CN110305330A - A kind of couple of CO2Cycloaddition reaction has the ferrous metals organic framework materials and the preparation method and application thereof of high catalytic activity - Google Patents
A kind of couple of CO2Cycloaddition reaction has the ferrous metals organic framework materials and the preparation method and application thereof of high catalytic activity Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 33
- -1 ferrous metals Chemical class 0.000 title claims abstract description 28
- 239000013384 organic framework Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 28
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 24
- 239000001632 sodium acetate Substances 0.000 claims description 18
- 235000017281 sodium acetate Nutrition 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 10
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 8
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003426 co-catalyst Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 6
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 4
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000007259 addition reaction Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 abstract description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 abstract description 4
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 3
- 239000012621 metal-organic framework Substances 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 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 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 241000272525 Anas platyrhynchos Species 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000007210 heterogeneous catalysis Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000013082 iron-based metal-organic framework Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 239000013118 MOF-74-type framework Substances 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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]
-
- B01J35/613—
-
- B01J35/633—
-
- B01J35/643—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
Abstract
The invention discloses a kind of couple of CO2Cycloaddition reaction has the ferrous metals organic framework materials and the preparation method and application thereof of high catalytic activity, the preparation method of the material is the following steps are included: by iron cluster and 4, and the powder of 4- dicarboxydiphenyl ether mixes, with N, dinethylformamide (DMF) dissolution, is then added acetic acid；Temperature programmed control solvent thermal reaction is carried out again, and ferrous metals organic framework materials are made.Material prepared by the present invention is to CO2Cycloaddition reaction has high catalytic activity, under equal conditions, to CO2The catalytic efficiency of cycloaddition reaction is 12 times or more of the traditional catalysts catalytic efficiency such as SBA-15, is 8 times or more of the metal-organic framework materials catalytic efficiency such as ZIF-8, and material shows good water stability.For being catalyzed CO2Cycloaddition reaction prepares widely used cyclic carbonate, which is a kind of catalyst of great potential.
Description
Technical field
The present invention relates to catalysis CO2Cycloaddition reaction technical field, in particular to a kind of couple of CO2Cycloaddition reaction has height
Ferrous metals organic framework materials of catalytic activity and the preparation method and application thereof.
Background technique
CO2It is a kind of resourceful, cheap, Ke Xunhuanliyong industrial chemicals, can be used to synthesize high added value
Chemical products, such as methanol, formic acid and cyclic carbonate.For CO2Cyclic carbonate is prepared with epoxide cycloaddition
For this reaction, atom utilization is 100%, and product circular carbonic ester can be used for synthesizing cosmetics, polymer, drug and
Cell electrolyte, purposes is very extensive, be industrially one it is very important chemical reaction [P.Patel, B.Parmar,
R.I.Kureshy,N. u.Khan,E.Suresh,ChemCatChem 2018,10,2401-2408.].But utilize CO2And ring
A major challenge that oxygen compound is chemically reacted is CO2Molecule is the molecule of high thermodynamic and dynamic stabilization, general next
It says, by CO2Activation needs a large amount of energy consumption.But work as CO2When molecule encounters the activated centre with high activity, it will promote CO2It is living
Change and is chemically reacted.Therefore, the catalyst with high catalytic activity is developed for CO2Chemical conversion it is significant.
Currently used for being catalyzed CO2The catalyst of cycloaddition can be divided into homogeneous catalyst and heterogeneous catalysis two major classes.?
