CN116870968A - Iridium complex functionalized nano graphene catalyst, and preparation method and application thereof - Google Patents

Iridium complex functionalized nano graphene catalyst, and preparation method and application thereof Download PDF

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CN116870968A
CN116870968A CN202311152646.7A CN202311152646A CN116870968A CN 116870968 A CN116870968 A CN 116870968A CN 202311152646 A CN202311152646 A CN 202311152646A CN 116870968 A CN116870968 A CN 116870968A
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catalyst
amide
pyridine
aminophenyl
graphene
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苏慧娟
赵立军
祁彩霞
孙逊
孙立波
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Yantai University
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Abstract

The invention discloses an iridium complex functionalized nano graphene catalyst, and a preparation method and application thereof. Belongs to the technical field of iridium complex functionalized nano graphene catalysts. The novel organic iridium (Ir) complex functionalized nano graphene catalyst Ir-PyPh-GC is prepared by a novel two-step strategy of amide ligand N- (4-aminophenyl) pyridine amide modification and metal-iridium coordination. The Ir-PyPh-GC shows ultrahigh hydrogenation activity and recoverability for various carbonyl derivatives at a low temperature of 40 ℃, is beneficial to reducing the application cost of the Ir complex and improves the industrial application value of the Ir complex.

Description

Iridium complex functionalized nano graphene catalyst, and preparation method and application thereof
Technical Field
The invention relates to an organometallic complex functionalized nano graphene catalyst, and also relates to a preparation method and application of the catalyst.
Background
Transition metal complexes, in particular Ir-, rh-and Ru-based semi-sandwich complexes, have been found to have very excellent catalytic properties for various hydrogen transfer TH reactions, including hydrogenation of acetophenone, CO 2 Hydrogenation of biological cofactors, hydrogenation of olefins and optoelectronic transport. Compared with the traditional heterogeneous hydrogenation catalyst, the homogeneous organic metal catalyst has more advantages in the aspects of catalytic activity, stereoselectivity, substrate diversity and the like. However, the industrial application of organometallic complex catalysts still faces many challenges, limited by their expensive price and poor recyclability. The preparation of heterogeneous catalysts based on organometallic complex catalysts has proven to be a viable process which can address the high price and low recovery of homogeneous complex catalystsProblems.
The development of heterogeneous catalysts of organometallic complexes has mainly utilized adsorption and coupling reactions between support materials and transition metal complexes. Several support materials, such as silica, carbon nanotubes, graphene, activated carbon, covalent organic framework materials, metal organic framework materials, polymeric supports, magnetic materials, and the like have been widely developed and commercialized. In contrast, functionalized ligands and transition metal complexes remain relatively scarce, which further limits the development and use of heterogeneous transition metal complex catalysts.
Disclosure of Invention
The invention aims to solve the technical problem of providing an iridium complex functionalized nano graphene catalyst, a preparation method and application thereof, wherein the catalyst has ultrahigh TH activity, stereoselectivity and recoverability on various carbonyl derivatives.
The invention adopts the following technical scheme:
the iridium complex functionalized nano graphene catalyst has the following structural formula:
。
the preparation method of the catalyst comprises the following steps: at N 2 Adding dichloro (pentamethylcyclopentadienyl) iridium (III) dimer and ammonium hexafluorophosphate to an ethanol solution of N-phenyl-2-pyridine amide modified graphene under an atmosphere; reflux; centrifuging; washing the solution, and drying to obtain the catalyst;
the preparation method of the N-phenyl-2-pyridine amide modified graphene comprises the following steps of:
(1) Preparation of N-hydroxysuccinimide activated carboxyl graphene: adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride aqueous solution and N-hydroxythiosuccinimide aqueous solution into carbonyl-functionalized graphene, and stirring to obtain N-hydroxythiosuccinimide-activated carboxyl graphene;
(2) Adding an amide ligand N- (4-aminophenyl) pyridine amide dissolved in acetonitrile to the N-hydroxysulfosuccinimide-activated carboxyl graphene, and stirring; centrifuging; washing; drying to obtain N-phenyl-2-pyridine amide modified graphene;
the structural formula of the amide ligand N- (4-aminophenyl) pyridine amide is as follows:
。
preferably, in the preparation method of the catalyst, the preparation method of the amide ligand N- (4-aminophenyl) pyridine amide is as follows: pyridine-2-formic acid is used as a raw material, activated by condensing agents of 1, 3-dicyclohexylcarbodiimide and N-hydroxysulfosuccinimide, and condensed with excessive 1, 4-diaminobenzene to obtain an amide ligand N- (4-aminophenyl) pyridine amide.
