CN112094180A - Method for catalytic oxidation of cycloalkane by bimetallic porphyrin MOFs PCN-224(Co & Zn) - Google Patents

Method for catalytic oxidation of cycloalkane by bimetallic porphyrin MOFs PCN-224(Co & Zn) Download PDF

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CN112094180A
CN112094180A CN202010894171.9A CN202010894171A CN112094180A CN 112094180 A CN112094180 A CN 112094180A CN 202010894171 A CN202010894171 A CN 202010894171A CN 112094180 A CN112094180 A CN 112094180A
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沈海民
郭阿兵
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Zhejiang University of Technology ZJUT
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    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Abstract

A method for catalytic oxidation of cycloalkanes with bimetallic porphyrin MOFs PCN-224(Co & Zn) disperses bimetallic porphyrin MOFs PCN-224(Co & Zn) in cycloalkanes, the mass of which is 1% -10% of the content of cycloalkanes; and sealing the reaction system, heating to 90-150 ℃ under stirring, introducing an oxidant, keeping the set temperature and pressure, stirring for reaction for 2.0-24.0 h, and performing aftertreatment on the reaction liquid to obtain the product naphthenic alcohol and naphthenic ketone. The method has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of the naphthenic hydroperoxide is low, and the safety coefficient is high. The invention provides a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon.

Description

Method for catalytic oxidation of cycloalkanes by bimetallic porphyrin MOFs PCN-224(Co & Zn)
Technical Field
The invention relates to a method for synthesizing cycloalkanol and cycloalkanone by catalytic oxidation of cycloalkane with bimetal porphyrin MOFs PCN-224(Co & Zn), belonging to the field of industrial catalysis and fine organic synthesis.
Background
Catalytic oxidation of cycloalkane is an important conversion process in chemical industry, and the oxidation products of cycloalkanol and cycloalkanone are not only important organic solvents, but also important intermediates in fine chemical industry, and are widely used in synthesis of fine chemical products such as pesticides, medicines, dyes, surfactants, resins, and the like, especially production of polyamide fiber nylon-6 and nylon-66. At present, the catalytic oxidation of cycloalkanes is industrially carried out mainly by homogeneous Co2+Or Mn2+As catalyst, oxygen (O)2) As an oxidizing agent, at 150 ℃ to 170 ℃, there are major problems of high reaction temperature, low substrate conversion, poor selectivity of the target product, and in particular, difficulty in inhibiting the formation of aliphatic diacids (Applied Catalysis a, General 2019,575: 120-131; catalysis Communications 2019,132: 105809). The main sources of the above problems are: (1) at present, O is industrially used2Oxidized cycloalkanes undergo mainly a disordered radical diffusion history; (2) the intermediate product of oxidation, the naphthenic base hydrogen peroxide, is converted to the target oxidation product of naphthenic alcohol and cycloalkanone by a free radical thermal decomposition path, thereby increasing the uncontrollable property of a reaction system and reducing the selectivity of the naphthenic alcohol and the naphthenic ketone. Thus, O is effectively controlled2The free radical diffusion in the process of catalytically oxidizing the cycloalkane and the catalytic conversion of the intermediate product of the oxidation, namely the cycloalkyl hydrogen peroxide, are beneficial to the improvement of the catalytic oxidation selectivity of the cycloalkane, and are a novel process improvement with great application significance in the field of catalytic oxidation of the cycloalkane in industry.
The metal-organic framework material PCN-224 is a series of porous materials with better Chemical stability and thermal stability, is applied to the field of organic catalysis, can realize the high-efficiency dispersion of catalytic active centers, can provide a certain micro-domain environment for Chemical reactions, can effectively limit the disordered diffusion of free radicals, and improves the reaction selectivity (Journal of the American Chemical Society 2013,135, 17105-17110; Journal of the American Chemical Society 2014,136, 16489-16492). In addition, the structural unit metalloporphyrin copper (II) in the bimetallic porphyrin MOFs PCN-224(Co & Zn) can promote the decomposition and conversion of naphthenic base hydrogen peroxide as an intermediate product of naphthenic hydrocarbon oxidation, limit the non-selective thermal decomposition and conversion of naphthenic base hydrogen peroxide and improve the selectivity of catalytic oxidation of naphthenic hydrocarbon (Catalysis Communications 2019,132: 105809).
