CN104744501A - Method for preparing metal-organic framework material Uio-66 with microwave solvothermal method and hydrogen storage property of Uio-6 - Google Patents
Method for preparing metal-organic framework material Uio-66 with microwave solvothermal method and hydrogen storage property of Uio-6 Download PDFInfo
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Abstract
The invention relates to a method for preparing a metal-organic framework material Uio-66 with a microwave solvothermal method and the hydrogen storage property of Uio-6, in particular to a method for preparing the metal-organic framework material Uio-66 through microwave solvothermal reaction by using formic acid as a template agent, wherein the Uio-6 has a very good hydrogen storage property. The preparation method is characterized in that ZrCl4 is adopted as a metal resource, terephthalic acid (H2bdc) is adopted as a ligand, formic acid is adopted as the template agent, and the microwave solvothermal method is utilized for synthesis. According to the method, the metal resource and ligand are subjected to ultrasonic dissolution by using a solvent DMF, then the metal resource, the ligand and the template agent are packaged together in a microwave sample tube for reaction, and the mixture is filtered and washed after the reaction, and then is soaked with dichloromethane and dried. Compared with a material prepared with a traditional hydrothermal method, the material prepared by the method disclosed by the invention has the following advantages that (1) the reaction time is short, and the preparation is simple; (2) the degree of crystallinity is better; (3) the metal-organic framework material Uio-66 has a good hydrogen storage property at 77.35K and 1bar.
Description
Technical field
The present invention relates to chemical field, specifically the method for a kind of microwave solvothermal legal system for metal-organic framework material Uio-66 and the hydrogen storage property of Uio-6.
Background technology
Along with the raising of industrial expansion and people's living standard, the demand of the energy also grows with each passing day, due to the energy that uses in recent decades mainly from fossil oil (as coal, oil and natural gas etc.), and it uses inevitably contaminate environment, add traditional energy oil, coal and natural gas reserves limited, exhaustion will be faced in 100 or two hundred years, so it is extremely urgent to find reproducible green energy resource, hydrogen is as rich reserves, wide material sources, the green energy resource that energy density is high, just causing the extensive concern of people, the discharge of the obnoxious flavour of greenhouse gases and other influences environment can effectively be avoided and reduce to hydrogen, but hydrogen is a kind of very unstable gas at normal temperatures and pressures, need to solve following 3 problems so want to utilize: producing of hydrogen, accumulating and application, the accumulating of Hydrogen Energy is then the applicable key of hydrogen, metal-organic framework materials has excellent pore performance, be easy to modify and functionalization, at adsorbed hydrogen, carbonic acid gas, the performance that the gas aspects such as methane have had, have and well should have prospect and space, some energy problems can be solved, again can environment purification.
2008, the people such as the JasminaHafizovicCavka of University of Oslo published an article on JACS, successfully synthesize Uio-66 (J. H. Cavka first, S. Jakobsen, U. Olsbye, N.Guillou, C. Lamberti, S. BordigaandK. P. Lillerud, J. Am. Chem. Soc., 2008,130,13850 – 13851.), Uio-66 has good thermostability and chemical stability, is the microporous crystal that specific surface area is larger.
The international Hydrogen Energy magazine of JianweiRen Deng Ren in South Africa in 2013 is published an article, synthesizes Uio-66 with formic acid as template, increase specific surface area and the particle size of crystal.(JianweiRen, H.W.Langmi, B.C.North, M.Mathe, D.Bessarabov, Int.J.Hydrogen Energy,2014,39,890-895.)
Microwave synthesize compares conventional solvent thermal synthesis, and to have generated time short, and nucleation evenly, fast, also likely obtain different pore passage structures.Therefore at this selection herein microwave solvothermal method synthesis Uio-66, in order to obtain the pore passage structure being more conducive to Chu Qing.
Summary of the invention
The object of the invention is for overcoming the deficiencies in the prior art, and the method for a kind of microwave solvothermal legal system for metal-organic framework material Uio-66 and the hydrogen storage property of Uio-6 are provided.
