CN105597783A - Preparation method of mesoporous SO4<2->/ZrO2 - Google Patents
Preparation method of mesoporous SO4<2->/ZrO2 Download PDFInfo
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Abstract
The invention discloses a preparation method of mesoporous SO4<2->/ZrO2. According to the preparation method, in-suit introduction of a sulfur-containing compound into a synthesis system of a zirconium-based MOFs material is carried out, and the sulfur-containing zirconium-based MOFs material is roasted in an oxygen-containing atmosphere at a certain temperature to prepare mesoporous SO4<2->/ZrO2. The preparation method is simple and convenient; the prepared mesoporous SO4<2->/ZrO2 possesses a uniform mesoporous structure, large specific surface, and specific morphology characteristics; and stability of loaded sulfur obtained via the preparation method is high, leaching is not easily caused, and the preparation method is an effective method used for preparing mesoporous SO4<2->/ZrO2.
Description
Technical field
The present invention relates to mesoporous SO4 2-/ZrO2Preparation method, particularly relate in the synthetic system of zirconium base MOFs material and introduce sulfur-containing compound, prepare mesoporous SO with the zirconium base MOFs material of sulfur-bearing4 2-/ZrO2Method.
Background technology
SO4 2-/ZrO2It is the potential multiphase solid acid catalyst of a kind of tool, because of the synergy of its higher acid intensity and acid centre (Bronsted acid and Lewis acid), can in the chemical reactions such as esterification, etherification reaction, hydration-dehydration, cracking reaction and hydrocracking, show good catalytic performance[B.M.ReddyandM.K.Patil,Chem.Rev.,2009,109,2185–2208;G.D.YadavandJ.J.Nair,Micropor.Mesopor.Mater.,1999,33,1-48]。
SO4 2-/ZrO2Preparation conventionally adopt following methods: first adopt the precipitation method to prepare ZrO2Carrier, then introduces sulfur species by impregnating method, the last zirconia material SO that obtains again sulfuration through high-temperature roasting4 2-/ZrO2. The material specific surface of adopting in this way preparation is very little, and its internal pore structure is wayward, is unfavorable for the particularly diffusion of macromolecular reaction thing and product of reactant and product in catalytic reaction.
One of measure addressing the above problem is the mesoporous ZrO of preparation2Carrier. Mesoporous ZrO2Preparation can obtain [A.Sinhamahapatra, N.Sutradhara, M.Ghoshb, H.C.BajajandA.B.Panda, Appl.Catal.A, 2011,402,87-93 by the route of synthesis of soft template or hard template; J.L.Shi, Chem.Rev., 2013,113,2139-2181], but not only complicated operation of these methods, and the ZrO of preparation2Carrier poor heat stability, removing in template or sulfidation roasting process, its pore structure is easily caved in. For these problems, people are again taking the mesoporous silicon based material with high-ratio surface and regular nano-pore structure as support (scaffold), adopt as dipping, precipitation or steam are induced the means such as hydrolysis, by ZrO2Coating is [A.Osatiashtiani, A.F.Lee, M.Granollers, D.R.Brown, L.Olivi, G.Morales, J.A.MeleroandK.Wilson, ACSCatal, 2015,5,4345-4352 on these materials; M.A.Ecormier, A.F.LeeandK.Wilson, Micropor.Mesopor.Mater.2005,80,301 310.], but not only complicated operation of this method, but also need to adopt several different methods to carry out finely regulating to coating procedure, to avoid ZrO2Uneven distribution and stop up support duct.
In addition, at SO4 2-/ZrO2Use procedure in also exist a major issue be the losses of sulfur loaded species in course of reaction. So, how to improve SO4 2-/ZrO2Stability is in use also the subject matter that this material in use faced. Therefore, preparation a kind of novelty of design and development, simple has the mesoporous SO of high stability4 2-/ZrO2Method very necessary.