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a metalloporphyrin MOFs PCN-224(Co)&Zn) catalytic oxidation of cycloalkane to synthesize cycloalkyl alcohol and cycloalkyl ketone, with bimetallic porphyrin MOFs PCN-224(Co)&Zn) porous material as catalyst, catalyzing O2The method for selectively synthesizing the naphthenic alcohol and the naphthenic ketone by oxidizing the naphthenic hydrocarbon has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, less by-products, small environmental influence and the like, and the method provided by the invention has low content of naphthenic hydroperoxide and high safety factor, and is an efficient, feasible and safe method for selectively catalytically oxidizing the naphthenic hydrocarbon to synthesize the naphthenic alcohol and the naphthenic ketone.
The technical scheme of the invention is as follows:
a method for synthesizing cycloalkanol and cycloalkanone by catalytic oxidation of cycloalkane with metalloporphyrin MOFs PCN-224(Co & Zn), said method comprises the following processes:
the double metalloporphyrin MOFs PCN-224(Co)&Zn) is dispersed in the cycloalkane, and the mass of the Zn) is 1 to 10 percent of the mass of the cycloalkane, g/mol; sealing the reaction system, and heating to 90-150 ℃ under stirring○C, introducing an oxidant, keeping the set temperature and pressure, stirring and reacting for 2.0-24.0 hours, and then carrying out post-treatment on the reaction liquid to obtain a product, namely the naphthenic alcohol and the naphthenic ketone;
the metalloporphyrin unit contained in the bimetallic porphyrin MOFs PCN-224(Co & Zn) is represented by a formula (I) and a formula (II):
Figure BDA0002657907900000021
r in the formulae (I) and (II)1、R2、R3、R4、R5Each independently is: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, nitro, cyano, carboxy, methoxycarbonyl, benzyl, fluoro, chloro, bromo, or iodo;
the quantity ratio of the substances of the structural unit metalloporphyrin formula (I) and the formula (II) in the bimetallic porphyrin MOFs PCN-224(Co & Zn) is 1: 2-2: 1 respectively, and the preferred quantity ratio of the substances of the structural unit metalloporphyrin formula (I) and the formula (II) is 1: 1;
the cycloalkane is one or a mixture of at least two of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane in any proportion;
furthermore, the mass of the metalloporphyrin MOFs PCN-224(Co & Zn) is 1% -10%, g/mol, preferably 4% -8%, g/mol of the mass of the substances of the cycloalkanes.
The reaction temperature is 90-150 DEG C○C, preferably 100 to 130○C; the reaction pressure is 0.10-2.0 MPa, preferably 0.60-1.20 MPa; the stirring speed is 600-1200 rpm, preferably 800-1000 rpm.
The oxidant is oxygen, air or a mixture of oxygen and air in any proportion.
The post-treatment method comprises the following steps: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution3The dosage of the catalyst is 3 percent of the amount of cyclane substances, and the catalyst is used at room temperature (20-30 percent)○C) Stirring for 40min to reduce the generated peroxide, distilling the crude product, vacuum rectifying and recrystallizing to obtain the oxidation product.
The method for analyzing the reaction result comprises the following steps: after the reaction is finished, peroxide generated by reduction of the reaction liquid by triphenylphosphine is sampled and analyzed. Diluting with acetone as solvent, performing gas chromatography with toluene as internal standard, and calculating conversion rate of cycloalkane and selectivity of cycloalkyl alcohol, cycloalkyl ketone and peroxide; performing liquid chromatography analysis by taking benzoic acid as an internal standard, and calculating the selectivity of the aliphatic diacid;
the invention uses bimetal porphyrin MOFs PCN-224(Co)&Zn) to construct a multi-metal center catalytic system for co-catalyzing O2The method for synthesizing the naphthenic alcohol and the naphthenic ketone by oxidizing the cycloalkane not only effectively inhibits the disordered diffusion of free radicals in the oxidation process, but also realizes the catalytic conversion of the oxidation intermediate product naphthenic hydrogen peroxide, greatly improves the selectivity of the target product naphthenic alcohol and naphthenic ketone, reduces the generation of byproducts, reduces the emission of environmental pollutants, and meets the practical requirements of the chemical industry on energy conservation and emission reduction at present. The invention not only provides a method for synthesizing naphthenic alcohol and naphthenic ketone by efficiently and selectively oxidizing naphthenic C-H bonds, but also has certain reference value for efficiently preparing alcohol and ketone compounds by selectively catalyzing and oxidizing other hydrocarbon C-H bonds.
