CN110305330B - To CO2Iron-based metal organic framework material with high catalytic activity in cycloaddition reaction and preparation method and application thereof - Google Patents
To CO2Iron-based metal organic framework material with high catalytic activity in cycloaddition reaction and preparation method and application thereof Download PDFInfo
- Publication number
- CN110305330B CN110305330B CN201910566150.1A CN201910566150A CN110305330B CN 110305330 B CN110305330 B CN 110305330B CN 201910566150 A CN201910566150 A CN 201910566150A CN 110305330 B CN110305330 B CN 110305330B
- Authority
- CN
- China
- Prior art keywords
- iron
- oba
- reaction
- metal organic
- organic framework
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 58
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 31
- 238000006352 cycloaddition reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012621 metal-organic framework Substances 0.000 title abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000013082 iron-based metal-organic framework Substances 0.000 claims abstract description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 239000000376 reactant Substances 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 24
- 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 24
- 239000001632 sodium acetate Substances 0.000 claims description 18
- 235000017281 sodium acetate Nutrition 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 5
- 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
- 238000006555 catalytic reaction Methods 0.000 description 13
- 239000011148 porous material Substances 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 239000002815 homogeneous catalyst Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 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
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 239000008117 stearic acid Substances 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
- 239000002841 Lewis acid Substances 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
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 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
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
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]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing CO2The preparation method of the iron-based metal organic framework material with high catalytic activity by cycloaddition reaction comprises the following steps: mixing iron cluster and 4, 4-dicarboxydiphenyl ether powder, dissolving with N, N-Dimethylformamide (DMF), and adding acetic acid; and carrying out programmed temperature control solvothermal reaction to obtain the iron-based metal organic framework material. The material prepared by the invention is to CO2The cycloaddition reaction has high catalytic activity and can be used for treating CO under the same conditions2The catalytic efficiency of the cycloaddition reaction is more than 12 times of that of traditional catalysts such as SBA-15 and the like and more than 8 times of that of metal organic framework materials such as ZIF-8 and the like, and the materials show good water stability. For catalyzing CO2Cycloaddition reaction to prepare cyclic carbonate with wide application range, and the material is one kind of catalyst with great potential.
Description
Technical Field
The invention relates to catalystsTo convert CO2The technical field of cycloaddition reaction, in particular to a catalyst for CO2An iron-based metal organic framework material with high catalytic activity in a cycloaddition reaction, and a preparation method and application thereof.
Background
CO2The method is a chemical raw material which is abundant in resources, low in cost and recyclable, and can be used for synthesizing high-added-value chemical products such as methanol, formic acid and cyclic carbonate. For CO2The atom utilization rate of the reaction for preparing the cyclic carbonate by cycloaddition with the epoxy compound is 100 percent, and the product cyclic carbonate can be used for synthesizing cosmetics, polymers, medicaments and battery electrolytes, has wide application and is a very important chemical reaction in industry [ P.Patel, B.Parmar, R.I.Kureshy, N.u.Khan, E.Suresh, ChemCATchem 2018,10, 2401-.]. But using CO2One of the challenges in chemical reactions with epoxy compounds is that of CO2The molecule is a thermodynamically and kinetically stable molecule, and in general, CO will be2Activation requires a large amount of energy consumption. But when CO is present2When the molecule encounters an active center with high activity, it will promote CO2Activating and carrying out chemical reactions. Therefore, catalysts with high catalytic activity for CO were developed2The chemical transformation of (A) is of great significance.
Is currently used for catalyzing CO2Cycloaddition catalysts can be divided into two broad classes, homogeneous catalysts and heterogeneous catalysts. Homogeneous catalysts for CO2Cycloaddition reactions have been extensively studied. For example, Kawanami et al [ H.Kawanami, A.Sasaki, K.Matsui, Y.Ikushima, Chemical Communications 2003, 896-.]By using [ C8-mim]+[BF4]-The ionic liquid catalyzes CO at 14MPa and 100 DEG C2The epoxy compound can be completely converted into the cyclic carbonate by cycloaddition reaction for 5 min. However, homogeneous catalysts have problems in that it is difficult to separate the catalyst from the product and in that the catalyst is difficult to recover. Heterogeneous catalysts have been receiving increasing attention from researchers because heterogeneous catalysts have advantages over homogeneous catalysts in that products and catalysts are easily separated, and the catalysts are easily regenerated. Heterogeneous catalysts have been reported to dateCan be broadly divided into two categories: has a class of catalysts to CO2Cycloaddition reactions have good catalytic activity, but the stability of the materials is poor, such 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.](ii) a Another class of catalyst materials has good stability but is CO tolerant2Cycloaddition reactions have low catalytic activity, 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-.]. In practical industrial applications, the stabilization of CO is developed2The cycloaddition reaction is a catalyst with high catalytic activity, which is a very urgent matter.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for treating CO2An iron-based metal organic framework material with high catalytic activity in a cycloaddition reaction, and a preparation method and application thereof.