Preferably, in the preparation method of the catalyst, the amide ligand N-holly is prepared according to the following steps
(4-aminophenyl) pyridinamide:
1) Dissolving pyridine-2-carboxylic acid and N-hydroxy-thiosuccinimide in dry dichloromethane, cooling at 0 ℃, adding 1, 3-dicyclohexylcarbodiimide, supplementing the dry dichloromethane, continuing stirring, and then completely precipitating dicyclohexylurea; filtering the precipitate and evaporating the filtrate; washing with diethyl ether to obtain pure product 3a;
2) Under the ice water bath condition, dissolving the pure product A in a dry mixed solvent consisting of acetonitrile and dry dichloromethane, adding 1, 4-diaminobenzene dissolved in acetonitrile, heating to room temperature and continuously stirring; next, methylene chloride and NaHCO are added to the reaction solution 3 Is a mixed solution of (a) and (b); washing with deionized water, separating and collecting an organic phase, drying, distilling under reduced pressure to remove a solvent, and purifying residues to obtain the amide ligand N- (4-aminophenyl) pyridine amide.
The catalyst is applied to carbonyl derivative hydrogenation reaction.
Preferably, the carbonyl derivative includes acetophenone analogs, benzaldehyde analogs, and quinone analogs.
Preferably, the hydrogenation reaction temperature is not higher than 40 ℃.
Preferably, the hydrogenation reaction system ph=2.0; the reaction temperature is 40 ℃; the reaction time is 6h; the catalyst was used in an amount of 1.0mg/mL of carbonyl derivative.
The invention has the beneficial effects that:
first, the invention can obtain stable N- (4-aminophenyl) pyridine amide (PyPh-NH) through modification 2 ) And utilize the resulting PyPh-NH 2 The novel organic Ir complex functionalized nano graphene catalyst (Ir-PyPh-GC) is successfully prepared. The prepared catalyst Ir-PyPh-GC shows ultrahigh TH activity, stereoselectivity and recoverability for various carbonyl derivatives (including acetophenone analogues, benzaldehyde analogues and quinone analogues) at lower temperature (such as below 40 ℃).
Secondly, the invention successfully converts the homogeneous metal complex catalyst into a heterogeneous catalyst, and can effectively solve the problems of waste and recovery of the high-activity noble metal catalyst.
Drawings
FIG. 1 is a flowchart of one embodiment of the invention, pyPh-NH 2 Is a composite roadmap of (a).
FIG. 2 is a synthetic route diagram of the example two catalysts Ir-PyPh-GC of the present invention.
FIG. 3 is a scanning electron microscope image of the catalyst Ir-PyPh-GC prepared in example two of the present invention.
FIG. 4 is a graph of the cycle life of a seventh catalyst of an embodiment of the present invention.
FIG. 5 is an XPS spectrum of a seven-catalyst Ir-PyPh-GC of the invention after reaction.
Detailed Description
The technical scheme and beneficial effects of the invention are further described below with reference to examples and experimental data.
Example one, amide ligand N- (4-aminophenyl) picolinamide (PyPh-NH) 2 ) Synthesis example
1) 1.23 g,10 mmol of pyridine-2-carboxylic acid and 1.15 g,10 mmol of N-hydroxysulfosuccinimide were dissolved in 20mL dry Dichloromethane (DCM), cooled at 0℃and then 2.5 g,12.5 mmol of 1, 3-Dicyclohexylcarbodiimide (DCC) were added dropwise, supplementing 15mL of dry dichloromethane solution, stirring was continued for 1 hour, and kept overnight in a refrigerator at 4℃to precipitate Dicyclohexylurea (DCU) completely. The precipitate was filtered and the filtrate evaporated in vacuo. The pale yellow solid formed was washed with diethyl ether to give pure product 3a (2.09 g, 98%).