The invention has the following beneficial effects: the method for synthesizing the naphthenic alcohol and the naphthenic ketone by catalyzing and oxidizing the cycloalkane with the metalloporphyrin MOFs PCN-224(Co & Zn) has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of the naphthenic hydroperoxide is low, and the safety coefficient is high. The invention provides a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon.
Detailed Description
The invention will be further illustrated with reference to specific examples, without limiting the scope of the invention thereto.
The metalloporphyrins MOFs PCN-224(Co & Zn) used in the present invention are referred to Journal of the American Chemical Society 2013,135, 17105-17110; journal of the American Chemical Society 2014,136, 16489-16492; journal of the American Chemical Society 2016,138, 3518-3525. All reagents used were commercially available analytical grade.
Examples 1 to 3 are syntheses of the metalloporphyrins MOFs PCN-224(Co & Zn).
Examples 4 to 40 are examples of catalytic oxidation of cycloalkanes.
Examples 41 to 46 are comparative experimental cases.
Examples 47 to 49 are enlarged experimental cases.
Example 1
PCN-224(Co&Synthesis of Zn) -1: in a 35mL pressure-resistant reaction tube, T (4-COOH) PPCo (II) (0.0282g,0.033mmol), T (4-COOH) PPZn (II) (0.0568g,0.067mmol), ZrCl4(0.2540g,1.090mmol), benzoic acid (3.3888g,27.50mmol) was dissolved in 17.0mL DMF and sonicated for 30min until all was dissolved. The mixture is put into an electric heating constant temperature air blast drying oven to be kept still for reaction for 48.0h at the temperature of 120 ℃. After the reaction is finished, the heating is closed, the reaction product is naturally cooled to room temperature, the crude product is filtered, washed by DMF and acetone sequentially and then transferred to a 10.0mL centrifuge tube, the centrifugation is carried out by a low-speed centrifuge for 5min (3000rpm), the upper layer liquid is poured out, dry DMF (3 × 8.0mL) is leached to clarify the upper layer liquid, dry acetone (3 × 8.0mL) is leached to clarify the upper layer liquid, the lower layer solid is taken down, and the drying is carried out for 8.0h at 90 ℃ to obtain brick red powder (0.08260g, 68.21% yield).
Example 2
PCN-224(Co&Synthesis of Zn) -2: in a 35mL pressure-resistant reaction tube, T (4-COOH) PPCo (II) (0.0424g,0.05mmol), T (4-COOH) PPZn (II) (0.0425g,0.05mmol), ZrCl4(0.2540g,1.09mmol), benzoic acid (3.3888g,27.50mmol) was dissolved in 17.0mL DMF and sonicated for 30min to dissolve all. The mixture is put into an electric heating constant temperature air blast drying oven to be kept still for reaction for 48.0h at the temperature of 120 ℃. After the reaction is finished, the heating is closed, the reaction product is naturally cooled to room temperature, the crude product is filtered, washed by DMF and acetone sequentially and then transferred to a 10.0mL centrifuge tube, the centrifugation is carried out by a low-speed centrifuge for 5min (3000rpm), the upper layer liquid is poured out, dry DMF (3 × 8.0mL) is leached to clarify the upper layer liquid, dry acetone (3 × 8.0mL) is leached to clarify the upper layer liquid, the lower layer solid is taken down, and the drying is carried out for 8.0h at 90 ℃ to obtain brick red powder (0.0835g,68.95 percent yield).
