阅读说明：本技术 一种三金属中心(Co&Cu&Zn)2D MOFs/紫外光催化氧化环烷烃的方法 (Method for catalytically oxidizing cycloalkane by using trimetal center (Co & Cu & Zn)2D MOFs/ultraviolet light ) 是由 沈海民 黄浩 于 2021-08-30 设计创作，主要内容包括：本发明涉及一种三金属中心(Co&Cu&Zn)2D MOFs/紫外光催化氧化环烷烃合成环烷醇和环烷酮的方法,属于工业催化和精细有机合成领域。所属应用方法是将金属卟啉三金属中心(Co&Cu&Zn)2D MOFs分散于环烷烃中,其中,金属卟啉三金属中心(Co&Cu&Zn)2D MOFs的质量为环烷烃的物质的量的0.01％～20％,g/mol,密封反应体系。通入氧化剂,紫外灯为光源,搅拌反应2.0～24.0h。反应液经后处理,得到产物环烷基醇和环烷基酮。本发明所述方法,反应温度低,反应条件温和,反应效率高,环烷基醇和环烷基酮选择性高,副产物少,环境影响小。本发明提供了一种高效、可行、安全的环烷烃选择性催化氧化合成环烷基醇和环烷基酮的方法。(The invention relates to a method for synthesizing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane with a trimetal center (Co & Cu & Zn)2D MOFs/ultraviolet light, and belongs to the field of industrial catalysis and fine organic synthesis. The application method is to disperse metalloporphyrin trimetal center (Co & Cu & Zn)2D MOFs in cycloalkane, wherein the mass of the metalloporphyrin trimetal center (Co & Cu & Zn)2D MOFs is 0.01-20% of the content of the cycloalkane, g/mol, and the reaction system is sealed. And (3) introducing an oxidant, taking an ultraviolet lamp as a light source, and stirring for reacting for 2.0-24.0 hours. And carrying out post-treatment on the reaction liquid to obtain the product naphthenic alcohol and naphthenic ketone. The method has the advantages of low reaction temperature, mild reaction conditions, high reaction efficiency, high selectivity of the naphthenic alcohol and the naphthenic ketone, few byproducts and small environmental influence. The invention provides a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon.)

1. A method for catalytically oxidizing cycloalkane by using 2D MOFs (metal organic frameworks)/ultraviolet light with a trimetal center is characterized in that the metal of the trimetal center is Co, Cu and Zn, the method comprises the steps of dispersing the 2D MOFs with the trimetal center in cycloalkane, sealing a reaction system, introducing an oxidant, stirring and reacting under a light source, and then carrying out post-treatment on reaction liquid to obtain a product, namely cycloalkyl alcohol and cycloalkyl ketone;

the structure of the 2D MOFs with the trimetal center is shown as a formula (I), wherein a metal node M₁Is Co (II) or Cu (II) or Zn (II), a metal node M₂Is Co (II) or Cu (II) or Zn (II), a metal node M₃Is Co (II) or Cu (II) or Zn (II), and M₁≠M₂≠M₃：

2. The method for the catalytic oxidation of cycloalkanes with trimetal-centered 2D MOFs/UV light according to claim 1, wherein the metalloporphyrin structural unit in the trimetal-centered 2D MOFs shown in formula (I) is shown in formula (II):

r in the formula (II)₁、R₂、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;

R₃comprises the following steps: a carboxyl group; m is Co (II) or Cu (II) or Zn (II).

3. The method for the catalytic oxidation of cycloalkanes with trimetal-centered 2D MOFs/ultraviolet light according to claim 1, wherein the ratio of the mass of trimetal-centered 2D MOFs to the mass of cycloalkanes is 1: 1000 to 1: 5.

4. The method of claim 3, wherein the ratio of the mass of the trimetallic-centered 2D MOFs to the mass of the cycloalkanes is 1: 100-2: 25.

5. The method for the trimetallic-centered 2D MOFs/uv catalyzed oxidation of cycloalkanes of claim 1, wherein the light source is an ultraviolet lamp.

6. The method for the catalytic oxidation of cycloalkanes with trimetal-centered 2D MOFs/ultraviolet light according to claim 5, wherein the light source is a 50-500W ultraviolet lamp.

7. The method for the catalytic oxidation of cycloalkanes with trimetal-centered 2D MOFs/ultraviolet light according to claim 1, wherein the reaction time is 2-24 h.