The technical scheme realizing the object of the invention is:
Microwave solvothermal legal system, for a method of metal-organic framework material Uio-66, comprises the steps:
(1) by the ZrCl of 0.20-0.30mmol
4ultrasonic disperse at 5-19ml DMF (DMF), the H of 0.20-0.30mmol
2both, in 5-19mlDMF, are mixed in microwave sample pipe by bdc ultrasonic dissolution, then add the formic acid of 0-0.75ml, after ultrasonic dissolution, install sample hose, 80-120 DEG C of reaction in microwave, insulation 30-60min;
(2) by solid resultant product collection, suction filtration, with DMF, methyl alcohol, absolute ethanol washing, dry 3-10h in atmosphere;
(3) gained white powder is immersed in 5-10ml methylene dichloride, changes a methylene dichloride every 24h, soak 3 days, after taking-up in air dry oven 150-180 DEG C of dry 5-10h, obtain required sample.
Described step 1) mol ratio is: ZrCl
4: H
2bdc: DMF: formic acid=1: 1: 300: 100 is adjustable, and adopt microwave heating synthesis, crystallization temperature 80-120 DEG C adjustable, and the reaction times, 30-60min was adjustable.
Described step 2) washing composition DMF and methanol temperature 40-60 is DEG C adjustable, and dehydrated alcohol is normal temperature.
High boiling solvent DMF in described step 3) low boiling point solvent methylene dichloride displacement duct.
Resulting materials is carried out to the test of hydrogen storage property, specific operation process is:
(1) take about 0.05g sample, degassed 4h at vacuum condition 200 DEG C, accurately takes sample quality after cooling;
(2) sample hose that sample is housed is placed in analysis station, select hydrogen at the adsorption process of 77K, the adsorptive value of computer-automatic collection different pressures point hydrogen, obtains the adsorption isothermal line of hydrogen.
The standby Uio-66 tool of microwave solvothermal legal system of the present invention has the following advantages:
1, synthesis is simple, largely can save generated time.
That 2, passes through different amount formic acid adds the material that can obtain variable grain size and degree of crystallinity.
3, the material that microwave solvothermal legal system is standby has good hydrogen storage property.
Accompanying drawing explanation
Fig. 1 is MW-100-30(embodiment 1 of the present invention), MW-50-30(embodiment 2) XRD spectra and the analogue spectrums of Uio-66.
Fig. 2 is MW-100-30(embodiment 1 of the present invention) SEM photo.
Fig. 3 is MW-50-30(embodiment 2 of the present invention) SEM photo.
Fig. 4 is MW-100-30(embodiment 1 of the present invention) and MW-50-30(embodiment 2) at 77K, the 1bar adsorption and desorption schematic diagram to nitrogen.
Fig. 5 is MW-100-30(embodiment 1 of the present invention) and MW-50-30(embodiment 2) at 77K, the 1bar adsorption and desorption schematic diagram to hydrogen.
Embodiment
embodiment 1
Microwave solvothermal legal system, for a method of metal-organic framework material Uio-66, comprises the steps:
1) by the ZrCl of 0.25mmol
4ultrasonic disperse at 5mlDMF (DMF), the H of 0.25mmol
2both, in 19mlDMF, are mixed in microwave sample pipe by bdc ultrasonic dissolution, then add the formic acid of 750ul, after ultrasonic dissolution, install sample hose, 120 DEG C of reactions in microwave, insulation 30min.
2) by solid resultant product collection, suction filtration, uses 20mlDMF respectively, 20ml methyl alcohol (50 DEG C), and 20ml dehydrated alcohol (50 DEG C) washs, dry 5h in atmosphere.
3) gained white powder is immersed in 10ml methylene dichloride, changes a methylene dichloride every 24h, soak 3 days.After taking-up in air dry oven 150 DEG C of dry 5h, (100 refer to molar weight than formic acid: ZrCl to obtain sample MW-100-30
4=100:1,30 refer to insulation 30min).
Carry out on Quantachrome company physical adsorption appearance (Autosorb iQ2) the hydrogen storage property test of described material, specific operation process is:
(1) take about 0.05g sample, degassed 4h at vacuum condition 200 DEG C, accurately takes sample quality after cooling;
(2) sample hose that sample is housed is placed in analysis station, select hydrogen at the adsorption process of 77K, the adsorptive value of computer-automatic collection different pressures point hydrogen, obtains the adsorption isothermal line of hydrogen.