Example 3
PCN-224(Co&Synthesis of Zn) -3: in a 35mL pressure-resistant reaction tube, T (4-COOH) PPCo (II) (0.0565g,0.067mmol), T (4-COOH) PPZn (II) (0.0284g,0.033mmol), ZrCl were placed4(0.2540g,1.09mmol), benzoic acid (3.3888g,27.50mmol) was dissolved in 17.0mL DMF and sonicated for 30min to complete dissolution. The mixture is put into an electric heating constant temperature air blast drying oven to be kept still for reaction for 48.0h at the temperature of 120 ℃. And after the reaction is finished, closing heating, naturally cooling to room temperature, carrying out suction filtration on the crude product, sequentially carrying out suction filtration on the crude product by using DMF (dimethyl formamide) and acetone, transferring the crude product to a 10.0mL centrifuge tube, centrifuging the crude product by using a low-speed centrifuge for 5min (3000rpm), pouring out the upper liquid, drying DMF (3 × 8.0mL) for leaching until the upper liquid is clear, drying acetone (3 × 8.0mL) for leaching until the upper liquid is clear, taking the lower solid, and drying the lower solid at 90 ℃ for 8.0h to obtain brick red powder (0.0846g, yield of 69.86%).
Example 4
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(2mg,0.01mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel sealed, stirred and heated to 120 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 3.32%, the cyclohexanol selectivity was 41.2%, the cyclohexanone selectivity was 35.4%, the cyclohexyl hydroperoxide selectivity was 18.9%, the adipic acid selectivity was 4.5%, and the formation of glutaric acid was not detected.
Example 5
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 120 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. Moving and taking 1Performing gas chromatography analysis on 0mL of the obtained solution by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.58%, cyclohexanol selectivity 42.6%, cyclohexanone selectivity 35.3%, cyclohexyl hydroperoxide selectivity 18.8%, adipic acid selectivity 3.3%, and no formation of glutaric acid was detected.
Example 6
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(12mg,0.06mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel sealed, stirred and heated to 120 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.89%, cyclohexanol selectivity 44.5%, cyclohexanone selectivity 34.6%, cyclohexyl hydroperoxide selectivity 16.9%, adipic acid selectivity 4.0%, and no formation of glutaric acid was detected.
Example 7
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(16mg,0.08mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel sealed, stirred and heated to 120 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion rate of 3.58%, cyclohexanol selectivity of 41.6%, and cyclohexanone separationThe selectivity was 37.2%, the selectivity for cyclohexyl hydroperoxide was 18.1%, and the selectivity for adipic acid was 3.1%, and the formation of glutaric acid was not detected.
Example 8
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(20mg,0.10mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel sealed, stirred and heated to 120 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.51%, cyclohexanol selectivity 42.8%, cyclohexanone selectivity 36.7%, cyclohexyl hydroperoxide selectivity 17.3%, adipic acid selectivity 3.2%, and no formation of glutaric acid was detected.
Example 9
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 90 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 90 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.33%, cyclohexanol selectivity 11.9%, cyclohexanone selectivity 37.8%, cyclohexyl hydroperoxide selectivity 50.3%, no diacid formation was detected.
Example 10
Stainless steel with polytetrafluoroethylene liner at 100mLIn a steel high-pressure reaction kettle, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 100 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 100 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 2.22%, cyclohexanol selectivity 15.8%, cyclohexanone selectivity 37.9%, cyclohexyl hydroperoxide selectivity 46.3%, no diacid formation was detected.
Example 11
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 110 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 110 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 2.75%, cyclohexanol selectivity 21.6%, cyclohexanone selectivity 39.4%, cyclohexyl hydroperoxide selectivity 39.0%, no diacid formation was detected.
Example 12
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 115 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 115 ℃ under 1.0MPa of oxygen pressure. After the reaction is finished, cooling the mixture to room temperature by ice water1.3115g (5.00mmol) of triphenylphosphine (PPh) were added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.19%, cyclohexanol selectivity 22.4%, cyclohexanone selectivity 35.1%, cyclohexyl hydroperoxide selectivity 42.5%, no diacid formation was detected.
Example 13
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel sealed, stirred and heated to 125 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 125 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.62%, cyclohexanol selectivity 37.2%, cyclohexanone selectivity 46.5%, cyclohexyl hydroperoxide selectivity 10.4%, adipic acid selectivity 5.5%, glutaric acid selectivity 0.4%.
Example 14
In a 100mL stainless steel autoclave with a Teflon liner, MOF PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed and subjected to gas phase chromatography using toluene as an internal standardCarrying out chromatographic analysis; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.59%, cyclohexanol selectivity 32.5%, cyclohexanone selectivity 54.6%, cyclohexyl hydroperoxide selectivity 4.5%, adipic acid selectivity 7.3%, glutaric acid selectivity 1.1%.