2) 0.44g,2.0mmol of pure product A is dissolved in 20mL of dry mixed solvent (acetonitrile: DCM=1:1) under ice-water bath conditions, 1, 4-diaminobenzene (2.16 g, i.e. 20 mmol) dissolved in 20mL of acetonitrile is added dropwise, warmed to room temperature and stirring is continued for 24 hours. After completion of the reaction, 100 mL of CH was used 2 Cl 2 And 50 mL saturated NaHCO 3 And diluting the mixed solution of the solutions. The organic layer was washed with saturated brine and dried over anhydrous Na 2 SO 4 And (5) drying. The solvent was evaporated in vacuo and the residue was purified by column 3 chromatography on silica gel to give ligand PyPh-NH as a white solid 2 (0.33 g, 76.5%). The synthetic route is shown in figure 1. Through detection, the obtained PyPh-NH 2 The nuclear magnetic resonance hydrogen spectrum and the carbon spectrum of (a) are respectively as follows:
1 H NMR (400 MHz, DMSO) δ 10.22 (s, 1H), 8.70 (d,J= 4.5 Hz, 1H), 8.17 – 7.99 (m, 2H), 7.69 – 7.58 (m, 1H), 7.52 (d,J= 7.8 Hz, 2H), 6.62 – 6.50 (m, 2H), 4.97 (s, 2H).
13 C NMR (101 MHz, DMSO) δ 161.88 (s), 150.79 (s), 148.78 (s), 145.87 (s), 138.48 (s), 127.86 (s), 126.95 (s), 122.46 (s), 122.11 (s), 114.20 (s). HRMS (EI): m / z calcd for (M+Na + ) C 6 H 6 O 2 S 236.0800; found 236.0798.
the prepared amide ligand N- (4-aminophenyl) pyridine amide has the following structural formula:
。
example two preparation example of organic Ir Complex functionalized nanographene catalyst (Ir-PyPh-GC)
1) 30mL,2mg/mL of carbonyl-functionalized graphene (GC-COOH) material was washed twice with deionized water, then 2mL,10mg/mL of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI) aqueous solution and 2mL,10mg/mL of N-hydroxysulfosuccinimide (NHS) aqueous solution were added, and stirred at 25℃for 30 minutes to give N-hydroxysuccinimide-activated carboxygraphene (NHS-GC).
2) Will contain 10.6mg,10.5mmol of the amide ligand N- (4-aminophenyl) pyridine amide prepared in example one (PyPh-NH) 2 ) To the above mixed solution (i.e., NHS-GC solution) and stirring was continued for 24 hours. After the reaction, the mixed solution was centrifuged, washed with 5mL of water and 5mL of acetonitrile, respectively, and then dried in vacuo to give N-phenyl-2-pyridineamide modified graphene (PyPh-GC).
3) At N 2 To a solution of 30 mg PyPh-GC in ethanol under an atmosphere were added 20 mg,0.025 mmol of dichloro (pentamethylcyclopentadienyl) iridium (III) dimer and 20 mg, 0.12 mmol of ammonium hexafluorophosphate NH 4 PF 6 And refluxed 24 h. And washing the solution obtained by centrifugation by using a dichloromethane-methanol equal proportion mixture, and vacuum drying to obtain the organic iridium complex functionalized nano graphene catalyst Ir-PyPh-GC. The Ir-PyPh-GC synthetic route of the catalyst is shown in figure 2.
The structural formula of the prepared catalyst Ir-PyPh-GC is as follows:
。
the scanning electron microscope diagram of the prepared catalyst Ir-PyPh-GC is shown in fig. 3, and the scanning electron microscope diagram is shown in fig. 3: the organic iridium complex functionalized nano graphene catalyst is a catalyst with a lamellar structure, and the organic iridium is successfully complexed into the graphene material.
Example III, pH Effect of catalyst Ir-PyPh-GC on acetophenone hydrogenation
This example relates to the pH effect of the prepared catalyst Ir-PyPh-GC on acetophenone hydrogenation, the substrate to catalyst ratio (S/C) being 1000, the pH range being 1.0-7.0, 40℃and HCOOH/HCOONa as hydrogen source for 5 hours. From the results in table 1, it can be seen that the best catalytic efficiency was observed at ph=2.0, with a yield of 82.7%.
