CN104072525B - A kind of 5-Isonicotinamide pyridyl different metatitanic acid Porous Cu title complex and its preparation method and application - Google Patents
A kind of 5-Isonicotinamide pyridyl different metatitanic acid Porous Cu title complex and its preparation method and application Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000004699 copper complex Chemical class 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 36
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 13
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 4
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical group [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000006482 condensation reaction Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- -1 titanate radical ion Chemical class 0.000 abstract description 3
- JJNZXLAFIPKXIG-UHFFFAOYSA-N 2-Chlorobenzylidenemalononitrile Chemical compound ClC1=CC=CC=C1C=C(C#N)C#N JJNZXLAFIPKXIG-UHFFFAOYSA-N 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000011365 complex material Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000013084 copper-based metal-organic framework Substances 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a kind of 5-Isonicotinamide pyridyl different metatitanic acid Porous Cu title complex and its preparation method and application, this Porous Cu title complex has (3,6) binode three-dimensional topology network structure, chemical expression is [Cu (L)] DMAcH
2o (L is the different titanate radical ion of 5-Isonicotinamide pyridyl); The different metatitanic acid of 5-Isonicotinamide pyridyl and mantoquita are prepared by solvent thermal reaction by preparation method, through washing, after oven dry, namely obtain constitutionally stable novel porous copper complex; This preparation method's process is simple, easy to operate, and productive rate is high; The 5-Isonicotinamide pyridyl different metatitanic acid Porous Cu title complex prepared has katalysis to the Knovevenagel condensation reaction between phenyl aldehyde and propane dinitrile, and catalytic selectivity is good, catalytic activity is high, and catalyzer can efficient recovery reusing.
Description
Technical Field
The invention relates to a 5-isonicotinamide pyridyl iso-titanic acid porous copper complex and a preparation method and application thereof, belonging to the technical field of porous layer columnar materials.
Background
The porous MOFs material combines the characteristics of designability and tailorability of the structure of an organic compound and easy functionalization of inorganic matters, and compared with the traditional porous materials such as zeolite, carbon nano tubes and activated carbon, the most remarkable advantage is that the surface property of a channel can be regulated and controlled by modifying an organic ligand, so that the aim of increasing the selective action on a specific reaction is fulfilled. The MOF has the ability to assemble well-defined molecular building blocks into microporous frameworks, and is particularly suitable for uniformly and dispersedly immobilizing organic metal with catalytic activity in open pore channels thereof, so that the MOF has the dual advantages of high-efficiency catalysis and easy separation from a reaction system. A novel complex material prepared from 1, 3, 5-benzenetricarboxylic acid tris [ N- (4-pyridyl) amide or 2-aminobenzoic acid shows certain catalytic activity on partial heterogeneous Knovevenagel condensation catalysis, but the catalytic reaction time of the complex material is as long as 12 hours, and the catalytic efficiency of the complex material is lower than 70%.
Disclosure of Invention
An object of the present invention is to provide a 5-isonicotinamide pyridylisotitanic acid porous copper complex which has a stable structure, high selectivity and high catalytic activity for knovenagel condensation reaction between benzaldehyde and malononitrile.
The invention also aims to provide a method for synthesizing the 5-isonicotinamide pyridyl isotitanic acid porous copper complex with simple and convenient operation and high yield, and the method has good reproducibility and can meet the requirement of industrial production.
The third purpose of the invention is to provide the application of the 5-isonicotinamide pyridyl iso-titanic acid porous copper complex in catalyzing Knovevenagel condensation reaction, the complex is used for catalyzing the Knovevenagel condensation reaction between benzaldehyde and malononitrile, and the complex has the characteristics of good selectivity, high catalysis efficiency, stable catalysis performance, and recoverable and reusable catalyst.
The invention provides a 5-isonicotinamide pyridyl iso-titanic acid porous copper complex, which has a (3,6) double-node three-dimensional topological network structure, and the chemical expression formula is shown as formula 1:
[Cu(L)]·DMAc·H2O
formula 1
Wherein,
l is an anionic ligand having a structure represented by formula 2;
the complex crystal belongs to a monoclinic system, and the space group is P21C, unit cell parameter of α＝90°，β＝112.046(2)°，γ＝90°，
The 5-isonicotinamide pyridyl-iso-titanic acid porous copper complex is in a three-dimensional layer columnar network structure: the Cu ions are in a penta-coordinate tetragonal pyramid coordination environment, the 5-isonicotinamide pyridyl isotitanium anion ligand is connected with the Cu ions to form a three-dimensional layer columnar network structure, a rectangular pore channel is formed in the network structure, and DMAc and water molecules are fixed in the pore channel through hydrogen bonds.