Example 15
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 135 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 135 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.66%, cyclohexanol selectivity 28.7%, cyclohexanone selectivity 54.5%, cyclohexyl hydroperoxide selectivity 0.2%, adipic acid selectivity 12.4%, glutaric acid selectivity 4.2%.
Example 16
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 140 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 140 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion rate of 12.58%, cyclohexanol selectivity of 24.3%, cyclohexanone selectivity of 54.1%, cyclohexyl hydroperoxide selectivity of 0.1%, and adipic acid selection17.9 percent and the selectivity of glutaric acid is 3.6 percent.
Example 17
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 145 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 145 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 15.38%, cyclohexanol selectivity 21.3%, cyclohexanone selectivity 48.5%, cyclohexyl hydroperoxide selectivity 0.2%, adipic acid selectivity 26.3%, glutaric acid selectivity 3.7%.
Example 18
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 150 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 150 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 17.64%, the cyclohexanol selectivity is 17.9%, the cyclohexanone selectivity is 46.7%, the cyclohexyl hydroperoxide selectivity is 0.1%, the adipic acid selectivity is 29.7%, and the glutaric acid selectivity is 5.6%.
Example 19
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn)-1(8mg,0.04mg/mmol) of the total amount of the components, dispersing the components in 16.8320g (200mmol) of cyclohexane, sealing the reaction kettle, stirring and heating the mixture to 130 ℃, and introducing oxygen to the mixture until the pressure is 0.1 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 0.1MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. No significant product was detected.
Example 20
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 0.4 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 0.4MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.42%, cyclohexanol selectivity 37.4%, cyclohexanone selectivity 45.3%, cyclohexyl hydroperoxide selectivity 8.8%, adipic acid selectivity 6.2%, glutaric acid selectivity 2.3%.
Example 21
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 0.6 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 0.6MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. Using acetone as solvent, and reactingThe mixture was brought to 100 mL. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 6.54%, the cyclohexanol selectivity was 36.6%, the cyclohexanone selectivity was 53.7%, the cyclohexyl hydroperoxide selectivity was 2.1%, the adipic acid selectivity was 6.3%, and the glutaric acid selectivity was 1.3%.
Example 22
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 0.8 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 0.8MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.33%, cyclohexanol selectivity 34.3%, cyclohexanone selectivity 55.6%, cyclohexyl hydroperoxide selectivity 1.4%, adipic acid selectivity 7.7%, glutaric acid selectivity 1.0%.
Example 23
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.2 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.2MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.41%, cyclohexanol selectivity 34.8 percent, the selectivity of cyclohexanone is 55.9 percent, the selectivity of cyclohexyl hydroperoxide is 1.1 percent, the selectivity of adipic acid is 7.1 percent, and the selectivity of glutaric acid is 1.1 percent.
Example 24
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.6 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.6MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.38%, cyclohexanol selectivity 33.7%, cyclohexanone selectivity 54.8%, cyclohexyl hydroperoxide selectivity 1.5%, adipic acid selectivity 8.7%, glutaric acid selectivity 1.3%.
Example 25
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.8 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.8MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.29%, cyclohexanol selectivity 32.4%, cyclohexanone selectivity 57.3%, cyclohexyl hydroperoxide selectivity 1.5%, adipic acid selectivity 7.3%, glutaric acid selectivity 1.5%.
Example 26
Having poly-tetra at 100mLIn a stainless steel high-pressure reaction kettle with a vinyl fluoride inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 2.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 2.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.11%, cyclohexanol selectivity 33.5%, cyclohexanone selectivity 55.5%, cyclohexyl hydroperoxide selectivity 1.3%, adipic acid selectivity 8.4%, glutaric acid selectivity 1.3%.
Example 27
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 600rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 6.81%, the cyclohexanol selectivity was 35.9%, the cyclohexanone selectivity was 54.2%, the cyclohexyl hydroperoxide selectivity was 1.2%, the adipic acid selectivity was 6.9%, and the glutaric acid selectivity was 1.8%.