Phase catalyst is used for CO2Cycloaddition reaction has been extensively studied.For example, Kawanami et al. [H.Kawanami,
A.Sasaki, K.Matsui, Y.Ikushima, Chemical Communications 2003,896-897.] utilize [C8-
mim]+[BF4]-Ionic liquid is catalyzed CO at 14MPa and 100 DEG C2Cycloaddition reaction 5min, can be complete by epoxide
It is converted into cyclic carbonate.But homogeneous catalyst presence is difficult to ask what catalyst and product separation and catalyst difficulty recycled
Topic.And heterogeneous catalysis is compared to homogeneous catalyst, advantage is to can be easily separated product and catalyst, catalyst regeneration letter
It is single, therefore heterogeneous catalysis is increasingly by the concern of researchers.Heterogeneous catalysis reported at present can substantially divide
For two classes: there is a kind of catalyst to CO2Cycloaddition reaction has good catalytic activity, but the stability of material is poor, than
As MOF-5 [J.Song, Z.Zhang, S.Hu, T.Wu, T. Jiang, B.Han, Green Chemistry 2009,11,
1031.] and Mg-MOF-74 [D.-A.Yang, H.-Y.Cho, J.Kim, S.-T.Yang, W.-S.Ahn, Energy&
Environmental Science 2012,5,6465-6473.]；There are also having good stability for a kind of catalyst material, still
To CO2The catalytic activity of cycloaddition reaction is lower, such as SBA-15 [E.E.Macias, P.Ratnasamy, M.A.Carreon,
Catalysis Today 2012,198,215-218.], ZIF-8 [C.M.Miralda, E.E.Macias, M.Zhu,
P.Ratnasamy, M.A.Carreon, ACS Catalysis 2012,2,180-183.] and UiO-66 [J.Liang, R.-
P.Chen,X.-Y.Wang,T.-T.Liu,X.-S.Wang,Y.-B. Huang,R.Cao,Chemical Science 2017,
8,1570-1575.].In actual industrial application, develop both stable to CO2Cycloaddition reaction has high catalytic activity again
Catalyst is very urgent something.
Summary of the invention
In order to solve problem above, the present invention provides a kind of couple of CO2Cycloaddition reaction has the iron-based of high catalytic activity
Metal-organic framework material and the preparation method and application thereof.
Ferrous metals organic framework materials (Fe-oba) of the invention are by iron cluster and organic ligand 4,4- dicarboxyl hexichol
Ether passes through three-dimensional porous metal-organic framework material made of solvent thermal reaction self assembly.Fe-oba has good water stability
It is primarily due to iron cluster and belongs to hard acid, 4,4- dicarboxydiphenyl ether organic ligands belong to hard base, according to hsab theory (hard acid
It is with good stability with the material of hard base synthesis), so material water stability is good.Fe-oba is to CO2With good
Catalytic performance is primarily due to material with biggish pore size, is conducive to the mass transfer rate for improving catalysis reaction；In addition, material
Material contains Fe3+Unsatuated metal position, belong to lewis acidity site, to CO2It is a kind of high catalysis work for cycloaddition reaction
Property site.The material is for being catalyzed CO2Cycloaddition reaction has good potential application foreground.
The purpose of the present invention is achieved through the following technical solutions.
A kind of couple of CO2Cycloaddition reaction has the preparation method of the ferrous metals organic framework materials of high catalytic activity, packet
Include following steps:
(1) by iron cluster and 4,4- dicarboxydiphenyl ether powder is mixed, then molten with DMF (n,N-Dimethylformamide) ultrasound
Solution, is then added acetic acid, obtains mixed liquor；
(2) mixed liquor obtained by step (1) is subjected to temperature programmed control solvent thermal reaction；
(3) product is immersed in DMF after reaction, then filters extraction product, product is dry, and obtaining ferrous metals has
Machine frame frame material is labeled as Fe-oba.
Preferably, step (1) the iron cluster preparation the following steps are included:
In water by Fe(NO3)39H2O and anhydrous sodium acetate difference ultrasonic dissolution, it obtains iron nitrate solution and sodium acetate is molten
Liquid；Sodium acetate solution is instilled again in the iron nitrate solution stirred, continues to stir after dripping off sodium acetate solution, obtain suspended
Liquid；Suspension is filtered, and successively uses water and ethyl alcohol repeated flushing filter cake, filtration cakes torrefaction is obtained into bronzing block, it will be blocky
Object grind into powder obtains iron cluster；Synthesis step see [D.Lv, R.Shi, Y.Chen, Y.Wu, H.Wu, H.Xi, Q.Xia, Z.Li,
ACS Appl Mater Interfaces 2018,10,8366-8373.]。
Preferably, step (1) the iron cluster, 4,4- dicarboxydiphenyl ether, acetic acid, DMF mass ratio be 1:(0.5~
1.5): (5.6~8.4): (94.4~157.4).
Preferably, the container of the reaction is glass scintillation bottle, and volume 20mL, bottle cap is resistant to 150 DEG C of high temperature.