The iron-based metal organic framework material (Fe-oba) is a three-dimensional porous metal organic framework material which is formed by self-assembling an iron cluster and organic ligand 4, 4-dicarboxydiphenyl ether through solvothermal reaction. The Fe-oba has good water stability mainly because the iron cluster belongs to stearic acid, the 4, 4-dicarboxydiphenyl ether organic ligand belongs to hard alkali, and the water stability of the material is good according to the theory of the soft and hard acid alkali (the material synthesized by stearic acid and hard alkali has good stability). Fe-oba on CO2The material has good catalytic performance mainly because the material has larger pore channel size, which is beneficial to improving the mass transfer rate of catalytic reaction; in addition, the material contains Fe3+The unsaturated metal site of (A) belongs to the Lewis acid site, and is directed to CO2Cycloaddition is a highly catalytically active site. The material is used for catalyzing CO2The cycloaddition reaction has good potential application prospect.
The purpose of the invention is realized by the following technical scheme.
To CO2The preparation method of the iron-based metal organic framework material with high catalytic activity by cycloaddition reaction comprises the following steps:
(1) mixing iron clusters and 4, 4-dicarboxydiphenyl ether powder, ultrasonically dissolving the mixture by using DMF (N, N-dimethylformamide), and then adding acetic acid to obtain a mixed solution;
(2) carrying out programmed temperature-controlled solvothermal reaction on the mixed solution obtained in the step (1);
(3) and after the reaction is finished, soaking the product in DMF, performing suction filtration to extract the product, and drying the product to obtain the iron-based metal organic framework material marked as Fe-oba.
Preferably, the preparation of the iron cluster in the step (1) comprises the following steps:
respectively ultrasonically dissolving ferric nitrate nonahydrate and anhydrous sodium acetate in water to obtain a ferric nitrate solution and a sodium acetate solution; then, dripping the sodium acetate solution into the stirring ferric nitrate solution, and continuously stirring after finishing dripping the sodium acetate solution to obtain a suspension; filtering the suspension, repeatedly washing the filter cake with water and ethanol, drying the filter cake to obtain a reddish brown block, and grinding the block into powder to obtain an iron cluster; the synthetic steps are shown in [ D.Lv, R.Shi, Y.Chen, Y.Wu, H.Wu, H.xi, Q.Xia, Z.Li, ACS Appl Mater Interfaces 2018,10, 8366-.
Preferably, the mass ratio of the iron cluster, the 4, 4-dicarboxydiphenyl ether, the acetic acid and the DMF in the step (1) is 1 (0.5-1.5): (5.6-8.4): 94.4-157.4).
Preferably, the reaction container is a glass scintillation bottle, the volume of the glass scintillation bottle is 20mL, and the bottle cap can resist the high temperature of 150 ℃.
Preferably, the temperature programming process of the solvothermal reaction in the step (2) is as follows:
a temperature programming stage: setting the heating rate to be 4-8 ℃/min, and heating the reactants to 140-160 ℃ from room temperature;
and (3) a constant temperature stage: keeping the temperature of the reactants at 140-160 ℃ for 8-48 h;
and (3) a program cooling stage: setting the cooling rate to be 0.05-0.15 ℃/min, and cooling the product from 140-160 ℃ to 25 ℃.
Preferably, the soaking time in the step (3) is 12-72 hours.
Preferably, the drying temperature in the step (3) is 40-60 ℃.
Preferably, the drying time in the step (3) is 12-48 h.
The iron-based metal organic framework material prepared by the preparation method is provided.
The iron-based metal organic framework material is applied to catalyzing CO2In the cycloaddition reaction.
Preferably, the above-mentioned application comprises the following steps:
mixing a catalyst Fe-oba, a cocatalyst tetrabutylammonium bromide and a reactant epichlorohydrin, and introducing CO2A cycloaddition reaction is carried out.