Example 28
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. At 130 ℃ and an oxygen pressure of 1.0MPaThe reaction was stirred at 1000rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.53%, cyclohexanol selectivity 34.8%, cyclohexanone selectivity 55.8%, cyclohexyl hydroperoxide selectivity 0.6%, adipic acid selectivity 7.1%, glutaric acid selectivity 1.7%.
Example 29
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 1200rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.38%, cyclohexanol selectivity 35.9%, cyclohexanone selectivity 54.2%, cyclohexyl hydroperoxide selectivity 0.8%, adipic acid selectivity 7.8%, glutaric acid selectivity 1.3%.
Example 30
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 2.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. Using acetone as solvent, and reactingThe mixture was brought to 100 mL. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.38%, cyclohexanol selectivity 46.8%, cyclohexanone selectivity 41.1%, cyclohexyl hydroperoxide selectivity 11.8%, adipic acid selectivity 0.3%, no detection of glutaric acid formation.
Example 31
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 6.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion rate 5.25%, cyclohexanol selectivity 43.8%, cyclohexanone selectivity 45.5%, cyclohexyl hydroperoxide selectivity 5.2%, adipic acid selectivity 5.5%, and glutaric acid production was not detected.
Example 32
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 12.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.35%, cyclohexanol selectionThe selectivity of the catalyst is 33.8 percent, the selectivity of cyclohexanone is 46.8 percent, the selectivity of cyclohexyl hydroperoxide is 1.4 percent, the selectivity of adipic acid is 12.8 percent, and the selectivity of glutaric acid is 5.2 percent.
Example 33
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 16.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 10.49%, cyclohexanol selectivity 29.2%, cyclohexanone selectivity 46.8%, cyclohexyl hydroperoxide selectivity 0.9%, adipic acid selectivity 18.5%, glutaric acid selectivity 4.6%.
Example 34
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 24.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 13.77%, the cyclohexanol selectivity was 18.3%, the cyclohexanone selectivity was 45.6%, the cyclohexyl hydroperoxide selectivity was 0.3%, the adipic acid selectivity was 28.7%, and the glutaric acid selectivity was 7.1%.
Example 35
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -2(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.65%, cyclohexanol selectivity 36.5%, cyclohexanone selectivity 55.3%, cyclohexyl hydroperoxide selectivity 1.2%, adipic acid selectivity 6.1%, glutaric acid selectivity 0.9%.
Example 36
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -3(8mg,0.04mg/mmol), dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.43%, cyclohexanol selectivity 35.5%, cyclohexanone selectivity 54.7%, cyclohexyl hydroperoxide selectivity 0.7%, adipic acid selectivity 8.6%, glutaric acid selectivity 0.5%.
Example 37
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 14.0280g (200mmol) of cyclopentane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. At 13Stirring and reacting at 0 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cyclopentane was 4.16%, the selectivity for cyclopentanol was 15.8%, the selectivity for cyclopentanone was 73.3%, the selectivity for cyclopentyl hydroperoxide was 8.2%, the selectivity for glutaric acid was 2.3%, and the selectivity for succinic acid was 0.4%.
Example 38
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 19.6540g (200mmol) of cycloheptane, the reaction vessel was sealed, stirred and heated to 120 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cycloheptane is 10.8%, the selectivity of cycloheptanol is 16.9%, the selectivity of cycloheptanone is 61.8%, the selectivity of cycloheptyl hydroperoxide is 11.7%, the selectivity of pimelic acid is 8.7%, and the selectivity of adipic acid is 0.9%.
Example 39
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 22.4400g (200mmol) cyclooctane, sealing the reaction kettle, stirring, heating to 120 deg.C, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. With 3CKetone as solvent, and the reaction mixture was made to 100 mL. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. 28.3 percent of cyclooctane conversion rate, 30.1 percent of cyclooctanol selectivity, 53.6 percent of cyclooctanone selectivity, 8.5 percent of cyclooctyl hydrogen peroxide selectivity, 6.7 percent of suberic acid selectivity and 1.1 percent of pimelic acid selectivity.
Example 40
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(8mg,0.04mg/mmol), dispersed in 19.6540g (200mmol) of cyclododecane, the reaction vessel was sealed, stirred and heated to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion of cyclododecane was 32.3%, the selectivity for cyclododecanol was 31.2%, the selectivity for cyclododecanone was 56.5%, and the selectivity for cyclododecyl hydroperoxide was 12.3%, and no formation of aliphatic diacid was detected.
