CN115555051B - Pd/CuMOF-x composite material catalyst, preparation method and application thereof - Google Patents
Pd/CuMOF-x composite material catalyst, preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- C—CHEMISTRY; METALLURGY
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- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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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
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- 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 Pd/CuMOF-x composite material catalyst, a preparation method and application thereof, wherein the chemical expression of the CuMOF is { [ Cu (L) (H) 2 O)]} n Wherein L is 2‑ 4-pyridine methylene phosphonic acid radical is represented, and is a metal organic framework material containing Cu ions and taking 4-pyridine methylene phosphonic acid as a ligand; x represents the mass percent of Pd in the composite material and 0<x<10. The Pd/CuMOF-x composite material is a Pd/Cu bimetallic heterogeneous catalyst, can efficiently catalyze 3, 4-dichloronitrobenzene to synthesize diuron technical by a one-pot method in CO atmosphere, avoids the use of highly toxic phosgene, and has the advantages of short synthetic route, convenient post-treatment, low cost, high reaction yield, environmental friendliness and the like.
Description
Technical Field
The invention relates to the field of pesticide synthesis catalysts, in particular to a Pd/CuMOF-x composite material catalyst, a preparation method and application thereof.
Background
Diuron (Diuron), which is known as N- (3, 4-dichlorophenyl) -N ', N' -dimethylurea, belongs to an unsymmetrical substituted urea herbicide, and is suitable for rice, cotton, corn, sugarcane, fruit, gum, mulberry, tea garden, barnyard grass, crab grass, green bristlegrass, knotweed, quinoa, potherb mustard and the like. The structure of the compound is shown as the following formula (I):
currently, the synthetic methods of diuron mainly comprise two methods, namely a phosgene method (CN201210191499. X; CN201710421976. X) and a non-phosgene method. Wherein, the phosgene method (also called isocyanate method) needs to undergo three steps of processes of reduction, esterification and water addition, and a plurality of times of extremely toxic gas phosgene is needed to be used, so that the safety requirement of the production process is extremely high, a large amount of chlorine-containing compounds with strong corrosiveness can be produced, and the post-treatment process and equipment are relatively complex. The non-phosgene method adopts CO to replace highly toxic phosgene as a carbonylation reagent, and diuron is directly synthesized by a selective oxidation-reduction carbonylation method (see below), so that the attention is paid to the fact that the reaction steps are few, the atom economy and the environmental friendliness are improved.
For example, zhang Xiaopeng et al report that selenium catalyzes the oxidation-reduction carbonylation reaction "one pot" synthesis of diuron (chemical report, 2016,79 (12): 1192-1195); wang Yan has similar reports in its published article "selenium catalyzed carbonylation of diuron, 4-pyridinium urea and benzimidazol-2-ylcarbamate". In addition, noble metal catalysts such as Rh, ru, pd and the like can catalyze the oxidation-reduction carbonylation reaction to synthesize various substituted urea compounds (diuron analogues) (journal molecular catalysis,1990 (1): L15-L18; chemical development, 2002, 14 (6): 433-437), and the non-phosgene method for synthesizing diuron has some defects, such as the method for synthesizing the diuron by selenium-catalyzed carbonylation also needs to add triethylamine with twice molar quantity of 3, 4-dichloronitrobenzene as a catalyst promoter, and the yield of the diuron is not high enough. Single noble metal Pd (CH) 3 COO) 2 In the method for synthesizing the substituted urea compound by catalytic reduction carbonylation reaction, PPh is also required to be added 3 And cocatalyst NEt 4 Cl.
According to the invention, the CuMOF material with large specific surface area, adjustable aperture and good stability is used as a catalyst carrier, and the active center Pd is grafted on the CuMOF carrier to prepare the Pd/CuMOF-x composite material catalyst, so that the combined action of Pd as the active center and Cu as the synergistic metal is exerted, and the high catalytic activity and higher reaction yield of the catalyst in the reaction process of synthesizing diuron by reducing and carbonylating 3, 4-dichloronitrobenzene are ensured under the CO atmosphere.