Preferably, the mass ratio of the catalyst Fe-oba to the cocatalyst tetrabutylammonium bromide to the reactant epichlorohydrin is (0.2-4): 2: 111.2.
Preferably, the reaction temperature is 60-80 ℃ and the reaction time is 18-48 h.
Compared with the prior art, the invention has the following advantages and effects:
1. the iron-based metal-organic framework material prepared by the invention has good water stability and can be stably kept in water for 4 weeks.
2. The iron-based metal organic framework material prepared by the invention is catalyzed for 24 hours at 80 ℃, and the conversion rate of catalytic reaction reaches 97%.
Drawings
FIG. 1a shows the structural asymmetry of Fe-oba-1 prepared in example 1 of the present invention.
FIG. 1b is a skeletal structure of Fe-oba-1.
FIG. 2 shows PXRD patterns of Fe-oba-1, Fe-oba-2, Fe-oba-3, and Fe-oba-4 prepared in examples 1-4 of the present invention.
FIG. 3 shows PXRD patterns of Fe-oba-1, Fe-oba-2, Fe-oba-3, and Fe-oba-4 materials prepared in examples 1-4 of the present invention after being soaked in water for 4 weeks.
FIG. 4 is a graph showing the effect of catalyst to reactant mass ratio on the catalytic performance of Fe-oba-1 prepared in example 1 of the present invention.
FIG. 5 is a graph showing the effect of catalytic reaction time on the catalytic performance of Fe-oba-1 prepared in example 1 of the present invention.
FIG. 6 is a graph showing the effect of catalytic reaction temperature on the catalytic performance of Fe-oba-1 prepared in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Example 1
(1) Synthetic metal cluster (iron cluster): respectively ultrasonically dissolving 8.08g of ferric nitrate nonahydrate and 25.4262g of anhydrous sodium acetate in 50mL of water to obtain a ferric nitrate solution and a sodium acetate solution; then, dripping the sodium acetate solution into the stirring ferric nitrate solution, and continuing stirring for 12 hours after finishing dripping the sodium acetate to obtain a suspension; filtering the suspension, repeatedly washing the filter cake with water and ethanol in sequence, drying the filter cake in a 70 ℃ oven for 12h to obtain a reddish brown block, and grinding the block into powder to obtain a final product iron cluster;
(2) synthesizing a novel iron-based metal organic framework material: adding powder of 15mg of iron clusters and 7.5mg of 4, 4-dicarboxydiphenyl ether into a 20mL glass scintillation bottle, ultrasonically dissolving the powder by using 1.5mL of DMF, and then adding 80uL of acetic acid to obtain a mixed solution; sealing the glass bottle and carrying out temperature programmed solvent thermal reaction, wherein the temperature programmed stage comprises the following steps: setting the heating rate to be 4 ℃/min, and heating the reactants to 140 ℃ from room temperature; and (3) a constant temperature stage: the temperature of the reactants is kept at 140 ℃ for 8 h; and (3) a program cooling stage: the cooling rate was set at 0.05 ℃/min and the product was cooled from 140 ℃ to 25 ℃. And after the reaction is finished, soaking the product in 60mL of DMF for 12h, performing suction filtration to extract the product, and drying the product at 40 ℃ for 12h to obtain the iron-based metal organic framework material marked as Fe-oba-1.
Example 2
(1) Synthetic metal cluster (iron cluster): respectively ultrasonically dissolving 8.08g of ferric nitrate nonahydrate and 25.4262g of anhydrous sodium acetate in 50mL of water to obtain a ferric nitrate solution and a sodium acetate solution; then, dripping the sodium acetate solution into the stirring ferric nitrate solution, and continuing stirring for 12 hours after finishing dripping the sodium acetate to obtain a suspension; filtering the suspension, repeatedly washing the filter cake with water and ethanol in sequence, drying the filter cake in a 70 ℃ oven for 12h to obtain a reddish brown block, and grinding the block into powder to obtain a final product iron cluster;
(2) synthesizing a novel iron-based metal organic framework material: adding powder of 15mg of iron clusters and 22.5mg of 4, 4-dicarboxydiphenyl ether into a 20mL glass scintillation bottle, ultrasonically dissolving the powder by using 2.5mL of DMF, and then adding 120uL of acetic acid to obtain a mixed solution; sealing the glass bottle and carrying out temperature programmed solvent thermal reaction, wherein the temperature programmed stage comprises the following steps: setting the heating rate to be 8 ℃/min, and heating the reactants to 160 ℃ from room temperature; and (3) a constant temperature stage: keeping the temperature of reactants at 160 ℃ for 48 hours; and (3) a program cooling stage: the cooling rate was set at 0.15 ℃/min and the product was cooled from 160 ℃ to 25 ℃. And after the reaction is finished, soaking the product in 100mL of DMF for 72h, performing suction filtration to extract the product, and drying the product at 60 ℃ for 48h to obtain the novel iron-based metal organic framework material which is marked as Fe-oba-2.
