CN107552004A - A kind of preparation method and application of metal-organic framework materials - Google Patents
A kind of preparation method and application of metal-organic framework materials Download PDFInfo
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- CN107552004A CN107552004A CN201710630175.4A CN201710630175A CN107552004A CN 107552004 A CN107552004 A CN 107552004A CN 201710630175 A CN201710630175 A CN 201710630175A CN 107552004 A CN107552004 A CN 107552004A
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- zirconium chloride
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- 239000000463 material Substances 0.000 title claims abstract description 28
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000013207 UiO-66 Substances 0.000 claims description 10
- 229910052735 hafnium Inorganic materials 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000779 smoke Substances 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000013110 organic ligand Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of preparation method and application of metal-organic framework materials, the metal ion in the metal-organic framework materials is provided by hafnium tetrachloride and zirconium chloride, and organic ligand is provided by 1,2,4,5 benzene tertacarbonic acid；Preparation method of the present invention is simple to operate, and generated time is short, and equipment is simple；Sulfur dioxide, carbon dioxide and the nitrogen that metal-organic framework materials prepared by the present invention can be used in absorption industrial smoke, absorption property is preferable, repeats and utilizes, and the advantage with high chemical stability and high thermal stability.
Description
Technical field
The invention discloses a kind of preparation method and application of metal-organic framework materials, belongs to crystalline material technology neck
Domain.
Background technology
With the continuous development of modern industry, atmosphere pollution is increasingly severe, and the main source of municipal pollution is fossil combustion
A large amount of burnings of material, most important municipal pollution type is the atmospheric pollution level of coal-smoke pollution, the at present some cities in China
The pollution level in developed country's age in last century 50-60 is reached, the sulfur-bearing or other acidic gas concentrations in air are tight
Weight is exceeded.At present, the method for capturing these gases mainly has：Amine Solutions absorption process, membrane separation process and absorption method etc..At this
In a little methods, based on the absorption method of porous material due to the advantage such as efficient, economic and environment-friendly, being widely regarded as one
The very promising method of kind.Common porous material mainly active charcoal, zeolite molecular sieve and metal-organic framework materials etc..
As a kind of new porous material, metal-organic framework materials（Metal-Organic Frameworks,
MOFs）Constructed and formed by coordinate bond with organic ligand by metal ion or metal cluster.It has superelevation specific surface area,
The advantages such as bigger porosity, variation and adjustable pore passage structure.Gas absorption with separating, being catalyzed, fluorescence, electrochemistry etc.
Field has potential application prospect.Its gas absorption and separate aspect research, even more cause domestic and international research work
The extensive attention of person.
The content of the invention
It is an object of the invention to provide a kind of preparation method of metal-organic framework materials, following steps are specifically included：
（1）It is 1 by mol ratio:1:Zirconium chloride, hafnium tetrachloride and the 1,2,4,5- benzene tertacarbonic acids of (2 ~ 4) are dissolved in volume ratio and are
(6~8):In the mixed liquor of 1 N, N'- dimethylformamide and formic acid, every 0.5 mM of zirconium chloride is, it is necessary at least add
30mL N, N'- dimethylformamides, 5-30min is stirred by ultrasonic, obtains homogeneous mixed solution；
（2）By step（1）Gained mixed solution is transferred to reactor, reacts 12-24h at 100 ~ 120 DEG C；
（3）After question response kettle is cooled to room temperature, suction filtration obtains powder；
（4）By step（3）Obtained powder first uses N, and N'- dimethylformamides and acetone wash three times respectively, then use methanol
Washing is dried in vacuo obtains metal-organic framework materials UiO-66 (Zr, Hf)-(COOH) three times, after suction filtration2。
Preferably, step（1）Middle ultrasonic agitation temperature is no more than 40 DEG C.
Preferably, step（4）Middle vacuum drying step is to be dried in vacuo 12-24h at 65-100 DEG C.
Obtained metal-organic framework materials UiO-66 (Zr, Hf)-(COOH)2For adsorbing the titanium dioxide in industrial smoke
Sulphur, carbon dioxide and nitrogen.
Beneficial effects of the present invention：
（1）Metal-organic framework materials of the present invention have the characteristics of high chemical stability and high thermal stability；
（2）Metal-organic framework materials of the present invention are used to adsorb sulfur dioxide, carbon dioxide and nitrogen adsorption better performances,
Material is repeatable to be utilized；
（3）The present invention has the characteristics of cost is low, preparation process is simple, preparation condition is simple.
