegrates as petal-shaped, continues growing after ultrasonic time (Fig. 2 d) again
It is assembled into laminated structure.Fig. 2 c can regard product as by the transition state of club shaped structure to laminated structure.
Embodiment 2
Metal-organic framework materials Ca3(BTC)2Removing heavy metal energy
In order to verify Ca3(BTC)2Metal-organic framework materials can remove the heavy metal in water, take garbage loading embeading first
Sewage near is tested.Weigh the Ca through 70 DEG C of ultrasonic reaction 10min of 25mg3(BTC)2It is added in sewage, utilizes electricity
Heavy metal concentration in the supernatant of exchange different time is tested in sense couple plasma mass spectrometer (ICP-MS), as a result such as
Shown in Fig. 3: rodlike Ca being added in sewage3(BTC)2The concentration of metal-organic framework materials 2h, heavy metal reduce nearly 50%,
As time increases, heavy metal concentration gradually decreases, and with the progress of reaction, when reacting 5-10h, the concentration of heavy metal is reduced
Slack-off, when reaction is to 10h, the concentration of heavy metal is basically unchanged.
Embodiment 3
In order to further investigate Ca3(BTC)2To the removal effect of heavy metal, the present invention is investigated the Ca of different-shape3
(BTC)2To Pb in solution2+Removing ability.
1., the determination of different ultrasonic time sample
The Ca that 60mg is respectively 5min, 10min, 15min, 20min through 70 DEG C of ultrasonic reaction times is weighed respectively3(BTC)2
4.0gL is added-1In chlorination lead solution, after absorption for 24 hours, centrifugation, dilution measure absorption Pb with ICP-MS2+Concentration such as table 1
It is shown:
The Ca of 1 differential responses time of table3(BTC)2To Pb2+Adsorption effect
According to the measurement result of ICP-MS it is found that Ca3(BTC)2To Pb2+Removal effect it is preferable, removal efficiency is all 80%
More than.Wherein ultrasonic time is the rodlike Ca of 10min3(BTC)2Removal efficiency highest, be 87.50%, ultrasonic time 15min
The irregular transition state sample of pattern removal efficiency minimum 82.75%, illustrate Ca3(BTC)2Removal efficiency and crystalline substance to heavy metal
The pattern of body has certain relationship.So the Ca that next heavy metal ions removal experiment is used3(BTC)2It is through 70 DEG C
Super ultrasonic time is sample obtained by 10min.
②、Ca3(BTC)2Adsorption process measurement to heavy metal ion
By the Ca of 60mg3(BTC)2Be added in the aqueous solution of the lead chloride containing 100mg, absorption 0.5h, 1h, 2h, 4h, 8h,
12h, for 24 hours after it is separately sampled, with ICP-MS measure Pb2+Concentration.Fig. 4 is Ca3(BTC)2Remove Pb in chlorination lead solution2+Mistake
Cheng Tu, as seen from Figure 4, the Pb in the 2h for reacting initial, in solution2+The decline of concentration sharply, removal effect are obvious.With
The increase of time, Pb in solution when from 2-8h2+Concentration variation slowly, illustrate that elimination reaction at this time basically reaches balance, when
The ion concentration being reacted to after 8h in solution is constant, and elimination reaction is completed.It can thus be seen that Ca3(BTC)2A removing huge sum of money
The speed of category ion is fast, effect is good, has great significance for future applied to heavy metal removing.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Design or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (8)
1. a kind of metal-organic framework materials Ca3(BTC)2Preparation method, which is characterized in that steps are as follows:
1), an acetate hydrate calcium utilization dehydrated alcohol and n,N-Dimethylformamide are dissolved and are uniformly mixed, solution A is obtained；
2) trimesic acid is mixed using N,N-dimethylformamide dissolution, and obtains solution B；
3), solution A and solution B are placed in beaker A and mixed, is retained spare；
4), n,N-Dimethylformamide and triethylamine are placed in beaker B and are uniformly mixed, and beaker mouth is sealed by preservative film,
It retains spare；
5), beaker B is placed in beaker A first, then beaker A is put into Ultrasound Instrument, reaction is sunk under ultrasound condition
It forms sediment, is finally filtered, washed, obtain metal-organic framework materials Ca through dry3(BTC)2。
2. preparation method as described in claim 1, which is characterized in that an acetate hydrate calcium, trimesic acid and triethylamine
Molar ratio is 1.5-1.7:1:1.4-1.6.
3. preparation method as described in claim 1, which is characterized in that every mono- acetate hydrate calcium utilization 30- of 1g in step 1)
The N,N-dimethylformamide dissolution of the dehydrated alcohol and 30-50mL of 50mL.
4. preparation method as described in claim 1, which is characterized in that every 1g trimesic acid utilizes 80-120mL in step 2)
N,N-dimethylformamide dissolution.
5. preparation method as described in claim 1, which is characterized in that every 1mL triethylamine utilizes the N of 5-15mL in step 4),
Dinethylformamide mixing.
6. preparation method as described in claim 1, which is characterized in that adjusting ultrasonic power in step 5) is 40-60W.
7. preparation method as claimed in claim 6, which is characterized in that the ultrasound condition lower reaction time is 1- in step 5)
30min, reaction temperature are 60-80 DEG C.
8. a kind of metal-organic framework materials Ca prepared using any one of claim 1-7 the method3(BTC)2It is removing
Application in heavy metal ion.
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| CN101531672A (en) * | 2008-03-12 | 2009-09-16 | 安徽大学 | Metal-organic framework material with nano pores and preparation method and application thereof |
| US20120065614A1 (en) * | 2010-09-10 | 2012-03-15 | University Of North Texas | Polyionic transitional metal phosphorescent complex/polymer hybrid systems for bioimaging and sensing applications |
| CN106328236A (en) * | 2016-09-21 | 2017-01-11 | 中国科学院高能物理研究所 | Material for treating typical radionuclides in wastewater and application thereof |
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| CN101531672A (en) * | 2008-03-12 | 2009-09-16 | 安徽大学 | Metal-organic framework material with nano pores and preparation method and application thereof |
| US20120065614A1 (en) * | 2010-09-10 | 2012-03-15 | University Of North Texas | Polyionic transitional metal phosphorescent complex/polymer hybrid systems for bioimaging and sensing applications |
| CN106328236A (en) * | 2016-09-21 | 2017-01-11 | 中国科学院高能物理研究所 | Material for treating typical radionuclides in wastewater and application thereof |
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