Example 3
(1) Synthetic metal cluster (iron cluster): respectively ultrasonically dissolving 8.08g of ferric nitrate nonahydrate and 25.4262g of anhydrous sodium acetate in 50mL of water to obtain a ferric nitrate solution and a sodium acetate solution; then, dripping the sodium acetate solution into the stirring ferric nitrate solution, and continuing stirring for 12 hours after finishing dripping the sodium acetate to obtain a suspension; filtering the suspension, repeatedly washing the filter cake with water and ethanol in sequence, drying the filter cake in a 70 ℃ oven for 12h to obtain a reddish brown block, and grinding the block into powder to obtain a final product iron cluster;
(2) synthesizing a novel iron-based metal organic framework material: adding powder of 15mg of iron clusters and 15mg of 4, 4-dicarboxydiphenyl ether into a 20mL glass scintillation bottle, ultrasonically dissolving the powder by using 2mL of DMF, and then adding 100uL of acetic acid to obtain a mixed solution; sealing the glass bottle and carrying out temperature programmed solvent thermal reaction, wherein the temperature programmed stage comprises the following steps: setting the heating rate to be 6 ℃/min, and heating the reactants to 150 ℃ from room temperature; and (3) a constant temperature stage: keeping the temperature of reactants at 150 ℃ for 28 h; and (3) a program cooling stage: the cooling rate was set at 0.1 ℃/min and the product was cooled from 150 ℃ to 25 ℃. And after the reaction is finished, soaking the product in 80mL of DMF for 42h, performing suction filtration to extract the product, and drying the product at 50 ℃ for 30h to obtain the novel iron-based metal organic framework material which is marked as Fe-oba-3.
Example 4
(1) Synthetic metal cluster (iron cluster): respectively ultrasonically dissolving 8.08g of ferric nitrate nonahydrate and 25.4262g of anhydrous sodium acetate in 50mL of water to obtain a ferric nitrate solution and a sodium acetate solution; then, dripping the sodium acetate solution into the stirring ferric nitrate solution, and continuing stirring for 12 hours after finishing dripping the sodium acetate to obtain a suspension; filtering the suspension, repeatedly washing the filter cake with water and ethanol in sequence, drying the filter cake in a 70 ℃ oven for 12h to obtain a reddish brown block, and grinding the block into powder to obtain a final product iron cluster;
(2) synthesizing a novel iron-based metal organic framework material: adding powder of 15mg of iron clusters and 22.5mg of 4, 4-dicarboxydiphenyl ether into a 20mL glass scintillation bottle, ultrasonically dissolving the powder by using 2mL of DMF, and then adding 80uL of acetic acid to obtain a mixed solution; sealing the glass bottle and carrying out temperature programmed solvent thermal reaction, wherein the temperature programmed stage comprises the following steps: setting the heating rate to be 8 ℃/min, and heating the reactants to 160 ℃ from room temperature; and (3) a constant temperature stage: keeping the temperature of reactants at 160 ℃ for 8 h; and (3) a program cooling stage: the cooling rate was set at 0.1 ℃/min and the product was cooled from 160 ℃ to 25 ℃. And after the reaction is finished, soaking the product in 80mL of DMF for 12h, performing suction filtration to extract the product, and drying the product at 40 ℃ for 12h to obtain the novel iron-based metal organic framework material which is marked as Fe-oba-4.
Single crystal diffraction structure analysis of Fe-oba iron-base metal organic frame material
The crystallographic data of the material, as shown in Table 1, were obtained by single crystal texture analysis of Fe-oba-1 synthesized in example 1 using a Bruker Smart 1000 CCD single crystal diffractometer, Germany.
TABLE 1
Table 1 shows that the chemical formula of Fe-oba-1 is Fe3O(C14O5H8)3·3H2O, the molecular mass is 1006.16g/mol, and the crystal belongs to a hexagonal system.