In recent years, one is referred to as MOFs, and the material of metal-organic framework structure (Metal-OrganicFrameworks) arouses great concern. This material is the metal-ligand complexing of utilizing between organic ligand and metal ion, the crystalline material with periodic network structure forming by self assembly. MOFs material is due to low-density pore structure, high specific surface and large adjustable porosity, gas storage with separate, the field such as sensor and catalysis shown potential application prospect. In addition, MOFs material also demonstrates some exclusive features preparing on metal oxide, successfully prepare the metal oxide with different-shape feature taking MOFs material as predecessor, for example ZnO hexagonal nano rod [S.Jung, W.Cho, H.J.LeeandM.Oh, Angew.Chem.Int.Ed., 2009,48,1459-1462], Fe2O3Nanometer rods [W.Cho, S.ParkandM.Oh, Chem.Commun., 2011,47,4138-4140] and micro-box (microboxes) [L.Zhang, H.B.Wu, S.Madhavi, H.H.HngandX.W.Lou, J.Am.Chem.Soc., 2012,134,17388-17391], In2O3Hollow Nano rod [W.Cho, Y.H.Lee, H.J.LeeandM.Oh, Chem.Commun., 2009,31,4756-4758] etc. These oxides not only can keep the peculiar shape characteristic of MOFs predecessor, and even its high preferred orientation is all consistent with MOFs predecessor.
Summary of the invention
The object of this invention is to provide a kind of zirconium base MOFs material taking sulfur-bearing and prepare mesoporous SO as predecessor4 2-/ZrO2Method, the mesoporous SO preparing with the inventive method4 2-/ZrO2Not only there is fixing particle diameter and shape characteristic, and the sulfur species stable performance of institute's load, be difficult for drop and go out.
Mesoporous SO of the present invention4 2-/ZrO2Preparation method be:
1) existing in taking solubility zirconates and organic acid as raw water thermal crystallisation, zirconium base MOFs material is prepared in reaction, in described zirconium base MOFs synthetic system, add sulfur-containing compound, hydrothermal crystallizing reaction original position is prepared the zirconium base MOFs predecessor of sulfur-bearing, wherein, described organic acid with the mol ratio taking the solubility zirconates of zirconium ion as (1～3): 1, in the solubility zirconates of zirconium ion with the mol ratio taking the sulfur-containing compound of sulphur as (5～10): 1,120～250 DEG C of described hydrothermal crystallizing reaction temperatures, crystallization time 1～10 day;
2) the zirconium base MOFs predecessor of sulfur-bearing described in calcination process in oxygen-containing atmosphere, prepares mesoporous SO4 2-/ZrO2。
Particularly, the present invention adds sulfur-containing compound in the synthetic system of any one zirconium base MOFs material below preparation simultaneously, hydrothermal crystallizing reaction original position is prepared the zirconium base MOFs predecessor of sulfur-bearing: UiO-66, UiO-67, UiO-68, UiO-66-R, UiO-67-R, UiO-68-R, DUT-67, ZrFA, MOF-801, MOF-802, MOF-804, MOF-805, MOF-806, MOF-808, MOF-812, MOF-841, PCN-777, PIZOF-2, wherein, described R is-NH2、-NO2,-Cl ,-Br ,-OH or-COOH.
Wherein, described sulfur-containing compound is the compound that contains sulfate radical or persulfuric acid radical ion.
Further, described sulfur-containing compound can be following any one: H2SO4、(NH4)2SO4、(NH4)2S2O8、Al2(SO4)3、Ce2(SO4)3。
The inventive method preferably in oxygen-containing atmosphere, the zirconium base MOFs predecessor of the sulfur-bearing of preparing with original position described in the sintering temperature calcination process of 300～1000 DEG C.
More preferably, the inventive method is with the heating rate of 1～10 DEG C/min, the zirconium base MOFs predecessor of described sulfur-bearing to be warming up to sintering temperature to carry out calcination process.