Example 41 (comparative experiment)
In a 100mL stainless steel autoclave with a teflon liner, cobalt acetate (1mg,2.8 x 10)- 5mol/mol) of the components, dispersing the components in 16.8320g (200mmol) of cyclohexane, sealing the reaction kettle, stirring and heating the reaction kettle to 130 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and subjected to liquid chromatography using benzoic acid as an internal standardAnd (6) analyzing. The cyclohexane conversion rate is 6.18%, the cyclohexanol selectivity is 31.3%, the cyclohexanone selectivity is 43.4%, the cyclohexyl hydroperoxide selectivity is 1.2%, the adipic acid selectivity is 17.2%, and the glutaric acid selectivity is 6.9%.
Example 42 (comparative experiment)
In a 100mL stainless steel autoclave with a teflon liner, zinc acetate (1mg,2.8 x 10)- 5mol/mol) of the components, dispersing the components in 16.8320g (200mmol) of cyclohexane, sealing the reaction kettle, stirring and heating the reaction kettle to 130 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.08%, cyclohexanol selectivity 38.2%, cyclohexanone selectivity 28.1%, cyclohexyl hydroperoxide selectivity 30.1%, adipic acid selectivity 3.1%, glutaric acid selectivity 0.5%.
Example 43 (comparative experiment)
T (4-COOH) PPCo (II) (2mg,1.2 x 10) was placed in a 100mL stainless steel autoclave with a Teflon liner-5mol/mol) of the components, dispersing the components in 16.8320g (200mmol) of cyclohexane, sealing the reaction kettle, stirring and heating the reaction kettle to 130 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.21%, the cyclohexanol selectivity is 32.3%, the cyclohexanone selectivity is 45.4%, the cyclohexyl hydroperoxide selectivity is 0.6%, the adipic acid selectivity is 15.4%, and the glutaric acid selectivity is 6.3%.
Example 44 (comparative experiment)
T (4-COOH) PPZn (II) (2mg,1.2 x 10) was placed in a 100mL stainless steel autoclave with a Teflon liner-5mol/mol) of the components, dispersing the components in 16.8320g (200mmol) of cyclohexane, sealing the reaction kettle, stirring and heating the reaction kettle to 130 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.11%, cyclohexanol selectivity 0.3%, cyclohexanone selectivity 16.5%, cyclohexyl hydroperoxide selectivity 82.2%, no diacid formation was detected.
Example 45 (comparative experiment)
In a 100mL stainless steel autoclave with a Teflon liner, the MOFs PCN-224(Co) (8mg,0.04mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the autoclave was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.87%, the cyclohexanol selectivity is 34.3%, the cyclohexanone selectivity is 47.4%, the cyclohexyl hydroperoxide selectivity is 1.0%, the adipic acid selectivity is 12.6%, and the glutaric acid selectivity is 4.7%.
Example 46 (comparative experiment)
The MOFs PCN-224(Zn) (8mg,0.04mg/mmol) was dispersed in 16.8320g (200 m) in a 100mL stainless steel autoclave with a Teflon linermol) in cyclohexane, sealing the reaction kettle, stirring and heating to 130 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.22%, cyclohexanol selectivity 18.3%, cyclohexanone selectivity 23.5%, cyclohexyl hydroperoxide selectivity 58.2%, no diacid formation was detected.
Example 47 (amplification experiment)
In a 1000mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -1(80mg,0.04mg/mmol), dispersed in 168.3200g (2000mmol) cyclohexane, the reaction vessel sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 13.115g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The reaction mixture was made to 1000mL using acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.40%, cyclohexanol selectivity 35.4%, cyclohexanone selectivity 54.8%, cyclohexyl hydroperoxide selectivity 1.0%, adipic acid selectivity 8.1%, glutaric acid selectivity 0.7%.