8. The method for the 2D MOFs/ultraviolet light catalytic oxidation of cycloalkanes with trimetallic centers according to claim 1, wherein the stirring speed is 50-1200 rpm.

9. The method for the trimetallic-centered 2D MOFs/UV catalyzed oxidation of cycloalkanes according to claim 1, wherein said oxidant is oxygen, air or a mixture of both at any ratio.

10. The method for the trimetallic-centered 2D MOFs/ultraviolet light catalyzed oxidation of cycloalkanes according to claim 1, wherein said cycloalkanes are one or a mixture of two or more of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane in any ratio.

Technical Field

The invention relates to a method for synthesizing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane with a trimetal center (Co & Cu & Zn)2D MOFs/ultraviolet light, and belongs 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, inThe main problems of the process are high reaction temperature, severe reaction conditions, poor selectivity of the target product, and increased conversion of the reaction, which results in the consumption of the partially oxidized product (Applied Catalysis A, General 2019,575: 120-131; Catalysis Communications 2019,132: 105809; Applied Catalysis A, General 2021,609: 117904). 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 is oxidized, and the naphthenic base hydrogen peroxide is converted to the target oxidation product of the naphthenic alcohol and the cycloalkanone through a free radical thermal decomposition path, so that the uncontrollable property of a reaction system is increased, and the selectivity of the naphthenic alcohol and the naphthenic ketone is reduced; (3) oxidizing the intermediate product, wherein the oxidizing property of the naphthenic base hydrogen peroxide is not fully utilized; (4) cycloalkanol and cycloalkanone are more active than the substrate cycloalkane. Thus, O is effectively controlled₂The disordered diffusion of free radicals in the process of catalytically oxidizing cycloalkane, the catalytic conversion and oxidation of intermediate product cycloalkyl peroxide and the oxidation of new cycloalkane by using the oxidation of the intermediate product cycloalkyl peroxide are beneficial to the improvement of the catalytic oxidation selectivity of cycloalkane and the improvement of the oxidation efficiency, and the method is a novel process improvement with great application significance in the field of catalytic oxidation of cycloalkane in industry.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a metalloporphyrin trimetal center (Co)&Cu&Zn)2D MOFs/ultraviolet light catalytic oxygen oxidation cycloalkane selective synthesis method of cycloalkyl alcohol and cycloalkyl ketone. Metal-Organic Frameworks (MOFs for short) are a series of porous materials with good Chemical stability and thermal stability, and are applied in the field of Organic catalysis, which not only can realize the efficient dispersion of catalytic active centers, but also can provide a certain micro-domain environment for Chemical reactions, effectively prevent the disordered diffusion of free radicals, and improve the reaction selectivity (Journal of the American Chemical Society 2017,139: 18590-. In addition, Co is used as a metal node to activate molecular oxygen; the introduction of the second metal Zn (II) into the MOF material is beneficial to regulating and controlling the catalytic conversion of the oxidation intermediate product naphthenic base peroxide in the catalytic oxidation process of the cycloalkane, promoting the conversion of the naphthenic base peroxide to the cycloalkanol cycloalkanone, preventing the disordered decomposition of the naphthenic base peroxide and improving the selectivity of the reaction. The third metal Cu (II) is introduced into the MOF material, so that the oxidation of the naphthenic base peroxide can be fully utilized, a new substrate is oxidized, the oxidation efficiency is improved, and the selectivity of the naphthenic alcohol and the cycloalkanone and the conversion rate of the substrate are improved at the same time. The photocatalytic reaction is generally regarded by people due to low reaction temperature, high selectivity and mild reaction conditions. Therefore, the invention uses metalloporphyrin as a trimetallic center (Co)&Cu&Zn)2D MOF material as catalyst, ultraviolet light catalyzing O₂Oxidizing cycloalkane to selectively synthesize cycloalkyl alcohol and cycloalkyl ketone, taking ultraviolet light as a reaction driving force, and providing a limited-domain environment by using a porous structure of an MOF material to inhibit disordered diffusion of free radicals; the conversion of the oxidation intermediate product naphthenic base peroxide is regulated and controlled by the trimetal center, and the oxidability of the oxidation intermediate product naphthenic base peroxide is enhanced, so that the efficient and high-selectivity catalytic oxidation of the naphthenic hydrocarbon is realized, and the substrate conversion rate and the selectivity of the naphthenic alcohol and the cycloalkanone are simultaneously improved. The catalytic oxidation method of cycloalkane provided by the invention has the advantages of cycloalkyl alcohol and cycloalkyl ketoneThe method has the advantages of high selectivity, low reaction temperature, mild reaction conditions, few oxidation byproducts, small environmental influence and the like, and is an efficient, feasible and safe method for synthesizing the naphthenic alcohol and the naphthenic ketone by selective catalytic oxidation of the naphthenic hydrocarbon.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a method for catalyzing and oxidizing cycloalkane by using a trimetal-centered 2D MOFs/ultraviolet light, wherein the trimetal-centered metal is Co, Cu and Zn, and the method comprises the following steps:

dispersing 2D MOFs (Co & Cu & Zn) of trimetal centers in cycloalkanes, sealing a reaction system, introducing an oxidant, stirring and reacting under a light source, and then carrying out post-treatment on reaction liquid to obtain a product, namely cycloalkyl alcohol and cycloalkyl ketone;

wherein the trimetallic center (Co)&Cu&Zn) the structure of the 2D MOFs is shown as a formula (I); in the formula (I), the black solid circle ● is a metal node M₁Is Co (II), Cu (II) or Zn (II), and gray solid circle ● is metal node M₂Is Co (II), Cu (II) or Zn (II), and the hollow circle O is a metal node M₃Is Co (II) or Cu (II) or Zn (II), and M₁≠M₂≠M₃I.e. M₁+M₂+M₃Co (ii) + cu (ii) + zn (ii); a trimetallic center (Co) of formula (I)&Cu&The structural unit of metalloporphyrin in Zn)2D MOFs is shown as the formula (II):

r in the formula (II)₁、R₂、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;

R₃comprises the following steps: a carboxyl group; m is Co (II) or Cu (II) or Zn (II).

Preferably, the cycloalkane is at least one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane or a mixture of two or more of them in any proportion.

Preferably, the ratio of the mass (g) of the trimetal center (Co & Cu & Zn)2D MOFs to the mass (mol) of the naphthenic hydrocarbon substances is 1: 1000-1: 5, namely the mass of the trimetal center (Co & Cu & Zn)2D MOFs is 0.1-20% g/mol of the amount of the naphthenic hydrocarbon substances; more preferably 1: 100 to 2: 25.

Preferably, the light source is an ultraviolet lamp, and more preferably, the light source is a 50-500W ultraviolet lamp.

Preferably, the oxidant is oxygen, air or a mixture thereof in any proportion.

Preferably, the stirring speed is 50-1200 rpm, and more preferably 800-1000 rpm.

Preferably, the reaction time is 2.0-24.0 h.

Preferably, the reaction is carried out at room temperature, which is 15-40 ℃.

Preferably, the post-treatment method comprises the following steps: after the reaction, triphenylphosphine (PPh) was added to the reaction solution₃The amount of the catalyst is 3% of the amount of the cycloparaffin material), and the catalyst is used at room temperature (15-40%)^○C) Stirring for 30min to reduce the generated peroxide to obtain the product naphthenic alcohol and naphthenic ketone; more preferably, the method also comprises the step of distilling, decompressing, rectifying and recrystallizing the crude product to obtain the purified oxidation product of the naphthenic alcohol and the naphthenic ketone.

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. Acetone is used as a solvent for dilution, toluene is used as an internal standard, gas chromatography analysis is carried out, and the conversion rate of the naphthenic hydrocarbon and the selectivity of naphthenic alcohol, naphthenic ketone and peroxide are calculated.

The invention uses metalloporphyrin as a trimetal center (Co)&Cu&Zn)2D MOFs to construct a three-metal center catalytic system, and ultraviolet light is used for catalyzing O₂Oxidizing cycloalkane to synthesize cycloalkyl alcohol and cycloalkyl ketone. The catalytic oxidation method of cycloalkane has mild reaction conditions and alcohol ketoneThe selectivity is high. The method not only effectively inhibits the disordered diffusion of free radicals in the oxidation process, but also fully utilizes the oxidability of the naphthenic base hydrogen peroxide of the oxidation intermediate product, obviously improves the selectivity of the target product naphthenic base alcohol and naphthenic base ketone and the conversion rate of a substrate, 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 provides a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon. Selective catalytic oxidation of other hydrocarbon C-H bonds, high-efficiency preparation of alcohols and ketones compounds also has certain reference value.