Mesoporous SO of the present invention4 2-/ZrO2Preparation method introduce sulfur-containing compound at the synthetic system situ of zirconium base MOFs material, zirconium base MOFs material roasting in the oxygen-containing atmosphere of uniform temperature of sulfur-bearing is prepared to mesoporous SO4 2-/ZrO2, preparation method is simple, prepared mesoporous SO4 2-/ZrO2Not only having uniform meso-hole structure, large specific surface and specific shape characteristic, and adopt the sulfur species of the inventive method institute load to have good stability, be difficult for drop and go out, is the mesoporous SO of preparation4 2-/ZrO2A kind of effective ways.
The present invention be directed to SO4 2-/ZrO2The problem that exists in preparation and use procedure, and the mesoporous SO of preparation that proposes at the potential of preparing in mesopore oxide of MOFs material4 2-/ZrO2New method. This preparation method is owing to introducing sulfate radical or over cure acid group in the synthetic system of zirconium base MOFs material, make prepared zirconium base MOFs material there is more defective bit, the defective bit of these generations can be carried out coordination with the acid group of the system of introducing, like this, sulfur species in system just can be evenly distributed in the defective bit of synthesized zirconium base MOFs material, make it fully to contact with zirconium component, participate in the process that roasting forms oxide, and carry out bonding with zirconium atom, thereby improve sulfur loaded constancy of species, be difficult for drop and go out. Simultaneously, MOFs material is the metal-ligand complexing of utilizing between organic ligand and metal ion, the crystalline material with periodic network structure forming by self assembly, in roasting process, by organic ligand combustion decomposition, can in generated oxide, produce mesoporous and make prepared oxide keep the specific shape characteristic of MOFs predecessor. Therefore the mesoporous SO that, prepared by the present invention4 2-/ZrO2Have uniform meso-hole structure, large specific surface and specific shape characteristic, preparation process is simple, need on the Zirconia carrier generating, not carry out the load of sulfur species again.
Mesoporous SO provided by the invention4 2-/ZrO2The dissimilar zirconium base MOFs material of the sulfur-bearing that preparation method is prepared taking original position is predecessor, described predecessor is carried out to roasting and prepare mesoporous SO4 2-/ZrO2, with respect to conventional infusion process, not only processing method is simple, can also save immersion solvent.
The present invention has not only successfully introduced sulfur-containing compound at zirconium base MOFs material preparation process situ, and has kept the original crystal structure of zirconium base MOFs material, by roasting, organic ligand is decomposed, at SO4 2-/ZrO2Middle formation is mesoporous uniformly. The mesoporous SO preparing with the inventive method4 2-/ZrO2As solid acid catalyst, in ester exchange reaction, show good reactivity.
Brief description of the drawings
Fig. 1 is UiO-66-S and mesoporous SO prepared by embodiment 14 2-/ZrO2XRD figure.
Fig. 2 is mesoporous SO prepared by embodiment 14 2-/ZrO2N2Adsorption-desorption isollaothermic chart.
Fig. 3 is UiO-66-S and mesoporous SO prepared by embodiment 44 2-/ZrO2SEM figure.
Detailed description of the invention
Embodiment 1
Get 25mmolZrCl4, 25mmol terephthalic acid (TPA), the dense HCl of 25mmol, 5mL1mol/LH2SO4Solution, joins 150mLN together, in dinethylformamide, stirs, pack into in teflon-lined 200mL stainless steel cauldron, crystallization 3d at 160 DEG C, takes out the white powder obtaining, 150 DEG C of vacuum drying, obtain the zirconium base MOFs material UiO-66-S of sulfur-bearing.
UiO-66-S is placed in to Muffle furnace, is warming up to 500 DEG C with the speed of 2 DEG C/min, roasting 6h, obtains mesoporous SO4 2-/ZrO2。
Adopt XRD to characterize making sample, can be found out by Fig. 1 (a), the sulfur-bearing zirconium base MOFs material UiO-66-S of preparation has shown and bibliographical information UiO-66[J.H.Cavka, S.Jakobsen, U.Olsbye, N.Guillou, C.Lamberti, S.Bordiga, K.P.Lillerud, J.Am.Chem.Soc.2008.130.13850-13851] consistent characteristic diffraction peak, show that the UiO-66-S of the sulfur-bearing of preparing through original position has still kept the original crystal structure of UiO-66. To after further UiO-66-S roasting, can make SO4 2-/ZrO2Sample (Fig. 1 (b)).