Example 48 (amplification experiment)
In a 1000mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -2(80mg,0.04mg/mmol), dispersed in 168.3200g (2000mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 13 was added to the reaction mixture.115g (50.00mmol) of triphenylphosphine (PPh)3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The reaction mixture was made to 1000mL using acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.49%, cyclohexanol selectivity 34.1%, cyclohexanone selectivity 55.2%, cyclohexyl hydroperoxide selectivity 0.9%, adipic acid selectivity 9.6%, glutaric acid selectivity 0.2%.
Example 49 (amplification experiment)
In a 1000mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, MOFs PCN-224(Co)&Zn) -3(80mg,0.04mg/mmol), dispersed in 168.3200g (2000mmol) cyclohexane, the reaction vessel was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 13.115g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The reaction mixture was made to 1000mL using acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.44%, cyclohexanol selectivity 36.3%, cyclohexanone selectivity 53.8%, cyclohexyl hydroperoxide selectivity 0.8%, adipic acid selectivity 8.1%, glutaric acid selectivity 1%.

Claims (7)

1. A method for catalytic oxidation of cycloalkanes with the bimetallic porphyrin MOFs PCN-224(Co & Zn), characterized in that it comprises the following steps:
dispersing bimetal porphyrin MOFs PCN-224(Co & Zn) in cycloalkane, wherein the mass of the bimetal porphyrin is 1% -10% of the mass of the cycloalkane, and the mass of the bimetal porphyrin is g/mol; sealing the reaction system, heating to 90-150 ℃ under stirring, introducing an oxidant, keeping the set temperature and pressure, stirring for reaction for 2.0-24.0 h, and performing aftertreatment on the reaction solution to obtain a product, namely cycloalkyl alcohol and cycloalkyl ketone;
the metalloporphyrin unit contained in the bimetallic porphyrin MOFs PCN-224(Co & Zn) is represented by a formula (I) and a formula (II):
Figure FDA0002657907890000011
r in the formulae (I) and (II)1、R2、R3、R4、R5Each independently is: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, nitro, cyano, carboxy, methoxycarbonyl, benzyl, fluoro, chloro, bromo, or iodo;
the quantity ratio of the metalloporphyrin in the structural unit of the bimetallic porphyrin MOFs PCN-224(Co & Zn) to the metalloporphyrin in the formula (I) and the formula (II) is 1: 2-2: 1 respectively.
The cycloalkane is one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane or a mixture of at least two of the above materials in any proportion.
2. The method for catalytic oxidation of cycloalkanes with the bimetallic porphyrin MOFs PCN-224(Co & Zn) as claimed in claim 1, wherein the ratio of the amounts of the metalloporphyrin represented by formula (I) and the metalloporphyrin represented by formula (II) as the structural units in the bimetallic porphyrin MOFs PCN-224(Co & Zn) is 1:2 to 2: 1.
3. The process for the catalytic oxidation of cycloalkanes with the bimetallic porphyrin MOFs PCN-224(Co & Zn) according to claim 1 or 2, wherein the mass of said bimetallic porphyrin MOFs PCN-224(Co & Zn) is 1% to 10% g/mol of the mass of cycloalkanes.
4. The method for catalytic oxidation of cycloalkanes with the bimetallic porphyrin MOFs PCN-224(Co & Zn) according to claim 1 or 2, wherein the reaction pressure is 0.10-2.0 MPa.
5. The method for catalytic oxidation of cycloalkanes with the bimetallic porphyrin MOFs PCN-224(Co & Zn) according to claim 1 or 2, wherein the stirring speed is 600-1200 rpm.
6. The process for catalytic oxidation of cycloalkanes with the bimetallic porphyrin MOFs PCN-224(Co & Zn) according to claims 1 or 2, wherein said oxidant is oxygen, air or a mixture thereof in any proportion.
7. The bimetallic porphyrin of claim 1 or 2, MOFs PCN-224(Co)&Zn) catalytic oxidation of cycloalkanes, characterized in that the post-treatment process is: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution3And the using amount of the peroxide is 3 percent of the amount of the cycloparaffin substance, the peroxide generated by reduction is stirred for 40min at room temperature (20-30 ℃), and the crude product is distilled, rectified under reduced pressure and recrystallized to obtain an oxidation product.
CN202010894171.9A 2020-08-31 2020-08-31 Method for catalytic oxidation of cycloalkane by bimetallic porphyrin MOFs PCN-224(Co & Zn) Pending CN112094180A (en)

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