The invention has the following beneficial effects: the method for synthesizing the naphthenic alcohol and the naphthenic ketone by catalyzing and oxidizing the naphthenic hydrocarbon with the metalloporphyrin trimetal center (Co & Cu & Zn)2D MOFs/ultraviolet light has the advantages of mild reaction conditions, high oxidation efficiency, high selectivity of the naphthenic alcohol and the naphthenic ketone, 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.

Examples 1 to 7 are syntheses of metalloporphyrin trimetallic centres (Co & Cu & Zn)2D MOFs.

Examples 8 to 28 are examples of catalytic oxidation of cycloalkanes.

Examples 29 to 35 are comparative experimental cases.

Example 36 is a magnified experimental case.

Example 1

Synthesis of metalloporphyrin trimetal center (Co & Cu & Zn)2D MOFs-1: 0.2910g (1.00mmol) of cobalt nitrate hexahydrate, 0.0426g (0.050mmol) of 5,10,15, 20-tetra (4-carboxyphenyl) copper porphyrin (CuTCPP), and 0.0427g (0.050mmol) of 5,10,15, 20-tetra (4-carboxyphenyl) zinc porphyrin (ZnTCPP) are placed in a 50mL agate ball milling tank and subjected to ball milling reaction at room temperature and 600rpm for 8.0 h. Stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After the reaction is finished, the obtained powder is transferred to a 10mL centrifuge tube, soaked and washed by anhydrous DMF (6X 5mL) until supernatant liquid is clear, soaked and washed by acetone (6X 5mL) until the supernatant liquid is clear, dried for 5.0h at 40 ℃, and dried for 12.0h in vacuum at 70 ℃ to obtain 0.0662g of a target product (Co & Cu & Zn)2D MOFs-1.

Example 2

Synthesis of metalloporphyrin trimetal center (Zn & Cu & Co)2D MOFs-2: 0.2911g (1.00mmol) of zinc nitrate hexahydrate; 0.0426g (0.050mmol) of copper 5,10,15, 20-tetrakis (4-carboxyphenyl) porphyrin (CuTCPP); 0.0427g (0.050mmol) of 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin cobalt (CoTCPP) was placed in a 50ml agate jar and reacted at room temperature and 600rpm in a ball mill for 8.0 h. Stopping ball milling once every 1.0h, and discharging gas in the ball milling tank; after the reaction is finished, transferring the powder into a 10mL centrifuge tube, soaking and washing the powder with anhydrous DMF (6X 5mL) until supernatant is clear, soaking and washing the powder with anhydrous acetone (6X 5mL) until the supernatant is clear, drying the powder at 40 ℃ for 5.0h, and drying the powder at 70 ℃ in vacuum for 12.0h to obtain 0.0584g of a target product (Zn & Cu & Co)2D MOFs-2.

Example 3

Synthesis of metalloporphyrin trimetal center (Cu & Co & Zn)2D MOFs-3: 0.2908g (1.00mmol) of copper nitrate hexahydrate; 0.0426g (0.050mmol) of zinc 5,10,15, 20-tetrakis (4-carboxyphenyl) porphyrin (ZnTCPP); 0.0427g (0.050mmol) of 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin cobalt (CoTCPP) was placed in a 50ml agate jar and reacted at room temperature and 600rpm in a ball mill for 8.0 h. Stopping ball milling once every 1.0h, and discharging gas in the ball milling tank; after the reaction is finished, transferring the powder into a 10mL centrifuge tube, soaking and washing the powder with anhydrous DMF (6X 5mL) until supernatant is clear, soaking and washing the powder with anhydrous acetone (6X 5mL) until the supernatant is clear, drying the powder at 40 ℃ for 5.0h, and drying the powder at 70 ℃ in vacuum for 12.0h to obtain 0.0653g of a target product (Cu & Co & Zn)2D MOFs-3.