TABLE 1 Ir-PyPh-GC yields for acetophenone hydrogenation at different pH values
Example IV influence of the reaction temperature and time on the use of the catalyst Ir-PyPh-GC for the hydrogenation of acetophenone
The effect of reaction temperatures of 20 ℃ to 80 ℃ and different reaction times on acetophenone hydrogenation was studied at ph=2.0, and the results (shown in table 2) indicate that the hydrogenation efficiency of Ir-PyPh-GC on acetophenone was still high even at lower temperatures of 20 ℃, and the yield of phenethyl alcohol reached 90% after 8h of reaction. Further, in 1.0h, the yield of phenethyl alcohol increases with increasing temperature. When the reaction temperature is lower than 70 ℃, the yield of phenethyl alcohol increases with the extension of the reaction time, and the phenethyl alcohol rapidly increases to 75% at 80 ℃, but as the reaction time extends, the yield decreases, which may be due to instability of the product under higher temperature conditions. Thus, 40℃and a reaction time of 6h were used as the optimum temperature for the Ir-PyPh-GC catalytic hydrogenation catalyst.
TABLE 2 yields of Ir-PyPh-GC for acetophenone hydrogenation at different reaction temperatures and times
Example five determination of optimal reaction conditions
As a hydrogen source, the concentration of HCOOH/HCOONa was investigated in the range of 0.1M to 4.0M. The yield of phenethyl alcohol increases with increasing HCOOH/HCOONa concentration and reaches a maximum at 3.0M. In addition, the amount of Ir-PyPh-GC used under optimum conditions (40 ℃ C., 6.0 hours and 3.0M HCOOH/HCl) was also investigated. The results showed that the yield of phenethyl alcohol was positively correlated with the amount of catalyst and that the best results were obtained with 1.0mg/mL Ir-PyPh-GC. Based on the above results, the optimal conditions (pH 2.0, 40 ℃,6.0h,3.0M HCOOH/HCOONa and 1.0mg/mL Ir-PyPh-GC) were used for the following experiments.
Example six productivity of catalyst hydrogenation reaction on various carbonyl derivatives
Using the best conditions of example five, the hydrogenation of various carbonyl derivatives (including acetophenone analogs, benzaldehyde analogs, and quinone analogs) was examined according to the reaction formula of formula 1, and the yield results of the products are shown in Table 3.
1 (1)
TABLE 3 yields of various carbonyl derivative hydrogenation reaction products
Example seven evaluation example of catalyst recyclability and reuse
For effective industrial applications, catalyst recyclability is a very important indicator for assessing production costs. Thus, the catalytic hydrogenation performance of the recovered catalyst Ir-PyPh-GC was tested using acetophenone as substrate. The recovered catalyst Ir-PyPh-GC was obtained from the catalytic reaction solution by centrifugation, washing with water and vacuum drying at 40℃for 24 hours. Then, the catalytic activity of the recovered catalyst was tested using a fresh reaction solution under the same conditions as the initial reaction. As shown in fig. 4, the catalyst Ir-PyPh-GC showed a maintained catalytic activity in six cycle experiments, and the yield of phenethyl alcohol was reduced from 96.5% to 76.8%, indicating good recyclability of Ir-PyPh-GC. As can be seen from fig. 5: the area ratio of Ir/Cl element after recovery is obviously increased, and the calculated area ratio of Ir/Cl element of the recovered catalyst is 3.87, which is caused by Cl falling off in the reaction process. While Ir as a reactive site is hardly affected and is present in HCOO - In the presence of the catalyst, the catalyst can quickly activate Ir-PyPh-GC-H and transfer H-to carbonyl, the carbonyl generates corresponding hydroxyl, and the Ir-PyPh-GC-H can also be converted into Ir-PyPh-GC-H in the process 2 O, to produce Ir-PyPh-GC-H 2 O will be againAnd then participate in the catalytic process of another molecular carbonyl compound, which is the main reason for the good circulating activity of the catalyst.
In summary, a new graphene-based heterogeneous catalyst Ir-PyPh-GC was developed by combining a high activity homogeneous catalyst Ir complex with a commercial carboxygraphene material. The prepared catalyst Ir-PyPh-GC shows ultrahigh hydrogenation activity, stereoselectivity and recoverability for hydrogenation reaction of various carbonyl derivatives under low temperature conditions. The strategies developed can successfully convert homogeneous metal complex catalysts to heterogeneous catalysts, which would be expected to improve the loss and recycling problems of high activity noble metal catalysts.