Microwave instrument used is the Multiwave PRO preparing system of microwave sample of Anton Paar company.
embodiment 2
1) by the ZrCl of 0.25mmol
4ultrasonic disperse at 5mlDMF (DMF), the H of 0.25mmol
2both, in 19mlDMF, are mixed in microwave sample pipe by bdc ultrasonic dissolution, then add the formic acid of 375ul, after ultrasonic dissolution, install sample hose, 120 DEG C of reactions in microwave, insulation 30min;
2) by solid resultant product collection, suction filtration, with 20mlDMF, 20ml methyl alcohol (50 DEG C), 20ml dehydrated alcohol (50 DEG C) washs, dry 5h in atmosphere;
3) gained white powder is immersed in 10ml methylene dichloride, changes a methylene dichloride every 24h, soak 3 days.After taking-up in air dry oven 150 DEG C of dry 5h, obtain sample MW-50-30.
Claims (6)
1. microwave solvothermal legal system is for a method of metal-organic framework material Uio-66, it is characterized in that: comprise the steps:
(1) by the ZrCl of 0.20-0.30mmol
4ultrasonic disperse at 5-19ml DMF (DMF), the H of 0.20-0.30mmol
2both, in 5-19mlDMF, are mixed in microwave sample pipe by bdc ultrasonic dissolution, then add the formic acid of 0-0.75ml, after ultrasonic dissolution, install sample hose, 80-120 DEG C of reaction in microwave, insulation 30-60min;
(2) by solid resultant product collection, suction filtration, with DMF, methyl alcohol, absolute ethanol washing, dry 3-10h in atmosphere;
(3) gained white powder is immersed in 5-10ml methylene dichloride, changes a methylene dichloride every 24h, soak 3 days, after taking-up in air dry oven 150-180 DEG C of dry 5-10h, obtain required sample.
2. method according to claim 1, is characterized in that: described step 1) mol ratio is: ZrCl
4: H
2bdc: DMF: formic acid=1: 1: 300: 100 is adjustable, and adopt microwave heating synthesis, crystallization temperature 80-120 DEG C adjustable, and the reaction times, 30-60min was adjustable.
3. method according to claim 1, is characterized in that: described step 2) washing composition DMF and methanol temperature 40-60 is DEG C adjustable, and dehydrated alcohol is normal temperature.
4. method according to claim 1, is characterized in that: the high boiling solvent DMF in described step 3) low boiling point solvent methylene dichloride displacement duct.
5. with metal-organic framework material Uio-66 prepared by the preparation method one of claim 1-4 Suo Shu.
6. the test of the hydrogen storage property of metal-organic framework material Uio-66 described in claim 5, is characterized in that: operation steps is:
(1) take about 0.05g sample, degassed 4h at vacuum condition 200 DEG C, accurately takes sample quality after cooling;
(2) sample hose that sample is housed is placed in analysis station, select hydrogen at the adsorption process of 77K, the adsorptive value of computer-automatic collection different pressures point hydrogen, obtains the adsorption isothermal line of hydrogen.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105001251A (en) * | 2015-07-15 | 2015-10-28 | 北京工业大学 | Metal organic framework material for Zr 4-carboxy cinnamic acid ligand, preparation method and application therefor |
| CN105218571A (en) * | 2015-07-15 | 2016-01-06 | 北京工业大学 | The 3-dimensional metal organic framework material of the Isosorbide-5-Nitrae-phenyl diacrylate of a kind of Zr and preparation method and application thereof |
| CN105289505A (en) * | 2015-11-07 | 2016-02-03 | 长春工业大学 | Cadmium selenide quantum dot and zirconium base coordination polymer composite material and preparation method |
| CN105727890A (en) * | 2016-03-28 | 2016-07-06 | 安徽建筑大学 | Synthetic method of zirconium metallic organic framework material |