FIG. 1a shows the structural asymmetry of Fe-oba-1, from which the manner in which the trinuclear iron cluster and 4, 4-dicarboxydiphenyl ether are coordinated by ligation can be seen. Wherein the iron atom is hexacoordinated, each iron atom being coordinated with six oxygens, four of the oxygens being derived from four different 4, 4-dicarboxydiphenyl ether ligands and one being derived from mu in the iron cluster3-O, the last one from H2And O. Each 4, 4-dicarboxydiphenyl ether ligand is attached to four iron atoms in two iron clusters. FIG. 1b is a structural diagram of the framework of Fe-oba-1, from which it can be seen that the framework of Fe-oba-1 is a three-dimensional ordered structure and mainly has two pore channels with different shapes and sizes.
(II) pore structure and specific surface area of Fe-oba iron-based metal organic framework material
The pore structures of Fe-oba-1, Fe-oba-2, Fe-oba-3 and Fe-oba-4 synthesized in examples 1-4 of the present invention were measured by using an ASAP 2460 pore size analyzer of Mimorrey instruments Ltd, and the results are shown in Table 1.
TABLE 2
As can be seen from Table 2, the BET specific surface area of the Fe-oba material prepared by the invention is 46.7-53.2m2Per g, total pore volume of 0.0687-0.0702cm3The pore diameters of the micropores are about 1.17-1.23nm, and the pore diameters of the mesopores are about 39.89-39.99nm, which indicates that the framework structures of the Fe-oba materials prepared in the embodiments 1-4 of the invention are all medium-micro double-pore structures, and the properties of the pore structures are very close. It is worth mentioning that the existence of the mesopores is beneficial to accelerating the mass transfer rate and improving the catalytic performance of the Fe-oba material during the catalytic reaction.
(III) X-ray powder diffraction analysis of Fe-oba Fe-based metal organic framework material
The crystal structures of Fe-oba-1, Fe-oba-2, Fe-oba-3 and Fe-oba-4 synthesized in examples 1-4 of the present invention were characterized by using Rigaku SmartLab SE type X-ray polycrystal diffractometer in Japan, and the operating conditions were as follows: the voltage and the current are respectively 40kV and 40mA, and Cu K is adoptedαAnd rays, scanned at a double diffraction angle in the range of 5-35 °, in a step size of 0.013 °.
FIG. 2 shows PXRD spectra of Fe-oba-1, Fe-oba-2, Fe-oba-3, and Fe-oba-4 synthesized in examples 1-4 of the present invention. FIG. 2 shows that the four Fe-oba samples synthesized in examples 1-4 of the present invention have nearly identical PXRD spectra, which indicates that Fe-oba material can be synthesized under all four synthesis conditions.
(IV) Water stability of Fe-oba Fe-based metal organic framework materials
The crystal structures of Fe-oba-1, Fe-oba-2, Fe-oba-3 and Fe-oba-4 synthesized in examples 1-4 of the present invention after being soaked in water for 4 weeks were characterized by using Rigaku SmartLab SE type X-ray polycrystal diffractometer in Japan, and the operating conditions were as follows: the voltage and the current are respectively 40kV and 40mA, and Cu K is adoptedαAnd rays, scanned at a double diffraction angle in the range of 5-35 °, in a step size of 0.013 °.
FIG. 3 is a PXRD spectrum of Fe-oba-1, Fe-oba-2, Fe-oba-3 and Fe-oba-4 after being soaked in water for 4 weeks, and comparing FIG. 2 with FIG. 3, it can be seen that the main characteristic peak of Fe-oba still remains after the four Fe-oba materials are soaked in water for 4 weeks, which indicates that the skeleton of Fe-oba still remains unchanged after the materials are soaked in water for 4 weeks, and indicates that the Fe-oba materials have good water stability. In addition, PXRD spectrograms of the four materials are almost consistent after the four materials are soaked in water for 4 weeks, and the fact that the Fe-oba synthesized by the four synthesis methods has the same water stability is shown.
(V) Mass ratio of catalyst to reactant for Fe-oba Fe-based metal organic framework materials catalyzing CO2Effect of the Properties of the cycloaddition reaction
The reaction conditions for researching the influence of the mass ratio of the catalyst Fe-oba to the reactant epichlorohydrin on the catalytic performance of Fe-oba are as follows: the mass ratio of the catalyst Fe-oba to the cocatalyst tetrabutylammonium bromide to the reactant epichlorohydrin is (0.2-4) 2:111.2, and CO is2A pressure of1bar, a reaction time of 24h and a reaction temperature of 60 ℃. The conversion of the reactants after the end of the reaction was determined by means of a 600M superconducting NMR spectrometer model AVANCE III HD 600 from Bruker, Germany.