Disclosure of Invention
The invention aims to provide a preparation method of a Pd/CuMOF-x composite material catalyst for synthesizing diuron by reducing and carbonylating 3, 4-dichloronitrobenzene, which solves the technical problems of unfriendly environment in the prior art and insufficient yield of target products of the existing catalytic system.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a Pd/CuMOF-x composite material catalyst is used for synthesizing diuron by 3, 4-dichloronitrobenzene reduction carbonyl, and the chemical expression of the CuMOF is { [ Cu (L) (H) 2 O)]N is Cu-containing ligand 4-pyridylmethylphosphonic acid 2+ Metal organic framework material of (2); l (L) 2- Represents 4-pyridine methylene phosphonate, pd is loaded on CuMOF, x represents mass percent of Pd in the composite material catalyst, and 0<x<10。
Each asymmetric unit of the CuMOF contains 1 deprotonated organic ligand L 2- 1 copper ion and 1 coordinated water molecule, the molecular structure of which is as follows:
preferably, the mass percentage of Pd in the composite material is 4.12%, and the prepared composite material is Pd/CuMOF-4.
A process for preparing Pd/CuMOF-x composite catalyst used for synthesizing diuron by reduction and carbonylation of 3, 4-dichloronitrobenzene includes such steps as preparing CuMOF (chemical expression is { [ Cu (L) (H) 2 O)]} n ) As a catalyst carrier, pd is loaded on the CuMOF carrier to prepare the bimetallic Pd/CuMOF-x composite material catalyst.
Preferably, the Pd/CuMOF-x composite catalyst is prepared by the following steps:
(1) Copper nitrate and 4-pyridine methylene phosphonic acid were dissolved in ultrapure water, mixed uniformly by ultrasonic, and the pH of the solution system was adjusted to 4.0, then the mixed solution was transferred to an autoclave having a polytetrafluoroethylene liner, and the reaction was carried out in an oven. And naturally cooling, filtering, washing and drying to obtain the CuMOF material.
(2) The CuMOF material and Pd (II) salt prepared in the step (1) are dissolved in DMF and are uniformly mixed by ultrasonic treatment. The mixture was then transferred to an autoclave lined with polytetrafluoroethylene and reacted in an oven. And naturally cooling, filtering, washing and drying to obtain the Pd/CuMOF-x composite material.
Further, in step (2), the Pd (II) salt is selected from PdCl 2 、Pd(OAc) 2 、Pd(TFA) 2 One of them.
Further, in the step (2), the reaction temperature in the oven is 120-160 ℃ and the reaction time is 36-72 h.
Still further, in the step (2), the mass percentage of Pd in the composite material is x% =1% -10%.
Compared with the prior art, the invention has the following beneficial effects:
1. the bimetallic Pd/CuMOF-x composite material taking 4-pyridine methylene phosphonate as a ligand is prepared for the first time.
2. The reaction yield of synthesizing diuron by reducing and carbonylating 3, 4-dichloronitrobenzene is effectively improved through the synergistic catalysis of Pd and Cu in the Pd/CuMOF-x composite material.
3. The method uses cheap and easily available CO to replace highly toxic phosgene and uses Pd/CuMOF-x composite material to replace Se as a catalyst to directly synthesize diuron technical, and has the advantages of short synthetic route, high reaction yield, environmental friendliness and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of a Pd/CuMOF-4 composite;
FIG. 2 is an infrared spectrum of a Pd/CuMOF-4 composite;
FIG. 3 is an infrared spectrum of diuron product prepared by a one-pot method;
FIG. 4 is a high resolution mass spectrum (ESI-HRMS) of diuron products prepared in a one pot process.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the present invention will be further described with reference to the embodiments and the accompanying drawings, and the implementation manner of the present invention includes, but is not limited to, the following embodiments.