| CN107441952A (en) * | 2017-08-07 | 2017-12-08 | 中国科学技术大学 | MOFs composite membranes, its preparation method and its application |
| CN108031303A (en) * | 2017-11-24 | 2018-05-15 | 大连理工大学 | A kind of preparation method of infiltration evaporation metal organic framework UiO-66 series gasoline desulfurizing films |
| CN109589934A (en) * | 2018-12-13 | 2019-04-09 | 常州大学 | It is adjusted based on benzoic acid and chloroform activates the method and adsorption applications for preparing UiO-66 |
| CN110105581A (en) * | 2019-04-24 | 2019-08-09 | 华南理工大学 | A method of multi-stage porous UiO-66 material is prepared by template of dodecyl sodium sulfate |
| CN110482487A (en) * | 2019-08-28 | 2019-11-22 | 桂林电子科技大学 | A kind of Zr-MOFs/ graphene oxide is composite porous and its preparation method and application |
| RU2719597C1 (en) * | 2019-09-25 | 2020-04-21 | Общество с ограниченной ответственностью "Инжиниринговый химико-технологический центр" (ООО "ИХТЦ") | Fast and scalable method of producing microporous terephthalate of zirconium (iv) |
| KR20220099260A (en) * | 2021-01-06 | 2022-07-13 | 경희대학교 산학협력단 | Method for preparing modified uio-66 |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001251A (en) * | 2015-07-15 | 2015-10-28 | 北京工业大学 | Metal organic framework material for Zr 4-carboxy cinnamic acid ligand, preparation method and application therefor |
| CN105218571A (en) * | 2015-07-15 | 2016-01-06 | 北京工业大学 | The 3-dimensional metal organic framework material of the Isosorbide-5-Nitrae-phenyl diacrylate of a kind of Zr and preparation method and application thereof |
| CN105289505A (en) * | 2015-11-07 | 2016-02-03 | 长春工业大学 | Cadmium selenide quantum dot and zirconium base coordination polymer composite material and preparation method |
| CN105727890A (en) * | 2016-03-28 | 2016-07-06 | 安徽建筑大学 | Synthetic method of zirconium metallic organic framework material |
| CN105727890B (en) * | 2016-03-28 | 2018-04-13 | 安徽建筑大学 | The synthetic method of zirconium metal-organic framework materials |
| CN107441952A (en) * | 2017-08-07 | 2017-12-08 | 中国科学技术大学 | MOFs composite membranes, its preparation method and its application |
| CN108031303A (en) * | 2017-11-24 | 2018-05-15 | 大连理工大学 | A kind of preparation method of infiltration evaporation metal organic framework UiO-66 series gasoline desulfurizing films |
| CN108031303B (en) * | 2017-11-24 | 2019-10-11 | 大连理工大学 | A kind of preparation method of infiltration evaporation metal organic framework UiO-66 series gasoline desulfurizing film |
| CN109589934A (en) * | 2018-12-13 | 2019-04-09 | 常州大学 | It is adjusted based on benzoic acid and chloroform activates the method and adsorption applications for preparing UiO-66 |
| CN110105581A (en) * | 2019-04-24 | 2019-08-09 | 华南理工大学 | A method of multi-stage porous UiO-66 material is prepared by template of dodecyl sodium sulfate |
| CN110105581B (en) * | 2019-04-24 | 2022-02-15 | 华南理工大学 | Method for preparing hierarchical pore UiO-66 material by using sodium dodecyl sulfate as template agent |
| CN110482487A (en) * | 2019-08-28 | 2019-11-22 | 桂林电子科技大学 | A kind of Zr-MOFs/ graphene oxide is composite porous and its preparation method and application |
| RU2719597C1 (en) * | 2019-09-25 | 2020-04-21 | Общество с ограниченной ответственностью "Инжиниринговый химико-технологический центр" (ООО "ИХТЦ") | Fast and scalable method of producing microporous terephthalate of zirconium (iv) |
| KR20220099260A (en) * | 2021-01-06 | 2022-07-13 | 경희대학교 산학협력단 | Method for preparing modified uio-66 |
| KR102568061B1 (en) * | 2021-01-06 | 2023-08-17 | 경희대학교 산학협력단 | Method for preparing modified uio-66 |
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