Brief description of the drawings
Fig. 1 is course of reaction schematic diagram of the present invention；
Fig. 2 is that the SEM of metal-organic framework materials made from embodiment 1 schemes；
Fig. 3 is the XRD of metal-organic framework materials made from embodiment 1；
Fig. 4 is metal-organic framework materials made from embodiment 1 to SO2Adsorption isotherm line chart；
Fig. 5 is metal-organic framework materials made from embodiment 2 to CO2Adsorption isotherm line chart；
Fig. 6 is metal-organic framework materials made from embodiment 2 to CO2The repetition experiment of absorption property；
Fig. 7 is metal-organic framework materials made from embodiment 3 to N2Adsorption isotherm line chart.
Embodiment
The present invention is described in further detail with reference to specific embodiment, but the scope of the present invention is not limited in described
Hold.
Embodiment 1
0.1165g zirconium chlorides, 0.1603g hafnium tetrachlorides and 0.2542g 1,2,4,5- benzene tertacarbonic acids are dissolved in 30mL N,
In the mixed liquor of N'- dimethylformamides and 5mL formic acid, water temperature is 20 DEG C in ultrasonic container, and 30min is stirred by ultrasonic, obtains
Homogeneous mixed solution；Reactor is transferred to, 24h is reacted in 100 DEG C of constant temperature oven, course of reaction is as shown in Figure 1；Question response kettle
After being cooled to room temperature, reactor is taken out, suction filtration obtains powder；Obtained powder is first used into N, N'- dimethylformamides and acetone
Wash three times, then washed three times with methanol respectively, being dried in vacuo 24h at 65 DEG C after suction filtration obtains metal-organic framework materials
UiO-66(Zr,Hf)-(COOH)2, its SEM figures are as shown in Fig. 2 XRD is as shown in Figure 3.
Weigh UiO-66 made from the present embodiment (Zr, Hf)-(COOH)2Powder 0.19g, constant weight is dried under vacuum at 65 DEG C
It is put into physics and inhales/be desorbed instrument, determines it under nitrogen protection to SO2Absorption property, be 0~1bar and 25 DEG C of condition in pressure
Under the SO that is collected into2Adsorption isotherm it is as shown in Figure 4.As shown in Figure 4, in 1.0bar, its adsorbance is about 3.08mmol/
g。
Embodiment 2
0.1165g zirconium chlorides, 0.1603g hafnium tetrachlorides and 0.381g 1,2,4,5- benzene tertacarbonic acids are dissolved in 35mL N,
In the mixed liquor of N'- dimethylformamides and 5mL formic acid, water temperature is 40 DEG C in ultrasonic container, and 5min is stirred by ultrasonic, and is obtained
Mix solution；The reactor of teflon lined is transferred to, 18h is reacted in 110 DEG C of constant temperature oven, course of reaction is as schemed
Shown in 1；After question response kettle is cooled to room temperature, reactor is taken out, suction filtration obtains powder；Obtained powder is first used into N, N'- diformazans
Base formamide and acetone wash three times respectively, are then washed three times with methanol, and being dried in vacuo 12h at 100 DEG C after suction filtration obtains gold
Belong to organic framework material UiO-66 (Zr, Hf)-(COOH)2。
Weigh UiO-66 made from the present embodiment (Zr, Hf)-(COOH)2Powder 0.19g, constant weight is dried under vacuum at 65 DEG C
It is put into physics and inhales/be desorbed instrument, determines it under nitrogen protection to CO2Absorption property, be 0~1bar and 25 DEG C of condition in pressure
Under the CO that is collected into2Adsorption isotherm it is as shown in Figure 5.As shown in Figure 5, in 1.0bar, its adsorbance is about 1.4mmol/g.
CO will have been adsorbed2UiO-66 (Zr, Hf)-(COOH)2CO absorption again after desorption2, circulating repetition experiment is carried out, as a result such as Fig. 6 institutes
Show, after circulating repetition 6 times, its adsorbance is about 1.35mmol/g, and absorption property is only declined slightly, and shows that the material repeats to inhale
Attached better performances.
Embodiment 3
0.1165g zirconium chlorides, 0.1603g hafnium tetrachlorides and 0.508g 1,2,4,5- benzene tertacarbonic acids are dissolved in 40mL N,
In the mixed liquor of N'- dimethylformamides and 5mL formic acid, water temperature is room temperature in ultrasonic container, and 10min is stirred by ultrasonic, obtains
Homogeneous mixed solution；The reactor of teflon lined is transferred to, 12h is reacted in 120 DEG C of constant temperature oven, course of reaction is such as
Shown in Fig. 1；After question response kettle is cooled to room temperature, reactor is taken out, suction filtration obtains powder；Obtained powder is first used into N, N'- bis-
NMF and acetone wash three times respectively, are then washed three times with methanol, and being dried in vacuo 18h at 80 DEG C after suction filtration obtains gold
Belong to organic framework material UiO-66 (Zr, Hf)-(COOH)2。
Weigh UiO-66 made from the present embodiment (Zr, Hf)-(COOH)2Powder 0.19g, constant weight is dried under vacuum at 65 DEG C
Be put into physics inhale/be desorbed instrument, determine it to N2Absorption property, the N being collected into the case where pressure is 0~1bar and 25 DEG C of bar2Suction
Attached thermoisopleth is as shown in Figure 7.As shown in Figure 7, in 1.0bar, its adsorbance is about 0.11mmol/g.
Claims (7)
1. a kind of preparation method of metal-organic framework materials, specifically includes following steps：
（1）Zirconium chloride, hafnium tetrachloride and 1,2,4,5- benzene tertacarbonic acids are dissolved in N, N '-dimethyl formamide and formic acid it is mixed
Close in liquid, 5-30min is stirred by ultrasonic, obtains mixed solution；
（2）By step（1）Gained mixed solution is transferred to reactor, reacts 12-24h at 100 ~ 120 DEG C；
（3）After question response kettle is cooled to room temperature, suction filtration obtains powder；
（4）By step（3）Obtained powder first uses N, and N'- dimethylformamides and acetone are washed three times respectively, and again with methanol is washed
Wash three times, be dried in vacuo after suction filtration and obtain metal-organic framework materials UiO-66 (Zr, Hf)-(COOH)2。
2. preparation method according to claim 1, it is characterised in that zirconium chloride, hafnium tetrachloride and 1,2,4,5- benzene four
Carboxylic acid mol ratio is 1:1:(2~4).
3. preparation method according to claim 1, it is characterised in that the volume ratio of N, N '-dimethyl formamide and formic acid
For (6 ~ 8):1.
4. preparation method according to claim 1, it is characterised in that every 0.5 mM of zirconium chloride needs more than 30mL
N, N'- dimethylformamide.
5. preparation method according to claim 1, it is characterised in that step（1）Middle ultrasonic agitation temperature is no more than 40 DEG C.
6. preparation method according to claim 1, it is characterised in that step（4）Middle vacuum drying step is in 65-100
12-24h is dried in vacuo at DEG C.
7. the metal-organic framework materials that the preparation method according to claim 1 to 6 any one obtains are used to adsorb two
Sulfur oxide, carbon dioxide and nitrogen.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786494A (en) * | 2018-05-31 | 2018-11-13 | 昆明理工大学 | A kind of preparation method of UiO-66 composite film materials |
| CN108872165A (en) * | 2018-04-02 | 2018-11-23 | 浙江大学 | A kind of mycotoxin colorimetric sensing method based on fluorescence metal organic framework materials |
| CN110394157A (en) * | 2019-07-05 | 2019-11-01 | 重庆科技学院 | It is a kind of for adsorbing the UiO-66-NH of palladium2Composite material and preparation method |
| CN112657558A (en) * | 2021-01-29 | 2021-04-16 | 昆明理工大学 | Application of plasma modified catalyst in removal of hydrogen sulfide, phosphine and arsine |
| CN114106693A (en) * | 2021-11-19 | 2022-03-01 | 江苏安纳泰环保科技有限公司 | graphene-Zr-MOF-polydimethylsiloxane magnesium alloy surface anti-corrosion composite coating and preparation method thereof |
| CN115073756A (en) * | 2021-10-28 | 2022-09-20 | 中国人民解放军国防科技大学 | Metal organic framework nano material and preparation method thereof, and composite material loaded with metal organic framework nano material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108872165A (en) * | 2018-04-02 | 2018-11-23 | 浙江大学 | A kind of mycotoxin colorimetric sensing method based on fluorescence metal organic framework materials |
| CN108786494A (en) * | 2018-05-31 | 2018-11-13 | 昆明理工大学 | A kind of preparation method of UiO-66 composite film materials |
| CN110394157A (en) * | 2019-07-05 | 2019-11-01 | 重庆科技学院 | It is a kind of for adsorbing the UiO-66-NH of palladium2Composite material and preparation method |
| CN112657558A (en) * | 2021-01-29 | 2021-04-16 | 昆明理工大学 | Application of plasma modified catalyst in removal of hydrogen sulfide, phosphine and arsine |
| CN115073756A (en) * | 2021-10-28 | 2022-09-20 | 中国人民解放军国防科技大学 | Metal organic framework nano material and preparation method thereof, and composite material loaded with metal organic framework nano material and preparation method thereof |
| CN115073756B (en) * | 2021-10-28 | 2023-09-12 | 中国人民解放军国防科技大学 | Metal-organic framework nano material and preparation method thereof, composite material loaded with metal-organic framework nano material and preparation method thereof |
| CN114106693A (en) * | 2021-11-19 | 2022-03-01 | 江苏安纳泰环保科技有限公司 | graphene-Zr-MOF-polydimethylsiloxane magnesium alloy surface anti-corrosion composite coating and preparation method thereof |
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