Example 1: preparation of CuMOF
0.483g Cu (NO) 3 ) 2 ·3H 2 O and 0.348 g of 4-pyridylmethylphosphonic acid were each added to 40mL of deionized water, the pH was adjusted to 4.0 with 1.0M NaOH, transferred to a 100mL autoclave, and reacted in an oven at 110℃for 72h. Cooling to room temperature, washing with ultrapure water and absolute ethyl alcohol, and drying to obtain blue crystals, namely the CuMOF. The CuMOF material was ground to small particles for use.
Example 2: preparation of Pd/CuMOF-2 composite catalyst
0.0505g of CuMOF material and 0.0035g of PdCl after grinding 2 Dissolving in 10mLDMF, and ultrasonic mixing. The mixture was then transferred to a 50mL autoclave lined with polytetrafluoroethylene liner and the sealed vessel heated at 120 ℃ for 36h. After natural cooling, filtering, thoroughly washing the obtained solid with ultrapure water and ethanol, and drying in a vacuum oven at 50-60 ℃ for 24 hours to obtain blue-black crystals, namely the Pd/CuMOF-x composite material with the load ratio of 2.32%, which is named as Pd/CuMOF-2.
Example 3: preparation of Pd/CuMOF-4 composite catalyst
0.0505g of CuMOF material and 0.0090g Pd (OAc) after grinding 2 Dissolving in 10mLDMF, and ultrasonic mixing. The mixture was then transferred to a 50mL autoclave lined with polytetrafluoroethylene and the sealed vessel heated at 140 ℃ for 48h. After natural cooling, filtering, thoroughly washing the obtained solid with ultrapure water and ethanol, and drying in a vacuum oven at 50-60 ℃ for 24 hours to obtain blue-black crystals, namely the Pd/CuMOF-x composite material with the load ratio of 4.12%, which is named as Pd/CuMOF-4.
The obtained Pd/CuMOF-4 has an X-ray diffraction pattern shown in figure 1 and an infrared spectrum shown in figure 2. IR (KBr, cm) for IR spectrum data -1 )：3016(m)，2948(m)，2915(m)，1608(s)，1419(m)，1250(m)，1216(m)，1130(s)，1042(s)，992(s)，831(m)，561(s)。
Example 4: preparation of Pd/CuMOF-6 composite catalyst
0.0505g of CuMOF material and 0.0200g of Pd (TFA) after milling 2 Dissolving in 10mLDMF, and ultrasonic mixing. The mixture was then transferred to a 50mL autoclave lined with polytetrafluoroethylene liner and the sealed vessel heated at 160 ℃ for 72h. After natural cooling, filtering, thoroughly washing the obtained solid with ultrapure water and ethanol, and drying in a vacuum oven at 50-60 ℃ for 24 hours to obtain blue-black crystals, namely the Pd/CuMOF-x composite material with the load ratio of 6.28%, which is named as Pd/CuMOF-6.
Example 5: preparation of Pd/CuMOF-8 composite catalyst
0.0505g of CuMOF material after milling and 0.0220g of PdCl were mixed 2 Dissolving in 10mLDMF, and ultrasonic mixing. The mixture was then transferred to a 50mL autoclave lined with polytetrafluoroethylene liner and the sealed vessel heated at 160 ℃ for 72h. After natural cooling, filtering, thoroughly washing the obtained solid with ultrapure water and ethanol, and drying in a vacuum oven at 50-60 ℃ for 24 hours to obtain blue-black crystals, namely the Pd/CuMOF-x composite material with the load ratio of 8.26%, which is named as Pd/CuMOF-8.
Correlation performance detection
The Pd/CuMOF-x composite material catalyst prepared in the examples 1-4 is subjected to catalytic reduction carbonylation reaction in the presence of CO to synthesize diuron.
Example 6: catalytic reduction carbonylation reaction of Pd/CuMOF-2 composite material to synthesize diuron
To a cold 100mL stainless steel reactor was added 3, 4-dichloronitrobenzene (5 mmol), dimethylamine hydrochloride (10 mmol), pd/CuMOF-2 catalyst (30 mg) and THF (20 mL) in this order, and the mixture was sealed. Air was replaced 3 times with 1.0MPa CO, and the CO pressure in the reaction vessel was increased to 3.0MPa. Starting the stirring device of the reaction kettle, and heating the reaction kettle to 180 ℃ for reaction for 3 hours.