Preferably, the temperature programmed control process of step (2) described solvent thermal reaction are as follows:
The temperature programming stage: heating rate is set as 4~8 DEG C/min, reactant is risen to 140~160 DEG C from room temperature；
The constant temperature stage: the temperature of reactant is in 140~160 DEG C of 8~48h of holding；
Program temperature-fall period: rate of temperature fall is set as 0.05~0.15 DEG C/min, product is down to 25 from 140~160 DEG C
℃。
Preferably, the time of step (3) described immersion is 12~72h.
Preferably, the temperature of step (3) described drying is 40~60 DEG C.
Preferably, the time of step (3) described drying is 12~48h.
The ferrous metals organic framework materials as made from above-described preparation method.
Above-described ferrous metals organic framework materials are applied to catalysis CO2In cycloaddition reaction.
Preferably, above-described application, comprising the following steps:
Catalyst Fe-oba, co-catalyst tetrabutylammonium bromide and reactant epoxychloropropane are mixed, then are passed through CO2Into
Row cycloaddition reaction.
Preferably, the catalyst Fe-oba, co-catalyst tetrabutylammonium bromide and reactant epoxychloropropane quality
Than for (0.2~4): 2:111.2.
Preferably, the temperature of the reaction is 60-80 DEG C, time 18-48h.
Compared with the prior art, advantages of the present invention and effect are as follows:
1. ferrous metals organic framework materials water stability prepared by the present invention is good, stable in water can be kept for 4 weeks.
2. ferrous metals organic framework materials prepared by the present invention are catalyzed the conversion ratio for being catalyzed reaction for 24 hours at 80 DEG C
Reach 97%.
Detailed description of the invention
Fig. 1 a is the structure asymmetric cell of Fe-oba-1 prepared by the embodiment of the present invention 1.
Fig. 1 b is the skeleton structure diagram of Fe-oba-1.
Fig. 2 is the PXRD of Fe-oba-1, Fe-oba-2, Fe-oba-3, Fe-oba-4 prepared by the embodiment of the present invention 1~4
Figure.
Fig. 3 is that Fe-oba-1, Fe-oba-2, Fe-oba-3, Fe-oba-4 prepared by the embodiment of the present invention 1~4 is immersed in
The PXRD of material schemes after 4 weeks in water.
The catalytic performance for the Fe-oba-1 that Fig. 4 is prepared the embodiment of the present invention 1 for the mass ratio of catalyst and reactant
Influence diagram.
Fig. 5 is the catalytic performance influence diagram for being catalyzed the Fe-oba-1 that the reaction time prepares the embodiment of the present invention 1.
Fig. 6 is the catalytic performance influence diagram for the Fe-oba-1 that catalytic reaction temperature prepares the embodiment of the present invention 1.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not
It is confined to the range of embodiment statement.
Embodiment 1
(1) synthesize metal cluster (iron cluster): by 8.08g Fe(NO3)39H2O and 25.4262g anhydrous sodium acetate, ultrasound is molten respectively
Solution obtains iron nitrate solution and sodium acetate solution in 50mL water；It is molten sodium acetate solution to be instilled again the ferric nitrate stirred
In liquid, continues to stir 12h after dripping off sodium acetate, obtain suspension；Suspension is filtered, and successively uses water and ethyl alcohol repeated flushing
Filter cake is put into 70 DEG C of baking ovens dry 12h and obtains bronzing block, by block grind into powder, obtains final product by filter cake
Iron cluster；
(2) synthesizing new ferrous metals organic framework materials: by 15mg iron cluster and 7.5mg 4,4- dicarboxydiphenyl ether
Powder is added in 20mL glass scintillation bottle, with the DMF ultrasonic dissolution of 1.5mL, 80uL acetic acid is then added, obtains mixed liquor；
Vial sealing is gone forward side by side line program temperature control solvent thermal reaction, the temperature programming stage: setting heating rate as 4 DEG C/min, will be anti-
Object is answered to rise to 140 DEG C from room temperature；The constant temperature stage: the temperature of reactant is in 140 DEG C of holding 8h；Program temperature-fall period: setting cooling
Rate is 0.05 DEG C/min, and product is down to 25 DEG C from 140 DEG C.Product is immersed in 12h in the DMF of 60mL after reaction,
Extraction product is filtered again, and product is dried into 12h at 40 DEG C, obtains ferrous metals organic framework materials, is labeled as Fe-oba-1.