The invention also provides a preparation method of the 5-isonicotinamide pyridyl-isotitanic acid porous copper complex, which comprises the steps of dissolving 5-isonicotinamide pyridyl-isotitanic acid and copper salt in DMAc according to the mol ratio of 1-2: 1-2 to obtain a mixed solution, carrying out solvothermal reaction on the mixed solution at the temperature of 110-130 ℃, naturally cooling and crystallizing after the reaction is finished, and washing and drying crystals to obtain the 5-isonicotinamide pyridyl-isotitanic acid porous copper complex.
The preparation method of the 5-isonicotinamide pyridylisotitanic acid porous copper complex of the present invention further includes the following preferable embodiments.
In the preferred preparation method, the solvothermal reaction time is 60-90 h.
The copper salt in the preferred preparation method is copper perchlorate and/or copper chloride.
In the preferable preparation method, the temperature of the mixed solution is raised to 110-130 ℃ from room temperature at a temperature raising rate of 5-15 ℃ per hour to perform the solvothermal reaction.
The solvent thermal reaction is to dissolve the raw materials in DMAc to prepare a solution with a certain concentration, seal the solution in a high-pressure reaction kettle and perform heating reaction at a certain temperature.
The invention also provides an application of the 5-isonicotinamide pyridyl-isotitanium acid porous copper complex, which is characterized in that the 5-isonicotinamide pyridyl-isotitanium acid porous copper complex is used as a catalyst for catalyzing Knovenangel condensation reaction between benzaldehyde and malononitrile.
The invention has the beneficial effects that: the invention obtains a complex with a (3,6) double-node three-dimensional topological network structure by taking 5-isonicotinamide pyridylisotitanic acid as a main ligand and copper as a central ion for the first time. The complex has the characteristics of high catalytic activity, high selectivity, high reaction conversion rate, stable catalytic performance and good catalyst reuse effect in the heterogeneous Knovenagel condensation reaction between benzaldehyde and malononitrile, and can be used as a special heterogeneous Knovenagel condensation catalytic material. The preparation method can prepare the 5-isonicotinamide pyridyl-iso-titanic acid porous copper complex by one-pot solvothermal reaction, and has the advantages of simple process, convenience in operation, high yield, strong repeatability and the like.
Drawings
FIG. 1 is a diagram showing the coordination environment of copper in the 5-isonicotinamide pyridylisotitanic acid porous copper complex prepared in example 1.
FIG. 2 shows the porous structure of the porous copper complex of 5-isonicotinamide pyridylisotitanic acid prepared in example 1.
FIG. 3 is a schematic diagram of the topological structure of the porous copper complex of 5-isonicotinamide pyridylisotitanic acid prepared in example 1.
FIG. 4 is a powder X-ray diffraction pattern of the porous copper 5-isonicotinamide pyridylisotitanate complex prepared in example 1.
FIG. 5 is a diagram showing the catalytic effect of the 5-isonicotinamide pyridyl isotitanic acid porous copper complex prepared in example 1.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the invention.
Example 1
Dissolving 5-isonicotinamide pyridylisotitanic acid (28.7mg, 0.1mmol) and copper perchlorate (37.2mg, 0.1mmol) in DMAc (10mL), sealing in a 16mL reaction kettle, heating to 130 ℃ at the rate of 10 ℃ per hour, maintaining the temperature for 3 days, naturally cooling to room temperature to obtain blue columnar crystals, separating the crystals, and sequentially washing and drying to obtain a target product with the yield of about 42%. The main infrared absorption peaks are: 3214m, 2928m, 2361m, 1615s, 1546s, 1429m, 1356m, 1278s, 1227s, 1089s, 1025m, 940s, 913s, 845s, 778s, 702 m.