Adopt nitrogen absorption to characterize making sample, as seen from Figure 2, SO4 2-/ZrO2The N of sample2Adsorption-desorption thermoisopleth demonstrates IV type thermoisopleth and hysteresis loop, shows SO4 2-/ZrO2In exist mesoporous. Can clearerly be found out SO by graph of pore diameter distribution4 2-/ZrO2Aperture concentrate be distributed in 3～6nm, further confirmed prepared SO4 2-/ZrO2Sample is mesoporous material.
Adopt the integrated constant sulphur appliance of YX-DL8300, record mesoporous SO4 2-/ZrO2Middle sulfur-bearing 1.384wt%.
Embodiment 2
Get 25mmolZrCl4, 25mmol terephthalic acid (TPA), the dense HCl of 25mmol, 5mmol (NH4)2SO4, join together 150mLN, in dinethylformamide, stir, pack into in teflon-lined 200mL stainless steel cauldron, crystallization 6d at 160 DEG C, takes out the white powder obtaining, 150 DEG C of vacuum drying, obtain the zirconium base MOFs material UiO-66-S of sulfur-bearing.
UiO-66-S is placed in to Muffle furnace, is warming up to 500 DEG C with the speed of 2 DEG C/min, roasting 6h, obtains mesoporous SO4 2-/ZrO2。
Embodiment 3
Get 0.227mmolZrCl4, 0.227mmol terephthalic acid (TPA), 0.1mL0.5mol/LH2SO4Solution, joins 340mmolN together, in dinethylformamide, stirs, pack into in teflon-lined 100mL stainless steel cauldron, crystallization 5d at 200 DEG C, takes out the white powder obtaining, 150 DEG C of vacuum drying, obtain the zirconium base MOFs material UiO-66-S of sulfur-bearing.
UiO-66-S is placed in to Muffle furnace, is warming up to 600 DEG C with the speed of 2 DEG C/min, roasting 6h, obtains mesoporous SO4 2-/ZrO2。
Embodiment 4
Get 0.8mmolZrCl4, 0.8mmol terephthalic acid (TPA), 14.1g acetic acid, 0.2mL1mol/LH2SO4Solution, joins 100mLN together, in dinethylformamide, stirs, pack into in teflon-lined 200mL stainless steel cauldron, crystallization 6d at 180 DEG C, takes out the white powder obtaining, 150 DEG C of vacuum drying, obtain the zirconium base MOFs material UiO-66-S of sulfur-bearing.
UiO-66-S is placed in to Muffle furnace, is warming up to 500 DEG C with the speed of 2 DEG C/min, roasting 6h, obtains mesoporous SO4 2-/ZrO2。
SEM figure by Fig. 3 can find out, the mesoporous SO of preparation4 2-/ZrO2(b) not only can keep the peculiar shape characteristic of UiO-66-S predecessor (a), even its high preferred orientation is all consistent with MOFs predecessor.
Embodiment 5
Get 0.227mmolZrCl4, the amino terephthalic acid (TPA) of 0.227mmol2-, 0.1mL0.5mol/LH2SO4Solution, joins 340mLN together, in dinethylformamide, stirs, pack into in teflon-lined 100mL stainless steel cauldron, crystallization 6d at 160 DEG C, takes out the white powder obtaining, 150 DEG C of vacuum drying, obtain the zirconium base MOFs material UiO-66-NH of sulfur-bearing2-S。
By UiO-66-NH2-S is placed in Muffle furnace, is warming up to 700 DEG C with the speed of 2 DEG C/min, and roasting 6h, obtains mesoporous SO4 2-/ZrO2。
Embodiment 6
Get 10mmolZrCl4, 10mmol4,4 '-biphenyl dicarboxylic acid, 300mLN, dinethylformamide, 2mL1mol/LH2SO4Solution is placed in 500mL round-bottomed flask and stirs, and adds successively the dense HCl of 10mmol, 10mmol4, and 4 '-biphenyl dicarboxylic acid stirs 10min, then adds 14mmolH2O and 50mLN, dinethylformamide, packs into in teflon-lined 500mL stainless steel cauldron, crystallization 8d at 180 DEG C, gained white powder, in 150 DEG C of vacuum drying, obtains the zirconium base MOFs material UiO-67-S of sulfur-bearing.