FIG. 4 is a graph showing the effect of catalyst to reactant mass ratio on the catalytic performance of Fe-oba-1 prepared in example 1 of the present invention. As can be seen from the figure, as the mass ratio of catalyst to reactant increases, the conversion of reactant increases first and then decreases. The reactant conversion reached 68.4% when the catalyst to reactant mass ratio was 0.01799(2:111.2), and dropped to 64.6% when the catalyst to reactant mass ratio was increased to 0.02698(3: 111.2). The catalyst increases and the catalytic sites provided by the catalyst also increase, so the conversion of the reactants increases, but when the catalyst quality is too high, the agglomeration between catalyst particles is severe, resulting in a decrease in effective contact between the catalyst particles and the reactants, so the catalytic efficiency begins to decrease.
(VI) reaction time for catalyzing CO for Fe-oba iron-based metal organic framework material2Effect of the Properties of the cycloaddition reaction
The reaction conditions to investigate the effect of reaction time on the catalytic performance of Fe-oba were: the mass ratio of the catalyst Fe-oba (16.6mg), the cocatalyst tetrabutylammonium bromide (32.2mg) and the reactant epichlorohydrin (1.564mL) is 1:2:111.2, and the mass ratio of CO is2The pressure was 1bar, the reaction time varied and the reaction temperature was 60 ℃. The conversion of the reactants after the end of the reaction was determined by means of a 600M superconducting NMR spectrometer model AVANCE III HD 600 from Bruker, Germany.
FIG. 5 is a graph showing the effect of catalytic reaction time on the catalytic performance of Fe-oba-1 prepared in example 1 of the present invention. Figure 5 shows that the conversion of the reactants increases with increasing reaction time. When the reaction time is 48h, the conversion of the reactants reaches 68.4%. The main reason for this is that as the reaction time increases, the contact time between the reactants and the catalyst increases, the reaction proceeds more thoroughly and therefore the conversion increases.
(VII) the reaction temperature is opposite to that of Fe-oba iron-based metal organic framework material to catalyze CO2Effect of the Properties of the cycloaddition reaction
The reaction conditions for investigating the effect of the reaction temperature on the catalytic performance of Fe-oba were: the mass ratio of the catalyst Fe-oba (16.6mg), the cocatalyst tetrabutylammonium bromide (32.2mg) and the reactant epichlorohydrin (1.564mL) is 1:2:111.2, and the mass ratio of CO is2The pressure was 1bar, the reaction time was 24h, and the reaction temperature was varied. The conversion of the reactants after the end of the reaction was determined by means of a 600M superconducting NMR spectrometer model AVANCE III HD 600 from Bruker, Germany.
FIG. 6 is a graph showing the effect of catalytic reaction temperature on the catalytic performance of Fe-oba-1 prepared in example 1 of the present invention. As is clear from fig. 6, the conversion of the reactant increased with the increase in the reaction temperature. When the temperature is raised to 80 ℃, the conversion rate of the epoxide is as high as 97.1%. The higher the temperature, the greater the conversion, and since the higher the temperature, the faster the mass transfer rate of the catalytic reaction, and therefore the more thorough the reaction. In addition, the higher the temperature, the more energy the reactants gain, the more favorable the reaction proceeds.
Under the same conditions, the catalytic performance of Fe-oba-1 exceeds that of most porous materials reported at present, and is more than 8 times of that of ZIF-8 materials (the catalytic conversion rate of ZIF-8 is 11%) [ J.Kim, S. -N.Kim, H. -G.Jang, G.Seo, W. -S.Ahn, Applied Catalysis A: General 2013,453, 175-.]More than 12 times of the catalytic efficiency of the SBA-15 material (the catalytic conversion rate of the SBA-15 is 8%) [ E.E.Macias, P.Ratnasamy, M.A.Carreon, Catalysis Today 2012,198,215-218 ].]The performance is at an international advanced level. The excellent catalytic performance is mainly due to the fact that the catalyst contains larger mesoporous size, already contains iron unsaturated metal sites, and is CO2Active sites for catalytic reactions.