Example 4

Synthesis of metalloporphyrin trimetal center (Co & Cu & Zn)2D MOFs-4: 0.2910g (1.00mmol) of cobalt nitrate hexahydrate, 0.0506g (0.050mmol) of 5,10,15, 20-tetra (2-bromo, 4-carboxyphenyl) copper porphyrin (CuTCPP), and 0.0507g (0.050mmol) of 5,10,15, 20-tetra (2-bromo, 4-carboxyphenyl) zinc porphyrin (ZnTCPP) are placed in a 50mL agate ball milling tank and subjected to ball milling reaction at room temperature and 600rpm for 8.0 h. Stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After the reaction is finished, transferring the obtained powder into a 10mL centrifuge tube, soaking and washing the powder with anhydrous DMF (6X 5mL) until supernatant is clear, soaking and washing the powder with acetone (6X 5mL) until the supernatant is clear, drying the powder at 40 ℃ for 5.0h, and drying the powder at 70 ℃ in vacuum for 12.0h to obtain 0.0640g of a target product (Co & Cu & Zn)2D MOFs-4.

Example 5

Synthesis of metalloporphyrin trimetal center (Co & Cu & Zn)2D MOFs-5: 0.2910g (1.00mmol) of cobalt nitrate hexahydrate, 0.0515g (0.050mmol) of 5,10,15, 20-tetra (2-nitro, 4-carboxyphenyl) copper porphyrin (CuTCPP), and 0.0517g (0.050mmol) of 5,10,15, 20-tetra (2-nitro, 4-carboxyphenyl) zinc porphyrin (ZnTCPP) are placed in a 50mL agate ball milling tank and subjected to ball milling reaction at room temperature and 600rpm for 8.0 h. Stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After the reaction is finished, the obtained powder is transferred to a 10mL centrifuge tube, soaked and washed by anhydrous DMF (6X 5mL) until supernatant liquid is clear, soaked and washed by acetone (6X 5mL) until the supernatant liquid is clear, dried for 5.0h at 40 ℃, and dried for 12.0h in vacuum at 70 ℃ to obtain 0.0588g of a target product (Co & Cu & Zn)2D MOFs-5.

Example 6

Synthesis of metalloporphyrin trimetal center (Co & Cu & Zn)2D MOFs-6: 0.2910g (1.00mmol) of cobalt nitrate hexahydrate, 0.0433g (0.050mmol) of copper 5,10,15, 20-tetrakis (2-methyl, 4-carboxyphenyl) porphyrin (CuTCPP), and 0.0434g (0.050mmol) of zinc 5,10,15, 20-tetrakis (2-methyl, 4-carboxyphenyl) porphyrin (ZnTCPP) are placed in a 50mL agate ball milling tank and subjected to ball milling reaction at room temperature and 600rpm for 8.0 h. Stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After the reaction is finished, the obtained powder is transferred to a 10mL centrifuge tube, soaked and washed by anhydrous DMF (6X 5mL) until supernatant liquid is clear, soaked and washed by acetone (6X 5mL) until the supernatant liquid is clear, dried for 5.0h at 40 ℃, and dried for 12.0h in vacuum at 70 ℃ to obtain 0.0731g of a target product (Co & Cu & Zn)2D MOFs-6.

Example 7

Synthesis of metalloporphyrin trimetal center (Co & Cu & Zn)2D MOFs-7: 0.2910g (1.00mmol) of cobalt nitrate hexahydrate, 0.0441g (0.050mmol) of 5,10,15, 20-tetra (2-methoxy, 4-carboxyphenyl) porphyrin copper (CuTCPP), 5,10,15, 20-tetra ((2-methoxy-4-carboxyphenyl) porphyrin zinc (ZnTCPP), 0.0442g (0.050mmol) are placed in a 50mL agate ball milling tank, the ball milling is stopped at room temperature and 600rpm for 8.0h after ball milling reaction, the ball milling is stopped every 1.0h, the gas in the ball milling tank is discharged after the reaction is finished, the obtained powder is transferred to a 10mL centrifuge tube, anhydrous DMF is soaked and washed (6X 5mL) until the supernatant is clear, acetone is soaked and washed (6X 5mL) until the supernatant is clear, the powder is dried at 40 ℃ for 5.0h, and is dried at 70 ℃ for 12.0h in vacuum, so that 0.0735g of target product (Co & Cu & Zn)2D MOFs-7 are obtained.

Example 8

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 4.01%, cyclohexanol selectivity 65.4%, cyclohexanone selectivity 30.0%, cyclohexyl hydroperoxide selectivity 4.6%, no other products were detected.