UiO-67-S is placed in to Muffle furnace, is warming up to 800 DEG C with the speed of 2 DEG C/min, roasting 6h, obtains mesoporous SO4 2-/ZrO2。
Embodiment 7
Get 0.25mmolZrCl4, 7.5mL formic acid, 0.1mL0.5mol/LH2SO4Solution, joins 4mLN, in dinethylformamide together, ultrasonic 10min, packs into in teflon-lined 25mL stainless steel cauldron, crystallization 4d at 160 DEG C, the white powder that taking-up obtains, 150 DEG C of vacuum drying, obtain the zirconium base MOFs material ZrFA-S of sulfur-bearing.
ZrFA-S is placed in to Muffle furnace, is warming up to 350 DEG C with the speed of 2 DEG C/min, roasting 5h, obtains mesoporous SO4 2-/ZrO2。
Embodiment 8
Get 0.5mmolZrOCl2·8H2O, 0.5mmol trimesic acid, 0.1mL1mol/LH2SO4Solution, add together N, in dinethylformamide/formic acid (20mL/20mL) mixed solution, stir, pack into in teflon-lined 100mL stainless steel cauldron, be warming up to 160 DEG C with the speed of 5 DEG C/min, crystallization 6d, the white powder that taking-up obtains, 150 DEG C of vacuum drying, obtain the zirconium base MOFs material MOF-808-S of sulfur-bearing.
MOF-808-S is placed in to Muffle furnace, is warming up to 600 DEG C with the speed of 2 DEG C/min, roasting 5h, obtains mesoporous SO4 2-/ZrO2。
Application examples 1
Get 25mmolZrCl4, 25mmol terephthalic acid (TPA), the dense HCl of 25mmol, join together 150mLN, in dinethylformamide, stir, pack into in teflon-lined 200mL stainless steel cauldron, crystallization 24h at 120 DEG C, the white powder that taking-up obtains, 150 DEG C of vacuum drying, obtain zirconium base MOFs material UiO-66.
By infusion process by SO4 2-Impregnated in UiO-66 upper, be placed in Muffle furnace, be warming up to 500 DEG C with the speed of 2 DEG C/min, roasting 5h, obtains mesoporous SO4 2-/ZrO2-Im。
With mesoporous SO4 2-/ZrO2-Im, as catalyst, is applied to the ester exchange reaction of soybean oil and methyl alcohol. Specifically by 1.3mmol methyl alcohol, 52mmol soybean oil, 0.1g catalyst (SO4 2-/ZrO2-Im) add with in teflon-lined 50mL stainless steel cauldron, under 800rpm rotating speed, 140 DEG C of reaction 6h.
Use Agilent gas chromatograph to analyze product, the conversion ratio of soybean oil is up to 99.9%.
By reacted catalyst filtration washing, under the same terms, be again applied to this reaction, the conversion ratio of soybean oil significantly reduces, and only has 45.7%.
Application examples 2
Mesoporous SO prepared by embodiment 14 2-/ZrO2As the catalyst of soybean oil and methyl alcohol ester exchange reaction, specifically by 1.3mmol methyl alcohol, 52mmol soybean oil, 0.1g catalyst (SO4 2-/ZrO2) add with in teflon-lined 50mL stainless steel cauldron, under 800rpm rotating speed, 140 DEG C of reaction 6h.
Use Agilent gas chromatograph to analyze product, the conversion ratio of soybean oil is up to 99.9%.
By reacted catalyst filtration washing, under the same terms, be again applied to this reaction, the conversion ratio of soybean oil is still up to 81.2%.
With the Comparison of experiment results of application examples 1, can prove mesoporous SO prepared by the inventive method4 2-/ZrO2The sulfur species of institute's load has good stability, is difficult for drop and goes out.