Embodiment 2
(1) synthesize metal cluster (iron cluster): by 8.08g Fe(NO3)39H2O and 25.4262g anhydrous sodium acetate, ultrasound is molten respectively
Solution obtains iron nitrate solution and sodium acetate solution in 50mL water；It is molten sodium acetate solution to be instilled again the ferric nitrate stirred
In liquid, continues to stir 12h after dripping off sodium acetate, obtain suspension；Suspension is filtered, and successively uses water and ethyl alcohol repeated flushing
Filter cake is put into 70 DEG C of baking ovens dry 12h and obtains bronzing block, by block grind into powder, obtains final product by filter cake
Iron cluster；
(2) synthesizing new ferrous metals organic framework materials: by 15mg iron cluster and 22.5mg 4,4- dicarboxydiphenyl ether
Powder is added in 20mL glass scintillation bottle, with the DMF ultrasonic dissolution of 2.5mL, 120uL acetic acid is then added, obtains mixed liquor；
Vial sealing is gone forward side by side line program temperature control solvent thermal reaction, the temperature programming stage: setting heating rate as 8 DEG C/min, will be anti-
Object is answered to rise to 160 DEG C from room temperature；The constant temperature stage: the temperature of reactant is in 160 DEG C of holding 48h；Program temperature-fall period: setting cooling
Rate is 0.15 DEG C/min, and product is down to 25 DEG C from 160 DEG C.Product is immersed in the DMF of 100mL after reaction
72h, then extraction product is filtered, product is dried into 48h at 60 DEG C, obtains new iron-based metal-organic framework material, is labeled as Fe-
oba-2。
Embodiment 3
(1) synthesize metal cluster (iron cluster): by 8.08g Fe(NO3)39H2O and 25.4262g anhydrous sodium acetate, ultrasound is molten respectively
Solution obtains iron nitrate solution and sodium acetate solution in 50mL water；It is molten sodium acetate solution to be instilled again the ferric nitrate stirred
In liquid, continues to stir 12h after dripping off sodium acetate, obtain suspension；Suspension is filtered, and successively uses water and ethyl alcohol repeated flushing
Filter cake is put into 70 DEG C of baking ovens dry 12h and obtains bronzing block, by block grind into powder, obtains final product by filter cake
Iron cluster；
(2) synthesizing new ferrous metals organic framework materials: by the powder of 15mg iron cluster and 15mg 4,4- dicarboxydiphenyl ether
End is added in 20mL glass scintillation bottle, with the DMF ultrasonic dissolution of 2mL, 100uL acetic acid is then added, obtains mixed liquor；By glass
Glass bottle seals line program temperature control solvent thermal reaction of going forward side by side, and the temperature programming stage: sets heating rate as 6 DEG C/min, by reactant
150 DEG C are risen to from room temperature；The constant temperature stage: the temperature of reactant is in 150 DEG C of holding 28h；Program temperature-fall period: setting rate of temperature fall
For 0.1 DEG C/min, product is down to 25 DEG C from 150 DEG C.Product is immersed in 42h in the DMF of 80mL after reaction, then is taken out
Product is extracted in filter, and product is dried 30h at 50 DEG C, obtains new iron-based metal-organic framework material, is labeled as Fe-oba-3.
Embodiment 4
(1) synthesize metal cluster (iron cluster): by 8.08g Fe(NO3)39H2O and 25.4262g anhydrous sodium acetate, ultrasound is molten respectively
Solution obtains iron nitrate solution and sodium acetate solution in 50mL water；It is molten sodium acetate solution to be instilled again the ferric nitrate stirred
In liquid, continues to stir 12h after dripping off sodium acetate, obtain suspension；Suspension is filtered, and successively uses water and ethyl alcohol repeated flushing
Filter cake is put into 70 DEG C of baking ovens dry 12h and obtains bronzing block, by block grind into powder, obtains final product by filter cake
Iron cluster；
(2) synthesizing new ferrous metals organic framework materials: by 15mg iron cluster and 22.5mg 4,4- dicarboxydiphenyl ether
Powder is added in 20mL glass scintillation bottle, with the DMF ultrasonic dissolution of 2mL, 80uL acetic acid is then added, obtains mixed liquor；It will
Vial seals line program temperature control solvent thermal reaction of going forward side by side, and the temperature programming stage: sets heating rate as 8 DEG C/min, will react
Object rises to 160 DEG C from room temperature；The constant temperature stage: the temperature of reactant is in 160 DEG C of holding 8h；Program temperature-fall period: setting cooling speed
Rate is 0.1 DEG C/min, and product is down to 25 DEG C from 160 DEG C.Product is immersed in 12h in the DMF of 80mL after reaction, then
It filters and extracts product, product is dried into 12h at 40 DEG C, obtains new iron-based metal-organic framework material, is labeled as Fe-oba-4.