After the reaction, the reaction vessel was cooled to room temperature, and the residual gas was discharged. The reaction vessel was opened and placed in air and stirred for a further 1h. And then filtering to remove filter residues, removing the solvent under reduced pressure, and finally obtaining the target product diuron through column chromatography (the volume ratio of the leaching agent to the petroleum ether to the ethyl acetate is 6:1). Yield: 77.4%.
The melting point of the synthetic diuron was determined to be 157-158℃and the literature value was 158-159℃as per Zhu Liangtian. Fine chemical products handbook-pesticide rolls Beijing: chemical industry Press 2004, 411-412.
The infrared spectrum (fig. 3) data are: IR (v, cm) -1 ) 3301,2928,1656,1587,863,814,755,635,574 wherein 3301cm -1 Is an N-H bond stretching vibration absorption peak; 2928cm -1 Is a methyl telescopic vibration absorption peak; 1656cm -1 Is carbonyl stretching vibration absorption peak; 1587cm -1 Vibrating the benzene ring framework; 863cm -1 、814cm -1 And 755cm -1 Substituting the benzene ring for the out-of-plane bending vibration and the out-of-plane bending vibration absorption peak of the skeleton; 635cm -1 And 574cm -1 The C-Cl bond stretches and contracts the vibration absorption peak.
High resolution mass spectrometry (HRMS (ESI), fig. 4) data are: m/z [ M+H ]] + The actual measurement value was 233.0246, which was in accordance with the theoretical value 233.0243 (calcd. ForC 9 H 11 Cl 2 N 2 O)。
Example 7: catalytic reduction carbonylation reaction of Pd/CuMOF-4 composite material to synthesize diuron
To a cold 100mL stainless steel reactor was added 3, 4-dichloronitrobenzene (5 mmol), dimethylamine hydrochloride (10 mmol), pd/CuMOF-4 catalyst (30 mg) and THF (20 mL) in this order, and the mixture was sealed. Air was replaced 3 times with 1.0MPa CO, and the CO pressure in the reaction vessel was increased to 3.0MPa. Starting the stirring device of the reaction kettle, and heating the reaction kettle to 180 ℃ for reaction for 3 hours.
After the reaction, the reaction vessel was cooled to room temperature, and the residual gas was discharged. The reaction vessel was opened and placed in air and stirred for a further 1h. And then filtering to remove filter residues, removing the solvent under reduced pressure, and finally obtaining the target product diuron through column chromatography (the volume ratio of the leaching agent to the petroleum ether to the ethyl acetate is 6:1). Yield: 84.5%.
Melting point, nuclear magnetic hydrogen spectrum, infrared, high resolution mass spectrum, and the like are the same as in example 6.
Example 8: catalytic reduction carbonylation reaction of Pd/CuMOF-6 composite material to synthesize diuron
To a cold 100mL stainless steel reactor was added 3, 4-dichloronitrobenzene (5 mmol), dimethylamine hydrochloride (10 mmol), pd/CuMOF-6 catalyst (30 mg) and THF (20 mL) in this order, and the mixture was sealed. Air was replaced 3 times with 1.0MPa CO, and the CO pressure in the reaction vessel was increased to 3.0MPa. Starting the stirring device of the reaction kettle, and heating the reaction kettle to 180 ℃ for reaction for 3 hours.
After the reaction, the reaction vessel was cooled to room temperature, and the residual gas was discharged. The reaction vessel was opened and placed in air and stirred for a further 1h. And then filtering to remove filter residues, removing the solvent under reduced pressure, and finally obtaining the target product diuron through column chromatography (the volume ratio of the leaching agent to the petroleum ether to the ethyl acetate is 6:1). Yield: 81.2%.
Melting point, nuclear magnetic hydrogen spectrum, infrared, high resolution mass spectrum, and the like are the same as in example 6.
