CN107552004B - 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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- CN107552004B CN107552004B CN201710630175.4A CN201710630175A CN107552004B CN 107552004 B CN107552004 B CN 107552004B CN 201710630175 A CN201710630175 A CN 201710630175A CN 107552004 B CN107552004 B CN 107552004B
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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 easy to operate, and generated time is short, and equipment is simple；Metal-organic framework materials prepared by the present invention can be used for adsorbing sulfur dioxide, carbon dioxide and nitrogen in industrial smoke, and absorption property is preferable, reusable, and the advantage with high chemical stability and high thermal stability.
Description
Technical field
The invention discloses a kind of preparation method and applications of metal-organic framework materials, belong to crystalline material technology neck
Domain.
Background technique
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 are coal-smoke pollution, at present the atmospheric pollution level in the certain cities in China
The pollution level in developed country's age in last century 50-60 is had reached, the sulfur-bearing or other acidic gas concentrations in atmosphere are tight
Weight is exceeded.Currently, 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 having the advantages such as efficient, economic and environmental-friendly, it is 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..
The porous material novel as one kind, metal-organic framework materials (Metal-Organic Frameworks,
It MOFs is) made of being constructed as metal ion or metal cluster and organic ligand by coordinate bond.Its specific surface area with superelevation,
The advantages such as bigger porosity, diversification and adjustable cellular structure.Gas absorption with separate, be catalyzed, fluorescence, electrochemistry etc.
Field has potential application prospect.It even more causes domestic and international research work in gas absorption and the research for separating aspect
The extensive attention of person.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of metal-organic framework materials, specifically includes the following steps:
(1) by molar ratio be 1:1:(2 ~ 4) zirconium chloride, hafnium tetrachloride and 1,2,4,5- benzene tertacarbonic acid be dissolved in volume
Than for (6 ~ 8): in the mixed liquor of 1 N, N'- dimethylformamide and formic acid, every 0.5 mM of zirconium chloride needs at least to add
Enter 30mL N, N'- dimethylformamide is stirred by ultrasonic 5-30min, obtains homogeneous mixed solution；
(2) mixed solution obtained by step (1) is transferred to reaction kettle, in 100 ~ 120 DEG C of reaction 12-24h；
(3) after reaction kettle is cooled to room temperature, suction filtration obtains powder；
(4) powder that step (3) obtains first is used into N, N'- dimethylformamide and acetone are washed three times respectively, then used
Methanol washs three times, and vacuum drying obtains metal-organic framework materials UiO-66 (Zr, Hf)-(COOH) after suction filtration2。
Preferably, ultrasonic agitation temperature is no more than 40 DEG C in step (1).
Preferably, vacuum drying step is to be dried in vacuo 12-24h at 65-100 DEG C in step (4).
Metal-organic framework materials UiO-66 (Zr, Hf)-(COOH) obtained2For 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 that high chemical stability and high thermal stability；
(2) metal-organic framework materials of the present invention are for adsorbing sulfur dioxide, carbon dioxide and nitrogen adsorption performance
Preferably, material is reusable；
(3) present invention has the characteristics that at low cost, preparation process is simple, preparation condition is simple.
Detailed description of the invention
Fig. 1 is reaction process schematic diagram of the present invention；
Fig. 2 is the SEM figure of metal-organic framework materials made from embodiment 1；
Fig. 3 is the XRD diagram of metal-organic framework materials made from embodiment 1；
Fig. 4 is metal-organic framework materials made from embodiment 1 to SO2Adsorption isotherm map；
Fig. 5 is metal-organic framework materials made from embodiment 2 to CO2Adsorption isotherm map；
Fig. 6 is metal-organic framework materials made from embodiment 2 to CO2The repetition of absorption property is tested；
Fig. 7 is metal-organic framework materials made from embodiment 3 to N2Adsorption isotherm map.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, but the scope of the present invention is not limited in described
Hold.
Embodiment 1
0.1165g zirconium chloride, 0.1603g hafnium tetrachloride and 0.2542g 1,2,4,5- benzene tertacarbonic acid are dissolved in 30mL
In the mixed liquor of N, N'- dimethylformamide and 5mL formic acid, water temperature is 20 DEG C in ultrasonic container, and 30min is stirred by ultrasonic, obtains
To homogeneous mixed solution；It is transferred to reaction kettle, is reacted in 100 DEG C of constant temperature oven for 24 hours, reaction process is as shown in Figure 1；Wait react
After kettle is cooled to room temperature, reaction kettle is taken out, suction filtration obtains powder；Obtained powder is first used into N, N'- dimethylformamide and third
Ketone washs three times respectively, is then washed three times with methanol, obtains metal-organic framework materials for 24 hours in 65 DEG C of vacuum drying after suction filtration
UiO-66(Zr,Hf)-(COOH)2, SEM figure is as shown in Fig. 2, XRD diagram is as shown in Figure 3.