Claims (6)
1. a mesoporous SO4 2-/ZrO2Preparation method, it is characterized in that:
1) existing in taking solubility zirconates and organic acid as raw water thermal crystallisation, zirconium base MOFs material is prepared in reaction, in described zirconium base MOFs synthetic system, add sulfur-containing compound, hydrothermal crystallizing reaction original position is prepared the zirconium base MOFs predecessor of sulfur-bearing, wherein, described organic acid with the mol ratio taking the solubility zirconates of zirconium ion as (1～3): 1, in the solubility zirconates of zirconium ion with the mol ratio taking the sulfur-containing compound of sulphur as (5～10): 1,120～250 DEG C of described hydrothermal crystallizing reaction temperatures, crystallization time 1～10 day;
2) the zirconium base MOFs predecessor of sulfur-bearing described in calcination process in oxygen-containing atmosphere, prepares mesoporous SO4 2-/ZrO2。
2. mesoporous SO according to claim 14 2-/ZrO2Preparation method, it is characterized in that in the synthetic system of any one zirconium base MOFs material, adding sulfur-containing compound below preparation simultaneously, hydrothermal crystallizing reaction original position is prepared the zirconium base MOFs predecessor of sulfur-bearing: UiO-66, UiO-67, UiO-68, UiO-66-R, UiO-67-R, UiO-68-R, DUT-67, ZrFA, MOF-801, MOF-802, MOF-804, MOF-805, MOF-806, MOF-808, MOF-812, MOF-841, PCN-777, PIZOF-2, wherein, described R is-NH2、-NO2,-Cl ,-Br ,-OH or-COOH.
3. mesoporous SO according to claim 14 2-/ZrO2Preparation method, it is characterized in that described sulfur-containing compound is the compound that contains sulfate radical or persulfuric acid radical ion.
4. mesoporous SO according to claim 34 2-/ZrO2Preparation method, it is characterized in that described sulfur-containing compound be following any one: H2SO4、(NH4)2SO4、(NH4)2S2O8、Al2(SO4)3、Ce2(SO4)3。
5. mesoporous SO according to claim 14 2-/ZrO2Preparation method, it is characterized in that in oxygen-containing atmosphere the zirconium base MOFs predecessor of the sulfur-bearing of preparing with original position described in the sintering temperature calcination process of 300～1000 DEG C.
6. mesoporous SO according to claim 54 2-/ZrO2Preparation method, it is characterized in that the heating rate with 1～10 DEG C/min, the zirconium base MOFs predecessor of described sulfur-bearing is warming up to sintering temperature and carries out calcination process.
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| CN110252408A (en) * | 2019-07-09 | 2019-09-20 | 北京化工大学 | A kind of MOF-808 (Zr) assemble nanometer metallic catalyst, preparation and application with CUS |
| CN110835091A (en) * | 2019-11-25 | 2020-02-25 | 晚叶保旺 | PAN-based porous carbon-magnesium alloy loaded Zr-based MOFs hydrogen storage material and preparation method thereof |
| CN112851704A (en) * | 2019-11-27 | 2021-05-28 | 武汉大学 | Metal-organic framework with fluorescence amplification detection effect, preparation method thereof and application thereof in tert-butylhydroquinone detection |
| CN112851704B (en) * | 2019-11-27 | 2021-12-21 | 武汉大学 | Metal-organic framework with fluorescence amplification detection effect, preparation method thereof and application thereof in tert-butylhydroquinone detection |
| CN112688021A (en) * | 2020-12-25 | 2021-04-20 | 河北工业大学 | Preparation method and application of metal organic framework MOF-808 film-based functional interlayer material |
| CN112958129A (en) * | 2021-02-03 | 2021-06-15 | 中国科学院兰州化学物理研究所 | Solid acid catalyst and preparation method and application thereof |
| CN113880769A (en) * | 2021-10-26 | 2022-01-04 | 华中科技大学 | Chelating agent for metal zirconium marking and synthetic method and application thereof |
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