Claims (8)
1. To CO2The preparation method of the iron-based metal organic framework material with high catalytic activity by cycloaddition reaction is characterized by comprising the following steps:
(1) mixing iron clusters and 4, 4-dicarboxydiphenyl ether powder, ultrasonically dissolving the mixture by using DMF (dimethyl formamide), and then adding acetic acid to obtain a mixed solution;
(2) carrying out programmed temperature-controlled solvothermal reaction on the mixed solution obtained in the step (1);
(3) after the reaction is finished, soaking the product in DMF, performing suction filtration to extract the product, and drying the product to obtain an iron-based metal organic framework material marked as Fe-oba;
the preparation of the iron cluster in the step (1) comprises the following steps:
respectively ultrasonically dissolving ferric nitrate nonahydrate and anhydrous sodium acetate in water to obtain a ferric nitrate solution and a sodium acetate solution; then, dripping the sodium acetate solution into the stirring ferric nitrate solution, and continuously stirring after finishing dripping the sodium acetate solution to obtain a suspension; filtering the suspension, repeatedly washing the filter cake with water and ethanol, drying the filter cake to obtain a reddish brown block, and grinding the block into powder to obtain an iron cluster;
the temperature program control process of the solvent thermal reaction in the step (2) is as follows:
a temperature programming stage: setting the heating rate to be 4-8 ℃/min, and heating the reactants to 140-160 ℃ from room temperature;
and (3) a constant temperature stage: keeping the temperature of the reactants at 140-160 ℃ for 8-48 h;
and (3) a program cooling stage: setting the cooling rate to be 0.05-0.15 ℃/min, and cooling the product from 140-160 ℃ to 25 ℃.
2. The method according to claim 1, wherein the mass ratio of the iron cluster in the step (1), the 4, 4-dicarboxydiphenyl ether, the acetic acid and the DMF is 1 (0.5-1.5): (5.6-8.4): (94.4-157.4).
3. The preparation method according to claim 1, wherein the soaking time in the step (3) is 12-72 hours.
4. An iron-based metal organic framework material produced by the production method according to any one of claims 1 to 3.
5. The use of the iron-based metal organic framework material of claim 4 for catalyzing CO2In the cycloaddition reaction.
6. Use according to claim 5, characterized in that it comprises the following steps:
mixing a catalyst Fe-oba, a cocatalyst tetrabutylammonium bromide and a reactant epichlorohydrin, and introducing CO2A cycloaddition reaction is carried out.
7. The use of claim 6, wherein the mass ratio of the catalyst Fe-oba to the cocatalyst tetrabutylammonium bromide to the reactant epichlorohydrin is (0.2-4): 2: 111.2.
8. The use according to claim 6, wherein the reaction is carried out at a temperature of 60-80 ℃ for a period of 18-48 h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910566150.1A CN110305330B (en) | 2019-06-27 | 2019-06-27 | To CO2Iron-based metal organic framework material with high catalytic activity in cycloaddition reaction and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910566150.1A CN110305330B (en) | 2019-06-27 | 2019-06-27 | To CO2Iron-based metal organic framework material with high catalytic activity in cycloaddition reaction and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110305330A CN110305330A (en) | 2019-10-08 |
CN110305330B true CN110305330B (en) | 2021-11-23 |
Family
ID=68076691
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910566150.1A Active CN110305330B (en) | 2019-06-27 | 2019-06-27 | To CO2Iron-based metal organic framework material with high catalytic activity in cycloaddition reaction and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110305330B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112812140B (en) * | 2021-01-26 | 2022-04-29 | 江苏奥克化学有限公司 | Complexes, process for their preparation and catalysts comprising them |
CN115178295B (en) * | 2022-05-09 | 2023-12-19 | 江西师范大学 | One-step synthesis method and application of enamine covalent organic framework supported non-noble metal monoatomic catalyst |
CN115785460B (en) * | 2022-09-30 | 2023-08-11 | 西安石油大学 | Manganese metal organic frame material and preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104370952A (en) * | 2014-10-22 | 2015-02-25 | 渤海大学 | Organic-ligand-based multifunctional zinc complexes and application thereof |
CN106478959A (en) * | 2016-09-23 | 2017-03-08 | 肇庆学院 | A kind of Cd MOF Ji Yu 4,4 ' dicarboxydiphenyl ether and preparation method thereof |