The prepared porous copper complex has the following catalytic performance experiment:
the catalytic reaction comprises the following steps: in a round bottom flask was added benzaldehyde (2.1mmol, 0.2229g), malononitrile (2.0mmol, 0.1321g), catalyst Cu-MOF (0.037g, 0.08mmol (4 wt%)), with benzene (6mL) as solvent, reacted at 30 ℃ for 4h with the conversion monitored by the gas phase and the product was further confirmed by GC-MS as described in figure 5.
Cyclic utilization experiment: the catalyst was recovered by filtration, and the residual organic compounds were washed with a certain amount of benzene and chloroform several times, and vacuum-dried for reuse. The steps and the amount of the recycling reaction are the same as the above, and the catalyst is recycled.
The 5-isonicotinamide pyridylisotitanic acid porous copper complex is used for catalyzing heterogeneous reaction of benzaldehyde and malononitrile, the conversion rate of benzaldehyde is 98.7%, the catalyst is circulated for 3 times, the conversion rate of benzaldehyde is not obviously reduced, and the catalyst is basically not lost.
The selective research of the catalytic performance of the 5-isonicotinamide pyridylisotitanic acid porous copper complex comprises the following steps:
the experimental steps and experimental conditions are based on that the 5-isonicotinamide pyridylisotitanic acid porous copper complex catalyzes the heterogeneous reaction of benzaldehyde and malononitrile; only replaces the raw materials, takes benzaldehyde and ethyl cyanoacetate as the raw materials to carry out the catalytic reaction of the 5-isonicotinamide pyridyl iso-titanic acid porous copper complex, and the conversion rate of the benzaldehyde is 19 percent. Therefore, the porous copper complex has higher selectivity on Knovenagel condensation catalysis.
The 5-isonicotinamide pyridyl copper iso-titanate complex prepared in example 1 was further characterized by the following procedure:
(1) crystal structure determination of the Complex
Selecting single crystal with proper size under microscope, performing X-ray diffraction experiment at room temperature, collecting diffraction data in Bruker ApexeIIX-ray single crystal diffractometer, and monochromating MoK α ray with graphite monochromator To be provided withThe diffraction data is collected. All data were corrected for Lp factor and empirical absorption, the crystal structure was solved by direct method using SHELXS-97 program, and the hydrogen atoms were synthesized by differential Fourier and fixed at the calculated optimal positions. All non-hydrogen atoms and their anisotropic thermal parameters were F-based using the SHELX-97 program2And (4) correcting by using a full matrix least square method. Detailed crystalThe measured data are shown in Table 1. The crystal structure is shown in fig. 1 and fig. 2, and the topological network of the complex is shown in fig. 3.
(2) PXRD phase purity characterization of complexes
PXRD characterization of the complex showed that it had a reliable phase purity, providing assurance for its use as a catalytic material, see figure 4. (Instrument model: Bruker/D8 Advance).
(4) Study of catalytic Properties of the Complex
Grinding the complex crystal sample, then carrying out a catalytic experiment on 0.5 wt% of porous compound, carrying out product separation after reacting for two hours, and carrying out a test on an Shimadzu gas chromatograph-mass spectrometer (GC/MS-QP2010), wherein the result is shown in figure 5. (instrument model: GC/MS-QP 2010).
As can be seen from the above characterization results, the complex crystal of the present invention is characterized in that the complex crystal belongs to the monoclinic system and has a space group of P21C, unit cell parameter of α＝90°，β＝106.4150(10)°，γ＝90°， The basic structure of the complex is a three-dimensional layer columnar network structure, and the coordination polymer of the three-dimensional structure has rectangular pore channels as shown in figure 2 (the solvent molecules are omitted). The pore channels contain guest DMA and water molecules.
Example 2
Dissolving 5-isonicotinamide pyridylisotitanic acid (43.1mg, 0.15mmol) and copper perchlorate (55.3mg, 0.15mmol) in DMAc (10mL), sealing in a 16mL reaction kettle, heating to 110 ℃ at the rate of 10 ℃ per hour, maintaining the temperature for 3 days, naturally cooling to room temperature to obtain blue columnar crystals, separating the crystals, and sequentially washing and drying to obtain a target product with the yield of about 51%.