Example 9

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(4.0mg,0.04mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 3.51%, cyclohexanol selectivity 72.3%, cyclohexanone selectivity 20.6%, cyclohexyl hydroperoxide selectivity 7.1%, no other products detected。

Example 10

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(12.0mg,0.12mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 3.81%, cyclohexanol selectivity 70.2%, cyclohexanone selectivity 20.6%, cyclohexyl hydroperoxide selectivity 9.2%, no other products were detected.

Example 11

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(20.0mg,0.20mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 3.26%, cyclohexanol selectivity 64.4%, cyclohexanone selectivity 27.0%, cyclohexyl hydroperoxide selectivity 8.6%, no other products were detected.

Example 12

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The mixture is stirred and reacted for 4.0h at 800rpm under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 toluene was used as an internal standardAnd gas chromatography was performed. Cyclohexane conversion 2.86%, cyclohexanol selectivity 61.4%, cyclohexanone selectivity 28.8%, cyclohexyl hydroperoxide selectivity 9.8%, no other products were detected.

Example 13

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. Stirring and reacting for 6.0h at 800rpm under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 3.75%, cyclohexanol selectivity 58.6%, cyclohexanone selectivity 32.9%, cyclohexyl hydroperoxide selectivity 8.5%, no other products were detected.

Example 14

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. Stirring and reacting for 10.0h at 800rpm under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 4.31%, cyclohexanol selectivity 48.4%, cyclohexanone selectivity 32.0%, cyclohexyl hydroperoxide selectivity 14.6%, no other products were detected.

Example 15

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The mixture is stirred and reacted for 12.0h at 800rpm under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) of triphenyl (triphenylene) was added to the reaction mixturePhosphine (PPh)₃) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 4.74%, cyclohexanol selectivity 50.9%, cyclohexanone selectivity 44.5%, cyclohexyl hydroperoxide selectivity 4.6%, no other products were detected.

Example 16

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 800rpm for 18.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 5.96%, cyclohexanol selectivity 55.1%, cyclohexanone selectivity 39.1%, cyclohexyl hydroperoxide selectivity 5.8%, no other products were detected.

Example 17

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The mixture is stirred and reacted for 24.0h at 800rpm under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 6.88%, cyclohexanol selectivity 51.1%, cyclohexanone selectivity 42.4%, cyclohexyl hydroperoxide selectivity 6.5%, no other products were detected.

Example 18

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) inDispersed in 8.4160g (100mmol) of cyclohexane. The reaction was stirred at 200rpm for 8.0h under 500W UV lamp irradiation. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 2.55%, cyclohexanol selectivity 74.6%, cyclohexanone selectivity 21.1%, cyclohexyl hydroperoxide selectivity 4.3%, no other products were detected.

Example 19

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 400rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 2.97%, cyclohexanol selectivity 73.8%, cyclohexanone selectivity 21.7%, cyclohexyl hydroperoxide selectivity 4.5%, no other products were detected.

Example 20

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction was stirred at 600rpm for 8.0h under 500W UV lamp irradiation. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 3.70%, cyclohexanol selectivity 71.6%, cyclohexanone selectivity 23.5%, cyclohexyl hydroperoxide selectivity 4.9%, no other products were detected.

Example 21

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction was stirred at 1000rpm for 8.0h under 500W UV lamp irradiation. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 3.65%, cyclohexanol selectivity 70.5%, cyclohexanone selectivity 24.1%, cyclohexyl hydroperoxide selectivity 5.4%, no other products were detected.

Example 22

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction was stirred at 1200rpm for 8.0h under 500W UV lamp irradiation. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 3.63%, cyclohexanol selectivity 70.4%, cyclohexanone selectivity 24.0%, cyclohexyl hydroperoxide selectivity 5.6%, no other products were detected.

Example 23

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction was stirred at 800rpm for 24.0h under 175W UV lamp irradiation. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. CyclohexaneThe alkane conversion was 4.91%, the cyclohexanol selectivity was 56.7%, the cyclohexanone selectivity was 37.8%, the cyclohexyl hydroperoxide selectivity was 5.5%, and no other products were detected.

Example 24

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 800rpm for 24.0h under the irradiation of a 300W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 5.37%, cyclohexanol selectivity 54.9%, cyclohexanone selectivity 39.3%, cyclohexyl hydroperoxide selectivity 5.8%, no other products were detected.

Example 25

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 7.0140g (100mmol) of cyclopentane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclopentane conversion 3.82%, cyclopentanol selectivity 74.4%, cyclopentanone selectivity 22.8%, cyclopentyl hydroperoxide selectivity 2.8%, and no other products were detected.