CN106832311A (en) * | 2016-11-28 | 2017-06-13 | 南京工业大学 | The multicolor luminous crystalline materials of Eu MOF and Tb MOF green light crystal materials and preparation method thereof |
CN109876776A (en) * | 2019-02-02 | 2019-06-14 | 北京建筑大学 | Indium base MOF micro-nano powder and its room temperature preparation method and application |
-
2019
- 2019-06-27 CN CN201910566150.1A patent/CN110305330B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104370952A (en) * | 2014-10-22 | 2015-02-25 | 渤海大学 | Organic-ligand-based multifunctional zinc complexes and application thereof |
CN106478959A (en) * | 2016-09-23 | 2017-03-08 | 肇庆学院 | A kind of Cd MOF Ji Yu 4,4 ' dicarboxydiphenyl ether and preparation method thereof |
CN106832311A (en) * | 2016-11-28 | 2017-06-13 | 南京工业大学 | The multicolor luminous crystalline materials of Eu MOF and Tb MOF green light crystal materials and preparation method thereof |
CN109876776A (en) * | 2019-02-02 | 2019-06-14 | 北京建筑大学 | Indium base MOF micro-nano powder and its room temperature preparation method and application |
Non-Patent Citations (1)
Title |
---|
"Synthesis of aryl-substituted pyridines via cyclization of N,N-dialkylanilines with ketoxime carboxylates under metal-organic framework catalysis";Phuong T.M. Ha et al.;《Journal of Industrial and Engineering Chemistry》;20170601;第54卷;第151-161页 * |
Also Published As
Publication number | Publication date |
---|---|
CN110305330A (en) | 2019-10-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110305330B (en) | To CO2Iron-based metal organic framework material with high catalytic activity in cycloaddition reaction and preparation method and application thereof | |
Ji et al. | Conversion of CO 2 into cyclic carbonates by a Co (ii) metal–organic framework and the improvement of catalytic activity via nanocrystallization | |
EP3708540A1 (en) | A preparation method for zeolitic imidazolate frameworks | |
CN112280052B (en) | Hierarchical pore ZIF-8 material and preparation method and application thereof | |
CN105728019A (en) | Application and preparation method of ZSM-5 molecular sieve with mesopores and micropores | |
CN108262073B (en) | Metal organic framework supported phosphotungstic acid catalyst, preparation method and application of catalyst in catalytic synthesis of adipic acid | |
CN109603912B (en) | Metal organic framework structure catalyst and application thereof | |
CN107876094B (en) | Three dish alkene polymer NTP/ zinc-cadmium sulfide Cd of one kind0.5Zn0.5The preparation method of S composite photo-catalyst | |
CN113198520B (en) | One-pot preparation method of molecular sieve supported palladium carbon catalyst and application of molecular sieve supported palladium carbon catalyst in synthesis of dimethyl carbonate by gas phase method | |
CN102125847A (en) | Copper nickel silicon catalyst for preparing ethylene glycol and preparation method thereof | |
CN105195188A (en) | Nickel-tungsten carbide/porous carbon nano-fiber composite catalyst, intermediate and preparation | |
CN112774707A (en) | Ru-N-C monatomic catalyst and preparation method and application thereof | |
CN101455976A (en) | Effective catalyst used in hydrogenation of dimethyl oxalate to synthesizing ethylene glycol and production method thereof | |
EP3827898A1 (en) | Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof | |
CN101439882B (en) | Method for synthesizing mesoporous ammonium nickel molybdate by using urea as precipitating agent | |
CN114160143B (en) | CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof | |
CN111116934A (en) | Preparation of MOFs derivative with hollow structure and application of MOFs derivative in catalyzing olefin epoxidation | |
CN106268856A (en) | Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application | |
CN113231102B (en) | Glutaric acid selective polyacid catalyst based on micro-mesoporous Zr-MOF material and preparation method and application thereof | |
CN110586094A (en) | Copper-based nanoflower catalyst for producing methanol and ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof | |
CN108722488B (en) | Bimetal center metal-organic framework material for enhancing Lewis acidity and preparation method thereof | |
CN115536860B (en) | Biological MOF material for electrocatalysis and photocatalysis, and preparation method and application thereof | |
CN111732736A (en) | Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof | |
CN111116321A (en) | Green synthesis method for preparing phenol by benzene hydroxylation | |
CN102814193B (en) | Copper-composite molecular sieve catalyst used for synthesis of diethyl carbonate through gas-phase oxidative carbonylation and its preparation method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |