CN113980287A - Preparation method and catalytic application of iron-based MOF material - Google Patents
Preparation method and catalytic application of iron-based MOF material Download PDFInfo
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- CN113980287A CN113980287A CN202111429786.5A CN202111429786A CN113980287A CN 113980287 A CN113980287 A CN 113980287A CN 202111429786 A CN202111429786 A CN 202111429786A CN 113980287 A CN113980287 A CN 113980287A
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- 239000000463 material Substances 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 59
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 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 abstract description 26
- 235000019253 formic acid Nutrition 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 238000006297 dehydration reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000011175 product filtration Methods 0.000 claims description 2
- 239000013206 MIL-53 Substances 0.000 abstract description 26
- 238000001308 synthesis method Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000012621 metal-organic framework Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical class [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 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
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UPIDXCYJXHFCOZ-UHFFFAOYSA-N n,n-dimethylformamide;sodium Chemical compound [Na].CN(C)C=O UPIDXCYJXHFCOZ-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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Abstract
The invention relates to crystal form conversion between iron-based MOF materials and application thereof. On the basis of the MIL-53(Fe) -based synthesis method, formic acid is added as a regulator, so that the stable conversion of the crystal form from MIL-53(Fe) to MOF-235(Fe) is realized. Compared with MIL-53(Fe), MOF-235(Fe) synthesized by crystal form conversion has higher catalytic activity.
Description
Technical Field
The invention relates to crystal form conversion between iron-based MOF materials and application thereof. Belong to.
Background
Metal Organic Frameworks (MOFs) are porous crystalline materials composed of inorganic nodes and organic ligands via coordination bonds. MOFs have the characteristics of high specific surface area, high porosity and structural diversity, and adjustable pore size/shape, and show great potential applications in gas storage/separation, molecular recognition, drug delivery, and heterogeneous catalysis. The MOFs is widely applied to catalysts and catalyst carriers, compared with metal oxides, MOFs nodes have almost uniform and definite structures, and meanwhile, the controllability of the structures also provides a potential possibility for the application of the MOFs catalysts. The iron-based MOFs have a large number of iron-oxygen clusters, and Fe has multiple valence states, so that the conversion between a divalent valence state and a trivalent valence state exists, and the possibility is provided for the application of the MOFs in crystal form conversion. However, how to realize the stable conversion of the iron-based MOFs between the divalent state and the trivalent state has been a troubling problem.
MOF-235 is a trimer of octahedral iron (Fe) sharing corners3O(CO2)3) Composed of 1, 4-terephthalic acid. In MOF-235, each iron atom is in the trivalent positive state, yielding Fe3O(bdc)3The charge is balanced by an anionic FeCl 4-. The MOF constructed by linking the trinuclear iron cluster taking oxygen as the center and benzene dicarboxylate forms a novel highly symmetrical topological structure of acs, namely a default arrangement mode of connecting the three-core iron cluster and benzene dicarboxylate together through a triangular prism; Mil-53-Fe is a compound of FeO having infinite number4(OH)2A one-dimensional porous structure consisting of octahedron and bi-bidentate terephthalate connectors. The MOFs have different metal cluster structures, MOF-235 is a trinuclear cluster, MIL-53 is a dioxygen cluster, and the trinuclear cluster is not in thermodynamic stabilitySuch as dimer stabilization. Therefore, how to realize the stable conversion of the two MOFs and make the iron-based MOFs realize the balance in dynamics and thermodynamics is a problem to be solved.
In addition, for the separation process under the catalytic condition of the alcohol aqueous solution, some methods in the prior art are alcohol dehydration reactions using oxides, and the catalytic active sites for alcohol dehydration have not been determined because of the difference in the structures of the oxides. However, in the MOF, since the MOF has a uniform and definite structure, the structure can be controlled, and the MOF has great advantages for researching catalytic active sites. In the MIL-53 methanol dehydration reaction research reported in the literature, the catalytic activity of MIL-53 is found to be very low, and after the post-treatment, the experiment proves that the catalytic activity site of MIL-53 is a defect site.
Disclosure of Invention
The first technical problem to be solved by the present invention is: MOF-235 is a trinuclear cluster, MIL-53 is a dimeric oxygen cluster, and from the aspect of thermodynamic stability, the trinuclear cluster is not as stable as a dimer, so that the MOF-235 material can be stably converted. According to the invention, through research, formic acid is used as a regulator to realize the crystal transformation of MOF-235 and MIL-53, and the transformation between the two iron-based MOFs can be realized under specific conditions by regulating different formic acid ratios, controlling reaction temperature and reaction time.
The second technical problem to be solved by the present invention is: the problem of low catalytic reaction rate exists in the catalytic separation process of alcohol-water solution in the prior art. The invention realizes the remarkable improvement of the catalytic activity by regulating and controlling the MIL-53 to be converted into the MOF-235, because the MOF-235 structure can have two active sites, the defect sites play a catalytic role, and the structural sites of the MOF-235 structure can also play a catalytic role. Thereby realizing the double-site synergistic catalysis.
The specific technical scheme is as follows:
a preparation method of an iron-based MOF material MOF-235 comprises the following steps:
adding iron salt, a metal salt ligand and formic acid into an organic solvent system, and uniformly dispersing; and after the temperature rise reaction, filtering, centrifugally washing and drying the product, and then carrying out vacuum activation treatment to obtain powder crystal MOF-235 (Fe).
The iron salt is selected from ferric chloride, ferric nitrate or ferric sulfate.
The metal salt ligand is selected from terephthalic acid.
The molar ratio of the ferric salt to the metal salt ligand is 1: 0.8-1.2.
The addition amount of the formic acid is 8-12 times of the molar amount of the ferric salt.
The temperature-rising reaction process refers to the reaction at 100-150 ℃ for 5-20 h.
The product filtration refers to filtration by using a 200-500-mesh sieve.
The centrifugal washing is carried out by adopting DMF (dimethyl formamide) and/or acetone at the rotating speed of 10000-13000 rpm.
The drying refers to drying at 50-120 ℃ for 1-5h, and the vacuum activation refers to activation at 110-130 ℃ for 5-20 h.
The invention also provides the MOF-235(Fe) material directly obtained by the preparation method.
The invention also provides application of the MOF-235(Fe) material in catalytic dehydration of an alcohol aqueous solution.
In the application, the dehydration reaction time is 1-30h, and the reaction temperature is-5 ℃.
Advantageous effects
(1) The invention discloses a novel method for stably synthesizing MOF-235(Fe), which is realized by acid regulation on the basis of a synthesis method of MIL-53 (Fe).
(2) Compared with MIL-53(Fe), MOF-235(Fe) synthesized by crystal form conversion has higher catalytic activity.
Drawings
FIG. 1 is an XRD spectrum of MIL-53(Fe) stably converted to MOF-235(Fe) after adjustment of different formic acid ratios.
FIG. 2 is a graph of the adsorption and desorption of MOF-235(Fe) from MIL-53(Fe) in nitrogen after 10-fold formic acid adjustment to achieve conversion.
FIG. 3 is a Fourier infrared spectrum of MOF-235(Fe) and MIL-53(Fe) after 10 fold formic acid adjustment to achieve conversion.
FIG. 4 is a graph of the methanol dehydration activity of MOF-235(Fe) versus MIL-53(Fe) after 10-fold formic acid adjustment to achieve conversion.
FIG. 5 is a graph of the ethanol dehydration activity of MOF-235(Fe) versus MIL-53(Fe) after 10-fold formic acid modulation achieved conversion.
FIG. 6 is a graph of the isopropanol dehydration activity of MOF-235(Fe) versus MIL-53(Fe) after 10-fold formic acid adjustment to achieve conversion.
FIG. 7 is an SEM image of MIL-53 without formic acid conditioning.
FIG. 8 is an SEM image of MOF-235 after 10-fold formic acid modulation achieved conversion.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The method selects aluminum chloride hexahydrate as metal salt of the MOF, terephthalic acid as metal salt ligand, Dimethylformamide (DMF) as reaction solvent, formic acid as regulator, a reaction vessel selects a stainless steel reaction kettle with 50ml of polytetrafluoroethylene as a lining, and a heating device is a high-temperature oven. The preparation method specifically comprises the following steps:
(1) ferric chloride hexahydrate (FeCl)3·6H2O) and terephthalic acid (H)2BDC) according to the mass ratio of 1.: adding 50mL of polytetrafluoroethylene into 1 to serve as an inner liner, adding 28mL of Dimethylformamide (DMF), adding a formic acid regulator, and carrying out ultrasonic dissolution treatment for 10min until the mixture is completely dissolved to obtain a reaction system A;
(2) transferring the reaction system A to a stainless steel reaction kettle with 50mL of polytetrafluoroethylene as an inner lining, reacting at 125 ℃ for 12h, naturally cooling to room temperature, filtering, centrifuging, washing, drying, and performing vacuum activation to obtain a converted powder crystal MOF-235 (Fe);
the concentration of the formic acid in the step (1) is 99%, and in the adjusting process, the amount of substances of the formic acid is 0 time, 3 times, 5 times, 10 times, 20 times, 30 times, 40 times and 50 times of that of the metal salt.
In the step (2), a 325-mesh sieve with the pore diameter of 0.044mm is selected for filtering to remove the organic ligand generated by unreacted and recrystallization.
In the step (2), the rotation speed of the centrifuge is 10000-13000 rpm, for example 10000rpm, 11000rpm, 12000rpm or 13000rpm, and the like, and the centrifuge is washed three times by 30mL DMF (sodium dimethyl formamide) in order to remove unreacted ligand and washed three times by 30mL acetone in order to remove DMF, and the obtained sample is further purified.
The drying process in the step (2) comprises pre-drying at 60-80 ℃ for 2h, then performing vacuum activation at 120 ℃ for 12h to obtain orange-red powder crystal MOF-235(Fe), and storing the activated sample in a glove box filled with argon for subsequent experiments and characterization.
Phase identification of the materials in the following real-time examples was performed using an X-ray diffractometer (Rigaku, Smartlab9 KW); the specific surface area is determined by a high-precision gas and steam adsorption instrument (Micromeritics Tristar II); the transmission infrared spectrum of the material was determined using a (Bruker IFS66v/S FTIR) spectrometer; reactivity data from catalytic experiments the products were analysed by Agilent 8890 gas chromatograph.
Example 1
1.3515g of iron chloride hexahydrate (FeCl)3·6H2O) and 0.8307g of terephthalic acid (H)2BDC) is added with 50mL of polytetrafluoroethylene as an inner liner, 28mL of Dimethylformamide (DMF) is added, formic acid regulator (for comparison, the amount of formic acid used is 0 time, 3 times, 5 times, 10 times, 20 times, 30 times, 40 times and 50 times of that of metal salt for comparison test, 1.91mL of formic acid is added when 10 times of formic acid is used), and the mixture is subjected to ultrasonic dissolution treatment for 10min until the mixture is completely dissolved to obtain a reaction system A; transferring the reaction system A to a 50mL stainless steel reaction kettle with polytetrafluoroethylene as an inner lining, reacting at 125 ℃ for 12h, naturally cooling to room temperature, filtering the reaction product by using a sieve with the aperture of 0.044mm, centrifuging and washing the reaction product by using DMF and acetone respectively for three times under the condition of 10000rpm, drying in an oven at 80 ℃, and performing vacuum activation at 120 ℃ to obtain the powder crystal MOF-235 (Fe).
Comparative example
The difference from example 1 is that: no formic acid regulator is added in the preparation process.
1.3515g of iron chloride hexahydrate (FeCl)3·6H2O) and 0.8307g are pairedPhthalic acid (H)2BDC) adding 50mL of polytetrafluoroethylene as an inner liner, adding 28mL of Dimethylformamide (DMF), and carrying out ultrasonic dissolution treatment for 10min until the materials are completely dissolved to obtain a reaction system A; transferring the reaction system A to a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at 125 ℃ for 12h, naturally cooling to room temperature, filtering the reaction product by using a sieve with the aperture of 0.044mm, centrifuging and washing the reaction product by using DMF (dimethyl formamide) and acetone respectively for three times under the condition of 10000rpm, drying in an oven at 80 ℃, and performing vacuum activation at 120 ℃ to obtain powder crystals MIL-53 (Fe); MIL-53(Fe) prepared as a reference sample;
testing of dehydration reaction
Respectively taking 200mg of the materials MOF-235 and MIL-53, putting the materials into a quartz reaction tube with the inner diameter of 9mm, and controlling the flow at 10ml/min by using nitrogen as carrier gas; the aqueous alcohol solution (methanol/ethanol/isopropanol, respectively) was prepared in chromatographic grade (99% concentration) with a feed partial pressure of 40mbar for methanol and 960mbar for nitrogen. Introducing alcohol steam carried by nitrogen into a quartz tube in a bubbler mode under the condition of the stability of an ice-water mixture at 0 ℃, wherein the dehydration reaction time lasts for 12 hours, and the gas components after the reaction are analyzed by Agilent 8890 gas chromatography of tail gas after the reaction.