Example 26

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 9.8270g (100mmol) of cycloheptane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) Stirring at room temperatureThe generated peroxide was reduced for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using toluene as an internal standard. The conversion of cycloheptane was 5.80%, the selectivity for cycloheptanol was 70.2%, the selectivity for cycloheptanone was 24.8%, and the selectivity for cycloheptyl hydroperoxide was 5.0%, and no other products were detected.

Example 27

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 11.2200g (100mmol) of cyclooctane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. The conversion rate of cyclooctane is 7.03 percent, the selectivity of cyclooctanol is 68.1 percent, the selectivity of cyclooctanone is 26.4 percent, the selectivity of cyclooctyl hydrogen peroxide is 5.5 percent, and other products are not detected.

Example 28

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(8.0mg,0.08mg/mmol) was dispersed in 16.8319g (100mmol) of cyclododecane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclododecane conversion 9.44%, cyclododecanol selectivity 62.7%, cyclododecanone selectivity 27.4%, cyclododecyl hydroperoxide selectivity 9.9%, no other products were detected.

Example 29 (comparative experiment)

In a 25mL quartz glass tube covered with an oxygen balloon, cobalt nitrate hexahydrate (1.0mg, 5X 10)^-3mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexaneIn (1). The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 0.12%, cyclohexanol selectivity 27.0%, cyclohexanone selectivity 21.7%, cyclohexyl hydroperoxide selectivity 51.3%, no other products were detected.

Example 30 (comparative experiment)

T (4-COOH) PPCo (II) (2mg, 1.2X 10) was put in a 25mL silica glass tube with oxygen balloon^-5mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 0.31%, cyclohexanol selectivity 27.0%, cyclohexanone selectivity 26.4%, cyclohexyl hydroperoxide selectivity 46.6%, no other products were detected.

Example 31 (comparative experiment)

Metalloporphyrin monometallic centre (Co)2D MOFs (16.0mg,0.08mg/mmol) were dispersed in 8.4160g (100mmol) cyclohexane in a 25mL quartz glass tube sheathed with an oxygen balloon. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 1.86%, cyclohexanol selectivity 30.8%, cyclohexanone selectivity 32.2%, cyclohexyl hydroperoxide selectivity 37.0%, no other products were detected.

Example 32 (comparative experiment)

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-4(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 3.44%, cyclohexanol selectivity 64.3%, cyclohexanone selectivity 31.0%, cyclohexyl hydroperoxide selectivity 4.7%, no other products were detected.

Example 33 (comparative experiment)

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-5(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 3.58%, cyclohexanol selectivity 65.5%, cyclohexanone selectivity 30.2%, cyclohexyl hydroperoxide selectivity 4.3%, no other products were detected.

Example 34 (comparative experiment)

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-6(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Ring (C)Hexane conversion 3.02%, cyclohexanol selectivity 66.1%, cyclohexanone selectivity 29.7%, cyclohexyl hydroperoxide selectivity 4.2%, no other products were detected.

Example 35 (comparative experiment)

In a 25mL quartz glass tube covered with an oxygen balloon, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-7(8.0mg,0.08mg/mmol) was dispersed in 8.4160g (100mmol) cyclohexane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, it was cooled to room temperature, and 0.7869g (3.00mmol) 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 analyzed by gas chromatography using toluene as an internal standard. Cyclohexane conversion 3.00%, cyclohexanol selectivity 66.5%, cyclohexanone selectivity 29.5%, cyclohexyl hydroperoxide selectivity 4.0%, no other products were detected.

Example 36 (amplification experiment)

In a 1L quartz glass reactor with oxygen, metalloporphyrin trimetallic center (Co)&Cu&Zn)2DMOFs-1(80.0mg,0.08mg/mmol) was dispersed in 84.160g (1mol) cyclohexane. The reaction is stirred at 800rpm for 8.0h under the irradiation of a 500W ultraviolet lamp. After completion of the reaction, ice water was cooled to room temperature, and 131.15g (500.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. Distilling, recovering 79.72g of cyclohexane, and obtaining a conversion rate of 5.27%; vacuum rectification is carried out to obtain 3.04g of cyclohexanol with selectivity of 57.6 percent, 2.12g of cyclohexanone with selectivity of 41.0 percent.

The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.