Example 9: catalytic reduction carbonylation reaction of Pd/CuMOF-8 composite material to synthesize diuron
To a cold 100mL stainless steel reactor was added 3, 4-dichloronitrobenzene (5 mmol), dimethylamine hydrochloride (10 mmol), pd/CuMOF-8 catalyst (30 mg) and THF (20 mL) in this order, and the mixture was sealed. Air was replaced 3 times with 1.0MPa CO, and the CO pressure in the reaction vessel was increased to 3.0MPa. Starting the stirring device of the reaction kettle, and heating the reaction kettle to 180 ℃ for reaction for 3 hours.
After the reaction, the reaction vessel was cooled to room temperature, and the residual gas was discharged. The reaction vessel was opened and placed in air and stirred for a further 1h. And then filtering to remove filter residues, removing the solvent under reduced pressure, and finally obtaining the target product diuron through column chromatography (the volume ratio of the leaching agent to the petroleum ether to the ethyl acetate is 6:1). Yield: 80.6%.
Melting point, nuclear magnetic hydrogen spectrum, infrared, high resolution mass spectrum, and the like are the same as in example 6.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (6)
1. The application of the Pd/CuMOF-x composite material catalyst in diuron synthesis is characterized in that: synthesizing diuron by a one-step method by taking 3, 4-dichloronitrobenzene, dimethylamine and carbon monoxide as raw materials and Pd/CuMOF-x composite material as a catalyst; the composite material catalyst is used for synthesizing diuron by reducing and carbonylating 3, 4-dichloronitrobenzene, and the chemical expression of CuMOF is { [ Cu (L) (H) 2 O)]} n Is Cu-containing with 4-pyridine methylene phosphonic acid as ligand 2+ Metal organic framework material of (2); l (L) 2- Represents 4-pyridine methylene phosphonate, pd is loaded on CuMOF, x represents mass percent of Pd in the composite material catalyst, and 0<x<10。
2. The use of the Pd/cumofx composite catalyst according to claim 1 in diuron synthesis, characterized in that: each asymmetric unit of the CuMOF contains 1 deprotonated organic ligand L 2- 1 copper ion and 1 coordinated water molecule, the molecular structure of which is as follows:
。
3. the use of the Pd/cumofx composite catalyst according to claim 1 in diuron synthesis, characterized in that: the mass percentage of Pd in the composite material is 4.12%, and the prepared composite material is Pd/CuMOF-4.
4. The use of the Pd/cumofx composite catalyst according to claim 1 in diuron synthesis, wherein the catalyst preparation steps are as follows:
(1) Dissolving copper nitrate and 4-pyridine methylene phosphonic acid in ultrapure water, uniformly mixing the copper nitrate and the 4-pyridine methylene phosphonic acid through ultrasonic, regulating the pH value of a solution system to 4.0, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting in an oven, naturally cooling, filtering, washing and drying to obtain a CuMOF material;
(2) Dissolving the CuMOF material and Pd (II) salt prepared in the step (1) in DMF, uniformly mixing the materials by ultrasonic treatment, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting in an oven, naturally cooling, filtering, washing and drying to obtain the Pd/CuMOF-x composite material.
5. The use of the Pd/cumofx composite catalyst according to claim 4 in diuron synthesis, wherein: the Pd (II) salt is selected from PdCl 2 、Pd(OAc) 2 、Pd(TFA) 2 One of the following。
6. The use of the Pd/cumofx composite catalyst according to claim 4 in diuron synthesis, wherein: in the step (2), the reaction temperature is 120-160 ℃ and the reaction time is 36-72 h.
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| 硒催化羰基化合成敌草隆、4-吡啶脲及苯并咪唑-2-基氨基甲酸酯;王岩;《中国优秀硕士学位论文数据库 工程科技Ⅰ辑》;第1-12页 * |
| 膦酸类金属-有机骨架材料对CO_2的吸附性能研究进展;牛照栋;关清卿;陈秋玲;宁平;谷俊杰;;化工进展(05);第233-241页 * |
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