Through adjustment of formic acid with different proportions, the MIL-53(Fe) is finally found to be transformed into MOF-235(Fe) in a crystal form during synthesis of 10 times formic acid, and the crystal form can be seen to be changed in an XRD spectrum of figure 1 and an SEM spectrum of figure 7 and figure 8. Furthermore, we can see from the Fourier infrared of FIG. 3 that MIL-53(Fe) is at 3635cm-1The peak at the corresponding hydroxyl structure disappeared in the infrared spectrum of the 10 fold formic acid-modulated MOF-235(Fe), which also indicates that the MIL-53(Fe) crystal form was converted to MOF-235 (Fe).
The catalytic activity of MIL-53(Fe) is obviously improved after the crystal form is converted into MOF-235 (Fe). FIG. 4, FIG. 5 and FIG. 6 are graphs showing methanol dehydration activity, ethanol dehydration activity and isopropanol dehydration activity of two materials, respectively. As can be seen from the activity diagram, after the crystal form conversion occurs, the catalytic activity performance of the material is improved.
Claims (10)
1. A preparation method of an iron-based MOF material MOF-235 is characterized by comprising the following steps: adding iron salt, a metal salt ligand and formic acid into an organic solvent system, and uniformly dispersing; and after the temperature rise reaction, filtering, centrifugally washing and drying the product, and then carrying out vacuum activation treatment to obtain powder crystal MOF-235 (Fe).
2. The method for preparing the iron-based MOF-235 from claim 1, wherein the iron salt is selected from ferric chloride, ferric nitrate or ferric sulfate.
3. The method for preparing the iron-based MOF material MOF-235 according to claim 1, wherein the metal salt ligand is selected from terephthalic acid.
4. The method for preparing the iron-based MOF-235, according to claim 1, wherein the molar ratio of the iron salt to the metal salt ligand is 1: 0.8-1.2; the addition amount of the formic acid is 8-12 times of the molar amount of the ferric salt.
5. The method for preparing the iron-based MOF-235 in claim 1, wherein the temperature-raising reaction process is carried out at 100-150 ℃ for 5-20 h.
6. The method for preparing the iron-based MOF-235 of claim 1, wherein the product filtration is 200-500 mesh filtration; the centrifugal washing is carried out by adopting DMF (dimethyl formamide) and/or acetone at the rotating speed of 10000-13000 rpm.
7. The method for preparing the iron-based MOF-235, according to claim 1, wherein the drying is performed at 50-120 ℃ for 1-5h, and the vacuum activation is performed at 110-130 ℃ for 5-20 h.
8. MOF-235(Fe) material obtained directly by the process of claim 1.
9. Use of the MOF-235(Fe) material of claim in the catalytic dehydration of aqueous alcohol solutions.
10. The use according to claim 9, wherein the dehydration reaction time is 1-30h and the reaction temperature is-5 ℃.
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| CN104525266A (en) * | 2014-12-30 | 2015-04-22 | 河南理工大学 | Preparation method of metal-organic framework material photocatalyst and application |
| CN109487370A (en) * | 2018-11-08 | 2019-03-19 | 河南科技学院 | MOF-235-500 DEG C of material of spinning and its preparation method and application |
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| CN104525266A (en) * | 2014-12-30 | 2015-04-22 | 河南理工大学 | Preparation method of metal-organic framework material photocatalyst and application |
| CN109487370A (en) * | 2018-11-08 | 2019-03-19 | 河南科技学院 | MOF-235-500 DEG C of material of spinning and its preparation method and application |
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| ZHENGYAN WANG ET AL.: "《Dialing in Catalytic Sites on Metal Organic Framework Nodes: MIL-53(Al) and MIL-68(Al) Probed with Methanol Dehydration Catalysis》", 《ACS APPLIED MATERIALS & INTERFACES》 * |
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