The heterogeneous reaction of benzaldehyde and malononitrile catalyzed by the 5-isonicotinamide pyridylisotitanic acid porous copper complex is carried out according to the steps and conditions of example 1, the conversion rate of benzaldehyde is 98.5%, the catalyst is circulated for 3 times, the conversion rate of benzaldehyde is not obviously reduced, and the catalyst is basically not lost.
Example 3
Dissolving 5-isonicotinamide pyridylisotitanic acid (43.1mg, 0.15mmol) and copper chloride (25.4mg, 0.15mmol) in DMAc (10mL), sealing in a 16mL reaction kettle, heating to 110 ℃ at the rate of 10 ℃ per hour, maintaining the temperature for 3 days, naturally cooling to room temperature to obtain blue columnar crystals, separating the crystals, washing and drying sequentially to obtain a target product, wherein the yield is about 47%.
The heterogeneous reaction steps and conditions of benzaldehyde and malononitrile catalyzed by the 5-isonicotinamide pyridylisotitanic acid porous copper complex are carried out according to the embodiment, the conversion rate of benzaldehyde is 98.6%, the catalyst is circulated for 3 times, the conversion rate of benzaldehyde is not obviously reduced, and the catalyst is basically not lost.
TABLE 1 Primary crystallographic data for the complexes
aR1(F)＝||Fo|-|Fc||/S|Fo|，wR2(F2)＝[Sw(Fo 2-Fc 2)2/Sw(Fo 2)2]1/2，w＝[s2(Fo 2)+(AP)2+BP]-1，withP＝(max(Fo 2，0)+2Fc 2)/3；bGoF(F2)＝[Sw(Fo 2-Fc 2)2/(nobs-nparam)]1/2。
Claims (6)
- The preparation method of the 1.5-isonicotinamide pyridylisotitanic acid porous copper complex is characterized in that 5-isonicotinamide pyridylisotitanic acid and copper salt are dissolved in DMAc according to the molar ratio of 1-2: 1-2 to obtain a mixed solution, the mixed solution is subjected to solvothermal reaction at the temperature of 110-130 ℃, after the reaction is finished, natural cooling is carried out for crystallization, and crystals are obtained after washing and drying;the 5-isonicotinamide pyridyl iso-titanic acid porous copper complex has a (3,6) double-node three-dimensional topological network structure, and the chemical expression is shown as formula 1:[Cu(L)]·DMAc·H2Oformula 1Wherein,l is an anionic ligand having a structure represented by formula 2;the complex crystal belongs to a monoclinic system, and the space group is P21C, unit cell parameter of α＝90°，β＝112.046(2)°，γ＝90°，
- 2. The method according to claim 1, wherein the 5-isonicotinamide pyridylisotitanic acid porous copper complex has a three-dimensional layered columnar network structure: the Cu ions are in a penta-coordinate tetragonal pyramid coordination environment, the 5-isonicotinamide pyridyl isotitanium anion ligand is connected with the Cu ions to form a three-dimensional layer columnar network structure, a rectangular pore channel is formed in the network structure, and DMAc and water molecules are fixed in the pore channel through hydrogen bonds.
- 3. The method according to claim 1, wherein the solvothermal reaction time is 60 to 90 hours.
- 4. The process according to claim 1, wherein the copper salt is copper perchlorate and/or copper chloride.
- 5. The method according to claim 1, wherein the mixed solution is subjected to the solvothermal reaction at a temperature rising rate of 5 to 15 ℃ per hour from room temperature to 110 to 130 ℃.
- 6. The use of the 5-isonicotinamide pyridylisotitanic acid porous copper complex prepared by the preparation method of claim 1, characterized in that it is used as a catalyst for catalyzing Knoevenagel condensation reaction between benzaldehyde and malononitrile.
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| Porous zinc(II) frameworks with 5-(isonicotinamido)isophthalate: Syntheses, structures and properties;Man-Sheng Chen et al.;《Microporous and Mesoporous Materials》;20101025;第139卷;第25—30页 * |
| Single-crystal-to-single-crystal transformations and selective adsorption of porous copper(II) frameworks;Man-Sheng Chen et al.;《Chemical Communication》;20110202;第47卷;第3787—3789页 * |
| The organic ligands with mixed N-/O-donors used in construction of functional metal–organic frameworks;Xiao-Liang Zhao et al.;《CrystEngComm》;20140123;第16卷;第3247—3258页 * |
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