Weigh UiO-66 made from the present embodiment (Zr, Hf)-(COOH)2Powder 0.19g is dried under vacuum to constant weight at 65 DEG C
It is put into physics and inhales/be desorbed instrument, measure it under nitrogen protection to SO2Absorption property, pressure be 0~1bar and 25 DEG C of condition
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 chloride, 0.1603g hafnium tetrachloride and 0.381g 1,2,4,5- benzene tertacarbonic acid are dissolved in 35mL
In the mixed liquor of N, N'- dimethylformamide and 5mL formic acid, water temperature is 40 DEG C in ultrasonic container, and 5min is stirred by ultrasonic, obtains
Homogeneous mixed solution；It is transferred to the reaction kettle of teflon lined, 18h is reacted in 110 DEG C of constant temperature oven, reaction process is such as
Shown in Fig. 1；After reaction kettle is cooled to room temperature, reaction kettle is taken out, suction filtration obtains powder；Obtained powder is first used into N, N'- bis-
Methylformamide and acetone wash three times respectively, are then washed three times with methanol, obtain after suction filtration in 100 DEG C of vacuum drying 12h
Metal-organic framework materials UiO-66 (Zr, Hf)-(COOH)2。
Weigh UiO-66 made from the present embodiment (Zr, Hf)-(COOH)2Powder 0.19g is dried under vacuum to constant weight at 65 DEG C
It is put into physics and inhales/be desorbed instrument, measure it under nitrogen protection to CO2Absorption property, pressure be 0~1bar and 25 DEG C of condition
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 institute
Show, after circulating repetition 6 times, 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 chloride, 0.1603g hafnium tetrachloride and 0.508g 1,2,4,5- benzene tertacarbonic acid are dissolved in 40mL
In the mixed liquor of N, N'- dimethylformamide and 5mL formic acid, water temperature is room temperature in ultrasonic container, and 10min is stirred by ultrasonic, obtains
To homogeneous mixed solution；It is transferred to the reaction kettle of teflon lined, 12h, reaction process are reacted in 120 DEG C of constant temperature oven
As shown in Figure 1；After reaction kettle is cooled to room temperature, reaction kettle is taken out, suction filtration obtains powder；Obtained powder is first used into N, N'-
Dimethylformamide and acetone wash three times respectively, are then washed three times with methanol, obtain after suction filtration in 80 DEG C of vacuum drying 18h
Metal-organic framework materials UiO-66 (Zr, Hf)-(COOH)2。
Weigh UiO-66 made from the present embodiment (Zr, Hf)-(COOH)2Powder 0.19g is dried under vacuum to constant weight at 65 DEG C
Be put into physics inhale/instrument is desorbed, measure it to N2Absorption property, the N being collected into the case where pressure is 0~1bar and 25 DEG C of item2Suction
Attached thermoisopleth is as shown in Figure 7.As shown in Figure 7, in 1.0bar, its adsorbance is about 0.11mmol/g.
Claims (6)
1. a kind of preparation method of metal-organic framework materials, specifically includes the following steps:
(1) zirconium chloride, hafnium tetrachloride and 1,2,4,5- benzene tertacarbonic acid are dissolved in N, N '-dimethyl formamide and formic acid it is mixed
It closes in liquid, 5-30min is stirred by ultrasonic, obtains mixed solution；
(2) mixed solution obtained by step (1) is transferred to reaction kettle, in 100 ~ 120 DEG C of reaction 12-24h；
(3) after reaction kettle is cooled to room temperature, suction filtration obtains powder；
(4) powder that step (3) obtains first is used into N, N'- dimethylformamide and acetone wash three times respectively, and again with methanol is washed
It washs three times, vacuum drying obtains metal-organic framework materials UiO-66 (Zr, Hf)-(COOH) after suction filtration2；
Wherein zirconium chloride, hafnium tetrachloride and 1,2,4,5- benzene tertacarbonic acid's molar ratio are 1:1:(2 ~ 4).
2. preparation method according to claim 1, which is characterized in that N, the volume ratio of N '-dimethyl formamide and formic acid
For (6 ~ 8): 1.
3. preparation method according to claim 1, which is characterized in that every 0.5 mM of zirconium chloride needs 30mL or more
N, N'- dimethylformamide.
4. preparation method according to claim 1, which is characterized in that ultrasonic agitation temperature is no more than 40 DEG C in step (1).
5. preparation method according to claim 1, which is characterized in that vacuum drying step is in 65-100 in step (4)
12-24h is dried in vacuo at DEG C.
6. being used to adsorb two to the metal-organic framework materials that preparation method described in 5 any one obtains according to claim 1
Sulfur oxide, carbon dioxide and nitrogen.
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| 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 |
| 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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