(1) Fe-oba ferrous metals organic framework materials single crystal diffraction structural analysis
Fe-oba-1 synthesized by embodiment 1 is carried out with German 1000 CCD single crystal diffractometer of Bruker company Smart
Single crystal structure analysis obtains the crystallographic data of material, as shown in table 1.
Table 1
Table 1 illustrates that the chemical formula of Fe-oba-1 is Fe3O(C14O5H8)3·3H2O, molecular mass 1006.16g/mol, it is brilliant
Body belongs to hexagonal crystal system.
Fig. 1 a is the structure asymmetric cell of Fe-oba-1, can learn tripleroller crusher and 4,4- dicarboxyl hexichol from the figure
Ether is attached the mode of coordination.Wherein iron atom is hexa-coordinate, each iron atom and six oxygen coordinations, wherein four oxygen come from
Four different 4,4- dicarboxydiphenyl ether ligands, a μ in iron cluster3- O, the last one comes from H2O.Each 4,4- bis-
Carboxyl diphenyl ether ligand is ined succession four iron atoms in two iron clusters.Fig. 1 b is the skeleton structure diagram of Fe-oba-1, can from figure
The skeleton for learning Fe-oba-1 is ordered 3 D structure, and there are two types of the ducts of different shape and size for main tool.
(2) pore structure and specific surface area of Fe-oba ferrous metals organic framework materials
Using 2460 Porosimetry of ASAP of Mike Mo Ruitike (Shanghai) Instrument Ltd. to the embodiment of the present invention
The pore structure of Fe-oba-1, Fe-oba-2, Fe-oba-3, Fe-oba-4 synthesized by 1-4 are tested, and the results are shown in Table 1.
Table 2
From table 2 it can be seen that the BET specific surface area size of Fe-oba material prepared by the present invention is 46.7-53.2m2/ g,
Total pore volume is 0.0687-0.0702cm3/ g, micropore size is in 1.17-1.23nm or so, and mesoporous pore size is in 39.89-39.99nm
Left and right, this illustrates that the skeleton structure of the Fe-oba material of 1-4 of embodiment of the present invention preparation is middle micro-diplopore structure, and pore structure
Property is very close.It is noted that mesoporous presence, which has, accelerates mass transfer speed when carrying out catalysis reaction conducive to Fe-oba material
Rate improves the catalytic performance of material.
(3) the X-ray powder diffraction analysis of Fe-oba ferrous metals organic framework materials
Using Japanese Rigaku SmartLab SE type X-ray polycrystalline diffractometer to synthesized by 1-4 of the embodiment of the present invention
The crystal structure of Fe-oba-1, Fe-oba-2, Fe-oba-3, Fe-oba-4 are characterized, operating condition are as follows: voltage and current point
Not Wei 40kV and 40mA, using Cu KαRay is to be scanned within the scope of 5-35 ° in twice of angle of diffraction, and the step-length of scanning is
0.013°。
Fig. 2 is the PXRD of Fe-oba-1, Fe-oba-2, Fe-oba-3, Fe-oba-4 synthesized by 1-4 of the embodiment of the present invention
Spectrogram.Fig. 2 shows that four kinds of Fe-oba samples synthesized by 1-4 of the embodiment of the present invention have substantially identical PXRD spectrogram,
This explanation can synthesize Fe-oba material using these four synthesis conditions.
(4) water stability of Fe-oba ferrous metals organic framework materials
Using Japanese Rigaku SmartLab SE type X-ray polycrystalline diffractometer to synthesized by 1-4 of the embodiment of the present invention
Crystal structure after Fe-oba-1, Fe-oba-2, Fe-oba-3, Fe-oba-4 duck in drink 4 weeks is characterized, operating condition
Are as follows: voltage and current is respectively 40kV and 40mA, using Cu KαRay is to be swept within the scope of 5-35 ° in twice of angle of diffraction
It retouches, the step-length of scanning is 0.013 °.