Dichloro (pentamethylcyclopentadienyl) iridium (III) dimer used in the present invention, formula C 20 H 30 Cl 4 Ir 2 The method comprises the steps of carrying out a first treatment on the surface of the The purity is 96 percent; CAS number 12354-84-6; molecular weight 796.7; MDL number MFCD00075435; pubCHem number 76030743.

Claims (8)

1. The iridium complex functionalized nano graphene catalyst is characterized by having the following structural formula:
。
2. the method for preparing the catalyst according to claim 1, wherein: at N 2 Adding dichloro (pentamethylcyclopentadienyl) iridium (III) dimer and ammonium hexafluorophosphate to an ethanol solution of N-phenyl-2-pyridine amide modified graphene under an atmosphere; reflux; centrifuging; washing the solution, and drying to obtain the catalyst;
the preparation method of the N-phenyl-2-pyridine amide modified graphene comprises the following steps of:
(1) Preparation of N-hydroxysuccinimide activated carboxyl graphene: adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride aqueous solution and N-hydroxythiosuccinimide aqueous solution into carbonyl-functionalized graphene, and stirring to obtain N-hydroxythiosuccinimide-activated carboxyl graphene;
(2) Adding an amide ligand N- (4-aminophenyl) pyridine amide dissolved in acetonitrile to the N-hydroxysulfosuccinimide-activated carboxyl graphene, and stirring; centrifuging; washing; drying to obtain N-phenyl-2-pyridine amide modified graphene;
the structural formula of the amide ligand N- (4-aminophenyl) pyridine amide is as follows:
。
3. the method for preparing the catalyst according to claim 2, wherein the preparation method of the amide ligand N- (4-aminophenyl) pyridine amide comprises the following steps: pyridine-2-formic acid is used as a raw material, activated by condensing agents of 1, 3-dicyclohexylcarbodiimide and N-hydroxysulfosuccinimide, and condensed with excessive 1, 4-diaminobenzene to obtain an amide ligand N- (4-aminophenyl) pyridine amide.
4. A process for the preparation of a catalyst as claimed in claim 3, characterized in that the amide ligand N- (4-aminophenyl) pyridine amide is prepared according to the following steps:
1) Dissolving pyridine-2-carboxylic acid and N-hydroxy-thiosuccinimide in dry dichloromethane, cooling at 0 ℃, adding 1, 3-dicyclohexylcarbodiimide, supplementing the dry dichloromethane, continuing stirring, and then completely precipitating dicyclohexylurea; filtering the precipitate and evaporating the filtrate; washing with diethyl ether to obtain pure product 3a;
2) Under the ice water bath condition, dissolving the pure product A in a dry mixed solvent consisting of acetonitrile and dry dichloromethane, adding 1, 4-diaminobenzene dissolved in acetonitrile, heating to room temperature and continuously stirring; next, methylene chloride and NaHCO are added to the reaction solution 3 Is a mixed solution of (a) and (b); washing with deionized water, separating and collecting an organic phase, drying, distilling under reduced pressure to remove a solvent, and purifying residues to obtain the amide ligand N- (4-aminophenyl) pyridine amide.
5. Use of the catalyst according to claim 1, characterized in that: the catalyst is applied to carbonyl derivative hydrogenation reaction.
6. The use of the catalyst according to claim 5, wherein: the carbonyl derivatives include acetophenone analogs, benzaldehyde analogs and quinone analogs.
7. The use of the catalyst according to claim 5 or 6, characterized in that: the hydrogenation reaction temperature is not higher than 40 ℃.
8. The use of the catalyst according to claim 5 or 6, characterized in that: the hydrogenation reaction system ph=2.0; the reaction temperature is 40 ℃; the reaction time is 6h; the catalyst was used in an amount of 1.0mg/mL of carbonyl derivative.
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US20180362566A1 (en) * 2015-12-18 2018-12-20 University Of Leeds Metal complexes
CN109265484A (en) * 2018-09-20 2019-01-25 江苏大学 A kind of metal iridium-triazole crystal-graphene oxide ternary nonlinear optical material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101128199A (en) * 2004-04-23 2008-02-20 布里斯托尔-迈尔斯斯奎布公司 Monocyclic heterocycles as kinase inhibitors
CN104725628A (en) * 2014-10-01 2015-06-24 厦门赛诺邦格生物科技有限公司 Single functional branched polyethylene glycol containing degradable radical, preparation method and biorelevant substance of single functional branched polyethylene glycol
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