Fig. 3 is the PXRD spectrogram after Fe-oba-1, Fe-oba-2, Fe-oba-3, Fe-oba-4 duck in drink 4 weeks, is compared
Fig. 2 and Fig. 3 can be seen that after four kinds of Fe-oba materials duck in drink 4 weeks, still maintain the principal character peak of Fe-oba, this
After illustrating soaked 4 weeks, the skeleton of Fe-oba still maintains constant, shows that Fe-oba material has good water stability.Separately
Outside, PXRD spectrogram is also almost consistent after four kinds of materials duck in drink 4 weeks, illustrates the Fe-oba tool of four kinds of synthetic method synthesis
There is identical water stability.
(5) mass ratio of catalyst and reactant is catalyzed CO for Fe-oba ferrous metals organic framework materials2Cycloaddition
The influence of reactivity worth
Influence of the mass ratio of Study of Catalyst Fe-oba and reactant epoxychloropropane to Fe-oba catalytic performance it is anti-
Answer condition are as follows: the mass ratio of catalyst Fe-oba, co-catalyst tetrabutylammonium bromide and reactant epoxychloropropane be (0.2~
4): 2:111.2, CO2Pressure is 1bar, and the reaction time is that for 24 hours, reaction temperature is 60 DEG C.The conversion of reactant after reaction
Rate is measured by the 600M NMR spectrometer with superconducting magnet that Germany's Bruker company model is AVANCE III HD 600.
The catalytic performance for the Fe-oba-1 that Fig. 4 is prepared the embodiment of the present invention 1 for the mass ratio of catalyst and reactant
Influence diagram.It can be seen from the figure that as the mass ratio of catalyst and reactant rises, under the conversion of reactant takes the lead in after rising
Drop.When the mass ratio of catalyst and reactant is 0.01799 (2:111.2), reaction-ure conversion-age reaches 68.4%, works as catalysis
When the mass ratio of agent and reactant increases to 0.02698 (3:111.2), reaction-ure conversion-age is down to 64.6%.Catalyst increases,
Catalytic site provided by catalyst also increases, so the conversion ratio of reactant will increase, but when catalyst quality is excessive,
Reunite between catalyst granules more serious, causes it effectively to contact reduction between reactant, so under catalytic efficiency starts
Drop.
(6) reaction time is catalyzed CO for Fe-oba ferrous metals organic framework materials2The influence of cycloaddition reaction performance
Study the reaction condition of influence of the reaction time to Fe-oba catalytic performance are as follows: catalyst Fe-oba (16.6mg),
The mass ratio of co-catalyst tetrabutylammonium bromide (32.2mg) and reactant epoxychloropropane (1.564mL) is 1:2:111.2,
CO2Pressure is 1bar, the different reaction time, and reaction temperature is 60 DEG C.The conversion ratio of reactant passes through Germany after reaction
The 600M NMR spectrometer with superconducting magnet that Bruker company model is AVANCE III HD 600 measures.
Fig. 5 is the catalytic performance influence diagram for being catalyzed the Fe-oba-1 that the reaction time prepares the embodiment of the present invention 1.Fig. 5
Show the growth with the reaction time, the conversion ratio of reactant rises.When being 48h between when reacted, the conversion ratio of reactant reaches
To 68.4%.The main reason is that the time of contact between reactant and catalyst increases, instead with the increase in reaction time
Carrying out for answering can be more thorough, so conversion ratio can be higher.
(7) reaction temperature is catalyzed CO for Fe-oba ferrous metals organic framework materials2The influence of cycloaddition reaction performance
Study the reaction condition of influence of the reaction temperature to Fe-oba catalytic performance are as follows: catalyst Fe-oba (16.6mg),
The mass ratio of co-catalyst tetrabutylammonium bromide (32.2mg) and reactant epoxychloropropane (1.564mL) is 1:2:111.2,
CO2Pressure is 1bar, and the reaction time is different reaction temperature for 24 hours.The conversion ratio of reactant passes through Germany after reaction
The 600M NMR spectrometer with superconducting magnet that Bruker company model is AVANCE III HD 600 measures.
Fig. 6 is the catalytic performance influence diagram for the Fe-oba-1 that catalytic reaction temperature prepares the embodiment of the present invention 1.From figure
In 6 it is found that with reaction temperature raising, the conversion ratio of reactant also rises with it.When temperature is increased to 80 DEG C, epoxidation
The high conversion rate of object is up to 97.1%.Temperature is higher, and conversion ratio is bigger, because temperature is higher, the mass transfer rate for being catalyzed reaction is faster,
So reaction progress is more thorough.In addition, temperature is higher, the energy that reactant obtains is bigger, is more conducive to the progress of reaction.
Under equal conditions, the catalytic performance of Fe-oba-1 has been more than most porous materials of current report, is
ZIF-8 material catalytic efficiency 8 times or more (ZIF-8 catalytic conversions be 11%) [J.Kim, S.-N.Kim, H.-G.Jang,
G.Seo, W.-S.Ahn, Applied Catalysis A:General 2013,453,175-180.], it is that SBA-15 material is urged
Change efficiency 12 times or more (SBA-15 catalytic conversions are 8%) [E.E.Macias, P.Ratnasamy, M.A.Carreon,
Catalysis Today 2012,198,215-218.], performance is in international most advanced level.Its superior catalytic performance is main
It is because having contained iron unsatuated metal position containing biggish mesopore size, being CO2It is catalyzed the active site of reaction.
Claims (10)
1. a kind of couple of CO2Cycloaddition reaction has the preparation method of the ferrous metals organic framework materials of high catalytic activity, feature
It is, includes the following steps:
(1) by iron cluster and 4, the mixing of 4- dicarboxydiphenyl ether powder, then with DMF ultrasonic dissolution, acetic acid is then added, is mixed
Liquid；
(2) mixed liquor obtained by step (1) is subjected to temperature programmed control solvent thermal reaction；
(3) product is immersed in DMF after reaction, then filters extraction product, product is dry, and obtaining ferrous metals has machine frame
Frame material is labeled as Fe-oba.
2. preparation method according to claim 1, which is characterized in that the preparation of step (1) the iron cluster includes following step
It is rapid:
In water by Fe(NO3)39H2O and anhydrous sodium acetate difference ultrasonic dissolution, iron nitrate solution and sodium acetate solution are obtained；
Sodium acetate solution is instilled again in the iron nitrate solution stirred, continues to stir after dripping off sodium acetate solution, obtain suspension；
Suspension is filtered, and successively uses water and ethyl alcohol repeated flushing filter cake, filtration cakes torrefaction is obtained into bronzing block, block is ground
It clays into power, obtains iron cluster.
3. preparation method according to claim 1, which is characterized in that step (1) the iron cluster, 4,4- dicarboxyl hexichol
Ether, acetic acid, DMF mass ratio be 1:(0.5 ~ 1.5): (5.6 ~ 8.4): (94.4 ~ 157.4).
4. preparation method according to claim 1, which is characterized in that the temperature programmed control of step (2) described solvent thermal reaction
Process are as follows:
The temperature programming stage: heating rate is set as 4 ~ 8 DEG C/min, reactant is risen to 140 ~ 160 DEG C from room temperature；
The constant temperature stage: the temperature of reactant is in 140 ~ 160 DEG C of 8 ~ 48 h of holding;
Program temperature-fall period: rate of temperature fall is set as 0.05 ~ 0.15 DEG C/min, product is down to 25 DEG C from 140 ~ 160 DEG C.
5. preparation method according to claim 1, which is characterized in that the time of step (3) described immersion is 12 ~ 72 h.
6. the ferrous metals organic framework materials as made from claim 1-5 described in any item preparation methods.
7. ferrous metals organic framework materials described in claims 6 are applied to catalysis CO2In cycloaddition reaction.
8. application according to claim 7, which comprises the following steps:
Catalyst Fe-oba, co-catalyst tetrabutylammonium bromide and reactant epoxychloropropane are mixed, then are passed through CO2Carry out ring
Addition reaction.
9. application according to claim 8, which is characterized in that the catalyst Fe-oba, co-catalyst tetrabutyl phosphonium bromide
The mass ratio of ammonium and reactant epoxychloropropane is (0.2 ~ 4): 2:111.2.
10. application according to claim 8, which is characterized in that the temperature of the reaction is 60-80 DEG C, time 18-
48 h。
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